Handbook of Research On Nanoscience, Nanotechnology, and Advanced Materials (2014) PDF

Handbook of Research
on Nanoscience,
Nanotechnology, and
Advanced Materials
Mohamed Bououdina
University of Bahrain, Bahrain
J. Paulo Davim
University of Aveiro, Portugal
A volume in the Advances in Chemical

and Materials Engineering (ACME) Book
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Handbook of research on nanoscience, nanotechnology, and advanced materials / Mohamed Bououdina and J. Paulo Davim,
editors.
pages cm
Summary: This book presents a detailed analysis of current experimental and theoretical approaches surrounding nanomaterials science and applications in fields such as biomedicine, renewable energy, and synthetic materials-Provided by publisher.
Includes bibliographical references and index.
ISBN 978-1-4666-5824-0 (hardcover) -- ISBN 978-1-4666-5825-7 (ebook) -- ISBN 978-1-4666-5827-1 (print & perpetual
access) 1. Nanotechnology. 2. Nanostructured materials. I. Bououdina, Mohamed, 1965- editor of compilation. II. Davim,
J. Paulo, editor of compilation.
T174.7.H367 2014
620.5--dc23
2013051201
This book is published in the IGI Global book series Advances in Chemical and Materials Engineering (ACME) (ISSN:
2327-5448; eISSN: 2327-5456)
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Advances in Chemical
and Materials
Engineering (ACME)
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J. Paulo Davim
University of Aveiro, Portugal
ISSN: 2327-5448
EISSN: 2327-5456
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Handbook of Research on Nanoscience, Nanotechnology, and Advanced Materials

Mohamed Bououdina (University of Bahrain, Bahrain) and J. Paulo Davim (University of Aveiro, Portugal)
Engineering Science Reference copyright 2014 375pp H/C (ISBN: 9781466658240) US $295.00 (our price)
Quantum and Optical Dynamics of Matter for Nanotechnology
Mihai V. Putz (West University of Timisoara, Romania)
Advanced Solar Cell Materials, Technology, Modeling, and Simulation
Laurentiu Fara (Polytechnic University of Bucharest, Romania) and Masafumi Yamaguchi (Toyota Technological
Institute, Japan)
Computational Gas-Solids Flows and Reacting Systems Theory, Methods and Practice
Sreekanth Pannala (Oak Ridge National Laboratory, USA) Madhava Syamlal (National Energy Technology Laboratory, USA) and Thomas J. OBrien (National Energy Technology Laboratory, USA)
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Editorial Advisory Board

J. L. Bobet, Universite de Boredaux I, France
R. Boukhanouf, Universit Lille 1, France
D. Fruchart, Institut Neel, France
Z. X. Guo, University College of London, UK
M. Ishaque Khan, Illinois Institute of Technology, USA
Nouar Tabet, Qatar Energy and Environment Research Institute, Qatar
G. Walker, University of Nottingham, UK
Yokoyama, Kent State University, USA
List of Reviewers
Esam H. Abdul-Hafidh, Yanbu University College, Saudi Arabia
H. A. Adnane, Yanbu University College, Saudi Arabia
Feroz Ahmad Mir, University of Kashmir, India
Iftikhar Ahmed, University of Malakand, Pakistan
Rashid Ahmed, Universiti Teknologi Malaysia, Malaysia
Cheknane Ali, Universit Amar Telidji de Laghouat, Algeria
Luc Aymard, University of Picardie Jules Verne, France
Rachid Belkada, Centre de Recherche en Technologie des Semi-Conducteurs Pour lEnergitique, Algeria
Yaakov (Kobi) Benenson, ETH Zrich, Switzerland
Samir Boulfrad, Solar and Photovoltaics Engineering Research Center, Saudi Arabia
Costas Charitidies, University of Athens, Greece
Ingram Conrad, University of West Indies, USA
Eithiraj Rajagopal Dashinamoorthy, Donostia International Physics Centre, Spain
E. Deligoz, Aksaray University, Turkey
Thierry Djenizian, Aix-Marseille Universit Equipe Chimie-Physique, France
Ayub Elahi, University of Engineering and Technology, Pakistan
Mohamed Fathi, Centre de Recherche en Technologie des Semi-Conducteurs Pour lEnergitique, Algeria
Khaldi Fouad, Universit de Batna, Algeria
Mark Franken, University of Bath, UK
Qiang Fu, University of Connecticut, USA
Mounir Gaidi, Research and Technology Centre of Energy, Tunisia
Rukan Genc, Mersin University, Turkey
Sevdalin Georgiev, Sofia University, Bulgaria

Gopukumar, Central Electro-Chemical Research Institute, India
Wolfgang Hess, Freiburg University, Germany
Tajammul Hussain, National Centre of Physics, Pakistan
Ishrat Khan, University of Florida, USA
S. S. Islam, Central University, India
Tariq-ul Islam, Central University, India
Yassin A. Jeilani, Spelman College, USA
Dinesh Jesrotia, GGM Science College Jammu, India
Anup Kale, Singapore Bioimaging Consortium, Singapore
Amal Kasry, Austrian Institute of Technology (AIT), Austria
G. Davon Kennedy, Georgia State University, USA
R. V. Krishnarao, Defence Metallurgical Research Laboratory, India
Huayang Li, Clark Atlanta University, USA
Jing Li, Eugene Applebaum College of Pharmacy and Health Sciences, USA
K. Maaz, Chinese Academy of Sciences, China
Shazim Memon, Department of Civil and Architectural Engineering, Hong Kong
Abdelkrim Merad, International Centre for Theoretical Physics (ICTP), Italy
Rahul Mitra, Indian Institute of Technology, India
Abdul Khader Mohammad, Pharmaceutics International Inc. (PII), USA
Sylvie Morin, York University, Canada
Maqbool Muhammad, Ball State University, USA
Gautam Mukherjee, Burdwan University, India
M. Nedil, Universit du Qubec, Canada
Kemal Ozdogan, Yildiz Technical University, Turkey
Liaqat Qureshi, University of Engineering and Technology, Pakistan
Michael Rajamathi, St. Josephs College, India
S. Rath, University of Delhi, India
James L. Reed, Northwestern University, USA
El Hadi Sadki, United Arab Emirates University, UAE
Patrik Schmuki, University of Erlangen Nuremberg, Germany
Muhammad Shahid, King Abdullah University of Science and Technology, Saudi Arabia
Dimtri Shtansky, National University of Science and Technology, Russia
Andrey L. Stepanov, Kazan State Technological University, Russia
N. Tabet, King Fahd King Fahd University of Petroleum and Minerals, Saudi Arabia
Bashir Tahir, Universiti Teknologi Malaysia, Malaysia
Muhammet Toprak, KTH Institute, Sweden
Jay Wadhawan, University of Hull, UK
Lon J. Wilson, Rice University, USA
Xing-Hua Xia, Nanjing University, China
Y. Yagoub, University of Ottawa, Canada
M. Zaabat, University of Oum El Bouaghi, Algeria
Zulkarnain Zainal, Universiti Putra Malaysia, Malaysia
Hadi Zareie, Gediz niversitesi, Turkey
List of Contributors
Assa, Brahim / MPB Technologies Inc., Canada . ........................................................................ 1, 108

Ali, Zahid / Sungkyunkwan University, Korea ................................................................................... 376
Al-Nashef, InasMuen / King Saud University, Saudi Arabia ............................................................ 376
Barbhuiya, Salim / Curtin University of Technology, Australia ........................................................ 164
Bayir, Ece / Ege University, Turkey .................................................................................................... 447
Benouaz, Tayeb / Tlemcen University, Algeria .................................................................................. 492
Bilgi, Eyup / Ege University, Turkey .................................................................................................. 447
Boukherroub, Rabah / Universit Lille 1, France .................................................................... 176, 196
Boumaza, Nawel / Tlemcen University, Algeria . ............................................................................... 492
Bououdina, Mohamed / University of Bahrain, Bahrain .................................................................. 312
Brimmo, Ayoola / Masdar Institute of Science and Technology, UAE .............................................. 268
Das, Manash R. / CSIR-North East Institute of Science and Technology, Jorhat, India ................... 196
Deshmukh, Ashvini B. / CSIR-National Chemical Laboratory, India .............................................. 196
Emziane, Mahieddine / Masdar Institute of Science and Technology, UAE . ........................... 226, 268
Fruchart, D. / CNRS de Grenoble, France ........................................................................................ 312
Goumri-Said, Souraya / King Abdullah University of Science and Technology (KAUST), Saudi
Arabia ................................................................................................................................... 431, 492
Guo, Z. X. / University College London, UK ..................................................................................... 312
Harruna, Issifu / Clark Atlanta University, USA . ............................................................................... 26
Hussain, Najrul / CSIR-North East Institute of Science and Technology, Jorhat, India ................... 196
Hussain, Rafaqat / Universiti Teknologi Malaysia, Malaysia ........................................................... 376
Kamaja, Chaitanya Krishna / National Chemical Laboratory (CSIR), India ................................. 176
Kang, DaeJoon / Sungkyunkwan University, Korea .......................................................................... 376
Kanoun, Mohammed Benali / King Abdullah University of Science and Technology (KAUST),
Saudi Arabia ................................................................................................................................. 431
Khayyat, Maha Mohamed / Umm al-Qura University, Saudi Arabia .......................................... 1, 108
Li, Huayang / Clark Atlanta University, USA ...................................................................................... 26
Li, Mingguang / Wayne State University, USA .................................................................................. 146
Melnyczuk, John M. / Clark Atlanta University, USA ........................................................................ 89
Nafady, Ayman / King Saud University, Saudi Arabia ...................................................................... 376
Palchoudhury, Soubantika / Yale University, USA . ........................................................................... 89
Penchovsky, Robert / Sofia University St. Kliment Ohridski, Bulgaria ........................................ 414
Rajaperumal, M. / National Chemical Laboratory (CSIR), India .................................................... 176
Rana, Usman Ali / King Saud University, Saudi Arabia ................................................................... 376
Roy, Manish / Defence Metallurgical Research Laboratory, India ..................................................... 62
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Sarfraz, Mansoor / King Saud University, Saudi Arabia .................................................................. 376

Shah, K. A. / Govt. Degree College for Women, Anantnag, India ..................................................... 131
Shah, M. A. / National Institute of Technology, Srinagar, India . ...................................................... 131
Shakir, Imran / Sungkyunkwan University, Korea & King Saud University, Saudi Arabia .............. 376
Sharma, Ponchami / CSIR-North East Institute of Science and Technology, Jorhat, India . ............ 196
Shelke, Manjusha V. / National Chemical Laboratory (CSIR), India ...................................... 176, 196
Souier, Tewfik / Masdar Institute of Science and Technology, UAE . ................................................ 343
Szunerits, Sabine / Institut de Recherche Interdisciplinaire Universit Lille 1, France .................... 196
Urkmez, Aylin Sendemir / Ege University, Turkey ........................................................................... 447
Walker, G. / University of Nottingham, UK ....................................................................................... 312
Yoosuf, Rahana / Masdar Institute of Science and Technology, UAE ............................................... 226
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Table of Contents
Preface .................................................................................................................................................. xx
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Chapter 1
Self-Healing Materials Systems as a Way for Damage Mitigation in Composites Structures
Caused by Orbital Space Debris..............................................................................................................1
Brahim Assa, MPB Technologies Inc., Canada
Maha Mohamed Khayyat, Umm al-Qura University, Saudi Arabia
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Chapter 2
Functionalization of Carbon Nanocomposites with Ruthenium Bipyridine and Terpyridine
Complex.................................................................................................................................................26
Issifu Harruna, Clark Atlanta University, USA
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Chapter 3
Nano Indentation Response of Various Thin Films Used for Tribological Applications......................62
Manish Roy, Defence Metallurgical Research Laboratory, India
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Chapter 4
Synthesis and Characterization of Iron Oxide Nanoparticles................................................................89
John M. Melnyczuk, Clark Atlanta University, USA
Soubantika Palchoudhury, Yale University, USA
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Chapter 5
Si-NWs: Major Advances in Synthesis and Applications...................................................................108
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Chapter 6
Principles of Raman Scattering in Carbon Nanotubes.........................................................................131
K. A. Shah, Govt. Degree College for Women, Anantnag, India
M. A. Shah, National Institute of Technology, Srinagar, India
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Chapter 7
Pharmacokinetics of Polymeric Nanoparticles at Whole Body, Organ, Cell, and Molecule .
Levels...................................................................................................................................................146
Mingguang Li, Wayne State University, USA
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Chapter 8
Applications of Nanomaterials in Construction Industry....................................................................164
Salim Barbhuiya, Curtin University of Technology, Australia
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Chapter 9
Silicon Nanostructures-Graphene Nanocomposites: Efficient Materials for Energy Conversion .
and Storage...........................................................................................................................................176
Chaitanya Krishna Kamaja, National Chemical Laboratory (CSIR), India
M. Rajaperumal, National Chemical Laboratory (CSIR), India
Rabah Boukherroub, Universit Lille 1, France
Manjusha V. Shelke, National Chemical Laboratory (CSIR), India
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Chapter 10
Metal Oxide-Graphene Nanocomposites: Synthesis to Applications..................................................196
Ponchami Sharma, CSIR-North East Institute of Science and Technology, Jorhat, India
Najrul Hussain, CSIR-North East Institute of Science and Technology, Jorhat, India
Manash R. Das, CSIR-North East Institute of Science and Technology, Jorhat, India
Ashvini B. Deshmukh, CSIR-National Chemical Laboratory, India
Manjusha V. Shelke, CSIR-National Chemical Laboratory, India
Sabine Szunerits, Institut de Recherche Interdisciplinaire Universit Lille 1, France
Rabah Boukherroub, Institut de Recherche Interdisciplinaire Universit Lille 1, France
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Chapter 11
In2X3 (X=S, Se, Te) Semiconductor Thin Films: Fabrication, Properties, and Applications..............226
Mahieddine Emziane, Masdar Institute of Science and Technology, UAE
Rahana Yoosuf, Masdar Institute of Science and Technology, UAE
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Chapter 12
Carbon Nanotubes for Photovoltaics....................................................................................................268
Ayoola Brimmo, Masdar Institute of Science and Technology, UAE
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Chapter 13
Overview on Hydrogen Absorbing Materials: Structure, Microstructure, and Physical .
Properties.............................................................................................................................................312
Mohamed Bououdina, University of Bahrain, Bahrain
Z. X. Guo, University College London, UK
D. Fruchart, CNRS de Grenoble, France
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Chapter 14
Conductive Probe Microscopy Investigation of Electrical and Charge Transport in Advanced
Carbon Nanotubes and Nanofibers-Polymer Nanocomposites............................................................343
Tewfik Souier, Masdar Institute of Science and Technology, UAE
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Chapter 15
Nanostructured Materials for the Realization of Electrochemical Energy Storage and Conversion
Devices: Status and Prospects..............................................................................................................376
Imran Shakir, Sungkyunkwan University, Korea & King Saud University, Saudi Arabia
Zahid Ali, Sungkyunkwan University, Korea
Usman Ali Rana, King Saud University, Saudi Arabia
Ayman Nafady, King Saud University, Saudi Arabia
Mansoor Sarfraz, King Saud University, Saudi Arabia
InasMuen Al-Nashef, King Saud University, Saudi Arabia
Rafaqat Hussain, Universiti Teknologi Malaysia, Malaysia
DaeJoon Kang, Sungkyunkwan University, Korea
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Chapter 16
Nucleic Acids-Based Nanotechnology: Engineering Principals and Applications.............................414
Robert Penchovsky, Sofia University St. Kliment Ohridski, Bulgaria
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Chapter 17
Theoretical Assessment of the Mechanical, Electronic, and Vibrational Properties of the
Paramagnetic Insulating Cerium Dioxide and Investigation of Intrinsic Defects................................431
Mohammed Benali Kanoun, King Abdullah University of Science and Technology (KAUST),
Saudi Arabia
Souraya Goumri-Said, King Abdullah University of Science and Technology (KAUST), Saudi
Arabia
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Chapter 18
Implementation of Nanoparticles in Cancer Therapy..........................................................................447
Ece Bayir, Ege University, Turkey
Eyup Bilgi, Ege University, Turkey
Aylin Sendemir Urkmez, Ege University, Turkey
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Chapter 19
Understanding the Numerical Resolution of Perturbed Soliton Propagation in Single Mode
Optical Fiber........................................................................................................................................492
Nawel Boumaza, Tlemcen University, Algeria
Tayeb Benouaz, Tlemcen University, Algeria
Arabia
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Compilation of References . .............................................................................................................. 505

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About the Contributors .................................................................................................................... 605

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Index ................................................................................................................................................... 615

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Detailed Table of Contents
Preface .................................................................................................................................................. xx
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Chapter 1
Caused by Orbital Space Debris..............................................................................................................1
10.4018/978-1-4666-5824-0.ch001
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The presence in space of orbital debris, particularly in low earth orbit, presents a continuous hazard
to orbiting satellites and spacecrafts. The development of self-healing materials offers the designer an
ability to incorporate secondary functional materials capable of counteracting service degradation whilst
still achieving the primary, usually structural, requirement. This chapter reviews the various self-healing
technologies currently being developed. Self-healing systems can be made from a variety of polymers and
metallic materials. An overview of various self-healing concepts over the past two decades is presented.
Finally, a perspective on current and future self-healing approaches using this biomimetic technique is
offered. The intention is to stimulate debate and reinforce the importance of a multidisciplinary approach
in this exciting field.
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Chapter 2
Functionalization of Carbon Nanocomposites with Ruthenium Bipyridine and Terpyridine
Complex.................................................................................................................................................26
Issifu Harruna, Clark Atlanta University, USA
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Ruthenium bipyridine or terpyridine complexes functionalized carbon-based nanocomposites have special

properties in the electromagnetic and photochemical research field. The aims of this chapter include
development of functionalized fullerene, carbon nanotubes, and graphene with ruthenium complex and
characterization of their nanostructural properties. Such nanocomposites can be accomplished using
either covalent or non-covalent functionalization methods.
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Chapter 3
Nano Indentation Response of Various Thin Films Used for Tribological Applications......................62
Manish Roy, Defence Metallurgical Research Laboratory, India
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Various thin films used for tribological applications are classified under four heads. Based on their load
vs. displacement curves, which have some characteristics features, the ratio of nanohardness to elastic
modulus and the ratio of cube of nanohardness to square of elastic modulus are evaluated in this chapter.
It is demonstrated that depending on the type of film used, these ratios vary within a certain range. For
soft self-lubricating films, these ratios are very low; whereas for hard self-lubricating film, these ratios
are quite high.
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Chapter 4
Synthesis and Characterization of Iron Oxide Nanoparticles................................................................89
John M. Melnyczuk, Clark Atlanta University, USA
Soubantika Palchoudhury, Yale University, USA
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Iron oxide nanoparticles show great promise in bio-applications like drug delivery, magnetic resonance
imaging, and hyperthermia. This is because the size of these magnetic nanoparticles is comparable to
biomolecules and the particles can be removed via normal iron metabolic pathways. These nanoparticles
are also attractive for industrial separations and catalysis because they can be magnetically recovered.
However, the size, morphology, and surface coating of the iron oxide nanoparticles greatly affect their
magnetic properties and biocompatibility. Therefore, nanoparticles with tunable characteristics are
desirable. This chapter elaborates the synthesis techniques for the formation of iron oxide nanoparticles
with good control over reproducibility, surface and magnetic properties, and morphology. The wellknown co-precipitation and thermal decomposition methods are detailed in this chapter. The surface
modification routes and characterization of these nanoparticles are also discussed. The chapter will be
particularly useful for engineering/science graduate students and/or faculty interested in synthesizing
iron oxide nanoparticles for specific research applications.
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Chapter 5
Si-NWs: Major Advances in Synthesis and Applications...................................................................108
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Surfaces and interfaces have a special significance to nanotechnology because the surface/volume
ratio of nanomaterials is larger than for the bulk ones. Therefore, interfaces of nanomaterials are more
important to the properties of the nanomaterials than for larger scale materials. Moreover, crystal growth
and more particularly Nanowires (NWs) growth occurs at the interfaces between the growing crystals
and the supply media. This chapter focuses on the silicon nanowires grown using a Vapor-Liquid-Solid
(VLS) concept. One of the key advantages of VLS is that controlled placement or templating of the
seed metal produces templated NW growth. This templating is required for integration of NWs with
other devices, which is desirable for many applications. The authors discuss issues on the discovery of
fundamentally new phenomena versus performance benchmarking for many of the Si-NW applications.
Finally, the authors attempt to look into the future and offer their personal opinions on the upcoming
trends in nanowire research.
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Chapter 6
Principles of Raman Scattering in Carbon Nanotubes.........................................................................131
K. A. Shah, Govt. Degree College for Women, Anantnag, India
M. A. Shah, National Institute of Technology, Srinagar, India
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Carbon nanotubes have attracted the scientific community throughout the world, and in the past decade, a
lot of work has been reported related with synthesis, characterization, and applications of carbon nanotubes.
This chapter is written for readers who are not familiar with the basic principles of Raman spectroscopy
in carbon nanotubes. The structure of carbon nanotubes, types of the carbon nanotubes, Brillouin zone
of carbon nanotubes, and band structure of carbon nanotubes are discussed at length, which will serve
as foundation for the study of Raman scattering in carbon nanotubes. The Density of States (DOS) of
single walled carbon nanotubes are illustrated by an example which will encourage readers to calculate
the DOS of any type of carbon nanotube. The Raman modes of vibration are discussed, and Raman
spectroscopic analysis is presented by considering the typical spectra of single-walled carbon nanotubes.
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Chapter 7
Pharmacokinetics of Polymeric Nanoparticles at Whole Body, Organ, Cell, and Molecule .
Levels...................................................................................................................................................146
Mingguang Li, Wayne State University, USA
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Polymeric nanoparticles have been increasingly studied and applied in a variety of areas, most commonly
in biomedicine. The efficiency and toxicity are two aspects that need to be considered for nanoparticles,
and both are closely related to the pharmacokinetics of nanoparticles. In this chapter, the pharmacokinetics
of polymeric nanoparticles were introduced at the whole body level (including absorption, distribution,
metabolism, and excretion), organism level (transportation within organs and pass through physiological
barriers), cell levels (binding to cell surface, endocytosis, intracellular transition, and exocytosis), and
molecule level (protein binding and ligand-receptor binding). Examples were also given to illustrate
the modeling of the pharmacokinetics of polymeric nanoparticles at different levels. A comprehensive
understanding of the pharmacokinetics of polymeric nanoparticles will facilitate the applications in
various areas such as drug delivery and disease diagnosis.
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Chapter 8
Applications of Nanomaterials in Construction Industry....................................................................164
Salim Barbhuiya, Curtin University of Technology, Australia
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The application of nanomaterials in various applied fields has gained worldwide recognition. Nanomaterials
have the ability to manipulate the structure at nano-scale. This leads to the generation of tailored and
multifunctional composites with improved mechanical and durability performance. Recognizing this, the
construction industry recently has started to use a variety of nanomaterials. The use of these materials is
found to improve various fundamental characteristics of construction materials including the strength,
durability, and lightness. In this chapter an attempt is made to review the use of various nanomaterials
in cementitous system. This is followed by a discussion of the challenges related to their use. Finally,
the strategies for using nanomaterials in construction industry for the next ten years are identified.
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Chapter 9
Silicon Nanostructures-Graphene Nanocomposites: Efficient Materials for Energy Conversion .
and Storage...........................................................................................................................................176
Chaitanya Krishna Kamaja, National Chemical Laboratory (CSIR), India
M. Rajaperumal, National Chemical Laboratory (CSIR), India
Rabah Boukherroub, Universit Lille 1, France
Manjusha V. Shelke, National Chemical Laboratory (CSIR), India
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Global demand of energy is increasing at an alarming rate, and nanotechnology is being looked at as a
potential solution to meet this challenge (Holtren, 2007). Although the efficiency of energy conversion and
storage devices depends on a variety of factors, the overall performance strongly relies on the structure
and properties of the component materials (Whitesides, 2007). Compared to conventional materials,
silicon (Si) nanostructures and graphene nanosheets possess unique properties (i.e. morphological,
electrical, optical, and mechanical) useful for enhancing the energy-conversion and storage performances.
Graphene can enhance efficiency of nano-Si based solar cells and battery due to its high electronic
conductivity, ultrahigh mobility, high transparency, and strong mechanical property. This chapter provides
a comprehensive review of recent progress and material challenges in energy conversion (solar cells)
and storage (batteries/supercapacitors) with specific focus on composites of Si nanostructures-graphene
nanosheets.
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Chapter 10
Metal Oxide-Graphene Nanocomposites: Synthesis to Applications..................................................196
Ponchami Sharma, CSIR-North East Institute of Science and Technology, Jorhat, India
Najrul Hussain, CSIR-North East Institute of Science and Technology, Jorhat, India
Manash R. Das, CSIR-North East Institute of Science and Technology, Jorhat, India
Ashvini B. Deshmukh, CSIR-National Chemical Laboratory, India
Manjusha V. Shelke, CSIR-National Chemical Laboratory, India
Sabine Szunerits, Institut de Recherche Interdisciplinaire Universit Lille 1, France
Rabah Boukherroub, Institut de Recherche Interdisciplinaire Universit Lille 1, France
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Graphene is one of the most interesting materials in the field of nanoscience and nanotechnology. Metal
oxide nanoparticles exhibit unique physical and chemical properties due to their reduced size and high
density of corner or edge surface sites. The metal oxide-graphene nanocomposites not only possess
favorable properties of graphene and metal oxide, but also greatly enhance the intrinsic properties due
to the synergistic effect between them. These composites are used for catalysis, supercapacitors, lithium
ion batteries, solar cells, sensors, removal of pollutants from water, etc. There is a very broad scope of
further research for the development of metal oxide-graphene nanocomposites with enhanced properties
for different applications. This chapter deals with a comprehensive review of the current research
activities from the viewpoint of chemistry and materials science with a special focus on the synthesis,
characterization, and applications of metal oxide-graphene nanocomposite materials.
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Chapter 11
In2X3 (X=S, Se, Te) Semiconductor Thin Films: Fabrication, Properties, and Applications..............226
Rahana Yoosuf, Masdar Institute of Science and Technology, UAE
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Indium chalcogenide thin film semiconductor compounds In2X3 (with X being a chalcogen atom, i.e., S,
Se, or Te) are important materials in many current technological applications such as solar cells, microbatteries, memory devices, etc. This chapter reviews the recent progress in In2X3 (X = S, Se, or Te) thin
film research and development, with a particular attention paid to their growth and processing methods and
parameters, and the effects that these have on the films microstructure. The intimate relationship between
their fabrication conditions and the resulting physico-chemical and functional properties is discussed.
Finally, results pertaining to the fabrication and characterization of these thin film materials, as well
as the main devices and applications based on them are also highlighted and discussed in this chapter.
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Chapter 12
Carbon Nanotubes for Photovoltaics....................................................................................................268
Ayoola Brimmo, Masdar Institute of Science and Technology, UAE
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Recent developments show that the exceptional physical, optical, and electrical properties of Carbon
Nanotubes (CNTs) have now caught the attention of the Photovoltaics (PV) industry. This chapter
provides an updated and in-depth review of some of the most exciting and important developments in the
application of CNTs in photovoltaics. The chapter begins with a discussion of the underlying properties
of CNTs that make them promising for PV applications. A review of the literature on the application
of CNTs in the photoactive layer of Silicon (Si)-based heterojunctions, as anchors for light harvesting
materials in Dye Sensitized Solar Cells (DSSCs) and as components of other organic solar cells (OPVs),
is then presented. Findings portend the promise of CNTs in bridging the gap between the two classes of
solar cells currently in the market. Since the technology is in its early stages, it is generally limited by a
general lack of understanding of CNTs and their adequate growth mechanisms.
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Chapter 13
Overview on Hydrogen Absorbing Materials: Structure, Microstructure, and Physical .
Properties.............................................................................................................................................312
Mohamed Bououdina, University of Bahrain, Bahrain
Z. X. Guo, University College London, UK
D. Fruchart, CNRS de Grenoble, France
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Hydrogen is a promising and clean fuel for transportation and domestic applications, but is difficult to
store. Many systems have been investigated in order to improve the maximum hydrogen storage capacity
(reversibility), high kinetics, moderate equilibrium pressure and/or decomposition temperature, and better
cyclability. In this chapter, a review of studies related to stability of Zr-based Laves phase system as
well as in-situ neutron diffraction investigation, the kinetics of TiFe, surface treatment of LaNi5 system,
mechanically alloyed Mg-based hydrides, and graphite nanofibers are reported.
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Chapter 14
Conductive Probe Microscopy Investigation of Electrical and Charge Transport in Advanced
Carbon Nanotubes and Nanofibers-Polymer Nanocomposites............................................................343
Tewfik Souier, Masdar Institute of Science and Technology, UAE
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In this chapter, the main scanning probe microscopy-based methods to measure the transport properties in
advanced polymer-Carbon Nanotubes (CNT) nanocomposites are presented. The two major approaches
to investigate the electrical and charge transport (i.e., Electrostatic Force Microscopy [EFM] and CurrentSensing Atomic Force Microscopy [CS-AFM]) are illustrated, starting from their basic principles. First,
the authors show how the EFM-related techniques can be used to provide, at high spatial resolution,
a three-dimensional representation CNT networks underneath the surface. This allows the studying of
the role of nanoscopic features such as CNTs, CNT-CNT direct contact, and polymer-CNT junctions
in determining the overall composite properties. Complementary, CS-AFM can bring insight into
the transport mechanism by imaging the spatial distribution of currents percolation paths within the
nanocomposite. Finally, the authors show how the CS-AFM can be used to quantify the surface/bulk
percolation probability and the nanoscopic electrical conductivity, which allows one to predict the
macroscopic percolation model.
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Chapter 15
Nanostructured Materials for the Realization of Electrochemical Energy Storage and Conversion
Devices: Status and Prospects..............................................................................................................376
Imran Shakir, Sungkyunkwan University, Korea & King Saud University, Saudi Arabia
Zahid Ali, Sungkyunkwan University, Korea
Usman Ali Rana, King Saud University, Saudi Arabia
Ayman Nafady, King Saud University, Saudi Arabia
Mansoor Sarfraz, King Saud University, Saudi Arabia
InasMuen Al-Nashef, King Saud University, Saudi Arabia
Rafaqat Hussain, Universiti Teknologi Malaysia, Malaysia
DaeJoon Kang, Sungkyunkwan University, Korea
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One of the greatest challenges for the modern world is the ever-increasing demand of energy, which
may soon outstrip the amount of natural resources that can be obtained using currently known energy
conversion and energy storage technologies such as solar cells, fuel cells, lithium ion batteries, and
supercapacitors. It appears that the maximum output efficiencies of these devices have already reached
the intrinsic limits of almost all electrocatalyst materials. Hence, it is a high time to think about new
material architectures by controlling size, shape, and geometry, as well as composition that can potentially
make a significant improvement in the performance of these electrochemical devices. Among several
known electrocatalyst materials are nanomaterials and their composites due to their unique electrical,
mechanical, physical, chemical, and structural characteristics. These materials have opened a whole
new territory of possibilities in designing high performance energy storage and conversion devices. In
this chapter, the authors review the recent progress in energy storage and conversion devices that utilize
various nanomaterials and their composite materials and identify future directions in which the field is
likely to develop.
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Chapter 16
Nucleic Acids-Based Nanotechnology: Engineering Principals and Applications.............................414
Robert Penchovsky, Sofia University St. Kliment Ohridski, Bulgaria
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Nanobiotechnology is emerging as a valuable field that integrates research from science and technology
to create novel nanodevices and nanostructures with various applications in modern nanotechnology.
Applications of nanobiotechnology are employed in biomedical and pharmaceutical research, biosensoring,
nanofluidics, self-assembly of nanostructures, nanopharmaceutics, molecular computing, and others. It
has been proven that nucleic acids are a very suitable medium for self-assembly of diverse nanostructures
and catalytic nanodevices for various applications. In this chapter, the authors discuss various applications
of nucleic-based nanotechnology. The areas discussed here include building nanostructures using DNA
oligonucleodite, self-assembly of integrated RNA-based nanodevices for molecular computing and
diagnostics, antibacterial drug discovery, exogenous control of gene expression, and gene silencing.
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Chapter 17
Theoretical Assessment of the Mechanical, Electronic, and Vibrational Properties of the
Paramagnetic Insulating Cerium Dioxide and Investigation of Intrinsic Defects................................431
Mohammed Benali Kanoun, King Abdullah University of Science and Technology (KAUST),
Saudi Arabia
Arabia
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First-principles calculations are performed by taking into account the strong correlation effects on ceria. To
obtain an accurate description including f electrons, the authors optimized the Coulomb U parameter for
use in Local-Density Approximation (LDA) and Generalized Gradient Approximation (GGA) calculation.
A good agreement with experimental data is obtained within the GGA+U (Wu-Cohen scheme). Elastic
stiffness constants are found in correct agreement with the available experimental results. Born effective
charge, dielectric permittivity, and the phonon-dispersion curves are computed using density functional
perturbation theory. The origin of magnetism in undoped ceria with intrinsic defects is investigated.
The authors show that both of Ce and O vacancies induce local moments and ferromagnetism without
doping ceria by magnetic impurities in this chapter.
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Chapter 18
Implementation of Nanoparticles in Cancer Therapy..........................................................................447
Ece Bayir, Ege University, Turkey
Eyup Bilgi, Ege University, Turkey
Aylin Sendemir Urkmez, Ege University, Turkey
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Cancer is a wide group of diseases and generally characterized by uncontrolled proliferation of cells
whose metabolic activities are disrupted. Conventionally, chemotherapy, radiotherapy, and surgery are
used in the treatment of cancer. However, in theory, even a single cancer cell may trigger recurrence.
Therefore, these treatments cannot provide high survival rate for deadly types. Identification of alternative
methods in treatment of cancers is inevitable because of adverse effects of conventional methods. In
the last few decades, nanotechnology developed by scientists working in different disciplinesphysics,
chemistry, and biologyoffers great opportunities. It is providing elimination of both circulating tumor
cells and solid cancer cells by targeting cancer cells. In this chapter, inadequate parts of conventional
treatment methods, nanoparticle types used in new treatment methods of cancer, and targeting methods
of nanoparticles are summarized; furthermore, recommendations of future are provided.
10.4018/978-1-4666-5824-0.ch018
Chapter 19
Understanding the Numerical Resolution of Perturbed Soliton Propagation in Single Mode
Optical Fiber........................................................................................................................................492
Nawel Boumaza, Tlemcen University, Algeria
Tayeb Benouaz, Tlemcen University, Algeria
Arabia
10.4018/978-1-4666-5824-0.ch019
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The authors solve the propagation soliton perturbation problem in a nonlinear optical system based on a
single mode optical fiber by introducing Rayleighs dissipation function in the framework of variational
approach. The adopted methodology has facilitated the variational approach to be applied on a dissipative
system where the Lagrangian and Hamiltonian are difficult to solve. The authors model the propagation
in a nonlinear medium by using a nonlinear Schrdinger equation (NLSE). This is a mathematical model
used to describe the optical fiber. The chapter is focused on the propagation of perturbed solitary waves
in single mode fiber.
10.4018/978-1-4666-5824-0.ch019
Compilation of References . .............................................................................................................. 505

10.4018/978-1-4666-5824-0.chcrf
About the Contributors .................................................................................................................... 605

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Index ................................................................................................................................................... 615

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xx
Preface
Nanoscience has been defined as the manipulation of matter as the nanoscale, as well as the discovery
of new nanomaterials with fascinating properties (mechanical, electrical, optical, thermal, catalytic, etc.)
and performances due to the quantum size effect, whereas Nanotechnology deals with the manufacturing of nanodevices. Nanotechnology offers a broad range of technological applications and industries
including semiconductors, auto and aerospace, pharmaceutical and biomedical, cosmetics, biotechnology,
energy and environment, food, forensic, military, etc. Known as the 5th industrial revolution, it has and
continues to attract a large number of scientists worldwide. It is reported that by 2015, Nanotechnology
may spawn a $ 1 trillion market and the job projection is around two million with additional 5 million
jobs in support industries. Additionally, the emergence of Nanotechnology has created a new dynamism
in our scientific and academic world: (1) drastic increase of the research funds towards nanotechnology
and national nanotechnology initiatives were developed by many countries; (2) the number of conferences
and publications (papers, books, proceedings) has increased drastically due to the extensive research
work carried out by the researchers; (3) new established academic programs at all levels; (4) new courses
and disciplines emerged including nano-chemistry, nano-physics, nano-biotechnology, nano-medicine,
nano-engineering, nano-ethics, etc; (5) commercialization of new products and the establishment of
new technologies and industries based on nanotechnology leading to the creation of new and important
number of jobs, which will have great effects on the future of global economy; (6) new journals and
books which attract a wide and large audience; etc.
The handbook consists of 2 volumes with a total number of 19 chapters covering a wide range of
topics from point of view experimental, fundamental, and applications view, written by experts and
eminent scientists in each field.
This handbook will present experimental and fundamental approaches and in depth understanding
of the chemical/physical/mechanical/electrical/biological/etc. properties of nanostructured/advanced
materials followed by some potential applications in biomedical field, renewable energy, semiconductors industry, etc. In addition, it will promote the emerging field of nanotechnology in various science
and engineering disciplines.
This handbook contains various hot topics related to energy conversion and storage, biomedical
field, semiconductors, construction, telecommunication, etc., and thus will target a large audience such
as academics, scientists, post-graduates students, engineers, etc.
The first chapter Self-Healing Materials Systems as a Way for Damage Mitigation in Composites
Structures Caused by Orbital Space Debris, consists of a review on materials self-healing when subjected
to any chemical or/and mechanical or/and thermal, etc. It contains some important concepts (such as
quantification of healing efficiency which can be assessed by various tests such as Fatigue, Tear, etc.)
xxi
and presents some self-healing systems including thermoplastic and thermosetting materials then coating systems for metallic structures, etc. The new concept/property of self-healing being considered in
engineering applications is incorporated as during the design and manufacturing of materials, thus adding
new functionality of self-repair for counteracting service degradation. Additionally, it was reported that
self-healing results in increasing material lifetime, reducing replacement costs, and improving product
safety. In terms of self-healing systems, a variety of polymers and metallic material can be used.
Chapter 2 is devoted to the study of functionalisation of carbon (fullerene, carbon nanotubes, graphene)based nanocomposites by ruthenium (Ru-bipyridine and Ru-terpyridine)-based complexes. This type
of material shows some particular catalytic, electrochemical, or magnetic properties, and offers some
potential applications in energy storage, biochemical sensors, photo-induced mechanical actuation, etc.
The chapter focuses the synthesis methods of Bipyridine/Terpyridine ligands followed by Complexation
with a metal center then Polymerization. After that, it presents the design of organic terpyridine Ligand
spacer and polymerization complex for Nanohybrid; then it gives a detailed overview on the functionalization (non-covalent and covalent) of some carbon nanostructures such as fullerene, carbon nanotubes,
and graphene, with Ru bipyridine and terpyridine complexes and finally self-assembly of Ru-terpyridine
metal-connected diblock metallopolymers on graphene nanoribbons.
Chapter 3, Nano Indentation Response of Various Thin Films Used for Tribological Applications,
addresses on of the most powerful technique to investigate the mechanical properties of nanostrucred
materials. The author focused particularly on three materials, where a detailed study is presented: (1)
ZrN films showing better corrosion resistance, improved mechanical properties, and warm golden color,
thus very suitable for tribology applications; (2) amorphous carbon (a-C) known as Diamond-Like
Carbon (DLC) and hydrogenated a-C:H films show the combination of some useful properties such
as high nanohardness, good thermal conductivity, low friction coefficient, excellent wear resistance,
ultra-smoothness, and chemical inertness (applications as magnetic hard disc, MEMS, biocompatible
coating, etc.); and (3) W-S-C films with a nanocomposite structure and showing reasonable nanohardness
and low friction coefficient, offering some potential applications such as space-related technologies, in
vacuum or in aggressive environment. It was found that H/E and H3/E2 ratios are considered as important
parameters for coatings (H: nanohardness; E: elastic modulus).
Chapter 4, Synthesis and Characterization of Iron Oxide Nanoparticles, covers various aspect of
Fe oxides including: (1) crystal structure and properties; (2) synthesis of different morphologies (nanospheres, nanowhiskers, nanocubes, nanoplates, nanoflowers, etc) using various methods; (3) dispersion
and functionalisation of NPs using chemical processes such as ligand exchange, lipid encapsulation,
polymer encapsulation, etc.; and (4) characterizations. Finally, some potential applications are presented.
Chapter 5, Si-NWs: Major Advances in Synthesis and Applications, is devoted to Si nanowires due
to their potential and broad applications including the fabrication of integrated circuit, DNA sensors,
array-based electrical and electrochemical systems, vertical surround-gate field effect transistor, high
resolution Atomic Force Microscope, etc. The authors discussed some synthesis aspects of Si-NWs
(lithography, physical, or chemical vapor deposition PVD or CVD methods, etc.) where a particular
emphasis on catalyst role during Vapor-Liquid-Solid (VLS) growth mechanism. After that, Nanoscale
Chemical Templating (NCT) using oxygen reactive materials was presented in detail followed by some
potential applications of Si-NWs such as high-resolution AFM tips, photovoltaic cells, thermoelectric
devices, and sensors to end up giving directions for future research on Si-NWs.
Chapter 6, Principles of Raman Scattering in Carbon Nanotubes, presents background and in-depth
theoretical study of carbon nanostructures (nanotubes-CNTs, nanofibers-CNFs, graphene-G) properties
xxii
then focusing mainly on CNTs. It presents crystal structure and Brillouin zone, electronic band structure,
and electronic Density Of States (DOS), which represent the backbone to access vibrational properties
through Raman spectroscopy technique.
Chapter 7, Pharmacokinetics of Polymeric Nanoparticles at Whole Body, Organ, Cell, and Molecule
Levels, deals with an important and crucial aspect of using Nanoparticles (NPs) for the biomedical
field in terms of interaction at different levels. It starts by discussing the fate of NPs in the human body
including efficiency and toxicity (which are strongly dependent on NPs shape, size, surface charge
modifications, chemical composition, etc.), through ADME (Absorption, Distribution, Metabolism, and
Excretion). Both experimental and modeling of pharmacokinetic of polymeric NPs have been presented.
Then, pharmacokinetics at different levels of interaction inside the body was discussed from point of
view of: (1) organ and sub-organ (lung, physiological, and biological barriers, tumor); (2) at cellular and
sub-cellular level (cell surface binding, cellular uptake [endocytosis] kinetics, intracellular traffic and
biotransformation kinetics, exocytosis kinetics); (3) at molecular level (protein binding, ligand-targeting).
Chapter 8, Applications of Nanomaterials in Construction Industry, presents a short overview of
the potential and challenging applications of Nanotechnology in some areas of construction industry. In
recent years, some studies devoted to the construction industry report on some interesting results such
as: (1) nanoparticles (Zn, Sio2, Fe2O3, and halloysite clay) were embedded into a commercial epoxy resin
for the enhancement of mechanical and chemical properties; (2) nano-SiO2 was investigated as additive
to cementation system, as well as nano-Fe2O3 and nano-Al2O3; (3) nano-TiO2 has been reported to produce self-cleaning and depolluting concrete as well as on roadway for pollution reduction; and (4)
Carbon Nanotubes/Nanofibres (CNTs/CNFs) as potential candidates for use as nano-reinforcements in
cement-based materials. Then the author discusses the challenges related to the use of nanomaterials as
well as strategies for using then for the next ten years with some concluding remarks.
Chapter 9, Silicon Nanostructures-Graphene Nanocomposites: Efficient Materials for Energy
Conversion and Storage, starts by highlighting energy resources/demand and that renewable energies
represent only 16% (mainly solar), as well as some background about some fundamental concepts of
solar cells energy efficiency and graphene as a potential material for energy conversion/storage. Then a
particular focus on the potential use of Si-graphene for energy conversion and stirage, Si-NWs/graphene
heterojunction device for photoelectrochemical water splitting, Si-nanostructures/graphene as anode
for Li-ion batteries showing high reversible discharge capacity, and supercapcitors. Finally, the authors
presents various methods for the preparation of various Si (NPs, NWs)/Graphene nanocomposites.
Due to the importance of graphene, Chapter 10, Metal Oxide-Graphene Nanocomposites: Synthesis
to Applications, was dedicated to metal oxides / graphene composites due to their potential application.
Several oxides / methods were presented: in-situ techniques such as precipitation (Fe3O4, CuO); sol-gel
(TiO2); hydrothermal/solvothermal (ZnO); photo-assisted reduction (TiO2); microwave-assisted synthesis
(Fe3O4 and Co3O4); atomic layer deposition (TiO2); followed by ex-situ methods such as layer-by-layer
self-assembly (TiO); etc. Then, the authors presented some potential applications of MO/graphene nanocomposites including Li-ion battery, supercapacitors, water purification, photovoltaic cells, biomedicine,
and end by giving some future research directions.
Chapter 11, In2X3 (X=S, Se, Te) Semiconductor Thin Films: Fabrication, Properties, and Applications,
presents a review on the recent progress on Indium chalcogenide thin film semiconductor compounds as
potential candidates as window/buffer-layer for photovoltaic devices. The authors discuss in more detail
the evolution of structure and microstructure as well as optical/electrical properties modifications due to
the deposition method (metal-organic chemical vapor deposition, atomic layer chemical vapor deposi-
xxiii
tion, chemical bath deposition, spray pyrolysis, molecular beam epitaxy, etc.); the effect of deposition
parameters (temperature, time, pH of the solution, type of substrate, etc.); and post-deposition treatment.
Then a particular interest is devoted to the synthesis, characterizations and properties of some selected
compounds including In2Se3, In2Te3, In2S3 then ternary compounds such as In2Se3-xTex.
Chapter 12, Carbon Nanotubes for Photovoltaics, reports an in-depth review about the use of CNTs
for PV. After introducing the outstanding physical properties of CNTs, the authors present some potential
applications of CNTs in various PV/DSSS/OPV: CNT-Si hetero-junction solar cells based on aligned
CNTs and Si-NWs, as well as some PV simulations based on molecular dynamics; Dye Sensitized Solar
Cell (DSSC) where CNTs replace Pt as CNT as counter electrode; incorporating CNT networks in the
cells conducting electrode to promote charge transport in the TiO2 layer, CNT as Transparent Conducting
Oxide (TCO) layer which is usually Indium Tin Oxide (ITO) in DSSC; and CNTs in Organic PV devices
(OPV). After that, the authors discuss a very important aspect of PV, trends to improve the efficiency,
followed by a discussion and some recommendations and concluding remarks.
Chapter 13, Overview on Hydrogen Absorbing Materials: Structure, Microstructure, and Physical
Properties, presents some important aspect of hydrogen storage in materials. The authors start by giving some fundamental background on hydrogen storage, thermodynamics, and kinetics, properties, and
mechanisms. Then a particular focus is devoted to some potential materials including: binary hydrides;
intermetallics (LaNi5, FeTi, Laves phases AB2); Mg-based materials; amorphous alloys; quasicrystals;
carbon nanostcuctures (nanofibers); light complex hydrides based on alkali-metals (Li, Na, Al, B); rareearth based hydrides thin films with optical switchable properties; and zeolites.
Chapter 14, Conductive Probe Microscopy Investigation of Electrical and Charge Transport in
Advanced Carbon Nanotubes and Nanofibers-Polymer Nanocomposites, is devoted to the fundamental
and some experimental aspects to access some properties of CNTs-Polymer nanocomposites by using
some advanced probe microscopies such as Atomic Force Microscopy (AFM); Electrostatic Force Microscopy (EFM); Current-Sensing Atomic Force Microscopy (CS-AFM). After that, a particular focus
is dedicated to DC(AC)-EFM imaging of embedded CNT-polymer nanocomposites films, followed by a
CS-AFM investigation of bulk and surface percolation as well as electrical conductivity measurements.
Chapter 15, Nanostructured Materials for the Realization of Electrochemical Energy Storage and
Conversion Devices: Status and Prospects, presents an interesting overview on some nanomaterials as
potential candidates for energy conversion and storage. After a good introduction related to fundamental
aspects of electrochemical energy storage, the authors discuss each application separately: (1) nanocatalysts (Pt, Pt-M core-shell, Pt3M, graphite-C3N4, etc.) for fuel cells; (2) photoelectrochemical water
splitting (such as nanocrystalline -Fe2O3 and nano-CdSe); (3) dye-sensitized solar cells DSSCs (oxide
semiconductors like TiO2/ZnO/SnO, nanoporous film coated with oxides Al2O3/SnO2/ZrO2/SrTiO3/ZnO,
etc.); cathode for Li-ion batteries (such as LiMO2 and spinel-type LiM2O4 where M=Co, Mn, etc.); and
anode for Li-ion batteries (graphite, Li2Si5).
Chapter 16, Nucleic Acids Based Nanotechnology: Engineering Principals and Applications,
focuses on the engineering of functional systems at the molecular level offering potential applications
such as molecular sensors, actuators, drug delivery devices, etc. After a good introduction on some very
important aspects such as nanobiotechnology, nanomedicine, etc., the author presents in more detail some
applications such as: (1) passive nanostructures based on DNA using self-assembly; (2) engineering active
nanostructures based on allosteric ribozymes; (3) RNA-based nanocircuits; (4) integrated RNA-based
nanodevices with a complex logic function as a tool for molecular diagnostics; (5) allosteric ribozymes as
xxiv
designer cis-acting gene control elements; and (6) gene silencing techniques via trans-acting ribozymes
to end up with some future research work in this field.
Chapter 17, Theoretical Assessment of the Mechanical, Electronic, and Vibrational Properties of the
Paramagnetic Insulating Cerium Dioxide and Investigation of Intrinsic Defects, presents a very detailed
study of some properties (ground-state properties, elastic stiffness constants, and electronic structure with
the inclusion of on-site Coulomb interaction, dielectric properties, lattice dynamic, and thermodynamic
properties) of CeO2 by ab-initio calculations (calculations based on Density Functional Theory [DFT]
as implemented in WIEN2K and CASTEP packages). A particular focus is dedicated to investigate the
presence of intrinsic defects (oxygen or cerium vacancies) in un-doped CeO2 (cubic structure of CaF2,
pace group Fm-3m) to create ferromagnetic behavior.
Chapter 18, Implementation of Nanoparticles in Cancer Therapy, is devoted to the application of
nanotechnology in the biomedical field. The authors start by stating conventional method used for cancer therapy (surgery, radiotherapy, chemotherapy, etc.) then present how Nanoparticles (NPs) present a
potential alternative. Then some general fundamental/experimental aspects related to some selected NPs
that are used in drug delivery and targeting in cancer therapy are presented, including Polymeric NPs,
Liposomal NPs, Dendrimer NPs, Protein NPs, Polymersome NPs, Inorganic NPs, etc. Additionally, the
authors discuss NP toxicity and safety, followed by some major cancer targets for NPs systems (including
cell marker targeting via antibodies, targeting signaling pathways, niche targeting, angiogenesis-associated
targeting) as well as targeting schemes (including passive, active, and triggered targeting), and end with
nanoparticle-mediated gene therapy with future research perspectives.
Chapter 19, Understanding the Numerical Resolution of Perturbed Soliton Propagation in Single
Mode Optical Fiber, deals with an important matter related to optical fibers used for telecommunications such as terrestrial broadcasting by a fundamental approach: how to reduce the noise to acceptable
levels by acting on device parameters such as the structure of the fiber device. Then, the authors present
a detailed theoretical background to study soliton propagation in a mono-modal optical fiber followed
by frequency domain filter system, which allow one to create a model followed by simulations using
numerical models that allow one to understand the behavior of solitons.
This handbook presents the recent advances and future prospects of several nanotechnology applications. In addition, it highlights various technological applications in biomedical, renewable energy,
electronics, etc., which will improve future life by offering solutions in health, energy, etc. It contains
chapters dealing with various topics starting from experimental approaches, simulation, and modeling,
and ending with applications and future perspectives.
Mohamed Bououdina
J. Paulo Davim
University of Aviero, Portugal
Chapter 1
Self-Healing Materials Systems

as a Way for Damage Mitigation
in Composites Structures
Caused by Orbital Space Debris
Brahim Assa
MPB Technologies Inc., Canada
Maha Mohamed Khayyat
Umm al-Qura University, Saudi Arabia
ABSTRACT
The presence in space of orbital debris, particularly in low earth orbit, presents a continuous hazard
to orbiting satellites and spacecrafts. The development of self-healing materials offers the designer an
ability to incorporate secondary functional materials capable of counteracting service degradation
whilst still achieving the primary, usually structural, requirement. This chapter reviews the various
self-healing technologies currently being developed. Self-healing systems can be made from a variety
of polymers and metallic materials. An overview of various self-healing concepts over the past two
decades is presented. Finally, a perspective on current and future self-healing approaches using this
biomimetic technique is offered. The intention is to stimulate debate and reinforce the importance of a
multidisciplinary approach in this exciting field.
1. INTRODUCTION
Polymers and structural composites are used in a
variety of applications. However, these materials
are susceptible to damage induced by mechanical,
chemical, thermal, UV radiation, or a combination of these factors (Bucknall, Drinkwater, &
Smith, 2004). When polymer composites used as
structural materials become damaged, there are

only a few methods available to attempt to extend
their functional lifetime. Ideal repair methods are
ones that can be executed quickly and effectively
directly on damaged site, eliminating thereby the
need to remove a component for repair. However,
the mode of damage must also be taken into consideration as repair strategies that work well for
DOI: 10.4018/978-1-4666-5824-0.ch001
Copyright 2014, IGI Global. Copying or distributing in print or electronic forms without written permission of IGI Global is prohibited.

one mode might be completely useless for another.

For example, matrix cracking can be repaired by
sealing the crack with resin, where fibre breakage
would require new fibres replacement or a fabric
patch to achieve recovery of strength. One of the
earlier healing methods for fractured surfaces was
hot plate welding, where polymer pieces were
brought into contact above the glass transition
temperature of the material, and this contact was
maintained long enough for interdiffusion across
the crack face to occur and restore strength to the
material. It has been shown, however, that the
location of the weld remains the weakest point in
the material and thus the favourable site for future
damage to occur (Liu, Lee, & Lu, 1993). For laminate composites, resin injection is often employed
to repair damage in the form of delamination. This
can be problematic, however, if the crack is not
easily accessible for such an injection. For fibre
breakage in a laminate composite, a reinforcing
patch is often used to restore some of the strength
to the material. Often, a reinforcing patch is used
in conjunction with resin injection to restore the
greatest amount of strength possible (Osswald &
Menges, 2003). None of these methods of repair
is an ideal solution to damage in a structural
composite material. These methods are temporary
solutions to prolong the lifetime of the material,
and each of these repair strategies requires monitoring of the damage and manual intervention to
enact the repair. This greatly increases the cost
of the material by requiring regular maintenance
and service.
Alternative healing strategies are therefore
of great interest. Moreover, with polymers and
composites being increasingly used in structural
applications space, automobile, defence, and construction industries, several techniques have been
developed and adopted by industries for repairing
visible or detectable damages on the polymeric
structures.
However, these conventional repair methods
are not effective, for example, for healing invisible
microcracks within the structure during its service

life. In response, the concept of self-healing
polymeric materials was proposed in the 1980s
(Jud, Kausch, & Williams, 1981) as a means of
healing invisible microcracks for extending the
working life and safety of the polymeric components. The publications in the topic by Dry and
Sottos (Dry & Sottos, 1993) in 1993 and then White
et al. (2001) further inspired world interests in these
materials (Kringos et al., 2011). Examples of such
interests were demonstrated through US Air force
(Carlson & Goretta, 2006) and European Space
Agency (Semprimosching, 2006) investments in
self-healing polymers.
Conceptually, self-healing materials have the
built-in capability to substantially recover their
mechanical properties after damage. Such recovery
can occur autonomously and/or be activated after
an application of a specific stimulus (e.g., heat,
radiation, pressure, etc.). As such, these materials
are expected to contribute greatly to the safety and
durability of polymeric components without the
high costs of active monitoring or external repair.
Throughout the development of this new range
of smart materials, the mimicking of biological
systems has been used as a source of inspiration
(since most materials in nature are themselves
self-healing composite materials) (Varghese, Lele,
& Mashelkar, 2006).
The number of publications dealing with various aspects of self-healing materials has increased
markedly in recent years. Figure 1 shows how the
number of refereed various articles in the self
healing field has steadily increased since 2001,
based on data collected from the Engineering
Village Web-based information service. Along
with the increase in the number of publications
in this area comes a need for a comprehensive
review work, and the objective of this chapter is
to address this need.
In addition, the vast majority of the surveyed
articles deal with polymer composites. Due to the
large number of articles involved and the lack of

Figure 1. (a) Recent refereed publications related to the field of self healing materials, together with
(b) their corresponding distribution of the employed key words vocabulary. All published languages
were included. All document types, including journal and conference articles, report paper, conference
proceeding, and monograph published chapters were recorded. Statistics are available from 2000 to
August 2013 inclusively. Data were collected from Engineering Village Web-based information service
electronic access to many conference proceedings, the emphasis of this chapter is on the more
accessible refereed journal articles. It was not
practical to cover all of these articles, and, since
a lot of articles had already been covered by
previous related paper articles, an attempt was
made to select representative articles in each of
the relevant categories.
This chapter briefly describes the traditional
methods of repairing damage in the polymeric
materials during the last decade. Table 1 provides
summary of some developments and achieved performances. It can be seen that both thermoplastic
and thermosetting materials were investigated for
self healing, where the research interests have been
more shifted to thermosetting-composite-based
systems in recent years.
We start by describing the methods for evaluating self healing efficiencies. We will then describe
briefly some examples of different approaches
proposed to heal the thermoplastic systems, and we
follow by emphasising the preparation and charac-
terization of the self healing of the thermosetting

ones. We will take a short view on the self-healing
coating for metallic structures systems, and we
conclude by future research outlooks.
2. QUANTIFICATION OF
HEALING EFFICIENCY
Healing of a polymeric material can refer to the
recovery of properties such as fracture toughness,
tensile strength, and surface smoothness. Due to
the range of properties that are healed in these materials, it can be difficult to compare the extent of
healing. Wool and OConnor (Wool & OConnor,
1981) proposed a basic method for describing the
extent of healing in polymeric systems for a range
of properties. This approach has been commonly
adopted and has been used as the basis for method
of comparing healing efficiency of different self
healing polymeric systems.

Table 1. Non exhaustive main developments in self-healing polymer composites

Host material
Thermosetting
and/or
thermosetting
composites
Healing system
Hollow Glass
Fibre
Stimulus
Test method
Ref.
24 hours at
ambient atm.
Flexure Strength
(Trask, & Bond,

2006)
Microencapsulation approach
80-93%
48 h at 80o C
24 h at Ambient
then 24 h at
80o C
Fatigue
resistance
Fracture
toughness
Tensile strength
(Sanada, Yasuda,
& Shindo, 2006)
Micro-vascular
network
60-70%
7- 30 cycles
12 hours at
ambient atm.
Fracture
toughness
(Toohey et al.,
2007)
Thermoplastic
additives
30-100%
10 min at 120o C
1- 2 h at 130160o C
Flexure strength
Tensile strength
Impact strength
(Hayes et al.,
2007)
77%
24 hours at
ambient atm.
Fracture
toughness
(Kirkby et al.,
2008)
46%
1-20 minutes,
70-120o C
Impact strength
(Murphy et al.,
2008)
70100%
48 hours at
ambient atm.
Tear strength
(Keller, White,
& Sottos, 2007)
100%
5 min. At 60o C.
Fracture
toughness
(Lin, Lee, & Liu,

1990)
26%
10 min. At
100o C
Flexure Strength
(Chung et al.,
2004)
Electrical
Carbon fibre
Elastomeric
Silicone rubber
Thermoplastic
Molecular
diffusion
Photo-induced
healing
Mechanical
Photo
There are different methods to effect healing

that are applicable for each individual mode of
damage as well as each unique damaged material. This makes quantifying the extent of healing
within the material and comparing it to healing in
other systems rather difficult. The susceptibility
of a given material to fracture can be expressed in
terms of the plane strain fracture toughness, KIC. It
has become standard practice to assess the healing
ability of a particular material by comparing the
fracture toughness of the material both before and
after healing. The healing efficiency is ,
(%) = K1C healed/ K1C virgin X 100
(1)
where K1C virgin is the fracture toughness of the virgin

specimen and K1C healed is the fracture toughness
of the healed specimen.
Healing
condition
93%
Shape memory
alloy
Mechanical
Best efficiency
achieved
2.1. Self-Healing Efficiency

Assessed by Fracture Test
For quasistatic fracture conditions healing efficiency is defined in terms of the recovery of
fracture toughness. Healing evaluation begins
with a virgin fracture test of an undamaged tapered
double cantilever beam (TDCB) sample (Figure
2(a)). A pre-crack is introduced to sharpen the
crack-tip, and loading of the specimen is increased
until the crack propagates along the centerline of
the sample until failure. The crack is then closed
and allowed to heal at room temperature with no
external intervention. After healing, the sample
is loaded again until failure.
Crack healing efficiency, , is defined as the
ability of a healed sample to recover fracture
toughness (Wool et al., 1981):

Figure 2. (Left) Schematic of the TDCB-based

fracture toughness and (Right) tear protocols to
evaluate healing performance
ics, and the rest periods employed (Brown, White,

& Sottos, 2005). The investigation considered
successful healing as the recovery of stiffness lost
due to damage induced by cyclic loading rather
than changes in crack growth rate or absolute
fatigue life.

Assessed by Tear Test
=KIC healed/KIC Virgin
(2)
where, KIC Virgin and KIC healed represent the fracture toughness of the virgin and healed samples,
respectively.

Assessed by Fatigue Test
For dynamic fracture conditions, healing efficiency based on static fracture toughness recovery is no longer meaningful. Instead, the fatigue
crack propagation behaviour of the self-healing
epoxy was evaluated using the protocol outlined
by Brown et al. who defined healing in terms of
the life extension factor (Brown, Sottos, & White,
2002):
d = N healed -N control/N control
(3)
where N healed is the total number of cycles to failure

for a self-healing sample and N control is the total
number of cycles to failure for a similar sample
without healing.
Characterization of fatigue response is more
complex than monotonic fracture because it depends on a number of factors such as the applied
stress intensity range, the loading frequency, the
ratio of applied stress intensity, the healing kinet-
For elastomeric self-healing material, the TDCBbased fracture toughness protocol to evaluate
healing performance is inappropriate. Instead, the
recovery of tear strength using a tear specimen is
used to define healing efficiency, where
c =T healed/T Virgin
(4)
A tear test utilizes a rectangular coupon of

material with a large axial pre-cut that produces
two loading arms. These arms are loaded in tension until the tear propagates through the rest of
the specimen (Figure 2(b)). Healing evaluation
begins with a virgin tear test of an undamaged
sample. After failure, the sample loading arms
are reregistered and healing occurs at room
temperature with no external intervention. After
healing, the tear sample is loaded again to failure.
Using this test protocol, more than 70% recovery
of the original tear strength was achieved in the
PDMS (polydimethylsiloxane) system (Keller et
al., 2007).
3. SELF-HEALING OF THE
THERMOPLASTIC MATERIALS
Crack healing of thermoplastic polymers has been
the subject of extensive research in the 1980s. The
polymers investigated cover amorphous, semi
crystalline, block copolymers, and fibre-reinforced
composites. It has been discovered that when

two pieces of the same polymer are brought into

contact at a temperature above its glass transition
(Tg), the interface gradually disappears and the
mechanical strength at the polymer-polymer interface increases as the crack heals due to molecular
diffusion across the interface. For example, by using thermoplastics chain mobility with a minimal
application of heat, Lin et al. (Lin et al., 1990)
have studied crack healing in PMMA (poly (methyl
methacrylate)) by methanol treatment from 40
to 60C. The authors have found that the tensile
strength of PMMA treated by methanol can be
fully recovered to that of the virgin material. On
the other hand, another example of photo-induced
self-healing in PMMA was reported by Chung et
al. (Chung et al., 2004). Mixture of photo linkable
TCE (1,1,1-tris-(cinnamoyloxymethyl) Ethane)
with UDME- (urethane-dimethacrylate-) and
TEGDMA- (triethyleneglycol-dimethacrylate-)
based monomers, blended with visible light photoinitiator CQ (camphorquinone), was polymerized
into a hard and transparent film after its irradiation for 10min with a 280 nm light source. The
healing was shown to only occur upon exposure
to the light of the correct wavelength, proving that
the healing was light initiated. Healing efficiencies in flexural strength up to 14% and 26% were
reported using light or a combination of light and
heat (100C). However, healing was limited to
the surfaces being exposed to light, meaning that
internal cracks or thick substrates are unlikely to
heal. In summary, self-healing of thermoplastic
polymers can be achieved via a number of different mechanisms, including (i) recombination of
chain ends, (ii) self-healing via reversible bond
formation, (iii) living polymer approach, and (iv)
self-healing by nanoparticles, in addition to the (v)
molecular inter-diffusion and (vi) photo-induced
healing reported here. The processes are well
known and have been well reported. A detailed
description of these approaches can be found in
(Wu, Meure & Solomon, 2008).
4. SELF-HEALING OF
THERMOSETTING MATERIALS
The search for self-healing thermosetting materials coincides with these materials being more
and more widely used in numerous structural
applications. These applications generally require
rigid materials with a thermal stability that most
thermoplastics do not possess. The rigidity and
thermal stability of thermosetting comes from their
cross-linked molecular structure, meaning that
they do not possess the chain mobility so heavily
utilized in the self-healing of thermoplastics. As a
result of their different chemistry and molecular
structure, the development of self-healing thermosetting has followed distinctly different routes.
The most common approaches for autonomic
self healing of thermosetting-based materials involve incorporation of self-healing agents within
a brittle vessel prior to addition of the vessels into
the polymeric matrix. These vessels fracture upon
loading of the polymer, releasing the low-viscosity
self-healing agents to the damaged sites for subsequent curing and filling of the microcracks. The
exact nature of the self-healing approach depends
on (i) the nature and location of the damage, (ii)
the type of self-healing resins, and (iii) the influence of the operational environment.
4.1. Hollow Glass Fibres Systems

The development of advanced fibre-reinforced
polymers (FRPs) to achieve performance improvements in engineering structures focuses on
the exploitation of the excellent specific strength
and stiffness that they offer. However, the planar
nature of a FRPs microstructure results in relatively
poor performance under impact loading. This is an
indication of their susceptibility to damage, which
manifests mainly in the form of delamination.
Hollow glass fibres have already been shown
to improve structural performance of materials
without creating sites of weakness within the

composite (Trask, Williams & Bond, 2007). These

hollow fibres offer increased flexural rigidity and
allow for greater custom tailoring of performance,
by adjusting, for example, both the thickness of
the walls and degree of hollowness (Hucker et
al., 2003). By using hollow glass fibres in these
compositesalone or in conjunction with other
reinforcing fibres it would be possible to not only
gain the desired structural improvements, but to
also introduce a reservoir suitable for the containment of a healing agent (Trask et al., 2007). Upon
mechanical stimulus (damage inducing fracture
of the fibres), this agent would bleed into the
damage site to initiate repair, not unlike biological
self healing mechanisms (Pang & Bond, 2005).
The first systems that have been investigated
in 1996 and 1998 by Dry (1996) and Li et al.
(1998), respectively, have validated that the proposed architecture for releasing chemicals from
repair fibres was totally possible and then have
used cyanoacrylate, ethyl cyanoacrylate (Li et al.,
1998), and methyl methacrylate (Dry & McMillan,
1996) as healing agents to heal cracks in concrete.
This methodology was then transferred to polymer
composite materials by Motuku et al. (1999) in the
late 1999. The healing agents contained within the
glass fibres have been either a one-part adhesive,
such as cyanoacrylate, or a two-part epoxy system,
containing both a resin and a hardener, where
either both are loaded in perpendicular fibres or
one embedded into the matrix and the other inside
fibres (Bleay et al., 2001).
One of the initial challenges encountered when
creating this type of self-healing systems is the
development of a practical technique for filling
the hollow glass fibres with repair agent. When
approaching this problem, the dimensions of the
glass fibre itself must be considered, including
diameter, wall thickness, and fibre hollowness,
as well as the viscosity and healing kinetics of
the repair agent. Bleay et al. (2001) were among
the first to develop and implement a fibre filling
method involving capillary action that is assisted
by vacuum, which is now the main commonly used

process. The chosen glass fibre should be also
evaluated for its capacity to survive to the composite manufacturing process without breakage,
while still possessing its ability to rupture during
a damage event in order to release the required
healing agent.
Motuku et al. (1999) have clearly determined
that hollow glass fibres were best suited for this
kind of application, as opposed to polymer tubes or
those made of metal, which often did not provide
controlled fracture upon impact damage.
In 2003, Hucker et al. (2003) have shown that
hollow glass fibres of a larger diameter offered
an increased compressive strength, while giving
larger volume of healing agent to be stored. The
second important parameter to investigate was the
capacity of the healing agent to adequately reach
the site of damage and subsequently undergo
healing. This mechanism will obviously depend
upon the viscosity of the healing material, as well
as the kinetics of the repair process.
For example, the cyanoacrylate system studied
by Bleay et al. (2001) was shown, indeed, to restore mechanical strength to damaged specimens
but also caused significant problems by curing
upon contact with the opening of the fibre, which
prevented the healing agent from reaching the site
of damage in the sample. Various groups (Pang et
al., 2005, Motuku et al., 1999, Trask et al., 2007)
have then used liquid dyes inside the composites in
order to serve as a damage detection mechanism,
providing hence a visible indication of the damage
site, while allowing a clear evaluation of the flow
of healing agents to those sites.
Finally, the third parameter to optimize is the
concentration of healing fibres within the matrix,
their special distribution, and the final dimensions
of the specimen, which have direct effects on the
mechanical properties of the resulting composite
material. As early demonstrated by Jang et al. (Jang
et al., 1990) in 1990, the stacking sequence of the
fibres within the composite plays a role in inhibit-

ing plastic deformation and delamination and will

also affect the response to an impact damage event.
In order to maintain high mechanical properties,
repair fibres need to be adequately spaced within
the composite. Motuku and coworkers (Motuku
et al., 1999) have shown that thicker composites
have shown better performances in healing studies.
These parameters, however, will depend upon the
dimension choice of fibre and chemical choice of
the healing agent employed, and so optimization
will depend on the specificities of the system
being studied.
Until recently, the majority of the works done on
self healing hollow fibre composites have focused
on demonstrating the feasibility of such concept for
self-repair and have reported qualitatively on the
healing capacity of the studied systems. Recently,
numerous works have reported quantitatively on
mechanical properties associated with healing of
the materials. The inclusion of hollow glass fibres
into a composite system was shown by Jang et
al. (1990) and Trask and Bond (2006) to give an
initial reduction in the strength of the material,
either by 16% in glass fibre reinforced polymer
(GFRP) composites and by 8% in carbon-fibre
reinforced polymer (CFRP) composites. These
self-repairing composites were shown to recover 100% of the virgin strength for GFRP and
97% of the virgin strength for CFRP, but in both
cases the composite materials were subjected to
a heat treatment to aid in delivery of the resin to
the damaged area as well as in curing of the healing agent. More recently, the work of Williams
et al. (2009) has considered the development of
autonomic self-healing within a carbon fibrereinforced polymer (CFRP), and has demonstrated
the significant strength recovery (>90%), which
was possible when a resin filled hollow glass fibre
system was distributed at specific interfaces within
a laminate, minimising thereby the reduction in
mechanical properties whilst maximising the efficiency of the healing event.
4.2. Systems Based on

Microencapsulated Healing Agents
As above mentioned, and since the first report of
the self repairing composites systems in the literature (White et al., 2001), conventional strategy
was achieved by embedding a microencapsulated
liquid healing agent and solid catalytic chemical
materials within a polymer matrix. Hence, upon
damage induced cracking in the matrix, microcapsules are supposed to release their encapsulated
liquid healing agent into the crack planes (Figure
3(a)). All the involved materials must be carefully engineered. For examples, encapsulation
procedure must be chemically compatible with the
reactive healing agent, and the liquid healing agent
must not diffuse out of the capsule shell during
its potentially long shelf-life. At the same time,
the microcapsule walls must be resistant enough
to processing conditions of the host composite,
while maintaining excellent adhesion with the
cured polymer matrix to ensure that the capsules
rupture upon composite fracture. Polymeric microcapsules are most often prepared via a mini
emulsion polymerization technique, as described
in the work of Asua (2002). The procedure involves
the well known oil-in-water dispersions mechanism of the polymeric material. In the majority
of self-healing composite systems that have been
studied, the microcapsules are made by a urea
formaldehyde polymer, encapsulating DCPD as
the liquid healing agent (White et al., 2001, Brown
et al., 2006) and/or epoxy resin (Yuan et al., 2006;
Blaiszik et al., 2009). In the case of DCPD, during
the in situ polymerization process, urea and formaldehyde react in the water phase to form a lowmolecular-weight prepolymer; when the weight
of this prepolymer increased, it deposited at the
DCPD-water interface. This urea-formaldehyde
polymer becomes highly cross-linked and forms
the microcapsule shell wall. The urea formaldehyde prepolymer particles are then deposited on
the surface of the microcapsules, providing a rough

Figure 3. Schematic of the autonomic healing concept incorporating encapsulated healing agent and
embedded catalyst particles in a polymer matrix; (i) damage event causes crack formation in the matrix;
(ii) crack ruptures the microcapsules, releasing liquid healing agent into crack plane; (iii) healing agent
polymerizes upon contact with embedded catalyst, bonding crack closed.
surface morphology that aids in the adhesion of

the microcapsules with the polymer matrix during
composite processing (Murphy & Wudl, 2010).
Moreover, composites using DCPD-filled urea
formaldehyde microcapsules have shown concrete

healing ability in monotonic fracture and fatigue
(White et al., 2001; Brown et al., 2006).

4.2.1. Size and Material

Microcapsules Effects
In 2003, Williams et al. (2009) have reported
that the microcapsules made in this oil-in-water
in situ process have an average size of 101000
m in diameter, with a smooth inner shell in the
160220 nm thick range, and fill content up to
8392% liquid healing agent. The mechanical
rupture of the microcapsule is the sine qua non
condition event for the healing process.
Hence, it is obviously important, therefore, to
fabricate microcapsules with optimal mechanical
properties and wall thickness. The relationship
between the stiffness of the capsule and the one
of the polymer matrix determines how the crack
will propagate in the sample. In 2006, Keller and
Sottos (2006) have described how a capsule that
has higher elastic modulus than the one of the
polymer matrix material should create a stress
field that tends to deflect cracks away from the
capsule; a more compliant shell wall, on the other
hand, will produce a stress field that attracts the
crack towards the microcapsule.
The influence of microcapsule diameter and
crack size on the performance of self-healing
materials was also investigated in 2007 by Rule
et al. (2007). They have used an epoxy based
material containing embedded Grubbs catalyst
particles and microencapsulated DCPD. The
amount of liquid that microcapsules could deliver
to a crack face was shown to scale linearly with
microcapsule diameter (and hence to the volume
1/3), for a given weight fraction of capsules.
Moreover, the size of the microcapsule also plays
a role in the performance of the system, in terms
of the effect on toughness of the composite, and
the nature of interface between microcapsule and
polymer matrix. Based on these relationships, the
size and weight fraction of microcapsules can
be rationally chosen to give optimal healing of a
given crack size.
However, as noted by Williams et al. (2009),
the shell wall thickness is largely independent of
10
manufacturing parameters and is typically between 160 and 220nm thick; nevertheless, slight
adjustments can be made during the encapsulation
procedure to alter the resulting microcapsules.
The microcapsule size is controlled mainly via the
rate of agitation during the encapsulation process;
typical agitation rates reported by Williams et al.
(2009) range from 200 to 2000 rpm, with finer
emulsions and therefore smaller diameter capsules
being produced with increasing rates.
In 2004, Brown et al. have noted (Brown,
White, & Sottos, 2004) that smaller microcapsules
exhibit maximum toughening at lower concentrations; on the other hand, Rule et al. (2007) have
reported, in 2007, that specimens that contain
larger microcapsules perform better than those
with smaller microcapsules at the same weight
fraction, presumably due to the amount of healing
agent present in the samples. In the latter study,
the best healing achieved was on a specimen
containing 10 wt. % of 386 m capsules, which
corresponds to 4.5mg of healing agent being delivered per unit crack area (assuming all capsules
in the crack plane rupture). The amount of healing
agent available for delivery to the crack plane was
calculated based on the microcapsule size and
weight fraction incorporated into the composite
and was verified by comparing the data from
these autonomously healing samples with that
of samples, in which a known volume of healing
agent was manually injected into the crack plane
to initiate the healing process.
In the light of synthesizing smaller microcapsules that exhibit maximum toughening at
lower concentrations, Blaiszik et al. (2008) have
reported in 2008 an in situ encapsulation method
demonstrating over an order of magnitude size
reduction for the preparation of urea-formaldehyde
(UF) capsules filled with a DCPD healing agent,
where capsules with diameters down to 220nm
were successfully achieved, using sonication
techniques and an ultrahydrophobe solution to
stabilize the DCPD droplets. The capsules were
found to possess a uniform UF shell wall (77 nm

average thicknesses) and display good thermal

stability. However, there are drawbacks with UF
microcapsules: first, (i) the formation of agglomerated nanoparticles debris that could act as crack
initiation sites within the host matrix, second, (ii)
rough and porous wall surfaces formed by agglomerated nanoparticles that may reduce the adhesion
between the microcapsules and matrix, and, finally,
(iii) rubbery and thin capsule walls (160220 nm
(Brown et al., 2003)) that lead to the loss of core
material during storage and cause handling difficulties during processing of the composites. In
addition to UF microcapsules, melamine formaldehyde (Yan et al., 2008) and polyurethane (Yang
et al., 2008) shell wall materials were successfully
used to prepare microcapsules of various healing
materials. We note also the works of Liu et al.,
in 2009 (Liu et al., 2009), which have produced
microcapsules for self healing applications with
a melamine-urea-formaldehyde (MUF) polymer
shell containing two different healing agent
candidates, 5-ethylidene-2-norbornene (ENB)
and ENB with 10 wt.% of a norbornene-based
cross-linking agent (CL), by in situ polymerization in an oil-in-water emulsion (Figure 4). The
microcapsules were found to be thermally stable
up to 300C and exhibited a 10 to 15% weight loss
when isothermally held at 150C for 2 h. Overall,
these MUF microcapsules exhibited superior properties compared to the urea-formaldehyde (UF)
microcapsules used extensively for self-healing
composites to date, and their manufacturing process is simpler than that made from UF. On the
other hand, it is worthy reported at this level the
innovative work of Mookhoek et al. (Mookhoek
et al. 2008), where microcapsules of size around
1.4 m dibutylphthalate-(DBP-) filled urea-formaldehyde (UF) were used as pickering stabilizers
to create larger (~140 m) microcapsules containing a second liquid phase of DCPD. The binary
microcapsules were made by encapsulating the
dispersed DCPD liquid (stabilized with the UF
(DBP) microcapsules in water), via an isocyanatealcohol interfacial polymerization reaction.
Various applications have been attempted
with more or less success. Microcapsules have
Figure 4. Optical microscopic images of 5E2N- microcapsules fabricated at MPB technologies Inc
11

been used in the paper industry for a range of

different purposes, for example, in self-copying
carbonless copy paper (White, 1998), and in the
food and packaging industries for applications
such as control of aroma release and temperature
or humidity indicators (Wu et al., 2008). Other
possible applications might include encapsulation
of antimicrobial agents or scavengers in active
packaging. Recently, Andersson et al. (2009) have
developed microcapsules with a hydrophobic core
surrounded by a hydrophobically modified polysaccharide membrane in aqueous suspension, to
obtain capsules fulfilling both the criteria of small
capsule size and reasonably high solids content to
match the requirements set on surface treatment
of paperboard for enhancement of packaging
functionality, and they have shown a reduced
tendency for deteriorated barrier properties and
local termination of cracks formed upon creasing.
4.2.2. Fatigue Cracks Retardation

To retard the growth of fatigue cracks, shapememory alloy (SMA) wires are well suited to
this application since they exhibit a thermoelastic
martensitic phase transformation, contracting
above their transformation temperature and exerting large recovery stresses of up to 800MPa,
when constrained at both ends (Tsoi, Schrooten,
& Stalmans, 2004). Moreover, Rogers et al. (1991)
have shown that, when an SMA wire is embedded
within an epoxy matrix, the full recovery force
acts at the free edges of the component.
Therefore, an SMA wire bridging a crack
should induce a large closure force on the crack.
Indeed, Kirkby et al. (2008) have reported on
the self-healing polymers with embedded shapememory alloy (SMA) wires, where the addition
of SMA wires shows improvements of healed
peak fracture loads by up to 160% (comparatively
with specimen without SMA), approaching the
performance of the virgin material. Moreover, the
repairs can be achieved with reduced amounts of
healing agent. The improvements in performance
12
were attributed mainly to the crack closure, which

reduces the total crack volume and increases the
crack fill factor for a given amount of healing
agent and the heating of the healing agent during
polymerization, which increases the degree of cure
of the polymerized healing agent.
4.2.3. Delaminating Substrate

Because of their excellent in-plane properties and
high specific strength, fibre-reinforced composites
with polymeric matrices have found many uses
in structural applications. Despite this success,
they are particularly prone to damage from outof-plane impact events. Although fibre damage
is usually localized at the site of impact, matrix
damage in the form of delaminations and transverse
cracks can be more widespread. Delaminations, in
particular, pose a serious issue because they can
significantly reduce compressive strength (Xiong
et al., 1995) and grow in response to fatigue loading
(Baker, Jones, & Callinan, 1985). In addition to
this problem, impact damage can be subsurface or
barely visible, necessitating the use of expensive
and time-consuming non-destructive inspection
(Baker et al., 1995). Once damage is located,
there are many repair techniques that have been
proposed and/or are currently practiced (Myhre &
Labor, 1981). As we have mentioned, most solutions rely on resin infiltration of delaminations or
composite patches, to provide load transfer across
the damaged region.
In cases of severe damage, damaged regions
are removed and replaced with new composite
material that is bonded or concurred to the original one (Myhre, 1981). These repair techniques
are generally time-consuming complicated and
require unhindered access. Recently, Patel et al.
(2010) have studied the autonomic self-healing of
impact damage in composite materials by using
a microencapsulated healing agent (DCPD liquid
healing agent and paraffin wax microspheres containing 10 wt.% Grubbs catalyst), which has been
successfully incorporated in a woven S2-glass-

reinforced epoxy composite. Low velocity impact

tests reveal that the self healing composite panels
are able to autonomically repair impact damage.
Fluorescent labelling of damage combined with
image processing shows that total crack length
per imaged cross-section is reduced by 51% after
self-healing.
On the other hand, flexible, laminated, selfhealing bladder material was investigated to
mediate the impact of small tears and punctures.
Previous attempts at healing puncture damage have focused on ionomers (Kalista, Ward,
& Oyetunji, 2007). A self-healing response in
ionomers initiates through the transfer of energy
from a fast moving projectile, which is typically
a few millimetres in diameter. Frictional heating
of the material from the passage of the projectile
leads to a reorientation of the polymer chains
in the ionomer. This rearrangement can, under
some conditions, seal the hole generated by the
projectile.
However, this healing occurs only when the
damaged area is heated to near the melt temperature of the material (Kalista et al., 2007). In 2009,
Beiermann et al. (2009) have manufactured a
three-layer flexible self-healing materials, capable
of repairing puncture damage. The used material
consisted of three layers: a poly (dimethylsiloxane)
(PDMS) composite, embedded with a self-healing
microcapsule system, sandwiched between two
layers of poly(urethane)-coated nylon. A protocol
was established in which samples were damaged
using a hypodermic needle or a razor blade, and
a successful heal was defined as the ability to
reseal the damage to withstand a pressure differential across the laminate of 103 kPa (at 1 atm.).
Healing was shown to vary significantly with
microcapsule size, with the maximum healing success rate (100% successfully healed) occurring in
samples with 220 m in diameter microcapsules.
Additionally, healing was found to increase with
composite layer thickness, and decreases with
increasing puncture size.
Finally, fracture testing, in the form of singleedge notched bending tests, has shown a healing
efficiency of 111%, when the concentration of
microcapsules and latent hardener were optimized.
Some preliminary tests on epoxy based fabric
laminates containing this self-healing system demonstrated a 68% recovery of virgin inter-laminar
fracture toughness. Yuan et al. (Yuan et al., 2007)
have reported another promising combination of
healing agent and catalyst for self healing polymer
composites. The healing agent, consisting of a mixture of diglycidyl ether of bisphenol A (DGEBPA)
along with a catalyst made from 1-butyl glycidyl
ether (BGE), was stored in poly(urea-formaldehyde) (PUF) microcapsules, which were prepared
by the conventional oil inwater emulsion process.
This process of preparing the PUF microcapsules
has promoted long shelf-life and good chemical
stability at temperatures below 238C. This system
is still in the early developmental stages, and its
self healing efficiency within a composite material is yet to be tested.
In sum, the microencapsulation approach is
by far the most studied self-healing concept in
recent years. Table 2 summarizes the type of
self-healing systems investigated in the literature,
and it is noticed that the self-healing system based
on living ring-opening metathesis polymerization (ROMP) has attracted most of the research
attention. There are some obvious similarities
between the microencapsulation and hollow fibre
approaches, but the use of microcapsules alleviates
the manufacturing problems experienced in the
hollow fibre approach. The microencapsulation
approach is also potentially applicable to other
brittle material systems such as ceramics and
glasses (Ritchie, 1988). On the other hand, the most
successful and extensively investigated self healing
system comprises the ROMP of dicyclopentadiene
(DCPD) with Grubbs catalyst. The synthesis and
characterization of the DCPD/Grubbs catalyst
system have recently been papered (Bielawski
& Grubbs, 2007), and their use as a self-healing
13

Table 2. Literature summary of self-healing chemicals investigated for the microencapsulation approach
Self-healing agent
Catalyst
Self-healing reaction
Reference
Dicyclopentadiene (DCPD)
Bis(tricyclohexylphosphine)
benzylidine ruthenium (IV)
dichloride (Grubbs catalyst)
Ring-opening metathesis
polymerization
(White et al., 2001)
5-Ethylidene-2-norbornene
(ENB)
polymerization
(Lee et al., 2004)
DCPD/ENB blends
polymerization
(Liu et al., 2006)
Mixture of hydroxyl end

functionalised
Polydimethylsiloxane
(HOPMDS) and
Polydiethoxysiloxane (PDES)
Di-n-butyltin dilaurate
Polycondensation
(Cho et al., 2006)
Epoxy
Amine
Polycondensation
(Yuan et al., 2006)
Styrene-based system
Cobalt naphthenate,
dimethylaniline
Radical polymerization
agent has been widely reported as we mentioned

here above. This system supposedly provides a
number of advantages such as long shelf-life, low
monomer viscosity and volatility, and completion
of polymerization at ambient conditions in several
minute. Further attempts were made to improve
the performance of the self-healing system by
replacing DCPD with 5-ethylidene-2-norbornene
(ENB) (Lee et al., 2004) or blending ENB with
DCPD (Liu et al., 2006). Microencapsulation of
ENB was also achieved by in situ polymerization
of urea and formaldehyde.
This system was supposed to overcome some
of the limitations of the DCPD including the low
melting point and the need to use a large amount
of catalysts. It is recognized that DCPD is capable
of forming a cross-linked structure with high
toughness and strength (Wu et al., 2008) whilst
ENB polymerizes to a linear chain structure
and may possess inferior mechanical properties.
However, ENB is known to react faster in the
presence of a lower amount of Grubbs catalyst,
has no melting point, and produces a resin with
a higher Tg (Wu et al., 2008). Hence, a blend
of DCPD with ENB was believed to provide a
14
(Wu et al., 2008)
more reactive healing system with acceptable

mechanical properties, making it more suitable
for practical use. Cho et al. (Cho et al., 2006)
chose to develop a completely different healing
system using di-n-butyltin dilaurate (DBTL) as
the catalyst and a mixture of HOPDMS (hydroxyl
end-functionalized polydimethylsiloxane) and
PDES (polydiethoxysiloxane) as the healing agent.
The polycondensation of HOPDMS with PDES
is alleged to occur rapidly at room temperature
in the presence of the organo tin catalyst even in
open air (Shah, 1998).
4.3. Three-Dimensional
Microchannel Structure Systems
As reported by the paper of Murphy and Wudl
(2010), complex microvascular networks are
widely observed in biological systems, such as
leaf venation (Sack & Frole, 2006) and blood
vascularisation (Jain, 2005). Indeed, in the latter
case, the human circulatory system is comprised
of vessels of varying diameter and length: arteries, veins, and capillaries. These vessels function
together in a branched system to supply blood to

all points in the body simultaneously. However,

due to their complex architecture, replication of
these microvascular systems remains a significant
challenge for those pursuing synthetic analogs. As
outlined in 2006 by Stroock and Cabodi (2006),
these microvascular networks can be created via
soft lithographic methods (Choi et al., 2007), in
which all microchannels can be fabricated at the
same time, laser ablation (Kam & Mazumder,
2008) or direct write methods (Therriault, White,
& Lewis, 2003), which are more suited for building
three-dimensional (3D) micro-channel structures
(Figure 3(c)). One of the main advantages of those
systems comparatively to both the hollow fibre
and microcapsule systems is their ability to heal
the same location in the material more than once.
Indeed, often, a second fracture event will occur
along the plane of the initial crack. By providing
a material with a quasi continuous flow of healing
agent, numerous healing cycles can be achieved.
In 2007, Toohey et al. (2003) have published
one of the first of these types of composite materials. Authors have reported self-healing systems that are capable of autonomously repairing
repeated damage events. The reported system
which bio-inspired coating-substrate design
delivered healing agent to cracks in a polymer
coating via a three-dimensional microvascular
network (Therriault et al., 2003) that was first
embedded into the substrate. This system utilized
the healing combination of liquid DCPD as the
healing agent and solid Grubbs catalyst to initiate ROMP polymerization of the DCPD. In the
reported work, the catalyst was incorporated into
a 700 m thick epoxy coating that was applied
to the top surface of the microvascular substrate,
and the 200 m wide channels were successfully
filled with DCPD and then sealed.
This system achieved a peak healing efficiency
up to 70% with 10 wt. % catalyst in the top coating and was able to demonstrate healing for up to
seven cycles. It is important to mention that the
amount of catalyst in the top epoxy layer did not
affect the average healing efficiency per cycle,
but rather limited how many cycles of testing

and healing could be performed successfully.
Indeed, once all of the catalyst has been used,
healing ceased due to depletion of catalyst in the
crack plane, even with a continuous supply of
monomer. To overcome this limitation, in 2009,
Toohey et al. (2009) have modified their design
by photolithographically patterning four isolated
regions within the embedded microvascular network. Authors have reported the repeated healing
of crack damage in a polymeric coating through
delivery of two-part epoxy, healing chemistry via
multiple microvascular networks embedded in
isolation within a polymeric substrate. They first
have created a continuous, interconnected microvascular network using the direct-write method.
Second, they then have isolated multiple networks
by infilling the network with a photo-curable resin
and selectively photo-polymerizing thin parallel sections of these resin-filled microchannels.
Epoxy resin and amine-based curing agents were
transported to the crack plane through two sets of
independent vascular networks embedded within
a ductile polymer substrate beneath the coating.
The two reactive components remain isolated and
stable in the vascular networks until crack formation occurs in the coating under a mechanical load.
Both healing components were wicked by capillary
forces into the crack plane, where they react and
effectively bond the crack faces closed. Several
epoxy and curing agent combinations were evaluated for their suitability in microvascular-based
autonomic systems, and healing efficiencies of
over 60% for up to 16 intermittent healing events
out of 23 cycles were successfully achieved. In
a related effort, Williams et al. have published
their version of a microvascular network containing mechanically stimulated healable material,
in the form of sandwich structure composite
configurations that contain either single (Williams, Trask, & Bond, 2007) or dual (Williams,
Trask, & Bond, 2009) fluidic networks. In the
single network design, sandwich structures use
high-performing skin materials, such as glass or
15

carbon fibre composites, separated by a lightweight core to obtain a material with very high
specific flexural stiffness. A vascular network
incorporated into a sandwich structure would address the larger damage volume expected of these
systems, as well as allowing for multiple healing
events to occur. Samples were fabricated with
channels containing a healing agent, which had
a negligible effect on the mechanical properties
of the composite. Rupture of the vessels released
the healing fluid, filling the void that formed as
a result of impact damage on the sample. Initial
tests were run on samples containing premixed
resin and hardener, to demonstrate the healing
capability of the system. Indeed, these samples
have shown consistent and complete recovery of
compressive stress at failure after impact damage.
In their dual network design, significant recovery
was also observed when samples were infiltrated
with pressurized unmixed dual fluids (Williams
et al., 2007).
5. SELF-HEALING COATING
SYSTEMS FOR METALLIC
STRUCTURES
The large economic impact of corrosion of metallic
structures is a very important issue all over the
world. Generally, rapid field-specific testing is
done when material failure is observed. Despite
intense research and developments in corrosion
protection coatings of metals and alloys, the
real-world performance results are not always
satisfactory.
Furthermore, development of all around
coatings to protect and prolong service life of
the infrastructure is still a big challenge, owing
to wide variations in environmental conditions.
Therefore, in order to improve the equipment
service prediction capabilities of infrastructure,
it is indispensable to develop new state-of-the-art
smart/self healing coating formulations for corrosion inhibition. In this context, autonomic healing
16
materials respond without external intervention

to environmental stimuli and have great potential
for advanced engineering systems (Cordier et al.,
2008). Self-healing coatings, which autonomically
repair and prevent corrosion of the underlying
substrate, are of particular interest. Notably, the
worldwide cost of corrosion has been estimated
to be nearly $300 billion per year (Koch et al.,
2001). Recent studies on self-healing polymers
have demonstrated repair of bulk mechanical damage as well as dramatic increases in the fatigue
life. The majority of these systems, however, have
serious chemical and mechanical limitations,
preventing their use as coatings. Polymer coating
systems are classically applied on a metal surface
to provide a dense barrier against the corrosive
species. Cathodic protection is also used for many
applications, in addition to coatings, to protect the
metal structures from corrosive attack when the
coating is damaged. Hence, self-healing coatings
are considered as an alternative route for efficient
anticorrosion protection while maintaining a low
demand in cathodic protection.
Cho et al. (2009) have explored two self-healing
coating approaches, starting from the siloxanebased materials system. In the first approach, the
catalyst was microencapsulated and the siloxanes
were present as phase-separated droplets. On
the second process, the siloxanes were also encapsulated and dispersed in the coating matrix.
Encapsulation of both phases (the catalyst and
the healing agent) is advantageous in cases where
the matrix can react with the healing agent. In the
other hand, Aramaki (2003) has prepared a highly
protective and self-healing film of organosiloxane
polymer containing sodium silicate and cerium
nitrate, on a zinc electrode previously treated in
a Ce(NO3)3 solution. Self-healing mechanism of
the film was investigated after it was scratched and
immersed in the NaCl solution for several hours,
where a passive film has been found to be formed
on the scratched surface, resulting in suppression
of pitting corrosion at the scratch. More recently,
the same group (Aramaki, 2010) has prepared

an ultrathin 2D polymer coating, on a passivated

iron electrode, which was subsequently healed
in NaNO3. Thus done, localized corrosion was
markedly prevented by coverage with the polymer
coating and the healing treatment in 0.1 M-NaNO3.
Indeed, prominent protection of iron from
corrosion in 0.1M-NaCl was observed. The protective efficiencies were found to be extremely
high in certain cases, where more than 99.9%
before the passive film was broken down. The
development of effective corrosion inhibitor
coatings for prevention of corrosion initiation
and suppression of galvanic activity of metals and
alloys has always been a challenging problem.
Recent concerted efforts of researchers at US
Army Engineering Research and Development
Center at the Construction Engineering Research
Laboratory (ERDC-CERL) and at other facilities
(Kumar, Stephenson, & Murray, 2006) have led
to development of self-healing corrosion inhibitors, to reduce and/or prevent corrosion of metal
hardware. Previously, heavy metal-based epoxy
primer pre-treatment systems (Kachurina et al.,
2002), including quaternary ammonium saltbased and multifunctional microencapsulated
corrosion inhibitor system (Kumar et al., 2006),
have demonstrated corrosion protection performance of metals and alloys. These studies have
demonstrated that the scribe or damaged film
area on otherwise corroded panels experienced
little lifting and blisters, among others, of the
film because of the presence of microcapsules
at the scribes. Mehta and Bogere (2009) have
evaluated the smart/self-healing microencapsulated inhibitor incorporated in epoxy primer
before painting on a steel surface, for its corrosion
protection effectiveness on exposure to ASTM
(American Society for Testing and Materials) D
5894 electrolyte in laboratory and natural tropical
seashore environment. The healant inhibitor
was industrial custom made. Their results have
indicated that the active components in ruptured
embedded inhibitor microcapsules were released
into an inflicted scribe primer and topcoat film on
steel surface on exposure to inhibit development of

an electrochemical cell. Undamaged surface film
of the test and control specimens exposed in the
environments demonstrated excellent corrosioninhibition performance as reflected by both visual
inspection and electrochemical impedance spectroscopy experimental data. All of those reported
results should provide an understanding of the
fundamental material-property relationships of
smart inhibitor coatings and, thus, should facilitate
the development of optimized paint compositions
in order to extend the useful service life of steel
infrastructure applications.
6. FUTURE OUTLOOKS
In summary, we finally know that the material degradation can occur for a wide variety
of reasons, such as fatigue loadings, thermal
effects, and corrosion, or, more in general, for
environmental effects of all kinds. However, the
materials durability is probably one of the main
challenges encountered today for structural as well
as coating applications. As the materials failure
normally starts at the nanoscale level and is then
amplified to the micro- up to the macro-scale level
until catastrophic failure occurs, the ideal solution
would be to block and/or eliminate damage as
it occurs at the nano/microscale and restore the
original material properties.
We have seen that the healing process can be
initiated by means of an external source of energy
(stimuli), as it was shown in the case of a bullet
penetration (Varley & Van der Zwaag, 2008)
where the ballistic impact caused local heating
of the material allowing self-healing of ionomers,
or in the case of self-healing paintings used in
the automotive industry. In the latter case, small
scratches can be restored by solar heating (Garcia
Espallargas, Fisher, & Van der Zwaag, 2011).
Single cracks formed in PMMA specimens
at room temperature were also shown to be
completely restored above the glass transition
17

temperature (Kausch, 1983). The presence of

noncovalent hydrogen bonds (Sijbesma et al.,
1997) in mechano-sensitive polymers can allow
a rearrangement of principal chemical bonds so
that they can be used for self-healing. Numerical
studies have also shown that nanoscopic gel particles, which are interconnected in a macroscopic
network by means of stable and labile bonds, have
the potential to be used in self healing applications.
To date, all the employed techniques are,
however, limited by the container size. Containers should be in the nanoscale range since larger
ones could lead to large hollow cavities that could
compromise the mechanical properties of the
hosting structural material, and/or the passive
protective properties of the coating material (Zako
& Takano, 1999). Moreover, up to date, advanced
materials are designed to be either tough or self
healing, but typically not both. It would be ideal
to have a material which could be at the same
time tougher and self-repairable, and this is still
not possible with current technologies.
Carbon nanotubes (CNTs) are considered to be
an ideal filler material for mechanical reinforcement as well as ideal molecular storage devices.
This is due to the fact that CNTs are very small,
thus they have an extremely large interfacial area.

CNTs have interesting mechanical and chemical
properties and have a hollow tubular structure.
Polymer/CNTs composites (Coleman, Khan, &
Gunko, 2006) have already shown many promising results, and various materials, such as hydrogen
(H2) (Liu et al., 1999), metal and/or metal carbide
(Guerret-Plecourt et al., 1994), C60 (Xue & Chen,
2006), CH4 (Ni et al., 2002) and DNA (Gao et al.,
2003), have been successfully inserted inside CNT.
Although a great deal of work has been done
with CNTs as self-storage devices, CNTs have
not been yet investigated as nanoreservoirs for
self-healing applications. The main challenges
related with this application are how to insert molecules into the carbon nanotubes, whether crack
can form on the sidewall of a carbon nanotube
during its propagation, and if the healing agent
will come out of the carbon nanotube when the
crack forms. In this avenue, recently, Lanzara et
al. (2009) have investigated the use of CNTs as
nanoreservoirs for automatic repairing applications, through a molecular dynamics (MD) study
with particular focus on the CNTs capacity of
delivering a healing agent. Authors have shown,
interestedly, that the CNTs were not only able to
Figure 5. Concept of the self-healing process using carbon nanotubes
18

carry the catalytic healing agent for local repair

but also can simultaneously play the role of filler
material for mechanical reinforcement prior and
after the delivery of the active material (Figure 5).
7. CONCLUSION
In conclusion, we have briefly presented a series
of recent results related to the various self-healing
concepts and systems. Research into self-healing
materials is an active and exciting field, with
an increasing number of research papers being
published every year. From the studies on healing
in concrete structures via embedded glass fibres
to the more recent work on healing using shape
memory alloy wires in a polymer composite, and/
or the use of multidimensional microvascular
network for the healing applications, the different
avenues being explored to achieve the common
end goal of prolonged functional lifetimes for
composite structural materials are astounding.
Beyond a strong interest of both academic and
commercial researchers in the hollow fibre and
microencapsulation approaches to self-healing
polymer development, new types of self healing
technology have been emerging at an increasing
rate over the last decade. Indeed, in recent years,
interesting perspectives have opened for the design
of innovative self-healing nanosystems. Computer
simulations have provided useful indications for
directing the efforts of scientists toward the fabrication of repairing systems.
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KEY TERMS AND DEFINITIONS

Autonomic: Reaction that is happening without external stimuli.
Biomimetic: The faculty to imitate the nature
in the light to fix complex problems.
Carbon Nanotube: Allotrope of carbon with
cylindrical shape nanostructures.
Delaminations: A mode of failure of composite materials occurring mainly in laminated
materials.
Microencapsulation: A process that organises liquid materials inside microspheres or
microcapsules.
Self-Healing Materials: A class of materials
having the ability to repair damage over time,
based on intrinsic property or by incorporating
appropriate materials.
Space Conditions: All environmental conditions characterizing space, including vacuum,
radiation, temperature fluctuations, and debris.
Space Debris: All manmade space waste in
orbit including old satellite debris, fragments from
disintegration, erosion and collisions.
Thermosetting: A type of petrochemical
materials (also called thermoset) which cure irreversibly under heat.
25
26
Chapter 2
Functionalization of Carbon
Nanocomposites with
Ruthenium Bipyridine and
Terpyridine Complex
Huayang Li
Clark Atlanta University, USA
Issifu Harruna
ABSTRACT
Ruthenium bipyridine or terpyridine complexes functionalized carbon-based nanocomposites have special properties in the electromagnetic and photochemical research field. The aims of this chapter include
development of functionalized fullerene, carbon nanotubes, and graphene with ruthenium complex and
characterization of their nanostructural properties. Such nanocomposites can be accomplished using
either covalent or non-covalent functionalization methods.
INTRODUCTION
Composite nanomaterials including fullerene,
carbon nanotubes and graphene are an exciting
area of current research offering a variety of applications such as energy storage (Aliev et al.,
2009), biochemical sensors (Siqueira et al., 2009)
and photo-induced mechanical actuation (Ahir &
Terentjev, 2005). Combinations of metal ions with
polymers and carbon-based nanomaterials such as
fullerene, carbon nanotubes and graphene provide
an interesting route towards supramolecular struc-
tures with well-defined catalytic, electrochemical,

or magnetic properties (Tasis, Papagelis, Prato,
Kallitsis, & Galiotis, 2007). Metalligand coordination bonding with bipyridine or terpyridine has
become a promising tool towards such structures
(Schubert & Eschbaumer, 2002). The combination
of well-established ruthenium bipyridine or terpyridine chemistry with carbon nanocomposites is,
in general, a promising approach to novel material
fabrication (Siqueira et al., 2009). In this chapter,
we will discuss functionalization of such carbon
nanomaterials with bipyridine or terpyridine com-
DOI: 10.4018/978-1-4666-5824-0.ch002

Functionalization of Carbon Nanocomposites with Ruthenium Bipyridine
plexes by chemically covalent and non-covalent

methods (excluding dopant functionalization).
Figure 1. Structures of 2,2-bipyridine and

2,2:6,2-terpyridine
BACKGROUND
Since 1987, supramolecular chemistry has become
a well-known concept and a major field in todays
research community. This concept has been defined as chemistry beyond the molecule, bearing
on the organized entities of higher complexity
that result from the association of two or more
chemical species held together by intermolecular
forces (Lehn, 1995). One of the most important
interactions found in supramolecular chemistry
is metal-ligand coordination. In this arena, chelate complexes derived from N-heteroaromatic
ligands, largely based on 2, 2-bipyridine and
2,2:6,2-terpyridine (Figure 1), have become an
ever-expanding synthetic and structural frontier.
Bipyridine has been known since 1888, (Paul,
Spey, Adams, & Thomas, 2004) ruthenium bipyridine complexes contained [Ru(bipy)3]2+have very
interesting photochemical properties making them
ideal candidates for solar energy conversion. This
is due to the long lifetime of the triplet excited
state and in part due to the fact that the structure
of the molecule allows for charge separation.
Its singlet-triplet transitions are forbidden and
therefore often slow. This unusual situation arises
because the excited state can be described as a
Ru3+ complex containing a bipy- ligand. Thus,
the photochemical properties of [Ru(bipy)3]2+ are
reminiscent of the photosynthetic assembly, which
also involves separation of an electron and a hole
(Bard & Fox, 1995). Ruthenium(II) complexes
of tris(bipyridine)ruthenium [Ru(bipy)3]2+ have
received considerable attention recently. The
stability and unique photophysical properties of
these systems have been exploited for artificial
photosynthesis, in sensors, in photorefractive
materials, in studies of electron transfer in proteins
and DNA, antitumor ability, and a wide range of
other purposes.
The chemistry of 2, 2:6,2-terpyridines

(designated as simply terpyridine or tpy) is much
younger than that of 2,2-bipyridines. In the early
1930s, terpyridine was isolated for the first time
by Morgan and Burstall (Storrier, Colbran, &
Craig, 1997; Lain et al., 2002), the well-known
characteristics of terpyridine Ruthenium complexes are their special redox and photophysical
properties, which greatly depend on the electronic
influence of the substituents. Therefore, terpyridine complexes may be used in photochemistry
for the design of luminescent devices (Loiseau et
al., 2001) or as sensitizers for light-to-electricity
conversion (Constable & Lewis, 1982; Newkome,
Hager, & Kiefer, 1986). In clinical chemistry
and biochemistry, functionalized terpyridines
have found a wide range of potential applications
from colorimetric metal determination to DNA
binding agents and anti-tumor research (Cave &
Raston, 2000, 2001; Cave, Raston, & Scott, 2001;
Fallahpour, Neuburger, & Zehnder, 1999; Sasaki,
Daran, & Balavoine, 1999). Absorption, as well
as emission spectra, revealed that a metal-ligand
27

charge transfer, takes place in these [Ru(tpy)2]2+

complexes. As opposed to bipyridine complexes,
where a phosphorescence phenomenon can be observed over a wide temperature range, no emission
is detected at ambient temperature in the case of
terpyridines because of a non-irradiative transition
of the excited triplet metal-to-ligand charge transfer (3MLCT) state by a triplet metal-centered (3MC)
state to the ground state. Photophysical properties
can, however, be fine tuned by the introduction
of a donor, an acceptor, or both, leading to roomtemperature luminescent [Ru(tpy)2]2+ complexes.
Another method to improve the luminescence
lifetime and quantum efficiency involves the attachment of aromatic groups.
For new functional materials, metallo-supramolecular polymers, dendrimers or micelles have
been of great interest for the last few years. Also
the combination of such stable complexes with
biopolymers such as DNA/RNA, peptides and
enzymes for labeling, intercalation and inhibition purposes is promising (Bard & Fox, 1995).
Another field which is rapidly growing due to
the technical advances made, is the build-up of
ordered structures on a molecular scale on different kinds of surfaces (Lain et al., 2002). Here,
terpyridine complexes play an increasing role for
applications such as solar cell devices or electrode
catalysis. Furthermore, such easily detectable
and multi-functional entities are of great use for
gaining a more fundamental understanding of self-
organization phenomena of organic or inorganicorganic hybrid materials on surfaces. (Figure 2)

Fullerene, carbon nanotubes and graphene are
molecules composed entirely of carbon. They
have been widely used in nanomaterials research
field. Fullerene, carbon nanotubes and graphene
are allotropes of carbon,which are valuable for
nanotechnology, electronics, and other fields of
material science and technology. In particular,
owing to their extraordinary super-thermal conductivity, mechanical and electronic properties.
But they have disadvantages in applications due to
their bundles as aggregations, hard to dispersion
in the solvents and non-affinity to biochemical
environment .The chemical functionalization
those carbon nanomaterials with polymer and
organic molecules will debundle their aggregation in polymer matrix or biological system;
solubilize them in organic solution and aqueous
media; enhance biological sensor application
and change their surface electronic properties
(Bunzli, 2010; Hirsch & Brettreich, 2005; Hirsch
& Vostrowsky, 2005). Fullerenes are of special
importance in contemporary chemistry because of
their photophysical and electrochemical properties
(Hirsch, 1994; Hirsch & Brettreich, 2005), thus
leading to the development of novel molecular
electronics or light-harvesting devices. Most of
the current research into these particular kinds of
potential solar cells includes fullerenes because
of their electron-accepting properties. Therefore,
the combination of fullerenes with [Ru(tpy)2]2+
Figure 2. Molecular structures of fullerene, carbon nanotubes and graphene
28

complexes has a special significance. The purpose

for functionalizing the fullerenes is to increase the
solubility of the molecule in cancer cells. Cancer
cells take up these molecules at an increased rate
because of an up-regulation of transporters in
the cancer cell, Once absorbed by the cells, the
C60 derivatives would react to light radiation by
turning molecular oxygen into reactive oxygen
which triggers apoptosis in the HeLa cells and
other cancer cells that can absorb the fullerene
molecule.
Carbon nanotubes (CNT) have raised much
interest due to their inherent electronic, mechanical, and thermal properties (Harris, 1999;
Tanaka, Yamabe & Fukui, 1999; Avouris, Dresselhaus, & Dresselhaus, 2000; Reich, Thomsen, &
Maultzsch, 2004) since they were made by Iijima
(NEC laboratories, Japan) in 1991 (Iijima, 1991).
MCNTs (multiwalled carbon nanotubes) have
extraordinary promise for applications in materials, new energy, and microelectronics; however,
their realistic application has been hindered by
processing and manipulation difficulties. The
functionalization of MWNT become necessary
to facilitate the application by improving ease of
dispersion and providing chemical attachment
to surface and polymer matrices (Bahr & Tour,
2002). There are two basic methods to functionalize multiwall carbon nanotubes: noncovalent
sidewall and covalent functionalization (Hirsch
& Vostrowsky, 2005). Carbon nanotubes (CNT)
non-covalent functionalization is mainly based
on supramolecular interaction, such as van der
Waalss and -stacking adsorption forces without
disrupting the conjugate -network (J. Chen et
al., 2002; R. J. Chen, Zhang, Wang, & Dai, 2001;
Ou & Huang, 2006; Petrov, Stassin, Pagnoulle,
& Jerome, 2003; Star et al., 2003; Steuerman et
al., 2002; Yang & Pan, 2008). Compared with
noncovalent functionalization, the covalent chemical modification (Lehn, 1995) using defect site
chemistry of CNT allows functional group to be
attached to the tube end and sidewall. Among
various covalent functionalization techniques
(Tasis et al., 2007) (Schubert & Eschbaumer,

2002), such as hydrogenation, halogenation, [2+1]
cycloaddition, radical additions and electrophilic
additions, the oxidation of CNT is probably the
most widely used and studied.
Oxidation of CNT with inorganic acid mixture, such as nitric and sulfuric acids will purify
the pristine CNT to remove metallic impurities
and will introduce carboxyl functional group to
the end of CNT. The further transformation and
modification of carboxylic group give access to
a large number of organic and polymer chemistry
of functional exploitation with amidation and
esterfication of COOH groups on the end and
surface of CNTs (Bahr & Tour, 2002; Karousis,
Tagmatarchis, & Tasis, 2010; Tasis, Tagmatarchis,
Bianco, & Prato, 2006).
In addition, graphene, a two-dimensional gapless semiconductor with -conjugated network,
has demonstrated intriguing electronic, thermal,
and mechanical properties (Geim, 2009; Geim
& Novoselov, 2007; Novoselov et al., 2004).
The high aspect-ratio of graphene and graphene
nanoribbons (GNRs) offers unprecedented opportunity for nanoscale functional interfaces that
have potential applications in electronics, sensors,
spintronics, nanoelectronics, and biodiagnostics
(Bunzli, 2010; Gokus et al., 2009; Hummers &
Offeman, 1958; Liu et al., 2010; Loh, Bao, Eda,
& Chhowalla, 2010; Xie, Ling, Fang, Zhang, &
Liu, 2009). GNRs have been fabricated using
metal particle-assisted and lithographic methods,
or oxidative longitudinal unzipping of multiwall
carbon nanotubes (MWCNTs). The modification
of graphene on the molecular level with noble
metal nanostructures is an example of a bottomup fabrication route towards nanometer-scale
devices as functional building blocks in biotechnology and nanotechnology.
All of these carbon based nanomaterials can
be modified by ruthenium bipyridine and terpyridine complexes.
29

MAIN FOCUS OF THE CHAPTER

Bipyridine Ligand Synthesis Method
2, 2-bipyridine (bipy) is prepared by the dehydrogenation of pyridine using Raney nickel
(Figure 3). The bipyridine core offers a myriad of
possibilities in terms of modification by different
substitution patterns which led to its manifold use
as attractive building blocks in supra-, nano- and
macromolecular chemistry, as well as, in the areas
of analytical and photochemistry.
Reflecting the popularity of this ligand design,
many substituted variants of bipy have been described in references (Hapke, Brandt, & Lutzen,
2008; George R. Newkome, Patri, Holder, &
Schubert, 2004; Okamoto, 2012; Smith, Lamba,
& Fraser, 2004; Smith, Savage, Love, & Fraser,
2004). For example, Negishi crossing-coupling
and derivation functional groups of substituted
2, 2-bipyridine are two methods that are usually
used. Recently, the metal-catalyzed [2 + 2 + 2]type cycloaddition reaction of alkynes and nitriles
(Figure 4) has attracted considerable interest as a
straightforward, atom-economical route to substituted pyridines and methods have been extensively
applied to bipyridine synthesis. Developments
in the field of 2, 2-bipyridine synthesis through
alkyne/nitrile [2 + 2 + 2] cycloaddition reactions
catalyzed by transition metals are reviewed in this
article involving two types of fully intramolecular
reaction, five types of partially intramolecular
reaction and fully intermolecular reactions .
The most prominent cross-coupling reactions
include the Stille, Negishi, SuzukiMiyaura,
Kumada and Hiyama coupling reaction(Figure
5). They have all found application in the synthesis and functionalization of heteroaromatic
compounds as well as in the preparation of 2,
2-bipyridines (Hapke et al., 2008; Smith, Savage,
et al., 2004). There are two main problems associated with the synthesis of the 2,2-bipyridine core
by cross-coupling reactions: (a) the coordination
ability of the product can have adverse effects on
30
the catalytic cycle, and (b) the synthesis of the

pyridyl derivative, especially with the appropriate
transmetallating group (TMG).
For symmetrical 2, 2-bipyridines, the synthetic approaches are in the predominant number of
cases modifications of the existing bipyridine core
structures or homo-coupling reactions of suitable
pyridine precursor molecules. For non-symmetrically substituted 2, 2-bipyridines the synthetic
approach is comparatively more complicated. The
Negishi coupling can combine the tolerance of a
large number of functional groups with a higher
transmetallation activity. For example, after the
synthesis of different ethynylated, especially the
2-chloro-5-([trimethylsilyl]ethynyl)- pyridine
(Smith, Lamba, et al., 2004), Negishi crosscoupling (Figure 6) with this 2-pyridyl chloride
derivative and electron-rich trialkylphosphane
PtBu3 gave superior yields compared to the standard catalyst PdCl2(PPh3)2, chelating phosphanes
such as 1,1-Bis(diphenylphosphino)ferrocene
dppf (Okamoto, 2012), or the biphenyl backbonebased Buchwald ligand (Hapke et al., 2008).
Terpyridine Ligand
Synthesis Method
The two basic synthetic approaches to terpyridine
are by either central ring assembly or coupling
methodologies. Ring assembly (Figure 7) is the
most prevalent strategy, but because of their
multiplicity and efficiency, modern Pd-catalyzed,
cross-coupling procedures have recently become
seriously competitive and may surpass the traditional ring-closure processes.
Modern Pd(0)-catalyzed coupling reactions
combine the desired efficiency and simplicity
with controllable substitution possibilities. Suzuki, Negishi, and Stille couplings are all based
on a Pd(0)/Pd(II) catalytic cycle. Particularly, the
Stille cross-coupling has become a popular route
to terpyridine, (Figure 8) because of its universal
building block principle, multi-gram product accessibility, and well-directed functionalization at

Figure 3. 2, 2-Bipyridine prepared by Raney nickel
Figure 4. 2, 2-Bipyridine synthesized by metal-catalyzed [2 + 2 + 2]-type cycloaddition reaction (Copyright 2012 The Japan Institute of Heterocyclic Chemistry)
Figure 5. The cross-coupling approaches for 2,2-bipyridines synthesis (Copyright 2004 Organic
Syntheses, Inc.)
31

Figure 6. Initial screening experiments for the modified Negishi cross-coupling reaction (Copyright
2008 Royal Chemistry Society)
almost every desired position(Crdenas & Sauvage, 1996; Fallahpour, 2000; Heller & Schubert,
2002; Miyaura & Suzuki, 1995; Nozaki, International Union of Pure and Applied Chemistry.
Organic Chemistry Division., Nihon Gakujutsu
Kaigi., & Nihon Kagakkai., 1983; Parks, Wagner,
& Holm, 1973; Stille, 1986; Ulrich, Bedel, Picard,
& Tisns, 2001).
32
Complexation of Bipyridine
and Terpyridine Ligands
with a Metal Center
Bisterpyridine metal complexes of the type [M
(tpy) 2(X) 2] (X = e.g. Cl, ClO4, PF6) have
been known for a long time (E. C. Constable
& Thompson, 1992; Sauvage et al., 1994; Tomasik, Ratajewicz, Newkome, & Strekowski,
1985). Complexation of terpyridine ligands with
an Ru(II) center can be conducted in a simple
two-step sequence. The Ru (III) intermediate
is generally isolated but not characterized, then

Figure 7. Ring-assembly methods to terpyridine: (a) and (b) Kronke reaction, (c) Potts methodology,
(d) Jameson methodology. (Copyright 2004 Wiley-VCH)
simply reacted in the next step with a second

equivalent of the same or different terpyridine
under reductive conditions to afford the desired
symmetric or asymmetric Ru(II) complex, respectively. The intermediate is subsequently suspended
with the second ligand in methanol containing
N-ethylmorpholine (Maestri, Armaroli, Balzani,
Constable, & Thompson, 1995) and refluxed for
14 h. The solvent can also act as a reducing agent
for the Ru (III)Ru (II) conversion. Alternatively,
an equimolar amount of AgBF4 can be added to
the initial Ru(III) complex in DMF or acetone to

remove chloride ion. (Figure 9)
Complexing bipyridine ligands with a Ru(II)
center can be conducted in a simple sequence.
Ru(bpy)Cl2, which was first prepared by ruthenium
(III) chloride reaction with 2, 2-bipyridine, and
then was added into one portion of bipyridine
ligands solution with ethanol as reductant and
solvent,. After refluxing and filtration, NH4PF6
was added as counter anion to make the complex
soluble in organic solvent (Figure 10).
33

Figure 8. Stille-coupling 2-trimethylstannylpyridines and 2,6-dihalopyridines (Copyright 2004 WileyVCH)
Figure 9. Complexation of terpyridine ligands with Ruthenium center (Copyright 2004 Wiley-VCH)
Figure 10. Complexation of bipyridine ligands with Ruthenium center
34

Polymerization Method for

Terpyridine and Bipyridine Ligand
To design different types of Terpyridine ligand and
precisely control molecular weight and molecular
distribution, several polymerization methods have
been explored and carried out to make suitable
metallo-terpydyl complex for nanohybrid. Most
synthetic approaches have involved the construction of systems with broad molecular weight distributions and lack of control over polymer architecture. To overcome these drawbacks, living and
controlled polymerization techniques have been
employed. All controlled radical polymerization
(CRP) techniques are quite complementary in the
synthesis of polymers with controlled architecture,
and they are much simpler and user friendly than
ionic polymerizations.
Reversible Addition-Fragmentation
Chain Transfer (RAFT) Polymerization
RAFT polymerization is accessible to control molecular weight and molecular weight distribution
as well as advanced architectures such as block,
comb, and star copolymers (Chiefari et al., 1998;
Cowie & Arrighi, 2008a, 2008b; Moad, Chong,
Postma, Rizzardo, & Thang, 2005; Sbastien Perrier.& Pittaya Takolpuckdee. 2005). In contrast,
the RAFT process is distinguished by its versatility with respect to both monomer choice and
polymerization conditions. The key to successful
operation of RAFT polymerization lies on the use
of a highly efficient chain transfer agent (CTA),
which is typically a thiocarbonylthio compound. In
general, the vast majority of RAFT-prepared (co)
polymer chains bear CTA fragment groups at both
ends. Our group has used this method to prepare
the terpyridine terminated macromolecules with
well-defined structures which were further used
for preparation of supramolecular diblock metallo
macromolecules (Zhou & Harruna, 2005; Zhou,

He, Harruna, & Geckeler, 2008).
Synthesis of bipyridine-functionalized RAFT
agents (Zhou & Harruna, 2004) will also be used
to prepare bipyridine-terminated polystyrene, as a
polymer bipyridine ligand chelating with Ru(bpy)2
ion to produce tris(bipyridine)ruthenium(II)-centered polystyrene metallopolymers. (Figure 11).
Design Organic Terpyridine

Ligand Spacer and Polymerization
Complex for Nanohybrid
The aim of synthesizing metallo-supramolecular
ligands is to create a novel molecular bridge that
can reveal specific and multifunctional properties
to carbon nanotube and graphene (Figure 12). The
metallo- terpydyl complexes have double functions: one is to assembly nanotubes, graphene or
fullerene into a whole functional nanostructure
with special electrochemical, optical, magnetic
properties; another is to form a communication
bridge for biofuctional target molecules (such as,
protein and DNA) and nanotubes, graphene or
fullerene, The building blocks should therefore be
carefully selected in order to engineer new materials with tunable and tailored properties. Beside the
use of low molar mass ditopic organic ligands,
telechelic polymers bearing suitable ligands at
their extremity are extremely valuable candidates
for the formation of metallo-supramolecular polymers. In this way, the properties of the designed
materials can be manipulated not only by the
careful choice of the metal ions, but also by the
polymer backbone (Figure 12). This allows the
formation of materials synergistically combining
the characteristic features of the metal ligands
complexes to carbon nanotube/gold nanoparticles.
The following are examples of design of organic
terpyridine and polymer ligands.
35

Figure 11. RAFT polymerization of bis terpyridine ruthenium connected diblock polymer and schematic
representation for preparation of tris(2,2-bipyridine)ruthenium(II)-centered polystyrene metallopolymers
(Copyright 2005, American Chemical Society)
36

Figure 12. Schematic overview of the properties of designed metallo-terpydyl complex (Copyright 2009
Wiley-VCH)
FUNCTIONALIZATION OF
FULLERENE, CARBON
NANOTUBES AND GRAPHENE
WITH RUTHENIUM BIPYRIDINE
AND TERPYRIDINE COMPLEXES
Functionalization of Fullerene with
Ruthenium Bipyridine Complexes
Incorporation of C60 molecules into macromolecular architectures provides an attractive opportunity
to combine the unique electronic and optical
properties of fullerenes with superior physicomechanical characteristics of polymers. Fullerenes
have been extensively modified with a variety
of polymers through various approaches (Dai &
Mau, 2001; Geckeler & Samal, 1999; Geckeler &
Samal, 2000; Giacalone & Martn, 2006; Wang,
Guo, Fu, Wu, & Zhu, 2004). Varieties of C60-bound
molecules have been incorporated into polymer
backbones, pendants, or the terminal groups as

components. Approaches accessible to fullerenecontaining polymers can be divided into five main
types. First, direct copolymerization with fullerene, in which C60 as comonomer reacts with some
monomers via either free-radical polymerization
or living anionic polymerization (Camp, Lary, &
Ford, 1995; Y. Chen, Zhao, Cai, Huang, & Xiao,
1998; Ford, Nishioka, McCleskey, Mourey, & Kahol, 2000). Second, homo- and copolymerization
of the fullerene-containing monomer, in which a
fullerene-functionalized monomer is first synthesized and further homo- and/or co-polymerized
by free radical polymerization, catalytic polymerization, ring-opening metathesis polymerization
(ROMP), coupling reaction and polycondensation
reaction processes (Iwamoto & Yamakoshi, 2006;
Nishimura, Takatani, Sakurai, Maeda, & Yashima,
2002; Ramos, Rispens, van Duren, Hummelen, &
Janssen, 2001; Scamporrino, Vitalini, & Mineo,
37

1999; Sivula, Ball, Watanabe, & Frchet, 2006;

Zhang et al., 1995). Third, the graft to method,
in which random and block copolymers with active sites along the polymer chain reacted with
C60 to produce C60-grafted polymers, It is worth
mentioning that some fullerene-bond dendrimers
were also prepared by the graft to method
(Barrau et al., 2008; Geckeler & Hirsch, 1993;
Hawker, Wooley, & Frechet, 1994; Nierengarten,
Armaroli, Accorsi, Rio, & Eckert, 2003; Stalmach,
de Boer, Videlot, van Hutten, & Hadziioannou,
2000). Fourth, chain end functionalization, in
which fullerene-functionalized initiators were first
synthesized and further initiated polymerization
of monomers to produce fullerene end-capped
polymers (Nierengarten et al., 2003). However,
in most cases, polymers with active end-groups
reacted with fullerene to form mono- and bi-C60end-capped polymers as well as C60-cored starshaped polymers and multi-armed C60-end-capped
polymers (Zhou, Chen, Li, Du, &Li, 2000; Wang,
Pramoda, & Goh, 2006; Nepal, Samal, & Geckeler, 2003, Cloutet, Gnanou, Fillaut, & Astruc,
1996; Zhou, Harruna, Zhou, Aicher, &Geckeler,
2007). Fifth, supramolecular association, in which
fullerene-containing supramolecular polymers
are formed by hydrogen bonding, charge transfer
complexation, or other noncovalent interaction
forces (Snchez, Rispens, & Hummelen, 2002;
Laiho, et al., 2006). Particularly, the synthesis
and studies of polypyridylruthenium complexes
with electron-accepting fullerene moieties that is
very interesting from the intramolecular electron
transfer between the ruthenium metal complex donor and the fullerene acceptor can be successfully
switched on/off through regulating the structure
and distance of the spacer linking them. So far,
there are no reports that such electronic communication can be regulated by external temperature.
The molecular weight and polydispersity of the
poly(N-isopropyacryamide) (PNIPAM) block
between fullerene and tris(bipyridine)ruthenium
end-groups can be controlled during the living
38
radical polymerization step. Preliminary results

show that these metallopolymers exhibit interesting self-assembly characteristics in aqueous
solutions (Figure 13).
Fuctionalization of Carbon
Nanotubes with Ruthenium
Bipyridine or Terpyridine Complexes
Non-Covalent Functionalization of
Carbon Nanotubes by Ruthenium
Non-covalent functionalization of carbon nanotubes (CNTs) by polymer wrapping, interaction
with DNA or peptides, and the adsorption of ionic
or non-ionic surfactants to promote their solubility
is preferred to organic functionalization because
the pristine sp2 hybrid state is preserved. Recently,
there has been considerable interest in bringing
metal complexes in close contact with SWCNTs
with applications that include catalysis, photoinduced electron transfer and information storage.
Scientists are currently exploring the photoinduced
electron transfer reactions from similar complexes
to SWCNTs and their possible applications in
energy storage and conversion. CNTs can be efficiently dispersed with a pronounced degree of
individualization by non-covalent interactions
with water soluble Ru(II) polypyridyl complexes
containing extended systems. The dispersion
of nanotubes in aqueous media can realized by
ruthenium (II) polypyridyl complexes (Jain, Saha,
&Mart, 2011). Ru(bpy)2(dppn)2(dppn = benzo[i]
dipyrido[3,2-a:2,3-c]phenazine) showed the
highest ability to disperse SWCNTs, probably due
to their more elongated p-electron system allowing a better interaction with the SWCNTs, while
at the same time minimizing the steric effect and
increasing the distance between the SWCNT and
the positive charges of the ruthenium complex.
(Figure 14)

Figure 13. Synthesis route for fullerene and ruthenium dual end-functionalized thermosensitive polymers
and aggregation of tris(bipyridine)ruthenium-terminated PNIPAM metallopolymers in water (Copyright
2007 Royal Society of Chemistry; Copyright 2008 Wiley-VCH)
Among many organic and inorganic electrogenerated chemiluminescence (ECL) systems, solidstate ECLs based on immobilized luminophor,
tris(2,2-bipyridyl)ruthenium(II) (Ru(bpy)32+)
and its derivatives, are always attractive for
chemical analysis, clinical testing, light emitting
devices and luminescent imaging due to their good
stability, reversible electrochemical properties,
high luminescent quantum yield and favorable
compatibility with a wide range of analyses.
SWCNTs were functionalized noncovalently

with a new tris(bipyridyl)ruthenium(II) derivative
bearing two pyrene groups though stacking
interactions (Ding, Shan, Cosnier, & Goff, 2012)
that preserve the pristine electronic structure of
SWCNTs (Figure 15). Thanks to the high conductivity and high surface area of SWCNTs, the
electrogenerated poly-/oligopyrene derivative
exhibits enhanced electrochemical behavior with
fast electron transfer and highly reversible redox
39

Figure 14. Non-covalent ruthenium polypyridyl

complexescarbon nanotubes composites (Copyright 2011 Royal Society of Chemistry)
the nanocomposites afford entry into the formation

of tailored molecular surfaces capable of yielding
dense electron storage and release devices as well
as components for photovoltaic devices due to the
ability of the macrocycles to act as in progress.
Covalent Functionalization of
Carbon Nanotubes by Ruthenium
process for Ru(III)/Ru(II). Luminophor redox

Ru(III)/Ru(II) in this novel pyrene-Ru/SWCNT
composite thus constitutes an attractive material
for solid state ECL both in organic and aqueous
solutions.
Ruthenium terpyridine complex also can be
non-colvantly attached onto CNTs surfaces by
the preparation of a water-soluble metallomacrocycle (Figures 16 and 17) possessing positive
charges that facilitate ionic coordination with the
negatively charged carboxylate moieties of OxiSWNTs thereby forming a nanotube composite
with unique electronic properties (Wang, et al.,
2007; Hwang, 2006). This self-assembly method
shows potential for use in solar cell conversion or
electronic nanodevices, since the components of
40
Ultraviolet illumination of carboxylated SWNTs

results in the filling of valence band states of the
semiconducting SWNTs. This process presumably
includes reduced dopants defective oxidized carbon sites, together with holes in the band electronic
structure, that are inevitably generated during the
purification of SWNTs by a strong acid treatment.(Itkis,etal 2003) Acid purification results
in p-doping of semiconducting SWNTs (Itkis, et
al., 2003; Kazaoui, et al., 2001; Hennrich, et al.,
2003). Therefore, changes in the SWNT valence
band population might alter SWNT conductivity,
thus making light modulation of their electrical
conductivity possible. Covalent attachment of
Ru(bpy)32+ to the SWNT surface makes the carbon
nanotubes selectively light-sensitive, and that illumination of Ru(bpy)32+-SWNT in the characteristic
Ru(bpy)32+ absorption band results in a persistent
increase in conductivity of the semiconducting
SWNT film (Khairoutdinov et al., 2004). The
observed photoconductivity of Ru(bpy)32+-SWNT
films is indicative of electron transfer from SWNT
to the photoexcited Ru(bpy)32+, and that this is the
major mechanism of luminescence quenching in
Ru(bpy)32+-modified SWNTs. (Figure 18)
The ruthenium(II) bipyridyl derivative,
[Ru(bpy)2(AMbpy)]Cl2 (AMbpy = 4,40-aminomethyl-2,20-bipyridine) (Ru(II)) covalently linked
CNTs hybrid (Li, Guo, L. Gao, W. Xia, & Zheng,
2009) shows good electrochemical activity and ca.
17 times higher luminescence quantum efficiency
than the adsorbed derivative Ru(bpy)3. The RuCNTs based solid state ECL sensor exhibits high
stability toward determination of triphenylamine

Figure 15. Schematic presentations of: A) pyrene-Ru, and B) pyrene-RuSWCNTs (Copyright 2012
Wiley-VCH)
Figure 16. Illustration of multi-ion pair association of Ru-hexamer 2 with Oxi-SWNT (Copyright 2007
Royal Society of Chemistry)
41

Figure 17. Illustration of hexamer/MWCNT nanohybrids TEM photograph. Red arrows indicate
single hexamers, and yellow arrows show the
agglomerates of several hexamers (Copyright
2006 American Chemical Society)
(TPA). The present Ru-CNTs hybrid could be used

as both electrochemical and luminescent labels for
ultrasensitive bioanalysis (Figure 19).
An inorganic metal complex, [ruthenium(4,4dicarboxy-2,2-bipyridine)(2,2-bipyridyl)2]
(PF6)2,([Ru(dcbpy)(bpy)2](PF6)2) can be covalent
attached to amino functionalized multiwall carbon
nanotubes. (Figure 20) The tubes were ball milled
in a stainless steel drum for 100 h in a NH3 atmosphere, resulting in shortened (200-300 nm) and
open-ended MWNT, functionalized with amino
42
(-NH2) groups [Ru(dcbpy)(bpy)2](PF6)2 (Figure

20) was dissolved in 15 mL of thionyl chloride.
The reaction mixture 1B was refluxed under
argon for 5 h. The thionyl chloride was removed
by vacuum distillation. The remaining solid was
partially dissolved in dichloromethane (DCM).
That MWNT are interconnected through more
than one ruthenium to form multiwall carbon
nanotube interconnects through amide linkage
with a ruthenium complex were successfully
created. Interconnects were visualized through
AMF imaging, which showed multiple T- and
Y-junctions (Frehill, et al., 2002).
Combinations of metal ions with polymers and
nanotubes provide an interesting route towards supramolecular structures with well-defined catalytic, electrochemical, or magnetic properties. Metal
ligand coordination bonding with terpyridine has
become a promising tool towards such structures
while the combination of well-established polymer
chemistry and the versatile functionality of metal
ions is, in general, a promising approach to novel
material fabrication. Surface functionalization of
CNTs (SWCNTs or MWCNTs) with dendronized
alkoxy terpyridine-Ru(II)-terpyridine complexes
has been accomplished using either the grafting
to or the grafting from approaches. Different
sets of easily processable hybrid metallo-CNTs
composites have been efficiently synthesized
bearing either monomeric or polymeric side chain
tpy-Ru(II)-tpy dicomplexes (Muller, et al., 2009;
Stefopoulos, et al., 2009).
Using the grafting from approach, SWCNTs
were decorated with polymeric side chain dendritic tpyRu(II)tpy complexes. Starting from
SWCNTs functionalized with ATRP initiator sites
we were able to polymerize a vinyl terpyridine
monomer. The free side-terpyridine groups of
SWCNT-poly(tpy) were then complexated with
the didodecyloxy-tpy-Ru(III)Cl3 monocomplex
(II) affording the finalhybrid nanotubemetallopolymeric complex SWCNT poly(tpyRu(II)
tpy2C12H25) (Figure 21). For solubility reasons
of the CNT-metallomonomers and CNT-metal-

Figure 18. Dynamics of resistance changes under illumination by visible light (440 nm < < 520 nm, I
=0.015 W/cm2) of the Ru(bpy)32+-SWNT film (Copyright 2004 American chemical Society)
Figure 19. Enhanced electrochemiluminescence efficiency of Ru(II) derivative covalently linked carbon
nanotubes hybrid (Copyright 2009 Royal Society of Chemistry)
43

Figure 20. MWNT are interconnected one ruthenium complex ([Ru(dcbpy)(bpy)2](PF6)2) (Copyright
2002 American Chemical Society)
lopolymers, long aliphatic chains were attached

on the terpyridines which effectively acted as
solubilizers of the final hybrid metallo-CNTs. As
it is well-known, such long aliphatic substituents
located on the outer sphere of dendrimers and
dendronized polymers lead to enhanced organizational features.
The ruthenium terpyridine complexes themselves have the electron donor properties with
metal ion centers; and CNTs are often utilized as
electron acceptors with their extended electron
conjugation. The functionalization of nanotubes
with ruthenium complex can potentially form an
electronic donoracceptor system. The interaction
of CNTs and ruthenium terpyridine complexes has
been demonstrated by electrochemical monitoring of the change in ruthenium redox potential or
photophysical switching of the contact between
CNTs and ruthenium complexes. MCNTs can be
efficiently functionalized with Ru(II) terpyridine
complexes using the simple and mild methodology
of directly covalent amidation (Li, Wu, Jeilani,
Ingram, & Harruna, 2012). The tpyRutpy moi-
44
eties are interconnected or attached as aggregated

structures (100200-nm range) on the surfaces of
the carbon nanotubes after functionalization. The
electrical property of RuMCNTs depicts higher
resistance than that of OX-MCNTs (Figure 22).
Base on the amidation functionalization method, oxidized-MWCNTs can directly connected
with bis(2,2:6,2-terpyridine) ruthenium(II)
connected diblock metallopolymers increase the
solubility of functionalized MWCNTs in organic
solvents and water. (Li, etal. 2012).Metallo-supramolecular polymers based on the bis(2,2:6,2terpyridine) ruthenium(II)-connected units have
reversibility upon the application of external
stimuli, such as pH, temperature, redox processes
or application of competitive ligands. The polymer
ligand of terpyridine-ended poly(N-isopropyacryamide)(TpyPNIPAM) has been synthesized with
RAFT polymerization. It has been reported that
bis(terpyridine) ruthenium connected PNIPAM
copolymer has good hydrophilic and smart
thermo-responsive nature Furthermore, once selfassembled, this thermo-responsive nature could be

Figure 21. CNTs functionalized with polymeric side chain dendritic tpyRu(II)tpy complexes (Copyright
2009 Wiley-VCH)
used to enable a change in morphology by shifting

the hydrophobic to hydrophilic ration of building
block. Considering above material advantages of
such metallopolymer and MWCNTs, MWCNTs
can be easily functionalized by using a kind of
metallopolymer (RuTpyPNIPAM) to design new
kind of ruthenium-CNT based nanomaterials that
combined advantages of both ruthenium metallopolymers and CNTs (Figure 23).
A novel full-conjugated 4-(2,2:6,2-terpyrid4-yl) benzenediazonium tetrafluoroborate
(diazo-tpy) was synthesized and used for surface modification of materials, such as quartz
wafers, ITO glass, silicon, and multiwall carbon
nanotubes (MWCNTs) (Pan et al., 2010). Under
UV irradiation, the diazonium group of diazotpy is decomposed and the residual terpyridine
group is covalently anchored to the surface of
substrates. The obtained tpy-modified MWCNTs
(tpy-MWCNTs) have good solubility in common
organic solvents. Multilayer films were fabricated
from tpy-MWCNTs and ruthenium ions [Ru(III)]
45

Figure 22. Amidation of MWCNTs with Ruthenium (II) terpyridine complex (Copyright 2009 Springer)
via the layer-by-layer self-assembled (LBL SA)

technique (Figure 24) on the tpy-modified quartz
wafer, ITO glass, or silicon. Under illumination,
the LBL SA films on ITO showed an effective
photoinduced charge transfer because of their
46
conjugated structure and the ITO current density

changed with the number of bilayers. Upon irradiation, photocurrent is generated, which indicates
that the tpy-MWCNT-Ru(III) film is an excellent
photosensitizer in the visible region.

Figure 23. Amidation of MWCNTs with bis(2,2:6,2-terpyridine) ruthenium(II) connected diblock

metallopolymers (copyright 2012 American Scientific Publishers, Inc.)
Self-Assembly of Bis(2,2:6,2Terpyridine) Metal-Connected

Diblock Metallopolymers on
Graphene Nanoribbons
In recent years the self-assembly of metallosupramolecular block copolymers has made significant progress toward achieving the synthesis
of novel and functional nanostructures through
versatile and facile strategies for many desirable
applications. Metal-containing polymers combine
the processability and mechanical properties of
polymers with the unique properties of metal
complexes. Metal-ligands interaction has been
widely utilized for building up supramolecular
system (Campagna, et al., 2007; Juris, et al., 1988).
A predominantly used metal complex building
block for construction is 2, 2: 6 2-terpyridine

which is capable of forming stable chelate complex
with metals. Graphene hybridized with polymer
is expected to be a good candidate for an acceptor
material because large donor/acceptor interfaces
for charge generation and a continuous pathway
for efficient electron transfer can be built by the
graphene component (Novoselov, et al., 2004;
Campagna, et al., 2007; Juris, et al., 1988). Oneatom thickness and large 2D plane of graphene can
expect a large specific surface area in a polymer
matrix, and thus very large functional interfaces
can be formed. The modification of GNR on the
molecular level with polymer nanostructures is an
example of a bottom-up fabrication route towards
nanometer-scale devices as functional building
blocks in biotechnology and nanotechnology
47

Figure 24. Formation of LBL SA films fabricated from transition-metal ions and tpy-MWCNTs on the
diazo-tpy-modified functional surface (Copyright 2010 American Chemical Society)
(Xie, Ling, Fang, Zhang, & Liu, 2009; Reuven,

Li, Harruna, & Wang, 2012; Jain, Saha, & Mart,
2011). The MWCNTs were unzipped and reduced
to produce graphene ribbon. A modified graphene
nanoribbon (GNR) purification procedure was
utilized, in which the product was isolated by
repeated mixing and centrifugation steps, for
the separation of exfoliated graphene ribbons
from unzipped MWCNT. The oxidation reaction
product was poured into 5 ml of liquid nitrogen
cooled 30% hydrogen peroxide, which prevented
the precipitation of potassium permanganate.
The resultant single and bilayer GNRs were spin
48
cast from an ethanol/water (50:50) solution onto

a silicon wafer with 300 nm SiO2 wafers. The
GNRs were reduced by their adsorption on the
SiO2 surface and subsequent treatment with 1 vol%
hydrazine monohydrate and 1 vol% concentrated
ammonium hydroxide. The reduced GNRs were
washed with deionized water and dried under
nitrogen gas flow.
The supramolecular self-assembly (Pocius
& Chaudhury, 2002) of bis(terpyridine) metalconnected diblock copolymer on graphene nanoribbons by the formation of donoracceptor
complexes is mediated by enhanced van der Waals

Figure 25. Chemical schemes and optimized molecular structures for bis (2, 2: 6 2-terpyridine)
zinc and ruthenium-connected diblock copolymers. PS, PNIPAM, and tpy refer to polystyrene, poly(Nisopropyacryamide), and terpyridine (Copyright 2012 Royal Society of Chemistry)
interactions. Our findings (Reuven, Li, Harruna,

& Wang, 2012) provide a basis for processing
a variety of metallopolymers into controllable
nanoscale arrangements. We have studied the
interaction of bis(2,2:62-terpyridine) metalconnected AA (PS/PS) and AB (PS/PNIPAM)
block copolymers with GNRs (Figure 25).
Zn-metallo-polymer forms a distinct beaded
interconnecting Web pattern when deposited onto
a random field of GNRs resting on a silicon oxide
(SiO2) surface (Figure 15a, b and d). Atomic force
microscopy AFM images reveal that the Webbed
film is composed of Zn-metallo-polymer (Figure
26), which has an estimated height of 20 nm at
the interconnect regions. The dark beaded features
have a height of 70 nm and are evidently attributed
to the self-assembly of the Zn(tpy)2 metal centers
together with layered GNRs.
The photoluminescence (PL) of the GNR/Zincmetallopolymer hybrid was studied by confocal
laser scanning microscopy (CLSM) and flores-
cence microscopy. CLSM dark Webbed-dendrite

features correspond to PSZn(tpy)2PNIPAM/
GNR as seen in AFM images[89]. The intrinsic
PL of polystyrene is closely connected to the
prospect of imaging the PS-Zn(tpy)2-PNIPAM/
GNR film. Luminescence of the composite was
detected using fluorescence modes. In contrast
to AB Zn-polymer, the AA Ru-polymer forms
a uniform film on Si/SiO2 surface, owing to the
absence of hydrophobic/hydrophobic polymer
interactions. The Ru-metallopolymer induces the
assembly of GNRs into a distinct pseudo-fractal
dendrite pattern.
CLSM reveals that PSRu(tpy)2PS polymer
orders GNRs (dark features) into a pseudo-fractal
branching pattern (Figure 27i). A higher magnification image of a branch of ordered GNRs
is shown in the inset. We attribute the observed
GNR order to self-exclusion of amphiphilic GNRs
from the hydrophobic PSRu(tpy)2PS polymer.
As to the photoluminescence of PSRu(tpy)2PS/
49

Figure 26. Confocal microscopy, CLSM photoluminescence, and AFM topology images of PNIPAM
Zn(tpy)2PS polymer and PNIPAMZn (tpy)2PS/GNR self-assembly on Si/SiO2 surface. (a) Confocal
microscope; (b) CLSM photoluminescence image; (c) Edge-enhanced 3D rendered AFM image of PNIPAMZn(tpy)2PS polymer spin cast onto Si/SiO2 surface from THF solution; and (d) Edge-enhanced
3D rendered AFM image of PNIPAMZn(tpy)2PS/GNR composite on Si/SiO2 surface (Copyright 2012
GNR film, the auto-fluorescence of polystyrene

block copolymer is apparent in GFP, DAPI and
rhodamine fluorescent microscope images of
PSRu(tpy)2PS polymer. The auto-fluorescence
of the PSRu(tpy)2PS /GNR composite film is
predominantly seen at the GNR branches (Figure
27). The branched features of the composite are
50
composed of GNRs and are of higher PL than the

polymer film counterpart.
The Raman microscope image of PSZn(tpy)2
PNIPAM/GNR composites on a SiO2 substrate
is shown in Figure 28. The GNRs bead features
(brown) decorated with interconnecting polymer
Web features (yellow), are spatially confined.

Figure 27. Bright-field/fluorescent confocal microscopy and CLSM photoluminescence images of PSRu
(tpy)2PS polymer and polymer/GNR films. (a) Confocal microscope PSRu(tpy)2PS polymer. Inset:
GFP, DAPI and rhodamine fluorescent images of PS-Ru-tpy2-PS polymer; (b) Confocal microscope
PSRu(tpy)2PS/GNR film. Inset: PS-Ru-tpy2-PS/GNR film GFP, DAPI and rhodamine fluorescent images, (c) CLSM photoluminescence image of PSRu(tpy)2PS/GNR film, Inset: Higher-magnification
CLSM image showing self-assembled GNRs structure. Scale bar in (b-d) and (f-h) is 100 m (Copyright
2012 Royal Society of Chemistry)
Figure 28. Multi-micron PNIPAMZn(tpy)2PS polymer pattern cantered on GNRs and PSRu(tpy)2PS
polymer induced ordering of GNRs. (a) Confocal microscope image of long-range polymer ordering of
PNIPAMZn (tpy)2PS cantered at GNRs, propagating on SiO2. Inset: Micro Raman map spectroscopy
of the peak width of the G (1603 cm-1) line intensity acquired on a 12 24 m2 scan window reveals
coloured features and Raman signatures consistent with chemically prepared GNRs; (c) Confocal microscope image of PSRu(tpy)2PS polymer induced GNR ordering on Si/SiO2surface. Inset: Micro
Raman map spectroscopy of the peak width of the G (1603 cm-1) line intensity acquired on a 20 80
m2 scan window (Copyright 2012 Royal Society of Chemistry)
51

Micro Raman mapping with a spatial resolution

of 1 micron was used to characterize the polymer
surface features. The Raman mapping of the G
line (1603 cm-1) peak (inset of Figure 28a) shows
that the beaded features are clearly attributable to
GNRs. As the smaller brown GNR features (<1
m) are coated with polymer, their Raman signal
is obscured. These results show that the GNRs
and PSZn(tpy)2PNIPAM are capable of mutual
self-assembly and propagation over several microns on a SiO2 surface, and the interconnecting
polymer structures retain the approximate width
of the nucleating GNR. The microscope image
of PSRu(tpy)2PS/GNR composites on a SiO2
substrate (Figure 28c) shows that the branched
GNR features (brown) are embedded in a Rupolymer film (yellow). The Raman mapping
of the G line (1603 cm-1) peak (inset of Figure
28a) shows that the branched GNR features are
attributed to GNRs. These results suggest that
hydrophobic PSRu(tpy)2PS self-excludes the
slightly amphiphilic GNRs over tens of microns
to form branched self-assembled structures.
Chemically produced GNRs have characteristic Raman (488 nm laser excitation) peaks of
graphene (G), graphene defect (D) band, and
secondary defect (2D) bands at 1603, 1354, and
2600-3200 cm-1, respectively. GNR, with adhered
Zn-metallopolymer, retains the characteristic Raman spectroscopy G and D peaks. In the case of
the Ru-metallopolymer/GNR composite, there
exists substantial splitting of the G and D peaks
(Figure 28). The Raman splitting of the G and D
peaks is. attributed to donoracceptor interactions between PSRu(tpy)2PS and GNR. The
observed PSZn(tpy)2PNIPAM/GNR supramolecular self-assembly arises from the formation
of donor-acceptor complexes between polymer
and graphene.
An explanation of how metallopolymer interaction with GNR, The electronic characteristic of
the PSZn(tpy)2PNIPAM adsorption on graphene
is shown in the band structure of the hybrid. The
oligomer flat bands have charge primarily confined
52
at Zn(tpy)2 complex. The close proximity of these

flat bands to the charge neutrality point of graphene
implies profound charge transfer between these
components. The unoccupied polymer flat bands
strongly interact with the * band of graphene.
This infers a strong donor-acceptor interaction and
charge transfer between PSZn(tpy)2PNIPAM
and graphene. Specifically, graphene serves as
a charge donor to PSZn(tpy)2PNIPAM, and
PSZn(tpy)2PNIPAM serves as an acceptor. As
a result, the hybrid stability requirement prefers
addition Zn(tpy)2 to graphene in order to shift the
flat bands away from the Fermi level. Ru(tpy)2 has
the same type of band structure interacting with
GNR, although there exist degenerate molecular
levels due to the symmetry of side chains.
These results confirm that the GNRs are capable of controlled propagation of PS-Zn(tpy)2PNIPAM on a SiO2 surface, and the AB copolymer
structure of PS-Zn(tpy)2-PNIPAM has much more
tendency to be self-assembling with GNR than
AA copolymer of PS-Zn(tpy)2-PNIPAM . Specifically, the self-assembling patterns of PS-Zn(tpy)2PNIPAM with GNR are dendrite, while those
of PS-Ru(tpy)2-PS/GNR hybrid are so different
that GNRs function as an ultra-strong adhesion
platform that uniquely promotes the self-assembly
of amphiphilic and hydrophobic metal-contained
diblock copolymers. On a SiO2 surface, the GNRs
are capable of inducing the controlled dendritic
ordering of PSZn(tpy)2PNIPAM, whereas the
hydrophobic PS-Ru(tpy)2-PS copolymer results
in the assembly of GNRs into a pseudo-fractal
branched pattern.
CONCLUSION AND OUTLOOK

The reports on the modification of carbon-based
nanocomposites with ruthenium bipyridine and
terpyridine complexes are very limited. The success and effectiveness of the functionalization enables the attachment of different ruthenium polymer and organic complexes to the surface carbon

based nanocomposites and enhanced solubility of

Ru-nanohybrid in organic solvents. The photoluminescence properties of Ru-nanocomposites are
due to energy transfer between carbon sp2 network
on the surfaces and ruthenium complexes opens
opportunities for further research, especially in the
development of new carbon based nanomaterials.
The systematic studies of the relationship between
the nature of the active sites in carbon nanocomposite and ruthenium complees are still limited.
This is a direction in which research should be
intensified. The properties of functional carbon
nanocomposite is largely associated with the presence of defects and edge sites, ruthenium complex
type and the interaction between nanocomposites
and metal center . Although conclusive evidence
on the nature of these functionalization and their
properties is still missing, also because in situ/
operando studies are lacking, large progress in
this direction has been definitively made in the
recent years. For example, a lot of dinuclear and
multinuclear ruthenium polymerization complex
have been prepared and the properties of complexes have been well researched and may be the
trends of functionalization carbon nanocomposites
with such multinuclear ruthenium complex for
application as sensors.
Aliev, A. E., Oh, J., Kozlov, M. E., Kuznetsov, A.

A., Fang, S., Fonseca, A. F., & Baughman, R. H.
(2009). Giant-stroke, superelastic carbon nanotube
aerogel muscles. Science, 323(5921), 15751578.
doi:10.1126/science.1168312 PMID:19299612
ACKNOWLEDGMENT
Camp, A. G., Lary, A., & Ford, W. T. (1995). Freeradical polymerization of methyl methacrylate
and styrene with C60. Macromolecules, 28(23),
79597961. doi:10.1021/ma00127a054
The authors thank the National Science foundation (NSF/CFNM/CREST program, grant Award
#HRD-11137751) for financial support for this
research.
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Bipyridine: A bypridine is a family of chemical compounds with the formula (C5H4N)2, which
are formed by the coupling of two pyridine rings.
Six isomers of bipyridine exist, but two isomers
are prominent: 2, 2-bipyridine is a popular ligand
in coordination chemistry. 2, 2-bipyridine is a
chelating ligand that forms complexes with most
transition metal ions.
Carbon Nanotube: A carbon nanotube is a
tube-shaped material, made of carbon and has a
diameter measuring on the nanometer scale. The
graphite layer appears somewhat like a rolledup wire with a continuous unbroken hexagonal
mesh and carbon molecules at the apexes of the
hexagons.
Fullerene: A fullerene is a pure carbon molecule composed of at least 60 atoms of carbon.
Because a fullerene takes a shape similar to a
soccer ball or a geodesic dome, it is sometimes
referred to as a buckyball after the inventor of the
geodesic dome, Buckminster Fuller, for whom the
fullerene is more formally named.
Graphene: A graphene is a 2-dimensional,
crystalline allotrope of carbon. In graphene,
carbon atoms are densely packed in a regular
sp2-bondedatomic-scale chicken wire (hexagonal)
pattern. Graphene can be described as a one-atom
thick layer of graphite.
Ruthenium Complex: Ruthenium forms a
variety of coordination complexes with organic
or inorganic ligands. Ruthenium (II) complex
chelated organic ligands can be utilized for photoillumination and anti-cancer durgs.
Terpridine: A Terpyridine is a tridentate ligand that binds metals at three meridional sites.
2, 2; 6, 2-terpyridine, often abbreviated to
terpy or tpy) is a heterocyclic compound derived
frompyridine. This colourless solid is used as a
ligand in coordination chemistry.
61
62
Chapter 3
Nano Indentation Response

of Various Thin Films Used
for Tribological Applications
Manish Roy
Defence Metallurgical Research Laboratory, India
ABSTRACT
Various thin films used for tribological applications are classified under four heads. Based on their
load vs. displacement curves, which have some characteristics features, the ratio of nanohardness to
elastic modulus and the ratio of cube of nanohardness to square of elastic modulus are evaluated in this
chapter. It is demonstrated that depending on the type of film used, these ratios vary within a certain
range. For soft self-lubricating films, these ratios are very low; whereas for hard self-lubricating film,
these ratios are quite high.
INTRODUCTION
Tribology deals with the study of friction, wear
and lubrication of interacting surfaces in relative
motion. The word tribology is derived from the
Greek word Tribos which means rubbing. Until lately, this study was considered as a branch
of mechanical engineering, and due to its ever
increasing presence in almost every branch of
science, it has now turned into an interdisciplinary field. Rapid growth of science and technology
has created increased demand for materials with
improved performances operated in demanding
environment. This has resulted in development of
several varieties of materials and more importantly
modification of surfaces with different surface

and bulk properties.
Surface engineering is one of the most effective
ways of enhancing the performance of industrial
components to make them suitable for functions
that are different from the primary function of
the bulk substrate. Although surface engineering
has been practiced from the dawn of civilisation,
the science and technology of surface modification has been explored only in recent past. Major
progress in this direction has been achieved only
when a significant gain in performance along with
financial benefit is realised by practicing surface
modification techniques. Even though surface
modification is practiced for several reasons
DOI: 10.4018/978-1-4666-5824-0.ch003

Nano Indentation Response of Various Thin Films
for protection against degradation such as wear,

corrosion, fatigue etc. surface engineering for
enhanced wear performances is most widely used
tools for performance enhancement. Deposition
of thin film for monitoring the tribology related
surface response has received increased attention
in recent days.
Various tribological thin films can be broadly
classified under four different heads. The first
variety films are hard film with high friction
coefficient. These films are used where the wear
should be low and high friction coefficient is
required. Second variety consists of films with
very high nanohardness and low friction coefficient with excellent inertness. These films are
used for tribological application under circumstances where corrosion or oxidation resistances
plays crucial role. When these films are used as
protective coating, wear of mating surface is an
important problem. Third varieties films known
as self-lubricating film have low nanohardness
along with low friction coefficient. Although
wear rate of these films are not important from
application point of view, the friction coefficients
of these films are very low. Finally forth variety
is films with reasonable nanohardness but low
friction coefficient. These films are used as selflubricating film where wear is also a concern.
The objective of the present chapter is to
critically examine the nano indentation response
of selected films pertaining to each variety of
films mentioned above. In order to achieve the
aforementioned objective, one example of each
variety of films is taken. The load vs. displacement
curves of each film is analysed. Their nanohardness, elastic modulus, ratio of nanohardness to
elastic modulus and elasticity are evaluated. The
characteristics features of these properties of each
variety of films are ascertained.
VARIOUS FILMS
Four different films pertaining to four varieties
referred in earlier section are selected for present
chapter. Nitrides of hard coatings are used for
wear reduction on cutting and die tools for long
time. More recently ZrN has received increased
attention due to its better corrosion resistance
improved mechanical properties and warm golden
colour (Chou, YU, & Huang, 2003; Kolesoguru,
Miterrer, & Urgen, 2002). ZrN is considered to
be an example of first variety of film. Although
the nanohardness of the investigated film is not as
high as reported for other ZrN film, this is a film
with high nanohardness and high friction coefficient. Nanocrystalline diamond film is second
variety film having high nanohardness and low
friction coefficient. Nano crystalline and ultra
nano crystalline diamond (NCD/UNCD) films
can be produced using a modified hot-filament
technique (Braza & Sundarshan, 1992). These
films can be deposited on a broad spectrum of
substrate materials such as tungsten carbides,
titanium and titanium alloys, refractory metals,
ceramics, glass, silicon, quartz, sapphire, graphite
and steel using a passive interlayer. Depending on
deposition parameters, i.e. gas mixture, temperature, pressure and substrate seeding, CVD growth
of diamond results in different types of films.
These are generally classified according to the
crystal grain size as micro crystalline (grain size
5 m), nano crystalline (NCD) (grain size about
50 nm) and ultra nano crystalline (UNCD) (grain
size < 5 nm). Crystallites with sizes down to 3
nm display special advantages. Due to the small
dimensions of nano crystallites, the relation of
volume-to-surface increases dramatically, leading
to an exceptionally high amount of surface atoms
and this results in distinct physical and chemical
properties (Braza & Sundarshan, 1992; Tasi &
Bogy, 1987).
63

Transition metal dichalcogenides films represent today an important variety of self lubricating
films. These films are finding increasing application in space related technologies (Briscoe, 1990;
Singer, Fayeulle, & Ehni, 1996) and other applications in vacuum or in aggressive environment
(Spalvins, 1974). Among various chalcogenides,
tungsten sulphide is considered potential self-lubricating film as this compound is readily available
and it has ability to withstand higher temperature
than molybdenum sulphide. It is noted previously
that, if WS2 film is alloyed with carbon, it results
in reduction of porosities and extent of oxygen
adsorption of the film (Nossa & Cavaleiro, 2001;
Grill, 1993). It is further observed that alloying
with carbon leads to improvement of mechanical
and tribological properties of these films (Grill,
1993; Lince & Hilton, 1995). It is demonstrated
that best combination of mechanical and tribological properties is obtained at around 50 at% C
(Spalvins, 1984). Thus a variety of W-S-C film
having nanocomposite structure has reasonable
nanohardness and low friction coefficient and can
be categorized under third variety films.
Finally, quasi non hydrogenated a-C and and
hydrogenated a-C:H film is taken as an example
of self lubricating film with reasonable nanohardness. Amorphous carbon films also known as
diamond-like carbon (DLC) films have shown
a number of useful properties such as high
nanohardness (Dean & Chalamala, 1999), good
thermal conductivity (Robertson, 2002), low
friction coefficients (Donnet, 1996), excellent
wear resistance (Zehnder & Patscheider, 2000),
ultra-smoothness and chemical inertness (Neuville
& Mathews, 1997). Owing to this unique combination of properties, DLC films have found a
wide range of applications as protective coatings
in magnetic hard disc, microelectromechanical
(MEMS) systems, or reported in recent years, as
biocompatible coatings (Robertson, 1991; Grill,
1999; Miyoshi, Wu, & Garscadden, 1992). In many
of these applications, in particular for magnetic
recording systems, very thin coatings with low
64
friction coefficients accompanied with excellent

wear resistance are desired.
DEPOSITION OF VARIOUS FILMS

Deposition of ZrN Film
ZrN film was deposited using reactive ion nitriding
unit. The coating unit has an annular zirconium
cathode located at the center of the coating chamber and surrounded by an anode. The samples
to be coated are located between the electrodes.
During the coating process the specimens are in a
planetary motion around the cathode. Zirconium
is removed from the cathode in the form of ions
by striking an arc between the cathode and the
anode. The bias voltage drives the ions towards the
samples. Since coating is carried out in nitrogen
atmosphere, Zr ions react with nitrogen to form
ZrN on the samples. The process condition under
which deposition was carried out were 750 volt
arc, 15 V bias voltage, 0.8 to 1.0 mtorr nitrogen
pressure, 850oC cathode temperature and approximately 10 mm/h deposition rate. Further
description about deposition method is available
elsewhere (Sundararajan, Roy, & Das 1997).
Deposition of Nanocrystalline
Diamond Film
Nano-crystalline diamond films are grown by
BeSt coating (rho-BeSt coating GmbH, Innsbruck,
Austria) on silicon substrates by modified hot-wire
chemical vapour deposition from a CH4 (2%)/H2
(98%) mixture. The deposition temperature is
chosen between 550 and 780C, depending on the
substrate specification. After the coating process,
the dangling bonds at the surface were hydrogen
terminated (H-NCD). Thermal treatment of the
nanocrystalline diamond surface at 400C for 4
hours with 21% oxygen, replaced hydrogen for
oxygen containing groups, i.e. ether carbonyl,

or hydroxyl groups (Hllaman, Wanstrand, &

Hogmark, 1998).
Deposition of W-S-C Film

The WSC coatings were deposited by radio
frequency magnetron sputtering of a WS2 target in
a basic ESM 100 Edwards unit following a similar
procedure as presented in a previous research
(Nossa & Cavalerio, 2004). Before deposition, the
substrates were cleaned for 30 min by establishing
the plasma close to the substrate electrode. A Ti
interlayer was deposited to improve the adhesion
of the W-S-C film. CH4 was used as reactive gas
for C containing WSC films. The mass flow
of the reactive gas CH4 was varied from 1 to 5
sccm and the argon flow was adjusted to reach the
final deposition pressure of 1 Pa. The discharge
power was 5.1 W cm-2. The total deposition time
was kept constant at 75 min (15 min for the Ti
interlayer and 60 min for the WSC films). No
substrate bias was applied during the depositions.
The substrate used was 100Cr6 steel.
Deposition of Quasi Non

Hydrogenated (a-C) and a-C:H Film
For deposition of quasi non hydrogenated (a-C) and
a-C:H films, an balanced industrial sized magnetron cathode (coating height: 400 mm) from AJA
(AJA International, North Scituate, MA, USA)
equipped with a graphite target (nominal purity
>99.95%) was used. The magnetron cathode was
powered with a ten kilowatt power supply from
Advanced Energy (Advanced Energy Industries,
Fort Collins, CO, USA) in the power regulation
mode. The pulsing unit was set to 80 kHz, where
a reverse voltage of 15% with a reverse time of 1
s was used. A power density of ~10 Wcm-2 was
applied on the carbon target for all depositions.
For deposition of a-C:H films, C2H2 (nominal
purity >99.96%) was introduced in the coating
chamber together with argon (Ar) (nominal purity
>99.999%) resulting in C2H2/Ar ratios from 0 to
0.43. For deposition of the a-C coatings, a total

flow of 30 sccm Ar was used.
Boron doped silicon wafers (100) with a thickness of 525 25 m were used as substrates. The
wafers were fixed on a grounded substrate holding
carrousel situated at a distance of approximately
10 cm from the sputtering source. In order to study
the influence of substrate bias, a Heiden (Prgen,
Germany) bias power supply was connected to
the carrousel. Films were deposited by oscillation of the carrousel with an amplitude of 9 cm
(left-right) symmetrically through the sputtering
plasma. The substrate temperature was monitored
with an electrically insulated K-type thermocouple
installed at the backside of the substrate holder. For
plasma cleaning of the wafers prior to deposition,
an ALS 340 linear ion beam source from Veeco
(Woodbury, NY, USA) was operated at a voltage
of 2 kV and an Ar flow rate of 20 sccm through
the ion gun. For all depositions, the chamber was
evacuated to a base pressure of 5 10-5 mbar.
During deposition and plasma etching, the pressure
in the chamber ranged from 1 10-3 mbar to 7
10-3 mbar. During deposition no extra heating was
applied to the substrates. The coating temperature
did not exceed 80C for all depositions.
MICROSTRUCTURAL FEATURES
ZrN Film
The SEM image of the cross section of ZrN film
is illustrated in Figure 1. The thickness of the
film is of the order of 5 m although the thickness is not uniform throughout and the film is
essentially crack free. The interface between
the film and substrate is also relatively smooth,
clean and continuous which is indicative of good
adhesion. Some places in the interface some void
like structure can be seen. These are essentially
artifacts of polishing. XRD pattern of the film is
produced in Figure 2. The film is pure ZrN. Few
peaks can be seen for substrate Fe.
65

Figure 1. SEM image of the cross section of the

ZrN film
Figure 2. XRD pattern obtained from the coated

surface
Nanocrystalline Diamond Films

The high magnification SEM images of the morphology of the H-terminated and O-terminated NCD
diamond films are presented in Figure 3. Both the
films exhibit ballas morphology with O-terminated
film particularly showing prominent ballas morphology. Transmission electron microscopy image shown
in Figure 4 clearly proves grain sizes in nanometer
level. Raman spectra obtained from all the films are
presented and described in ref (Liu, Klauser, Memmel, Bertel, Pichler, Knupfer, Kromka, & Steinmuler
Nethl, 2008). Both films show peaks at wave number
(1340 cm-1) corresponding to sp3 bond. The corresponding bond for pure diamond is at 1330 cm-1.
As received H-terminated film exhibits peak at 1160
cm-1 and 1470 cm-1. Both peaks are characterised by
nanocrystalline diamond. In contrast, O-terminated
film exhibits peak at 1330 cm-1 for microcrystalline
diamond and another peak at 1560 cm-1 which can
be identified as G band of microcrystalline graphite.
Thus part of nanocrystalline diamond is possibly
converted to microcrystalline graphite. Three dimensional AFM images showing the topographies
of both films are presented in Figure 5. Topographies
show presence of sharp peaks. There is no apparent
difference in topographies by H-termination and
O-termination. RMS value for O-terminated film
is higher than H-terminated film and is around 13
nm implying very smooth film.
Figure 3. SEM images showing the morphologies of a) H-terminated and b) O-terminated nanocrystalline diamond film
66

Figure 4. TEM image of nanocrystalline diamond

film
W-S-C Film
Figure 6 shows the cross section morphology of
W-S-C coatings with two different C content. It can
be stated that there is a progressive densification
of the coatings with a significant decrease of the
number of pores which results in a decrease of the
exposed surface area where O can be adsorbed.
As a consequence, the final O content decreases
with increasing C. It is also noted that the S content in relation to the stoichiometry (S/W = 2) is
lower. This fact is related to the preferential resputtering of S by energetic species during these
films deposition (Winters, 1982). Furthermore,
the presence of H species in the plasma phase,
due to the use of CH4 as reactive gas, promoted

the formation of H2S compound, which being a
gas is pumped out from the chamber leading to
the depletion of sulphur from the film.
The XRD patterns of the films are illustrated
in Figure 7 The most important points worth
noting is domination of the XRD patterns by a
main broad asymmetric peaks which are indexed
with the general form (10L) corresponding to a
turbostrating stacking of the family of plans (10L)
with L = 0,1,2,3 (Regula, Ballif, Moser, & Lvy,
1996) of the hexagonal WS2 phase. A small peak
close to 2 ~70 can be indexed as the (110) plan
of WC. A progressive decrease in the crystallinity degree with increasing C content as shown by
either the progressive broadening or the decrease
in the intensity of the diffraction peaks can also be
noted. It is hard to detect any vestiges of any other
crystalline phase excepting those related to the
underlying steel substrate (2 ~~52). and the small
features on the right shoulder of the main broad
peak which can be related with the presence of a
W-C phase. The microstructure of the films can,
thus, be described as a nanocomposite consisting
of W-S nanocrystals (and in some cases of W-C
nanocrystals) embedded in a C-rich amorphous
layer, in agreement with the transmission electron
microscopy analysis and X-ray photoelectron
spectroscopy (XPS) study performed in a previous research (Nossa & Cavalerio, 2004; Nossa,
Cavaleiro, Carvalho, Kooi, & De Hosson, 2005).
Figure 5. AFM images showing topographies of a) H-terminated and b) O-terminated nanocrystalline

diamond film
67

Figure 6. SEM images of transverse sections of W-S-C coatings a) 28 at. % C, b) 54 at. % C
Figure 7. X-ray diffraction pattern of various

W-S-C films
to 10 nm except film containing 69 at. % C. The

roughness of this film is quite low and equal to
6.5 nm. However, the RMS values of these films
are comparable to the RMS value of Ti/a-C: H
film and PECVD DLC film (Kvasnica, Schalko,
Benardi, Eisenmenger-Sittner, Pauschitz, & Roy,
2006).
Quasi Non Hydrogenated

(a-C) and a-C:H Film
The three dimensional AFM images showing

the topography of these films are illustrated in
Figure 8 All films exhibit presence of sharp peaks.
The root mean square (RMS) values characterising the roughness of the films indicates that
most of the films are having a RMS value close
68
The high magnification image obtained from

high resolution transmission Electron microscopy
(HRTEM) of a representative quasi non hydrogenated (a-C) film is illustrated in Figure 9. High
amorphicity of the deposited films could also be
proven by HRTEM investigations. Figure 9 shows
the non-crystalline nature of our deposited films.
However, small atomic aggregates in the range
of 2 to 3 nm were found in the DLC matrix. The
three dimensional AFM images showing the topographies of these films are illustrated in Figure
10. Film deposited at high Ar flow rate exhibits
presence of sharp peaks. The sharpness of the
peaks decreases with decreasing Ar flow rate.
A limited number of spikes can be seen in the
deposited film. Various topographical parameters
indicate that the root mean square (RMS) roughness value of these films varies between 0.6 nm

Figure 8. AFM images showing topographies of various W-S-C films containing a) 14 at. 5 C, b) 20 at.
% C, c) 28 at. % C, d) 54 at. % C and e) 69 at. % C
to 1.4 nm authenticating the fact that these films

are ultra smooth films.
Figure 11 illustrates a Raman spectrum (with
additional Gaussian function fits for the D and
G-band) of a quasi a-C film structure, deposited
with pure Ar as sputtering gas. The bands were
found to be at spectral positions of 1356 8
cm-1 (D-band) and 1550 4 cm-1 (G-band). To
investigate the structure of the deposited films in

more detail it is necessary to focus also on the full
width at half maximum of G band (FWHM (G)).
In order to investigate the trends in the C-C sp3
binding content, the FWHM (G) is used to reveal
information about the structural variance induced
by changes in the C2H2/Ar-rate. The variation of
FWHM (G) with C2H2/Ar ratio is presented in
69

Figure 9. High resolution transmission Electron

microscopy (HRTEM) of a representative quasi
non hydrogenated (a-C) film
Figure 12. It can be noted, that the increase of

the C2H2/Ar-rate showed a decreased structural
disorder verified by the decreased FWHM (G)
from 1913 cm-1 to 1731 cm-1.
NANOINDENTATION RESPONSE
ZrN Film
The load vs. displacement curves of ZrN films
is given in Figure 13. The load vs. displacement
curve is smooth without any pop up and pop in.
The maximum depth of indentation is 428.4 nm as
oppose to 335.1 nm residual depth of indentation.
Figure 10. AFM images showing topographies of various Quasi non hydrogenated (a-C) and a-C:H
film deposited under a) C2H2/Ar = 0.0, b) C2H2/Ar = 0.11, c) C2H2/Ar = 0.25 and d) C2H2/Ar = 0.43
70

Figure 11. An exemplary Raman spectrum of a quasi a-C film structure, deposited with pure Ar as
sputtering gas
Figure 12. The variation of full width at half maximum (FWHM) with C2H2/Ar ratio
During the hold at maximum load, the displacement increases in the film indicating drift due
to the creep as the load vs. displacement curves
are plotted after incorporating the correction due
to thermal drift. The plot of load as function of

square of distance is provided in Figure 14. The
nature of curve shows high cohesive strength and
high fracture toughness.
71

Figure 13. Load vs. displacement curve of ZrN film
Figure 14. Load vs. square of displacement curve of ZrN film
Nanocrystalline Diamond Film

The load vs. displacement curves of NCD films
are given in Figure 15. Highly elastic nature of
the curves is evident. The load vs. displacement
curves are smooth and there is no pop up and pop
in ruling out possible failure during indentation.
For NCD-H terminated film the maximum depth of
indentation is 60.7 nm as oppose to 9.5 nm residual
depth of indentation. The corresponding values for
72
O-terminated NCD film are 59.5 nm and 7.8 nm.

The nanohardness of the film increases marginally due to O-termination treatment. According
to the theories of plasticity of contact mechanics,
the load changes with the square of the depth of
penetration. Further to examine the possibility of
failures of these films across the interface of different microstructural features within the film, the
load was plotted against square of the penetration
depth as shown in Figure 16. All the curves show

Figure 15. Load vs. displacement curve of NCD film
Figure 16. Load vs. square of displacement curve of NCD film
a smooth curve with one turning point during

loading and no step is noted before and after the
turning point. Thus, all the film possesses high
cohesive strength and high fracture toughness
(Ding, Meng, & Wen, 2000). Within the range of
applied load, there is no cracking in these films.
W-S-C Film
The load vs. displacement curves of these films
obtained at an applied load of 2 mN are illustrated
in Figure 17. Each curve is obtained by averaging
ten different curves. Similar to nanocrystalline
diamond film, all the curves are smooth and none
73

of the curves shows the presence of pop in or pop

out events indicating no evidence of fracture of
the film. It is clear that, films with lower carbon
content exhibit higher depth of penetration. The
highest depth of penetration of 220.8 nm and the
highest residual depth of 146.0 nm are obtained
for film containing 14 at. % carbon whereas the
lowest depth of penetration of 143.8 nm and the
lowest residual depth of 58.0 nm pertain to the
film containing 54 at. % carbon. Interestingly, film
containing the highest amount of carbon (69 at. %
C) exhibits the highest elastic deformation. Dur-
ing the hold at maximum load, the displacement

increases in all the films indicating drift due to
the creep as the load vs. displacement curves are
plotted after incorporating the correction due to
thermal drift. This feature is completely different
than what is observed for nanocrystalline diamond
film where no such drift is noticed. The extent of
this drift decreases with increasing carbon content,
being minimum at 54 at. % carbon. On further
increase of carbon the drift increases.
The load of these films are also plotted against
square of the penetration depth as shown in Fig-
Figure 17. Load vs. displacement curve of W-S-C film
Figure 18. Load vs. square of displacement curve of W-S-C film
74

ure 18. Again all the curves show a straight line

during loading and no turning point or step is
noted. Thus all the film possesses high cohesive
strength and high fracture toughness (Ding, Meng,
& Wen, 2000). Within the range of applied load,
there is no cracking in these films. As the coating deforms in response to maximum Hertz-like
shear stress lying within the coating depth, it is
apparent that this shear stress is not enough to
make the substrate yield.
Quasi Non Hydrogenated

(a-C) and a-C:H Film
The load versus displacement curves of these films
obtained at an applied load of 0.5 mN are shown
in Figure 19. As usual each curve is obtained by
averaging ten measured curves. All curves are
smooth and none of the curves shows the presence of pop in or pop out events. The highest
depth of penetration of 33.6 nm and the highest
residual depth of 7.21 nm were obtained for the
film deposited at a C2H2/Ar-ratio of 0.43, whereas
the lowest depth of penetration of 28.12 nm and
the lowest residual depth of 2.6 nm pertain to the
film obtained by an applied bias voltage of -100
V. The load was plotted against the square of the
penetration depth as shown in Figure 20. All the

curves show behaviour similar to previous cases
and no step is seen in these curves.
Elastic Modulus and Nanohardness

Variation of nanohardness of H-terminated and
O-terminated nanocrystalline diamond films as
function of contact depth is illustrated in Figure
21. The nanohardness increases with contact depth
with load for both variety of film and then reaches
a constant value at higher contact depth. Initial
increase in nanohardness is certainly not related
to size effect as in that case nanohardness would
have decreased with increase of contact depth.
Rather this effect is due to slipping of the indentor
or invalid indentation test. This is possible given
the depth of indentation as compared to roughness parameters of the film surface. It can also
be noted that the nanohardness of O-terminated
film is higher than the H-terminated film at lower
contact depth and higher contact depth nanohardness of both films are comparable. Thus it can
be concluded that O-termination is near surface
phenomenon and at very low load the influence
of O-termination is visible. This effect do not play
important role at higher load.
Figure 19. Load vs. displacement curve of carbon film
75

Figure 20. Load vs. square of displacement curve of carbon film
Figure 21. The variation of nanohardness with contact depth for NCD films
The variation of nanohardness and elastic

modulus as a function of carbon percentage of
W-S-C films is illustrated in Figure 22. Both the
nanohardness and elastic modulus are improved
with increasing at. % of carbon up to a threshold
value and then drop down with a further increase
of C. The maximum value of the nanohardness
76
is attained for 54 at. % of carbon whereas the

maximum elastic modulus is noted at 28 at. % of
C. As discussed in previous publication (Nossa
& Cavalerio, 2004) such a variation can be attributed to the fact that the film becomes denser with
increasing carbon content. Moreover, the possible
formation of W-carbide nanograins in coatings

Figure 22. Variation of nanohardness and elastic modulus as function of at. % of carbon of W-S-C film
Figure 23. The influence of the applied load on the nanohardness of W-S-C films
with C contents in the range from 40 to 55 at. %,

as demonstrated by XPS measurements (Nossa
& Cavalerio, 2004), can justify the maximum of
nanohardness for that value. Once the amount
of carbon reaches a saturation point a further
increase in carbon results only in a decrease on
the relative amount of W-carbide nanocrystals.
This phenomenon is reflected by a decrease of
both the nanohardness and the elastic modulus.
Figure 23 represents the influence of the applied load on the nanohardness of these films.
Two different trends can be observed. Films with
20 at. % C, 28 at. % C and 69 at. % C exhibit low
nanohardness at low applied loads and the nanohardness increases with the applied up to certain
load. On further increase of load the nanohardness assumes a constant value. In contrast, films
14 at. % C and 54 at. % C possesses minimum
77

nanohardness at applied load of 1 mN. When the

size effect plays an important role in determining
the nanohardness, it decreases with increase of the
applied load. Thus, the size effect is not relevant
for most of the cases in the range of the load used
in this investigation. The depth of indentation at
low load being around 50 to 75 nm and the film
thickness is around 0.85 to 2.5 m. Hence, this
variation of nanohardness is certainly not because
of substrate effect. The lower nanohardness at low
applied load may be related to slipping of indenter
at low load. In order to find the exact reason for
the observed behaviour further investigation needs
to be done. Film with 14 at. % C) and 54 at. % C
showed higher nanohardness at load of 0.5 mN
than at a load of 1 mN. This may be related to
the size effect.
The influence of contact depth on the nanohardness of these films is given in Figure 24. Contact
depth is determined from the load displacement
data using equation given below (Pharr, 1998):
hc = hmax
Pmax

S
(1)
where Pmax is the maximum indentation load, S is

the slope of the initial part of the unloading curve
(in N/m) and is a constant which is dependent on

the geometry of the indenter, for Berkovich tip
= 0.75 (Bhushan & Li, 2003). The dependence of
nanohardness on contact depth follows the same
trend as that of dependence of nanohardness on
applied load signifying minimum substrate effect. It should be stated that all the films exhibit
lower nanohardness at a contact depth of 100
nm. The reason for this is not clear and requires
further investigation in terms of possible formation of soft complex layer or strain induced phase
transformation close to the surface. At very low
contact depth of the order of 50 nm, there is a possibility of size effect and this may be responsible
for slightly higher nanohardness at lower load
of the film with 28 at. % C. Similar variation in
nanohardness with respect to applied load is noted
for film having 28 at. % C for the same reason. It
should be noted that above mentioned size effect
is visible with film having 54 at. % C at a contact
depth of 50 nm whereas size effect can be seen
in the film with 14 at. % C at a contact depth of
80 nm. This difference can be attributed to higher
density of film having 54 at. % C than the density
of film with 14 at. % C.
The variation of nanohardness and elastic
modulus as a function of C2H2/Ar-ratio for Quasi
non hydrogenated (a-C) and a-C:H film is shown
Figure 24. Variation of nanohardness with contact depth for W-S-C film
78

Figure 25. The variation of nanohardness and elastic modulus as a function of C2H2/Ar-ratio for quasi
non hydrogenated (a-C) and a-C:H film
in Figure 25. It can be seen, that the nanohardness

and the elastic modulus decreases with increase
in C2H2/Ar ratio. This decrease is consistent
with the decrease of HWFM (G) of with C2H2/
Ar-ratio indicating that decrease in structural
order responsible for decrease in nanohardness
and elastic modulus
H/E Ratio
Recently it has been shown that the ratio of
nanohardness to elastic modulus (H/E) is a very
important material parameter (Musil & Jirout,
2007). The ratio H/E multiplied by geometric
factor, which is ratio of the diameter of plastic
zone to total deformed zone gives plasticity index. Plasticity index describes the deformation
properties of contacting surfaces. This quantity
also appears in various expressions for fracture
toughness.
The variation of H/E ratio as function of
contact depth of nanocrystalline diamond film
is illustrated in Figure 26. This ratio increases
with increase of contact depth for both varieties

of films. This ratio is higher for O-terminated
film as compared to H-terminated film at lower
contact depth and comparable at higher contact
depth. Thus O-termination improves H/E ratio
at low load. O-termination becomes ineffective
at higher load. It should also be stated that this
ratio is comparable for amorphous carbon film
and Ti containing nanocomposite carbon film at
lower contact depth (Ctvrlik, Stranyanek, Bohak,
Kulikoasky, & Suchanek, 2008). However, this
ratio for nanocrystalline diamond film is significantly higher than this ratio of amorphous and
nanocomposite carbon films at higher contact
depth. Ignoring this ratio at low contact depth,
it is noted that this ratio varies between 0.1 and
0.15. The variation of H/E ratio as function of wt
% of carbon for W-S-C film is presented in Figure
27. It is clear that the ratio H/E increases with
carbon content in the film. This ratio is within
the range of 0.04 to 0.09. Thus with increase in
carbon content the film improves its deformation
properties and fracture toughness.
79

Figure 26. The variation of H/E ratio as function of contact depth of nanocrystalline diamond film
Figure 27. The variation of H/E ratio as function of wt % of carbon for W-S-C film
Bar diagram showing the ratio of H/E for a

series of quasi non hydrogenated carbon film as
function of deposition condition is provided in
Figure 28. It is interesting to note that this ratio is
independent of the processing condition signifying that the fracture toughness or the deformation
properties cannot be altered significantly for pulsed
sputtered deposited non hydrogenated carbon film.
80
H3/E2 ratio
The expression H3/E2 which contains nanohardness and elastic modulus is a measure of the
elasticity exhibited by the film (Charitidis &
Logothetidies, 2005). A high value of H3/E2 is an
indicator of a high elastic behaviour and a low value
of H3/E2 suggests a plastic behaviour of the layer.
This ratio for various films are discussed below.

Figure 28. Bar diagram showing the ratio of H/E for a series of quasi non hydrogenated carbon film
Figure 29. The variation of H3/E2 with the contact depth for nanocrystalline diamond film
Figure 29 represents the variation of H3/E2 with

the contact depth for nanocrystalline diamond film.
It is clear from Figure 29 that H3/E2 increases with
the contact depth indicating that the film becomes
more elastic at higher applied load. The elasticity
is always higher for O-terminated film than Hterminated film. According to some investigators
(Galvan, Pie, & De Hosson, 2006) the toughness
of the film increases with elasticity and hence

O-terminated films are expected to have higher
toughness than H-terminated film. It is clear that
at higher contact depth this ratio is in excess of
1.0. Interestingly, the elasticity of nanocrystalline diamond film is significantly higher than the
elasticity of carbon alloyed W-S-C film (Koch,
Evaristo, Pauschitz, Roy, & Cavaleiro 2009).
81

Figure 30. The variation of H3/E2 with the percentage of carbon for W-S-C film
Figure 31. Bar diagram showing the ratio of H3/E2 for a series of quasi non hydrogenated carbon film
Figure 30 represents the variation of H3/E2

with the percentage of carbon for W-S-C film. It
is clear from Figure 30 that H3/E2 increases with
the carbon content indicating that the film becomes
more elastic. Thus, a higher amount of carbon is
beneficial for a film where wear resistance and
elasticity are expected. The value of this ratio is
around 0.02.
82
Figure 31 illustrates the H3/E2-ratios, of various

carbon films. The elasticity tends to decrease with
increase in C2H2/Ar ratio. The elasticities of these
films are in between 0.17 to 0.20. Examination of
the H3/E2-ratios obtained by various investigators
indicates result of present work is in conformity
with the data reported by Charitidis et al. (2005)
and Ctvrtlik et al. (2008) for amorphous carbon
film but higher than nanocomposite diamond film
obtained by same investigators.

EXAMINATION OF DATA
FROM LITERATURE
Nanohardness elastic modulus, H/E ratio and H3/
E2 ratio of a series of nitride films are listed in
Table 1. It can be seen that for these variety of
coatings nanohardness and elastic modulus being very high, H/E generally vary between 0.11
to 0.15. In contrast, H3/E2 generally around 0.57
to 0.64. However, Cu containing coating exhibit
higher H3/E2 and this value is around 1.06 to 1.08.
Nanohardness elastic modulus, H/E ratio and
H3/E2 ratio of various diamond films as reported
in literature are summarised in Table 2. For diamond films both H/E and H3/E2 ratio are high and
within small range. H/E ratio changes between
0.1 to 0.15 whereas H3/E2 ratio is reasonably high
and in the range of 1.0 to 2.0. Only diamond film

with coarse ballas morphology exhibits low H3/
E2 ratio which is approximately 0.63.
H3/E2 ratio of a series of transition metal dichalchogenide films are listed in Table 3. The H/E
ratio is very low and of the order of 0.05 to 0.07.
In contrast, low value of H3/E2 ratio are found in
the range of 0.01 to 0.06. However, if these films
are made as a nanocomposite film containg metal,
both these ratios increase. These ratios for such
film can be as high as 0.1 and 0.2 respectively.
3
H /E2 ratio of a series of carbon based films are
provided in Table 4. In case of carbon based self
lubricating film the ratio of nanohardness to elastic
modulus tends to vary with in a very close range
Table 1. H, E, H/E and H3/E2 for a series of nitride film

Films
H (GPa)
E (GPa)
H/E
H3/E2 (GPa)
Zr-Y-N, (Musil, Kunc, Zenam and Polakova, 2002)
31.6
229
0.14
0.6
Cr-Ni-N, (Musil, Kunc, Zenam and Polakova, 2002)
39.2
307
0.12
0.64
Ti-Mo-N, (Musil, Kunc, Zenam and Polakova, 2002)
46
413
0.11
0.57
Al-Cu-N, (Musil, and Vicek, 2001)
47
313
0.15
1.06
45.6
405
0.11
0.58
Zr-Cu-N, (Musil, and Vicek, 2001)
56
399
0.14
1.08
CrN
25
375
0.067
0.11
Ti-Al-V-N
Table 2. H, E, H/E and H3/E2 for a series of diamond film

Films
H (GPa)
E (GPa)
H/E
H3/E2 (GPa)
Nano crystalline diamond film, H-terminated, (Roy, Steinmuller

Nethl, Tomala, Tomastik Koch and Pauschitz, 2011)
54.1
403.0
0.13
0.98
Nano crystalline diamond film, O-terminated, (Roy, Steinmuller

Nethl, Tomala, Tomastik Koch and Pauschitz, 2011)
58.7
419.0
0.14
1.2
Microcrystalline diamond film, faceted morphology, (Bogus,

Gebeshuber, Pauschitz, Roy and Haubner, 2008)
82.9
535.5
0.15
1.99
Microcrystalline diamond film, coarse ballas morphology

(Bogus, Gebeshuber, Pauschitz, Roy and Haubner, 2008)
58.5
563.5
0.10
0.63
Microcrystalline diamond film, fine ballas morphology, (Bogus,

Gebeshuber, Pauschitz, Roy and Haubner, 2008)
59.3
379.2
0.15
1.5
Microcrystalline diamond film, (Chowdhury, Barra and Laugier,

2005)
110
1156
0.09
1.06
83

Table 3. H, E, H/E and H3/E2 for a series of of transition metal dichalchogenide film
Films
H (GPa)
E (GPa)
H/E
H3/E2 (GPa)
W-S-C, (Koch, Evaristo, Pauschitz, Roy, and Cavaleiro, 2009)
4.6
66.0
0.07
0.02
WSe2, (Pauschitz, Badisch, Roy and Shtansky, 2009)
5.9
81.5
0.06
0.03
Mo-Se-C, (Tomala, Roy, and Franek, 2010)
4.0
40.0
0.1
0.04
WS2 (Li-na, Cheng-bio, Hai-dou, Bin-shi, Da-ming, Jia Jug and

Gou-lu, 2010)
15.4
354.0
0.05
0.06
MoS2 (Renevier, Lobiondo, Fox, Teer and Hampshire, 2000)
4.7
70
0.06
0.01
CrN-WS2, (Deepthi, Barshilia, Rajam, Konchady, Pai and

Shankar, 2011)
24
250
0.1
0.22
Ti-MoS2, (Renevier, Lobiondo, Fox, Teer and Hampshire, 2000)
15
138
0.1
0.18
Table 4. H, E, H/E and H3/E2 for a series of carbon based self lubricating film
Films
H (GPa)
E (GPa)
H/E
H3/E2 (GPa)
Ti-C:H, (Pauschitz, Kvasnica Jisa, Bernardi, Koch and Roy,

2008)
15.5
164.0
0.1
0.14
a-C, (Krumpiegl, Meerkamm, Fruth, Schaufler, Erkens and

Bohner, 1999)
11.9
117.6
0.10
0.12
a-C: H, (Krumpiegl, Meerkamm, Fruth, Schaufler, Erkens and

Bohner, 1999)
25.0
162.4
0.15
0.59
Ti-C: H, (Krumpiegl, Meerkamm, Fruth, Schaufler, Erkens and

Bohner, 1999)
16.7
113.9
0.15
0.35
a-C:H, (Michel, Muhlen, Achete and Lepiensky, 2006)
14
180
0.08
0.08
Nanocomposite diamond film, (Pauschitz, Schalko, Koch,

Eisenmenger-Sittner, Kvasnica and Roy, 2003)
6.1
76.9
0.08
0.04
a-C, (Charitidis and Logothetidies, 1999)
27
290
0.09
0.23
17.9
148.8
0.12
0.26
18
172
0.1
0.2
a-C, (Huang, Zhou, Xu and Lu, 2002)

a-C, (Tomala, Pauschitz, Roy, 2013)
and it is in between 0.08 to 0.15. The ratio H3/

E2 however, varies over a wide range and can be
taken a characteristics feature.
FUTURE RESEARCH DIRECTIONS

The classification of the tribological thin film as
described in this chapter is in very much rudimentary stage and by no means a last word. There is
enormous scope and demand to classify all thin
film used for tribological application under different category. Naturally the features stated in
84
relation to nanohardness and elastic modulus are

also far from complete. In this chapter, several other
variety of coating such as self adapting thin film,
nanocomposite thin film etc. are not discussed.
Thus there is a need to examine the entire gamut
of coatings available and classify them under a
broader spectrum of features.
The data base on nanohardness and elastic
modulus of thin film meant for tribology, is quite
comprehensive. However, it is very difficult to
carry out a meaningful comparison as these data
are generated under different loading system, for
films with different thickness, under different en-

vironmental condition and for films with different

microstructural features. In view of this, a more
comprehensive data base on these properties can
be contemplated.
Last but not least is the fact that theories of
plasticity of contact mechanics indicates load
scales with the square of penetration. Thus nature
of load vs. square of displacement curve is very
important to understand the deformation behavior
of the film under indentation condition. Unfortunately this aspect of nanoindentation has been
reported by few investigators. There is a genuine
requirement to analyse the load vs. square of
displacement curves of tribological thin films.
CONCLUSION
Various thin films suitable for tribology related
applications are classified under four heads.
The load vs. displacement curves and load vs.
square of displacement curves of these films are
characterized. It is stated by several investigators
previously and the authors also agree with the fact
that H/E and H3/E2 are important parameter for
these coatings. The above discussion brings out
the fact that the value of H/E for nitride coatings
which are very hard and having high friction
coefficient and used for such application where
friction coefficient is either not very important or
high friction coefficient is required, varies between
0.11 to 0.15 whereas H3/E2 ratio is in the range of
0.57 to 0.64. The value of H/E for hard film with
high nanohardness and low friction coefficient
and where wear of counterbody is an issue varies
from 0.1 to 0.15. Interestingly the value of H3/E2
for such film is quite high and is around 1.0 to 2.0.
For soft self lubricating films where wear rate is
not crucial, these ratios are from 0.05 to 0.07 and
0.01 to 0.06 respectively. Finally for reasonably
hard but self lubricating film where wear rate is an
important consideration, H/E ratios vary between
0.08 to 0.15 and H3/E2 vary over a wide range and
no characteristics range can be stated.
ACKNOWLEDGMENT
The author is grateful to director DMRL for giving permission to publish this work. The author is
grateful to Dr. Thomas Koch of Vienna University
of Technology and Dr. A. Tomala of Austrian
Center of Competence for Tribology for carrying
out nanoindentation and AFM work, respectively.
The author is also grateful to Prof. A. Cavaleiro
University of Coimbra, Portugal, Dr. Markus
Kahn from Joanneum Research, Laser Center
Leoben, Austria, and D. Steinmller-Nethl of
-BeSt coating GmbH, Innsbruck, Austria, for
providing W-S-C, carbon, and nanocrystalline
diamond films, respectively.
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88

Elasticity: The expression H3/E2 which contains hardness and elastic modulus.
Nanocomposite: Composite materials with
sizes of each phase less than 50 nm.
Nanocrystalline: Crystalline materials with
crystal sizes less than 50 nm.
Nanohardness: Resistance to indentation at
very low load.
Nanotribology: Tribology at low load with
wear rate in nm level.
Self Lubrication Film: Films which provides
lubrication without addition of lubricant.
89
Chapter 4
Synthesis and Characterization

of Iron Oxide Nanoparticles
John M. Melnyczuk
Soubantika Palchoudhury
Yale University, USA
ABSTRACT
Iron oxide nanoparticles show great promise in bio-applications like drug delivery, magnetic resonance
imaging, and hyperthermia. This is because the size of these magnetic nanoparticles is comparable to
biomolecules and the particles can be removed via normal iron metabolic pathways. These nanoparticles
are also attractive for industrial separations and catalysis because they can be magnetically recovered.
However, the size, morphology, and surface coating of the iron oxide nanoparticles greatly affect their
magnetic properties and biocompatibility. Therefore, nanoparticles with tunable characteristics are
desirable. This chapter elaborates the synthesis techniques for the formation of iron oxide nanoparticles
with good control over reproducibility, surface and magnetic properties, and morphology. The wellknown co-precipitation and thermal decomposition methods are detailed in this chapter. The surface
modification routes and characterization of these nanoparticles are also discussed. The chapter will be
particularly useful for engineering/science graduate students and/or faculty interested in synthesizing
iron oxide nanoparticles for specific research applications.
INTRODUCTION
Recently iron oxide nanoparticles (NPs) have
attracted tremendous attention as candidates
for magnetic resonance imaging (MRI) contrast
enhancer, drug delivery, and magnetic fluid hyperthermia (Mahmoudi, Sant, Wang, Laurent, &
Sen, 2011). Superparamagnetic magnetite and
maghemite based MRI contrast agents like Feridex, Combidex, Resovist, and CLIO have been
approved by the Food and Drug Administration
(FDA) (Bin Na, Chan Song, & Hyeon, 2009).
These dextran-coated iron oxide NPs are used to
dephase the proton magnetic moments of water
surrounding the tumor site to induce a darker
contrast compared to healthy tissues (Pankhurst,
DOI: 10.4018/978-1-4666-5824-0.ch004

Synthesis and Characterization of Iron Oxide Nanoparticles
Connolly, Jones, & Dobson, 2003). The contrast

agents can be targeted to the tumor and are less
cytotoxic compared to the commonly used gadolinium chelates (Qiao, Yang, & Gao, 2009). Iron
oxide NPs can be passively phagocytosed by the
reticuloendothelial cells or can be actively targeted
to the biomarkers on tumor cells with specific
binding ligands (C. Sun, Lee, & Zhang, 2008).
The large surface and tunable coating of the iron
oxide NPs allow surface conjugation of anti-tumor
drugs like doxorubicine (Xing et al., 2012). This
targeted drug delivery enables accumulation of
therapeutically relevant drug doses at the tumor site
for effective chemotherapy. When the iron oxide
NPs at the tumor site are subjected to an alternating
magnetic field, the magnetic moments reorient.
This magnetic energy is dissipated as heat at the
tumor and elevates the local temperature (42-45
C) to selectively kill the cancer cells (Al-Saie et
al., 2011). The healthy tissues surrounding the
tumor are protected in this form of treatment called
the magnetic fluid hyperthermia (Laurent, Dutz,
Hafeli, & Mahmoudi, 2011). However, iron oxide
NPs with good reproducibility as well as tunable
size and surface properties need to be synthesized
for the above applications (LaConte et al., 2007).
For example, superparamagnetic iron oxide NPs
(< 15 nm) do not aggregate in the presence of a
magnetic field and show a good blood circulation
time. Therefore, these NPs are ideal for MRI and
hyperthermia applications. The surface coating
on the iron oxide NPs is also a major influence
on the proton relaxation rates in MRI. The NPs
with completely hydrophilic surfactant coatings
are most suitable as MRI contrast agents because
they are accessible to the surrounding water protons (Smolensky, Park, Berguo, & Pierre, 2011).
This chapter will focus on the reproducible
synthesis of iron oxide NPs of varying size, morphology, and surfactant coating. The widely used
co-precipitation and thermal decomposition routes
will be elaborated. In explaining these synthetic
techniques emphasis will be given to the condi-
90
tions required for different shapes of iron oxide

NPs. The synthesis of iron oxide nanospheres,
nanocubes, nanoplates, nanoflowers, nanoworms,
and nanowhiskers will be detailed. The methods to
characterize the size, morphology, crystal phase,
and magnetic properties of the NPs via transmission electron microscopy (TEM), x-ray diffraction
(XRD), and alternating gradient field magnetometry (AGM) will be covered next. Finally, the
surface coating and biocompatibility of the iron
oxide NPs will be addressed. The iron oxide NP
products from the thermal decomposition method
are coated with hydrophobic ligands. Surfactant
exchange and polymer encapsulation routes will
be used for aqueous phase transfer of such NPs.
BACKGROUND
Crystal Structure and
Magnetic Properties of Iron
Oxide Nanoparticles
The most interesting crystal phases of iron
oxide nanoparticles are the magnetite (Fe3O4),
maghemite (-Fe2O3), and hematite (-Fe2O3).
(Gubin, Koksharov, Khomutov, & Yurkov, 2005).
Of these hematite is weakly magnetic. However,
the magnetite and maghemite NPs show strong
magnetic properties and are attractive for various
bio-applications (Roca et al., 2009).This could be
attributed to the unpaired 3d electrons (4 or 5) and
the inverse spinel crystal structure of magnetite
and maghemite. Spinel compounds are known
to crystallize in a cubic system and generate an
octahedral crystal structure (Siddiquah, 2008). The
normal spinel has a chemical formula of AB2O4
(A= divalent metal ion and B= trivalent metal ion).
The spinel lattice contains at least eight AB2O4
molecules with the large oxygen anions in a facecentered cubic (fcc) arrangement. This leaves two
types of crystal sites for cation occupancy: the 64
tetrahedral (T-) sites each with four surrounding

oxygen anions and the 32 octahedral (O-) sites

each containing six neighboring oxygen anions.
Generally, the larger divalent cations occupy the
T- sites and the trivalent metal ions fill the Osites. However, the inverse spinel structures of
magnetite and maghemite are formed with Fe2+
at the T- sites and Fe3+ distributed equally at both
the T- and O- sites. In maghemite NPs (> 20 nm),
the trivalent cations fill up the O- sites leaving
ordered vacancies to reduce the lattice energy. This
crystallographic arrangement gives magnetite and
maghemite NPs their unique magnetic properties.
Both magnetite and maghemite are ferrimagnetic at room temperature. Ferrimagnetic materials retain the magnetization after removal of the
external magnetic field, similar to ferromagnets
(O Handley, 2000). However, in a ferrimagnet
the anion directly couples two dissimilar cations
(Ma and Mb) via the trademark superexchange
interaction. This induces the Ma-Ma or Mb-Mb
type interactions favoring parallel arrangement
of magnetic moments and the Ma-Mb type interactions favoring anti-parallel arrangements. The
result is a net magnetic moment lower than that of
a ferromagnet. Bulk magnetite shows a saturation
magnetization of 92 emu/g compared to 78 emu/g
for bulk maghemite (S. H. Choi et al., 2008). The
saturation magnetization is lower for the iron oxide
NPs because the surfactant forms a magnetically
dead layer on the NP surfaces (Gangopadhyay et
al., 1992). When the size of the iron oxide NP is
small (< 20 nm), the thermal fluctuations within
the NP is sufficient to flip the magnetic spin energy at room temperature (Krishnan et al., 2006).
Therefore, the small NPs can rapidly magnetize
and demagnetize with an applied magnetic field
(J. Chatterjee, Haik, & Chen, 2003). This unique
behavior called superparamagnetism is attractive for in vivo applications because it prevents
aggregation of the iron oxide NPs through rapid
demagnetization. Additionally, the morphology of
the NP also influences the magnetic properties.
This led to great interest in controlled synthesis
of iron oxide NPs during the last decade.
Synthesis of Iron Oxide

Nanoparticles
The first synthesis of iron oxide NPs was reported
in 1852 (Lefort, 1852). Several physical and wetchemical routes for iron oxide NP fabrication
were developed since then (Laurent et al., 2008).
The physical techniques like gas phase deposition, electron-beam lithography, and mechanical
grinding provide less control over the size of the
NPs compared to the wet-chemical methods. Coprecipitation and thermal decomposition are two
widely used chemical synthetic techniques for the
iron oxide NPs (Lu, Salabas, & Schueth, 2007).
Co-Precipitation Method
Co-precipitation of Fe2+ and Fe3+ salts in an
alkaline aqueous medium is one of the simplest
methods for the synthesis of iron oxide NPs (Gupta
& Gupta, 2005). Hydrophilic capping molecules
such as humic acid, citrate, or polyacrylic acid are
added during or after synthesis to prevent aggregation of the NPs. An oxygen-free environment is
essential for the synthesis otherwise the iron oxide
can be oxidized to ferric hydroxide in the reaction
medium (Zheng, Cheng, Bao, & Wang, 2006).
The following chemical reaction summarizes the
co-precipitation synthesis.
Fe2+ + 2 Fe3+ + 8OH Fe3O4 + 4 H 2O

This method is facile and eco-friendly because
no toxic organic reactants are used. Here, the end
NP product is in aqueous phase and can be used
for biomedical applications. However, the product
is polydisperse and the reaction temperature is
limited by the boiling point of water. As a result,
the NPs show low crystallinity and poor magnetic
properties. Therefore, the thermal decomposition
method was developed to improve the properties
of the iron oxide NPs.
91

Thermal Decomposition Method

This approach provides excellent control over
the size, size distribution, yield, crystallinity, and
shape of the iron oxide NPs. Here, an iron precursor
complex is decomposed at elevated temperatures
(~ 300 C) in the presence of capping molecules in
an organic solvent. There are two types of thermal
decomposition method; hot-injection and heat-up.
Hot-Injection: Alivisatos et al. first found
that the hot-injection of iron precursor, Fe(Nnitrosophenylhydroxylamine)3-octylamine into
boiling long-chain amine solvents (250-300 C)
leads to monodisperse maghemite NPs (Rockenberger, Scher, & Alivisatos, 1999). The size
distribution can be improved further using Fe(CO)5
precursor, as shown by Hyeon et al. (Hyeon,
Lee, Park, Chung, & Bin Na, 2001). However,
hot-injection into the boiling solvent at such elevated temperatures raises safety concerns. It also
provides less control over the reaction parameters
because the sudden burst injection can induce
undesired reaction intermediates. Therefore, Sun
et al. developed the heat-up method (S. H. Sun
& Zeng, 2002).
Heat-Up: In this organic phase synthesis, the
reactants are heated up to elevated temperatures
(300- 320 C) at a constant heating rate. This
provides better control over the reaction. Sun
et al. used Fe(C5H7O2)3 precursor complex in
phenyl ether solvent to synthesize monodisperse
magnetite NPs of sizes below 20 nm. However,
the limitation of this precursor is the multi-step
seed-mediated growth required for larger NP sizes.
Therefore, Hyeon et al. used iron oleate precursor for a large-scale synthesis of monodisperse
magnetite NPs of controllable sizes (J. Park et al.,
2004). The heat-up method using iron oleate shows
great potential because the precursor is less toxic
than Fe(CO)5 and the NP product of tunable size
is reproducibly synthesized in one-step.
Modified Heat-Up: In most traditional heatup methods, oleic acid is used as the surfactant
because it prevents aggregation and maintains the
92
spherical morphology of the iron oxide NPs via

a strong surface binding. However, a modified
heat-up method uses a weak binding ligand along
with oleic acid to modify the shape and surface
of the iron oxide NPs (Palchoudhury, Xu, An,
Turner, & Bao, 2010).
The iron oxide NPs from the thermal decomposition route are limited by the toxic organic surface
coating. Therefore, an aqueous phase transfer via
ligand exchange or encapsulation is required before
the NPs are used for bio-applications. Additionally, the size, shape, magnetic properties, and
surface characteristics of the NPs have to be well
characterized prior to the applications to prevent
any harmful effect.
Characterization of Iron
Oxide Nanoparticles
The size, morphology, and a qualitative chemical
composition of the iron oxide NPs is determined
on a TEM because the NPs are too small for the
normal eye or the optical microscopes (Figure
1a). In a TEM (e.g., Tecnai F-20, 200 keV), the
high energy electron beam interacts with the NP
specimen to form bright field (BF) or dark field
(DF) images of the sample (Williams & Carter).
The interacted electron beam contains specimen
information that is displayed using a charge
coupled device camera (CCD). In a BF image, the
NPs appear as dark spots on a bright background
because the image is constructed with the transmitted electron beam. The BF image provides a
general overview of the size, size distribution,
and morphology of the NP sample. However, a
high resolution transmission electron microscope
(HRTEM) image is required to determine the
crystallinity and morphology of the NPs at the
atomic resolution. Here, the heavily diffracted
electron beam interacts with the transmitted beam
to form the high magnification image with visible
parallel phase contrast lines called lattice fringes.
The lattice fringes indicate good crystallinity of
the sample. Additionally, an HRTEM image of

Figure 1. Characterization of maghemite NPs via modified heat-up method. (a) BF TEM image, (b) XRD
plot, (c) XPS plot, and (d) M-H curve using AGM
the tilted sample can provide an estimate of the

sample thickness. However, a high angle annular
dark field (HAADF) image is ideal for viewing
ultrasmall NPs (< 5 nm) or surface details because
the image is negligibly affected by the defocus
and sample thickness (Braggs reflections) compared to a BF image. The TEM can also provide a
general chemical composition of the NPs via the
energy-dispersive-spectrophotometry (EDS). The
NP sample preparation for the TEM is relatively
simple. The NPs are washed with ethanol and
hexane to remove the excess organic surfactants
and dispersed in a volatile solvent such as hexane.
The sample is then dropped on a carbon-coated
copper TEM grid (3 mm) with formvar support
for best results.
The XRD (e.g., Bruker AXSD8 Advanced

XRD) is used to determine the crystal phase of the
iron oxide NPs (Cullity & Stock, 2001). Here, the
organic surfactant coating on the NPs is washed
completely to form well-dried powdered NP
sample (Klug & Alexander, 1996). The incident
x-rays (~ 1 ) are elastically scattered or diffracted (Bragg diffraction) by the powdered NPs
towards the detector. The sample and the detector are rotated at and 2 respectively to obtain
a 20- 80 2 scan (Kittel, 1985). The complete
diffraction scan can identify the crystal phase of
the NPs when matched with the reference data
(International Center Diffraction Data, ICDD).
The diffraction profiles of both maghemite and
magnetite are closely related. Maghemite shows
93

2 peaks at 35.1, 41.4, 50.4, 63.1, 67.5, 74.4,

and 88.7 on a Co K source ( = 1.79 ) corresponding to the (220), (311), (400), (422), (511),
(440), and (533) crystal planes (Figure 1b). The
(220) peak is not seen for magnetite. This difference is outweighed by the size broadening effect
for small iron oxide NPs. Therefore, XRD patterns
cannot conclusively differentiate maghemite and
magnetite crystal phases (Jia et al., 2008).
X-ray photoelectron spectroscopy (XPS, e.g.,
Kratos AXIS 165 Multitechnique Electron Spectrometer) is used to study the Fe and O valence
states to differentiate these two common iron
oxide crystal phases (Cornell & Schwertmann,
2003). Here, the surface chemical composition
(100 atom% - 0.1 atom% concentration) of the
powdered NP sample is reported as a survey scan
of the emitted photoelectron count corresponding
to the binding energies. The XPS Fe2p core-level
spectra for iron oxide NPs show peaks around 712
and 726 eV corresponding to 2p3/2 and 2p1/2 corelevel respectively (Figure 1c). However, a satellite
peak after 2p3/2 (~ 718 eV) is characteristic to the
maghemite crystal phase (Yamashita & Hayes,
2008). Additionally, the O1s core-level binding
energy of maghemite is lower than magnetite.
Therefore, the O1s shoulder and the satellite peak
around 718 eV can be used to accurately predict
the maghemite from the magnetite crystal phase.
The magnetic property of the iron oxide NPs
is determined with a magnetometer. The AGM
(e.g., Princeton AGM) is the simplest and a highly
accurate magnetometer used for a fast magnetic
measurement of powdered NP samples. The AGM
reports the magnetic moment of the NPs relative
to the applied magnetic field (Figure 1d). Superparamagnetic iron oxide NPs show zero coercivity
at zero magnetic field while a hysteresis loop is
observed for ferromagnetic NPs. The saturation
magnetization of the NPs gives an estimate of
the highest magnetization attainable with the applied field. This value is slightly lower for NPs,
compared to the bulk iron oxide, likely from the
magnetically dead layer of surfactant. The M-H
94
curves provide useful information on the sample.

For example, a ferromagnetic loop in small iron
oxide NPs indicates heavy aggregation. Another
simple method to predict aggregation within the
NP solution is via DLS.
The DLS (e.g., Zetasizer Nano, Malvern) is a
rapid and non-destructive technique to measure
the hydrodynamic diameter of NPs in solution.
Here, the incident laser light is scattered by the
Brownian motion of the NP solution. The diffusion
rate of the NP molecules in solution and hence
the hydrodynamic diameter can be estimated
from the detected fluctuations in the scattered
light. The DLS can determine the surface charge
as well as the extent of polydispersity of the NP
sample. Figure 1 shows the characterization of
organic phase maghemite NPs via TEM, AGM,
XRD, and XPS.
MAIN FOCUS OF THE CHAPTER:

METHODS FOR IRON OXIDE
NANOPARTICLE SYNTHESIS
This section will report the widely used synthetic methods for iron oxide NPs with varying
morphologies and surface coatings. This will be
useful for students and academic personnel aiming to conduct application based research with
iron oxide NPs. The synthesis of engineered iron
oxide NPs is currently an emerging field with
tremendous possibilities.
Iron Oxide Nanospheres

Co-precipitation: This is the most effective route
for the synthesis of aqueous dispersions of iron
oxide NPs. FeCl2.4H2O (2 g) and FeCl3.6H2O (5.46
g, Fe2+:Fe3+ molar ratio 1:2) are mixed with the
surfactant, polyethylene glycol (PEG)-2000 in an
aqueous acid solution (60 mL; 10 mL 1 M HCl in
50 mL de-ionized water). This Fe solution is added
dropwise to 100 mL NaOH (1 M)/PEG-2000 (1 g)
solution mixture under vigorous stirring at 60 C.

Figure 2. Iron oxide NPs using modified heat-up method. (a) BF TEM image and (b) HRTEM image
The mixture is stirred for 2 h. The entire reaction

is conducted in an inert atmosphere with nitrogen
purging using the classical Schlenk line technique.
The black NP product is washed multiple times
with de-ionized (DI) water until it is neutral (Gao,
Li, Dong, Zhang, & Yang, 2011).
Modified Heat-up: This method gives iron
oxide NPs with excellent size, shape, yield, and
size distribution compared to the co-precipitation
(Palchoudhury, Xu, Goodwin, & Bao, 2011b).
First, the iron oleate precursor is prepared as follows: FeCl3 (13 g), potassium salt of oleic acid
(192.4 g) is mixed in a solvent mixture (hexane,
280 mL and ethanol, 160 mL) at 65 C for 4 h.
The mixture is phase separated. The upper organic
phase contained the iron oleate complex. This
is washed 3 times with DI water to remove byproducts such as KCl. The paste-like iron oleate
complex is left to dry overnight in the chemical
hood. This precursor complex is used for iron
oxide NP synthesis.
Monodisperse iron oxide NPs (12 nm) are
synthesized via thermal decomposition of the iron
oleate precursor (1.8 g) in the organic solvent,
1-octadecene (13 mL) at 320 C for 2.5 h in presence of oleic acid (OA, 0.1 mL)/trioctylphosphine
oxide (TOPO, 0.2 g; OA:TOPO molar ratio 0.6:1)
surfactant mixture (Figure 2a). The NPs show excellent crystallinity, according to the clear lattice
fringes in the HRTEM image (Figure 2b).
Iron Oxide Nanowhiskers

In a typical synthesis of iron oxide nanowhiskers,
the iron oleate complex (1.8 g) is heated at 150
C in 1-octadecene (13 mL) for 2.5 h using the
usual OA/TOPO surfactant mixture. The product
is ultrathin iron oxide nanowiskers of dimensions
2x20 nm, as seen in the BF TEM image (Figure
3a). The high aspect ratio of the nanowhiskers
makes imaging at high magnification challenging.
However, the clear lattice fringes in the HRTEM
image indicate good crystallinity of the iron oxide
nanowhiskers (Figure 3b) (Palchoudhury, An, et
al., 2011).
Iron Oxide Nanoworms

Co-precipitation: FeCl3.6H 2O (0.63 g) and
FeCl2.4H2O (0.25 g) are mixed in DI water (10
mL) at room temperature. To neutralize this
acidic Fe solution, 1 mL concentrated aqueous
ammonia is added dropwise under vigorous stirring. The reactants are magnetically stirred and
95

Figure 3. Iron oxide nanowhiskers. (a) TEM image and (b) HRTEM image
Figure 4. Iron oxide nanoworms via modified heat-up method. (a) TEM and (b) HRTEM
heated at 70 C for 1 h. The complete reaction is

conducted in an oxygen-free environment under
steady nitrogen purge. The magnetic NPs are purified with a centrifuge filtering column (100,000
MW CO, Millipore) and crosslinked in a strong
base (5 M aqueous NaOH) with epichlorohydrin.
The product containing chain-like nanoworms
(NW) is filtered through a 0.1 m pore diameter
membrane to obtain 50-80 nm long NWs (J. H.
Park et al., 2008).
Modified Heat-up: Here, the iron oleate
complex is heated in 1-octadecene (13 mL) in
presence of OA (0.1 mL). During this reaction, a
96
solution of TOPO (0.8 g) in 1-octadecene (7 mL)

is injected to the reaction at 290 C. The reaction
mixture is then heated to 320 C for a total time
of 2.5 h to obtain highly crystalline iron oxide
NWs (~12x100 nm). Figure 4 shows the TEM and
HRTEM images of iron oxide NWs synthesized
via a modified heat-up method (Palchoudhury,
Xu, Goodwin, & Bao, 2011a).
Iron Oxide Nanocubes

The iron oleate precursor complex for the iron
oxide nanocubes is synthesized via an overnight

reaction of FeCl3 (1.298 g, 8 mmol) and sodium

oleate (7.3 g, 24 mmol) in a solvent mixture
(hexane, 28 mL; ethanol, 16 mL; water, 12 mL) at
room temperature. The top organic part containing the precursor complex is phase separated in a
separatory funnel and washed five times with DI
water to remove impurities. This black complex
is dried at 105 C under reduced pressure to form
the viscous, brown iron oleate precursor. The
entire process is conducted at room temperature
without inert gas protection.
The iron oleate precursor (1.034 g, 1.15 mmol)
is reacted with sodium oleate (47.5 mg, 0.15
mmol)/oleic acid (168 mg, 0.595 mmol) surfactant
mixture in squalene (10 g). The reaction mixture
is stirred at 150 C for one hour and 175 C for
another hour before heating the reactants to the
boiling point of the solvent (320 C) at 25 C/min
for an hour. An inert atmosphere is maintained
throughout. The resulting iron oxide nanocubes are
about 10 nm in size (Shavel & Liz-Marzan, 2009).
Iron Oxide Nanoplates

and Nanoflowers
The iron oleate complex for the iron oxide nanoplates and nanoflowers is prepared with a slight
modification to the existing route. Potassium
oleate (96.2 g) is mixed to a partial dissolution in
DI water (60 mL) prior to addition of the hexane
(140 mL)/ethanol (80 mL) solvent mixture. The
paste-like potassium oleate is mixed in the solvent
for an additional 1 h for complete dissolution.
FeCl3 (6.5 g) is added to this potassium oleate
complex solution to prevent any reaction of the
iron salt with water. The mixture is reacted for 4
h at 60 C to form the iron oleate complex. The
hexane phase containing the iron oleate complex
is separated and washed with DI water to remove
by-products. The procedure is conducted at room
temperature without inert gas protection. This
iron oleate complex is less viscous and easy to
handle compared to the well-dried iron oleate
waxy paste because the hexane accounted for 6.5%

of its weight. The brown liquid-like precursor is
used for the synthesis of iron oxide nanoplates
and nanoflowers (Palchoudhury, Xu, Rushdie,
Holler, & Bao, 2012).
Nanoplates: Typically, the iron oxide nanoplates are synthesized via thermal decomposition
of the less viscous iron oleate complex (1.8 g) in
1-octadecene (13 mL) for 1 h in the presence of
OA (0.1 mL)/TOPO (0.2 g) surfactant mixture.
The reaction is conducted at the reflux temperature
(290 C) with steady argon purging. The product
is iron oxide nanoplates of dimension 3x15 nm
(Figure 5a). The nanoplates are crystalline, according to the prominent lattice fringes in the
HRTEM image (Figure 5b).
Nanoflowers: Interestingly, iron oxide nanoflowers are formed when a higher percentage of
TOPO (1 g; TOPO/OA molar ratio, 8.35:1) is used
keeping all other reaction conditions the same as
that of the nanoplates. The nanoflowers are made
from an aggregation of small (~ 5 nm) singlecrystalline iron oxide NPs (Figure 5c). However,
the nanoflowers show good crystallinity, as seen
from the HRTEM image (Figure 5d).
Sample Preparation for

Nanoparticle Characterization
The NPs are centrifuged out of the solution using a 1:1 volume ratio of ethanol and hexane
and re-dispersed in hexane for TEM analysis.
This solution is dropped on the TEM grids for
viewing. Alternatively, the dry powder samples
for XRD, XPS, and magnetic measurements are
prepared via magnetic separation. Here, the NPs
are dissolved in a volatile solvent, chloroform.
Acetone is added to induce precipitation of the
iron oxide NPs. The NPs are separated from this
solution using a strong magnet. The clear solution
is discarded and the process repeated two times,
prior to vacuum drying of the NPs.
97

Figure 5. Iron oxide nanoplates and nanoflowers. (a) TEM image of nanoplates, (b) HRTEM image of
nanoplates, (c) TEM image of nanoflowers, and (d) HRTEM image of nanoflowers
Aqueous Phase Transfer of

Iron Oxide Nanoparticles
Several promising methods such as ligand exchange, bilayer formation, and lipid/polymer
encapsulation are developed to make the organic
phase iron oxide NPs water soluble (Prakash et al.,
2009). Typically, equilibrium between the 4 attractive and repulsive forces governs the stability of
these NPs in a biological medium. The short-range
Van der Waals forces and the magnetic dipolar
interactions induce inter-particle aggregation.
This can be controlled using electrostatic repulsive forces with a charged NP surface and steric
hindrances of the surfactant coating on the NPs.
98
Ligand Exchange: The iron oxide NPs are magnetically separated out of solution and vacuumdried to completely wash off the organic surfactant
layer. The dried powder sample is dissolved well
in chloroform under sonication to form the stock
solution (5 mg/mL). Freshly prepared polyacrylic
acid (PAA, Mw, 100,000) in dimethylsulfoxide
(DMSO, 4 mL) is mixed with the NP stock solution
and DMSO (45 mL) under sonication (15 min).
The homogeneous solution containing the NPs
and the biocompatible surfactant, PAA is reacted
overnight at 20 C in the shaker for phase exchange.
The iron oxide NPs in solution are magnetically
separated and redispersed in DI water. The final
pH is adjusted to ~ 7-8 using one drop of NaOH

solution to stabilize the anionic PAA polymer. The

clear brown solution of aqueous iron oxide NPs
remains stable over a long period (> 1 month)
(Xu, Qin, Palchoudhury, & Bao, 2011).
Lipid Encapsulation: This is a simple technique
to coat the entire hydrophobic iron oxide NPs
with a lipid layer for aqueous phase transfer. The
hydrophobic NPs are first washed and redispersed
in chloroform via sonication. Biocompatible lipid
molecules such as 1,2-dipalmitoyl-sn-glycero-3phosphocholine (DPPC) in chloroform is mixed
with this NP solution. The volatile chloroform
can be easily evaporated overnight under a gentle
stream of argon to form the dried NP/lipid cake.
The phosphate buffered saline is used to rehydrate
the NP/lipid cake under sonication at 50 C for 2
h. The product is a hydrophilic solution of lipid
encapsulated iron oxide NPs or magnetoliposomes
(Gonzales & Krishnan, 2005).
Polymer Encapsulation: Polymer encapsulation is useful to allow iron oxide to have a wider
range of application. Adding a biopolymer like
polyethylene glycol or dextran allows the NPs
not to induce an immune response. Applications
started in the late 1990s were employed in making
smart materials that will behave in a prescribed
way (Ebara, Hoffman, Stayton, & Hoffman;
Kim, Jeong, Lee, Kim, & Park, 2008; Miller
& Peppas, 1988; Nakayama et al., 2006; Song,
Labhasetwar, Cui, Underwood, & Levy, 1998).
The use of smart materials for curing cancer was
adopted in 2004 by The National Cancer institute
(NCI) to target, treat, report, and image tumor
cells (Cancer NANOTECHNOLOGY Plan: A
Strategic Initiative To Transform Clinical Oncology and Basic Research Though the Directed
Application of Nanotechnology, 2004). One of
the current methods for controlled release in deep
tissue can be as simple as encapsulating the drug
into a polymer matrix but the main challenge is
to control the release though an external stimulus
(Lonsdale, 1982). Hydrogels were explored in the
1960s because they held up to harsh conditions

like solvent and recently they are being combined
with NPs to perform controlled release (Kim &
Bae, 1992; Wichterle & Lim, 1960). Hydrogels
are networks that are chemically or physically
cross linked for the express purpose of slowing
down the diffusion of water through the system
(Kinam Park, Waleed .S.W. Shalaby, & H.Park,
1993; Peppas, 1987). These can then be used to
retain the drugs into the pocket. The rate in which
the drugs diffuse out of the system is defined
by the amount of crossing link (Chiellini, 2001)
and the addition of different reactive polymers.
Researchers have exploited the polymer-solvent
lower critical solution temperature (LCST), in
which the polymers will phase separate from the
solvent (Rathbone, Hadgraft, Roberts, & Lane,
2008). There are 2 main polymers explored today
Poly(N-isopropylacrylamide) and the Federal
Drug Administration (FDA) accepted biocompatible hydroxypropyl cellulose polymer that have
LCST of 32 C and 41 C, respectively (Heskins
& Guillet, 1968; Lee & Lawandy, 2002). Since
37 C is normal body temperature research have
found mixing with PNIPAAm different monomers
to form a block co-polymer will tune the LCST
from 32 C to higher temperature. This is useful for
deep tissue hyperthermia and chemotherapy. By
combining the use of NPs with macroporouse gel,
hydrogels or micelles with an AC magnetic field
could induce a controlled release (Kato & Gehrke,
2004; Liu, Wang, Gao, Liu, & Tong; Trapani, Sitterberg, Bakowsky, & Kissel, 2009; Wei, Cheng,
Zhang, & Zhuo, 2009). In 2009 Trapani showed
NPs coated with chitosan could work for controlled
release applications (Trapani et al., 2009). The
Gehrke group showed that HPC in a microporous
gel could be used for magnetothermally-triggered
release (Kato & Gehrke, 2004). Other research
groups use thermally sensitive micelles to achieve
the same results as Gehrke (Wei et al., 2009).
99


The most attractive features of iron oxide NPs
are the chemical stability and biocompatibility.
The human body contains approximately 3.5 g
of iron in the form of hemosiderin, ferritin, and
transferring (Reimer & Balzer, 2003). Therefore,
water-soluble iron oxide NPs can be potentially
assimilated via normal metabolic pathways such
as liver based excretion. However, the NPs should
be of sizes 5-200 nm to avoid rapid clearance
from the body (H. S. Choi et al., 2007). Despite
the tremendous progress in the synthesis and
reproducibility of iron oxide NPs, it remains a
challenge to fabricate stable aqueous phase iron
oxide NPs with controlled size and shape. The
heat-up method can provide high quality iron
oxide NPs with good size distribution and tunable
properties. However, an additional phase transfer
step is required to coat the NPs with biocompatible
surfactants via ligand exchange or encapsulation.
Increase in the hydrodynamic diameter of the NPs
from inter-particle interaction and aggregation are
the main issues during this phase transfer.
Therefore, a primary direction of future research will be to design an aqueous phase synthesis
for iron oxide NPs with the advantages of the heatup method. Alternatively, the aqueous route should
provide an engineered surface and morphology of
the NPs as that of the heat-up method. Such a facile
route will enable direct synthesis of hydrophilic
iron oxide NPs suitable for MRI contrast agents,
drug delivery, or hyperthermia applications. Ongoing efforts are made towards an aqueous phase
thermal decomposition of inexpensive iron salts
(FeCl3) using high boiling pyrrolidone (Li, Sun,
& Gao, 2005) and polyethylene glycol (Li, Wei,
Gao, & Lei, 2005).
Another aspect of future concern will be the
environmental effect of the NPs (S. Chatterjee,
Bandyopadhyay, & Sarkar, 2011). The impact of
extensive industrial application of the NPs on the
surrounding eco-system must be studied. To this
end, cytotoxicity studies are performed on all new
100
formulations of iron oxide NPs before use (Banerji,

Pramanik, Mandal, Maiti, & Chaudhuri, 2012).
CONCLUSION
This chapter summarized the growing interest in
the synthesis of iron oxide NPs for biomedical
applications such as MRI, drug delivery, and
hyperthermia. The specific focus was on the coprecipitation and heat-up methods. A systematic
report was made on the detailed synthetic procedures for iron oxide nanospheres, nanocubes,
nanoplates, nanoflowers, nanoworms, and nanowhiskers. The methods to characterize the NPs such
as the TEM, XRD, XPS, AGM, and DLS were
also described. While the co-precipitation method
provides a biocompatible aqueous phase synthesis, a better control of the size, size distribution,
shape, and crystallinity of the iron oxide NPs is
achieved with the heat-up method. Therefore, the
future scope lies in a synthetic approach combining the simplicity of the co-precipitation with the
reaction control of the heat-up method.
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Co-Precipitation: Reacting Fe2+ and Fe3+
salts in aqueous solution to form iron oxide
nanoparticles.
Heat-Up Method: Heating up the reactants
in an organic solvent to form the iron oxide
nanoparticles.
Iron Oxide Nanoparticle: Small particles of
iron oxide with at least one dimension < 100 nm
(1 nm = 10-9 m).
Ligand Exchange: Method of partially or
completely replacing the hydrophobic coating
layer (ligand) on nanoparticles with hydrophilic
molecules to render the particles water-soluble.
Nanoflowers: Iron oxide nanoparticles with
flower-like morphology.
Nanoplates: Plate-shaped iron oxide nanoparticles.
Nanowhiskers: Rice whisker-like iron oxide
nanoparticles.
Polymer Encapsulation: Coating the hydrophobic nanoparticles with an additional polymer
layer to render them hydrophilic.
107
108
Chapter 5
Si-NWs:
Major Advances in Synthesis

and Applications
Maha Mohamed Khayyat
Umm al-Qura University, Saudi Arabia
Brahim Assa
MPB Technologies Inc., Canada
ABSTRACT
Surfaces and interfaces have a special significance to nanotechnology because the surface/volume ratio
of nanomaterials is larger than for the bulk ones. Therefore, interfaces of nanomaterials are more important to the properties of the nanomaterials than for larger scale materials. Moreover, crystal growth
and more particularly Nanowires (NWs) growth occurs at the interfaces between the growing crystals
and the supply media. This chapter focuses on the silicon nanowires grown using a Vapor-Liquid-Solid
(VLS) concept. One of the key advantages of VLS is that controlled placement or templating of the
seed metal produces templated NW growth. This templating is required for integration of NWs with
other devices, which is desirable for many applications. The authors discuss issues on the discovery of
fundamentally new phenomena versus performance benchmarking for many of the Si-NW applications.
Finally, the authors attempt to look into the future and offer their personal opinions on the upcoming
trends in nanowire research.
INTRODUCTION
Silicon nanowires (Si-NWs) have recently attracted considerable attention due to the historical
role of Si in devices fabrication and in the integrated circuits (IC) industry. Continued high
performance from Si may require integration of
innovative architectures of NWs with the exciting
functional devices. Si-NWs may provide new avenues in these directions. Recently, Si-NWs have
been used in the fabrication of DNA sensors (Li
et al.,, 2004). The ability to control the unique
morphological and mechanical properties of SiNWs arrays demonstrated by Paulo and coworkers
(Paulo et al., 2007) opens new perspectives for
the development of array based electrical and
DOI: 10.4018/978-1-4666-5824-0.ch005

Si-NWs
electrochemical systems. In addition, there are

studies (Schmidt and coworkers, 2006 & Cui and
coworkers, 2003) of fabricating Si-NWs vertical
surround-gate field effect transistor (VS-FET).
It has been reported (Huo et al., 2004) that room
temperature electroluminescence has been appeared from undoped Si-NWs that were grown
from disilane at a wavelength excitation of 600 nm.
It has been as well shown recently that Si-NWs
have been used to produce high resolution Atomic
Force Microscope (AFM) (Cohen et al., 2012).
Device applications utilizing Si-NWs have
been demonstrated in many different applications
including optoelectronic and electrical devices, as
well as solar cells (Huang et al., 2004; Kayeset
et al., 2005; Law, 2004; Samuelson, 2004). This
chapter will focus on wires grown using a vaporliquid-solid (VLS) concept or similar three phase
process (Givargizov, 1975; Wacaserand et al.,
2009; Wagner & Ellis, 1964).One of the key
advantages of the VLS process is that the controlled placement or templating of the seed metal
produces templated NW growth. This templating
is required for the straightforward integration of
NWs with other devices which is desirable for
many applications. Templated growth of NWs
have been achieved using various noble metals
like Au, Ag and Cu as the seed sites (Fan et al.,
2006; Kayesand et al., 2007; Westwater, 1997)
but for more reactive metals like Al, Sn and Sb
templating has often proven difficult. The noble
metals can often negatively affect the semiconductor properties of the nanowire from an application
perspective (Fan et al., 2006; Renardand coworkers., 2009; Wacaserand et al., 2009; Whang et al.,
2007; Ke et al., 2009; Chaudhari et al., 2010). For
example Au is a deep level trap in Si. Whereas
the more reactive metals like Al, Sb, and Sn are
less parasitic and can even be positive in terms
of acting as desirable dopants when incorporated
in the semiconductors (Tutuc et al., 2006; Roberts et al., 1981; Krug, 2008).Controlling spatial
placement of VLS grown nanowires with oxygen
reactive seed metals is therefore of great interest
for nanotechnology based applications (Wang and

coworkers2010).
It is our intent to describe in general the growth
of Si-NWs in a three-phase system. Therefore
general terms describing the three phases of the
system to be used throughout this chapter will
first be defined. In this chapter the term supply is
used to indicate the phase that supplies the growth
species to the surfaces. Common supply media are
vapors, solutions, melts, or even molecular beams
through vacuums. The term crystal or wire, as
defined above, will be used to describe the solid
crystalline phase. The term collector is used to
describe the third phase, which is small in comparison to the vapor crystal interface. This term
is used to replace more specific terms like: liquid
droplet, crystalline particle, catalysts, etc. The 1-D
crystal growth occurs at the interface between the
collector and the wire with the collector either at
the base or on the tip of the wire, see the following
figure. Unlike conventional crystal growth with
only two components or phases nanowires are often
grown in a three phase system. The vapor-liquidsolid (VLS) growth mechanism describes such a
three-phase system where the third phase is also
important to the crystal growth. This or similar
growth mechanisms are currently the accepted
mechanism for the enhancement of the epitaxial
growth of most free standing wire-like crystals
(Samuelson et al., 2004; Lauhon et al., 2004; Fan
et al., 2006). The VLS mechanism is based on a
specific system there are three components; a vapor
which supplies the source materials for crystal
growth, a liquid droplet, and the solid crystal. In
order for 1-D growth to result from this three-phase
system, the surface area of the liquid phase must be
physically small in comparison to the surface area
of the vapor/crystal interface. One-dimensional
crystal growth results when the growth rates at
the phase boundary between the liquid phase and
the solid crystal surface is higher than the growth
rate at the vapor/solid phase boundary. The commonality being that there are three phases and the
VLS mechanism is used as a basis to say that the
109

Si-NWs
existence of three phases is sufficient explanation

of the growth mechanism. Some examples are the
vapor-solid-solid (VSS), (Bootsma et al., 1971;
Kamins et al., 2001; Perssonet al.,, 2004) vaporadsorption layer-solid (VAdS), (Bootsma and co
workers1971) solid-liquid-solid (SLS), solutionliquid-solid (SLS) and supercritical-fluid-solid or
liquid-solid (SFSS or SFLS) growth processes,
(Trentler et al., 1995; Fang et al., 2006). The VLS
growth mechanism is therefore examined in order
to reveal the atomistic processes involved in crystal
growth in a three-phase system.
ASPECTS OF SYNTHESIS
Investigation of Si-NWs or Si wiskers dates back
to the pioneering work on vapor-liquid-solid (VLS)
approach by Wagner and Ellis (Zhang and coworkers, 2003; Tian and coworkers, 2006). The key to
NWs growth in any three phase system is that the
nucleation and growth rate at the collector/crystal
(liquid/solid) interface is greater than the growth
rate at the supply/crystal (vapor/solid) interface.
This means that the crystal grows more rapidly
under the collector, forming a nanowire with approximately the same diameter as the collector.
The aspect ratio of the nanowire is dependent on
the selectivity of the growth rates at the different
collector/crystal and supply/crystal interfaces.
The Si-NWs grown via VLS reaction are single
crystals but exhibit growth defects such as bending
and kinking. Lowering the silane (SiH4) partial
pressure leads to an increase in the wire width and
a reduction in the tendency to form kinks. The
VLS reaction using silane as the Si source gas
allows the growth of the very thin wires with high
aspect ratio (length-to-width ratio) (Westwater
and coworkers, 1997).
There are three main production schemes for
forming nanowires. In the top-down approach,
lithography or some other means is used to pattern a planar substrate material. An anisotropic
etch is then used to remove the material between
110
the nanowires. In the bottom-up approach, either

a seed particle or a patterned surface is used to
define where the nanowires will grow. Physical
or chemical vapor deposition (CVD) methods are
then used to supply growth precursors which feed
the growth of crystalline nanowires. Nanowires
can also be produced by forming the crystalline
nanostructures from an amorphous material.
A summary of the VLS growth process steps of
Si-NWs catalyzed for instance with Au is shown
in Figure 1.Similar process can be applied to grow
Si-NWs seeded with Al collector particles over a
relatively wide process window.
Systematic changes in the nanowire morphology have been identified with respect to the Al
film thickness, growth temperature, and pressure.
The Si-NWs can be grown with high growth rates,
good morphology, i.e., epitaxially with low diameter dispersion and tapering), and at high density
over a large range of growth conditions (Wacaser
et al., 2009). In fact, from our experience growing
nanowires with both Au and Al we have found
that it is simpler to achieve high densities, low
diameter dispersion, and good alignment with
Al than it is with Au. However, the key to good
growth with Al is careful deposition and treatment
of the Al layer prior to growth, particularly with
respect to avoiding oxidation; dramatic changes
in the results can be attributed to small changes
in the base pressure used to deposit the Al films.
Post growth and in-situ studies with varied thermal treatment of the Al film allow the state of
the collector to be probed and suggest that the
collector is an under cooled liquid during growth.
This understanding may be important in forming
more complex nanowire-based structures in this
materials system, particularly in terms of the pregrowth conditions. We also confirmed that Al is
incorporated in the nanowires during growth as
an active dopant and as a species that can later
be activated by high temperature treatment of the
nanowires. The incorporation levels are higher
than the projected bulk solid solubility, which
could lead one to conclude that if this high in-

Si-NWs
Figure 1. Schematic representation of growth steps of VLS-assisted growth of Si-NWs. (After Civale et.
al, 2006)
corporation is possible with Al it is also possible

when growing nanowires with other metals. The
structure and electronic characteristics of these
Al grown Si wires are highly relevant to many
applications, for example, in photovoltaics, where
it is advantageous to eliminate Au, where p-type
doping is helpful in forming the structures, and
where novel faceted structures like the pyramidal
structure presented here may be useful in terms of
multiple internal scattering of photons to increase
efficiency.
Catalyst Choice
The metal nanoparticle has a major role in vaporliquid-solid assisted nanowire growth. The metal
particle plays the act of the catalyst and determines
the diameter of the nanostructures. Consequently,
the choice of the metal, based on its physical
and chemical properties, determines many of
the nanowires properties. To be processed via
the VLS growth mechanism, the metal has to
be physically active, but chemically stable. To

find an eligible metal, the phase diagram is first
consulted to choose a material that forms a liquid
alloy with the nanowire material of interest. The
phase diagram (Figure 2) is also helpful for estimating the optimal composition and temperature
for nanowire growth.
In the vapor-liquid-solid process, the GibbsThomson equation places a lower limit on the wire
diameters that can be achieved under a given set
of conditions. Givargizov (1975) studied also in
detail the VLS crystal growth technique in 1975,
according to his study the equilibrium state is
given by the following equation;
NW = B 4
B = B V
(1)
(2)
111

Si-NWs
Figure 2. Binary phase diagram of alloy suitable for VLS mechanism
NW = NW V
(3)
where NW , B , V are the effective chemical

potentials of silicon in the nanowire, in the bulk
material, and in the vapor phase respectively, d is
the diameter of the nanowire, is the atomic
volume of silicon, and is the specific surface
free energy of the wire.
There is a critical nanowire diameter at which
the growth stops completely, the relation is as
follows;
B
4 1

=
kT
kT d c
(4)
where k is the Boltzmans constant and T the

temperature, dc the critical diameter.
Interestingly, the VLS growth is not actually a
catalytic process and the seed metal is not really a
catalyst. The metal droplet just receives the source
material and when super saturation is reached, the
excess material precipitates out of the droplet in
the form of a NW. Thus, the seed metal is only a
soft template (Hutchby et al., 2002; Johansson
et al., 2006) to collect the material and facilitate
112
NW precipitation, guidance, and elongation in

the axial direction.
A catalyst, as well known in chemistry literature and chemical industry, is a material that
increases the rate of a chemical reaction while
remaining intact in the process. The activation
energy for Si-NW growth using Au seeds and Si
thin film growth in microelectronics industry is
about the same at about 130 kJ/mol(Jae-Ryoung
et al., 2002), indicating that Au does not aid in
increasing the reaction rate.
Au is the most favored seed metal in the literature for NW growth due to the ease of handle.
However, Au is viewed as a contaminant in
semiconductor processing. It can modulate carrier
recombination in both n-type and p-type materials
because high-mobility interstitial Au atoms can
transform into electrically active low-mobility
substitutional sites. Gold is not desirable also
in optoelectronics applications since, as a deep
level trap in Si, it causes fast non-radiative decay
of excited carriers. For this reason, Si-NWs with
Au catalyst are not capable of light emission
whereas the NWs produced with other seed metals or oxide-assisted grow this known to produce
light emission in the visible and near IR ranges.
Another disadvantage is the high eutectic composi-

Si-NWs
tion of Au-Si system at 371oC (31 atm. % of Si),

which would make it impossible to obtain abrupt
heterojunctions in a NW by rapidly switching the
gas phase precursors.
For these reasons, several alternatives to Au
have been investigated in Si-NW (Meyyappan
& Sunkara, 2012). Gallium is a metal with low
melting point which forms a eutectic at a low
temperature (29.8 C) with low Si content (only 5
x10-8 atm %). TiSi2 has been successfully used as a
catalyst for Si-NW growth (Guichard et al., 2006).
Titanium sputtered onto a silicon wafer forms
small islands of TiSi2 when annealed at 900 C in
hydrogen for 5 min. Similarly, a thin layer of Pt
on Si wafer obtained by physical vapor deposition
forms PtSi when annealed at high temperatures.
PtSi commonly used as interconnects, has also
been used in Si-NW growth (Baron et al., 2006).
Templated Si-NWs seeded with Au using

standard photolithography is shown in Figure
3 on Si(100) substrate. The work presented in
Figure 3 is carried out by the author as a starting
point to catalyze the growth of Si-NWs, as it is
a well-established material. The knowledge of
parameters determine the diameter of Si-NWs
using Au as a collector was used to grow Si-NWs
using Al. The interest in other metals for Si-NWs
has arisen from the fact that Au historically has
poor compatibility with Si devices because Au
impurities act as a deep level trap decreasing the
carrier mobility, lifetime, and diffusion length.
The cost and the availability of Au is especially
important for photovoltaic applications, leading
to recent efforts using Aland other non-gold metals for NWs growth of photovoltaic Si structures
based on nanowires.
Figure 3. Si-NWs catalyzed with Au, patterned growth using photolithography. Experiments were carried
out by one of the authors (Dr. Maha Khayyat) in 2009 at T. J. Watson Research Center
113

Si-NWs
Nanoscale Chemical
Templating (NCT) Using
Oxygen Reactive Materials
Why we need to control the growth place of
NWs? Applications for NWs grown using the
VLS process have been demonstrated in many
optoelectronic and electronic devices. In order
to broaden this application space and make NW
based devices commercially viable, control of
the placement or templating of the nanowires
is desired. Templating is well established using
noble metals like Au, Ag and Cu, but for more
reactive metals like Al, Sn and Sb templating
has been difficult. Array of vertically aligned SiNWs were grown over areas >1 cm2 by standard
photolithography (Kayes and coworkers, 2007).
This is because when the seed metal reacts with
oxygen or oxygen containing materials prior to the
growth, the VLS process is hence impeded. Here
we describe a process we call nanoscale chemical
templating (NCT) which takes advantage of the
reactivity of the seed metal to template the NW
growth. NCT uses oxygen containing mask layer
like SiO2 to prevent the growth of NWs in undesired locations. In the desired growth locations
the mask is removed prior to metal deposition so
that NWs can grow in the holes in the oxide mask.
NCT can have a selectivity of 100%, meaning
that where there is oxide NWs do not grow. The
growth yield depends on the processing parameters and mask dimensions. High yields of single
vertically aligned NWs per sight are possible.
Preliminary optimization produced a 76% yield
of single wires and 97% yield per mask opening.
Most of the excess yield is multiple vertically
aligned wires per sight.
Most of the conventional NW templating
techniques do not work with oxygen reactive seed
materials like Al. The reason is that they require
liquid based chemistries that would oxidize reactive materials rendering the entire layer inactive
for seeding NW growth. In a typical templating
process consists of the following five steps:
114
1. A mask with holes through to the substrate

where NW growth is desired is formed;
2. A metal is blanket layer is deposited over
the mask;
3. The substrate with the over-layer is annealed
and the Au reacts with the substrate in the
holes and forms the NW seeds;
4. A liftoff of the metal is performed by removing the mask;
5. NWs are grown. Depending on the mask the
order of step (III) and (IV) can be reversed.
When the order kept as stated the mask, such
as a SiO2 mask, can prevent surface migration of metal during the annealing process.
If liftoff is performed first, metal migration
during annealing can become a problem for
pattern fidelity. If the metal is not removed
from the areas above mask, NWs will grow
in disordered crystallographic directions
on top of the amorphous mask. Thus for a
typical templated growth process with high
fidelity a liftoff process is required after
the annealing of the seed material with the
substrate.
NTC starts with the same processes as conventional NW templating (see Figure 1).
1. Forming a mask with holes where NW
growth is desired: The only constraint here
is that this mask must be a material that will
chemically react with the desired seed material and render it unsuitable as a NW seed,
2. A blanket deposition of the seed material is also the same: In NCT this layer
must however be protected from oxidation
however. In this paper this is achieved by
depositing the metal layer in the load lock
chamber of the ultra high vacuum- chemical
vapor deposition (UHV-CVD) system and
not exposing the deposited layer to air before
the next steps,
3. Annealing, and

Si-NWs
4. Growth: It is believed that another method

for preserving this layer would be to deposit
an amorphous layer of the desired nanowire
material over the non-oxidized metal layer.
This layer will protect the seed layer from
oxidation but still allow NW growth. In NCT
the metal layer does not require additional
patterning processes like lift off but is only
deposited as a blanket and annealed. This
seed layer could be removed after NW growth
by selective etching of the oxidized metal, or
it can remain as an isolation layer between
the NWs. In fact liftoff is one of the liquid
based processes that would oxidize the entire
reactive seed layer preventing NW growth.
The Si(111) sample, which has opening between a layer SiO2 of 50 nm thick, were placed
in the load lock of a custom built ultra-high
vacuum chemical vapor deposition (UHVCVD)
tool operated under low pressure conditions
(LPCVD). Then a layer of 6 nm thick Al was
thermally evaporated on the oxide patterned Si
(111) sample, where the Al evaporator and a
quartz crystal monitor were installed in the load
lock. The load lock base pressure is in the range1 x

10-7Torr and the growth chamber has a base pressure of 2 x 10-8Torr at 600C. Then the samples
were transferred to the hot growth chamber to be
annealed at 750C, for 20 minutes. The annealing
temperature is higher than the eutectic temperature
(577C) to agglomerate into relatively large islands
on the opening. Then the furnace was cooled to
the desired growth temperature at 490C. Then
the silane (SiH4) was introduced at a fixed flow
rate of 10 sccm (standard cubic centimeter per
minute), along with the diborane (B2H6) with
a flow rate of 1 sccm. The growth time was 60
mins. The growth pressure was 550 mTorr. After
NWs growth the SiH4 and B2H4 were pumped out,
and then the samples were transferred to the load
lock and allowed to cool down for few minutes.
The NWs morphology was studied by scanning
electron microscopy. Figure 4 shows an SEM
image of patterned growth using NCT along with
zones showing non-patterned growth of Si-NWs.
To demonstrate the versatility of NCT we have
used patterns produced with both photolithography
and nanosphere lithography. The type of photolithography used is not thought to be an important
Figure 4. Scanning electron microscopy (SEM) micrograph showing patterned and un-patterned growth
of NWs on Si(111) substrate
115

Si-NWs
parameter in NCT. In order to produce single NW

per opening, holes on the order of 200 nm were
required. This was achievable by the deep UV
lithography, but could have been performed by
e-beam lithography of nano-inprint lithography.
The photolithography substrates were 200 mm
p-type (111) Si wafers which were processed by
first growing a 50 nm thick layer of SiO2 at 950
o
C in a standard oxide growth process. This oxide
layer was then patterned with a 90 nm thick antireflection coating (ARC) followed by 450 nm
thick photo resist (UV1 1 0G) using a 248 nm
ASML UV- excimer laser stepper to expose the
pattern. The pattern consisted of circular holes
with a center to center spacing of 1.95 m and a
nominal diameter of 200 nm. After development
of the resist and ARC open/resist trim by reactive
ion etching in N2/O2, the wafers were subsequently
broken up into samples of approximately 1 cm2
for further individual processing.
The pattern in the resist was transferred into
the oxide by etching the oxide with buffered HF
(BOE 9:1 Seidler Chemical Company) solution,
typically for 60 s. The photo resist and ARC were
removed from the remaining area with acetone
followed by IPA and finally by an O2 ash treatment (100 W, 15 sccm, 1 Torr). This produced
2335 nm openings in the 50 nm oxide, varying the
buffered HF. Directly before loading the substrate
into the load lock of the UHV-CVD chamber the
samples were treated again in the buffered HF
for 4 seconds to remove residual oxides that were
formed during processing and storage. The etch
time was tuned to completely clear the oxide from
the openings without expanding the openings. The
UHV-CVD load lock chamber has been modified
with capabilities for Al evaporation, and after
pumping the chamber to below 10-6torr, 6 nm Al
was deposited as described previously. The sample
was then annealed at 730 C for 10 minutes. This
annealing temperature is higher than the eutectic
temperature (577 1 C) for Si and Al, the Al
deposited on clean Si as in the mask openings
reacts with the Si substrate to form Si:Al eutectic
116
droplets from which nanowires can subsequently

grow. However, thin Al deposited on the SiO2 does
not produce NWs.
After annealing, the growth of nanowires was
carried out by cooling the furnace to the desired
growth temperature at 490 C. Pure silane was
introduced at a fixed flow rate of 10 sccm, along
with a diborane helium gas mixture (B2H6: He
1:1000) with a flow rate of 1 sccm. Following
the procedure used in (Parlevliet et al., 2007),
typical conditions were 60 minutes growth at
a pressure of 550 mTorr. After NW growth the
SiH4 and B2H4 were pumped out and the samples
were transferred to the load lock for cooling. A
schematic flow of NCT is included in Figure 5, in
addition to scanning electron microscopy (SEM)
micrographs of experiments were conducted by
one of the authors (Dr Maha Khayyat).
The substrates for nanosphere lithography were
pieces of a p-type (111) Si wafers ~ 2 cm2 and
were cleaned using standard techniques leaving a
thin oxide on after cleaning. Silica microspheres
are commercially available with narrow size
distributions, and when dispersed properly on a
surface they can form a close-packed array that
defines gaps through which a NW seed material
can be deposited. In our case a drop of solution
taken directly from the bottle was dispersed onto
the substrate. Variable speed spin routines were
used on a resist spinner to remove the liquid
and disperse the particles. After spinning on the
microspheres the substrates were processed like
the photolithography samples after the resist
strip. Namely they were cleaned with O2 plasma,
etched with HF, inserted into the load lock, and
Al was deposited. In Figure 5 a1) and b1) a NCT
scheme using microspheres is illustrated. In this
scheme an Al seed layer forms at the gaps between
microspheres and on top of the microspheres the
Al layer reacts with the oxides in the spheres.
Al deposition, annealing, and NW growth were
performed under the same conditions as with the
photolithography samples.

Si-NWs
Figure 5. (a-c) Illustration of NCT of NWs, and corresponding SEM images, cross sectional (a1, b1,
c1 and c4) and plan view (a2, b2, c2 and c3). (a) Patterned SiO2 layer after photolithography, etching
and resist removal; notice the clean openings and smooth surface. (b) Surface after Al deposition and
730C anneal. Notice the unreacted Al has agglomerated in the openings forming a NW seed per opening
and that the Al in contact with SiO2 has reacted with and roughened the surface. (c) After epitaxial NW
growth. The NWs appear as bright spots in surface view. In the cross sectional view a thin non-seeded
Si layer smaller than 1/100 of the length of the nanowire is also visible. Notice that a single NW per
opening is achieved. c3) and c4) show a larger area containing both a patterned area on the right and
an area with no oxide where random growth occurs on the left. The scale bars are: a1) and b1) 100 nm;
c1) 300 nm; a2), b2), and c2) 200 nm; c3) and c4) 20 m. After Khayyat and coworkers, 2013
In both conventional nanowires templating

and NCT advantages appropriate mask, deposition, and annealing processing conditions can be
found that form well-defined NW seeds. These
seeds control the growth of the NWs with no NW
growth occurring between mask openings. Also
depending on the width of the opening, it is possible to grow a plurality of NWs or a single NW
within each opening. The advantages of choosing NCT with an oxygen reactive material like
Al as the seed material for Si nanowires rather
than conventional templating with Au are: (a)

The fundamental problem of low lifetime due to
deep level traps caused by incorporation of Au
into the Si can be avoided; (b) Al provides lightly
p-doped Si NWs, so that p doped nanowires can
be grown without the morphological changes in
NWs which typically occur during in situ doping
by B2H6 are avoided; (c) The reaction of Al with
the SiO2 mask during an initial anneal avoids the
need for removing the unwanted seed material by
liftoff. No NWs grow between the desired spots
117

Si-NWs
Figure 6. Schematic representation of the use of NCT with silica microspheres. (a) The microspheres dispersed on a Si substrate. (b) After Al deposition and heating, Al reacts with the oxide in the microspheres
but on the substrate in between the microspheres Al seeds form for NW growth. (c) On exposure to silane,
NWs grow from seeds between the microspheres and unseeded growth occurs on the microsphere and
substrate surface. (d) A cross sectional SEM image showing single NW growth between microspheres.
Note the darker contrast at the microsphere surface due to unseeded Si growth and the brighter line at
the interface where the Al was deposited. (The scale bar is 500 nm)
even when the seed material is not removed.

This simplifies the processing by requiring fewer
processing steps; (d) Al remaining post-growth
at the tips of the NWs can easily be removed by
a simple HF treatment. To remove Au from the
tips more exotic etching chemicals are needed that
can affect device performance.
Applications on Silicon Nanowires

It is of great interest to present applications for
Si-NWs, which could benefit in unprecedented
ways from both the unique and tunable properties of nanowires and the small size of these
nanostructures, for use in the miniaturization of
conventional devices. As the synthetic methods for
the production of NWs are maturing and NWs can
118
be made in reproducible and cost-effective ways,

it is only a matter of time before applications will
be explored seriously. This is a timely development, as the semiconductor industry will soon be
reaching what seems to be its limit in feature-size
reduction. At the same time the field of biotechnology is expanding through the availability of
tremendous genome information and innovative
screening assays. Since NWs are of the size of the
shrinking electronic components and of cellular
bio molecules, it is only natural for nanowires to
be good candidates for applications in these fields.
Commercialization of NW devices, however, will
require reliable mass-production, effective assembly techniques and quality-control methods. In
this section, applications of nanowires to Atomic
Force Microscopy (AFM), thermoelectric, and
energy sector will be presented.

Si-NWs
Production-Scale Fabrication
Method of High Resolution AFM Tips
It is a method of fabricating high resolution AFM
tips that have a controllable diameter and a high
aspect ratio (Cohen and coworkers, 2012). The
AFM is one of the foremost tools for imaging, measuring, and manipulating matter at the nanoscale
level. Conventional AFM tips are fabricated by
anisotropic etching of Si. These tips are formed
at the end of a Si cantilever and typically have a
shape of a pyramid with triangular sides defined
by Si (111) surfaces. The drawback of such prior
art AFM tips is their poor lateral imaging resolution due to their low aspect ratio and large radius
of curvature of about 5 nm-30 nm (in the best
case). The present method provides a method of
fabricating high resolution AFM tips including a
single semiconductor nanowire grown at an apex of

a semiconductor pyramid of each AFM tip which
has a controllable diameter (from 5 nm to 200 nm
with additional thinning) and a high aspect ratio,
e.g., length to width ratio, (on the order of greater
than 100), without significant tapering from the
tip of the semiconductor nanowire to its base.
A patterned oxide layer is formed on the
AFM probe (see Figure 7). The patterned oxide
layer has an opening that exposes the apex of the
semiconductor pyramid. A single Si-NW is grown
on the exposed apex of the Si pyramid utilizing
a non-oxidized Al seed material as a catalyst for
NW growth. Since the single Si-NW is grown
from the exposed apex of the Si pyramid, the SiNW grows epitaxial. The Si-NW that is formed
includes a p-doped Si-NW core that is surrounded
by an undoped Si shell. The non-oxidized Al seed
Figure 7. Schematic representations of the various steps of Fabrication of high resolution AFM tips.
119

Si-NWs
material is present at the tip of the p-doped SiNW core. The non-oxidized Al seed material and
the undoped semiconductor shell can be removed
providing a p-doped Si-NW extending from the
apex of the Si pyramid.
Also, the p-doped Si-NW that is provided by
the present method is stiff enough such that it
can be inserted into a biological cell. Moreover,
the method of the present technique can be used
to tailor the dimension and the direction of the
p-doped Si-NW that is produced according to
specific imaging needs. Furthermore, the present
method can also be employed for the mass production of AFM tips which can be easily implemented
into any standard Si AFM cantilever. The method
of fabrication of high resolution AFM tips is a
direct application of NCT explained in the previous section and there are more applications to be
built on the technique of NCT.
Photovoltaic Cells Based on Si-NWs

With the increasing demand for energy and the
detrimental effect of fossil fuels on the environment, renewable energy sources are fast emerging
as an important alternative to traditional energy

sources. Among the alternatives, solar energy
holds great potential due to the enormous amount
of solar radiation the earth receives. It is estimated
that the earth receives about 162,000 TW of solar
energy every hour, which is more than 10,000
times the total worldwide energy consumption in
a year even if 0.1 of the land area is covered with
10% efficient solar cells, we can meet our energy
demands (Office of Science, 2005). In addition to
energy conversion, energy storage devices are also
gaining increased importance due to the emergence
of portable electronic devices and hybrid vehicles.
Si-NWs arrays promise to reduce manufacturing
costs and increase the power conversion efficiency
of photovoltaic devices. In addition to better charge
transport characteristics, nanowires exhibit better
light harvesting properties (see Figure 8).
In Figure 9 we compare the light absorption
and the carrier diffusion length of thin and thick
planar solar cells with a freestanding NW array
solar cell. The main advantages of NWsin terms
of technical performance are illustrated here. The
wires create a shape that promotes scattering,
thus increasing light absorption efficiencies to
Figure 8. The reflectance of bulk Si (pristine) and Si-NWs (C2PV07). A magnified graph of the reflectance of Si-NWs shows that the reflectance is less than 0.006 (a.u.)
120

Si-NWs
Figure 9. (a) Thin Planar Solar Cell: Short carrier length, Poor absorption of light. (b) Thick planar
Solar Cell: Long carrier diffusion length, Good absorption of light (c) Free standing nanowire solar
cell: Short carrier Diffusion length, Good absorption of light
equivalent or better than a similarly thick planar

layer. At the same time core-shell p-n NWs structures can be grown by controlling the doping and
growth parameters during and after the growth of
the nanowires (Kelzenberg et. al, 2010). These
core-shell PV devices allow for shorter carrier
diffusion length than for planar devices of light
absorptive thickness.
Photovoltaic cells based on Si-NWs exhibit
lower power conversion efficiencies than conventional cells due to the enhanced photocarrier
recombination associated with the nanostructures.
It has been identified and separately measured
surface recombination and Auger recombination
in wafer-based nanostructured silicon solar cells
(Oh et al., 2012). By identifying the regimes of
junction doping concentration in which each
mechanism dominates, Oh and coworkerswere
able to design and fabricate an independently
confirmed 18.2%efficient nanostructured blacksilicon cell that doesnot need the antireflection
coating layer(s) normally required to reach a comparable performance level. The results presented
by Oh et al. suggested design rules for efficient
high-surface-area solar cells with nano- and microstructured semiconductor absorbers.
The p-n junction solar cells based on nanowires have been demonstrated in two different
configurations. In the first case, the junction is
radial, while in the other, the junction is planar,
but with the nanowire arrays acting as an antireflecting material. Vertically aligned single
crystal Si NWs were grown on a p-Type Si wafer
and the excellent antireflection properties of the
NWs gave conversion efficiencies of up to 9.31%
(Peng and coworkers, 2005). Further improvement
in the efficiencies to 11.37% was obtained for Si
NW-based p-n junction solar cells by improving
their antireflection properties and better electrical contact of the cells by employing slanted NW
structure (Hui andcoworkers, 2008). Their efficiencies are however; lower than the single-crystal
Si solar cells inspite of higher antireflectivity due
to increased carrier recombination.
A simple method has been developed (Kelzenberg et al., 2008) for cresting rectifying contacts
that yield photovoltaic behavior from single SiNWs. These devices can be used to gain insight
into the performance determining properties for
Si-NWs photovoltaics, such as resistivity and
diffusion length, as well as the rates of bulk and
surface recombination. In radial junction devices,
the tradeoff between small-diameter NWs, which
121

Si-NWs
yield higher photovoltages due to decreased in

junction areas, is optimized when the wire radius
is approximately equal to the minority carrier
diffusion length.
All structures have a fixed wire spacing of
100nm and wire length of 2.33 m, but the wire
diameter varies (Gang &Hu, 2008). It has been
demonstrated that larger filling ratios give higher
absorption at the low-frequency regime, while
in the high-frequency regime NWs with smaller
filling ratios, a NW structure can have overall
absorption efficiency close to that of thin film.
It has been demonstrated that Si-NWs have the
advantages of small reflectance across a wide
spectrum and can be achieved without specially
designed antireflecting coatings.
Another factor in the cost is that VLS growth
is inherently a vapor phase crystal growth scheme
and as such must occur in a closed atmosphere
controlled environment. This usually includes
vacuum transfers and other procedures that can
affect throughput of the samples and thus production costs negatively. This added cost to the solar
cell manufacture can be mitigated somewhat by
the relatively high growth rate of NWs. Compared
to growing planar films, NWs grow at orders of
magnitude higher growth rates in similar growth
systems and parameters. This is due to the fact
that vapor phase crystal growth rates are limited to
some extent by volume growth rate. If one grows
a continuous planar film of a certain thickness,
then a given amount of growth precursors will be
consumed from the vapor. On the other hand,if
one consumes the same amount of precursor to
grow nanowires, their height will be orders of
magnitude taller than the thickness of the planar
film. This is because most of the volume (between
60-90%) between the substrate and the top of the
nanowires is void, i.e. there is no crystal growing
there. Thus, all the precursor material is included
in the crystalline nanowires that comprise the
remaining 10-40% of the volume. In essence the
much higher growth rate of the PV devices will
122
Figure 10. TEM cross section of a core-shell p-n

diode nanowire, showing defects propagating
from the center of the nanowire to the outside.
The original wire had a diameter of ~50 nm and
was defect free
increase the throughput to a level that will allow

for lower production costs.
As mentioned earlier this void volume in the
NW PV devices is not considered dead space
because light scattering can allow the NW-void
layer to absorb as much or more of the incoming
light as an equivalently thick solid layer would absorb. This means that an equivalently thick planar
layer takes much longer to grow than a NW layer.
Even though the processing must include vacuum
based processes that typically add higher costs
due to lower throughput the higher throughput
of the growth process can allow for this process
to be comparably fast and thus more competitive
than other planar PV vapor phase grown devices.
Microscopy and microanalysis are crucial to
improving and understanding NWs growth processes and solar cell performance. The interfaces
and surfaces of the nanowires and what impact
they have on the solar cell device performance?
These interfaces, especially the interface between
the p and n areas of the solar cell diode, are critical
to the quality and efficiency of solar cells. Often

Si-NWs
these interfaces are difficult to control, resulting

in defects (see Figure 10) that can affect the performance of the device.
There is one negative aspect to using NWs in
large scale PV device that is fundamental to the
diode itself. The VOC of any PV devices is dependent on the area of the p-n junction. The VOC
is defined in Equation 5 where is a constant at
constant temperature, IL is the light induced current and ISis the dark saturation current.
VOC
1 I
ln L + 1
I S
(5)
The dark saturation current is directly proportional to the area of the p-n diode. In a NW-PV
device the area of the p-n diode is orders of magnitude larger than for a planar device because of
the core shell structure. This means that the VOC
of the NW device can be lower than for a planar
device. However, as mentioned above, the NW
device has potentially better absorption properties
and carrier collection properties which increase IL
this may not fully compensate for the large increase
in IS, but the increase IL the IS which makes the

NW PV potentially more efficient than its planar
counterpart (see Figure 11).
Extensive theoretical calculations predict that
there are indeed parameter spaces for which the
NW-PV devices outperform planar devices (Kayes
et al., 2005).
Thermoelectric Devices and Sensors

Thermoelectrics are devices for which a temperature gradient causes an electric current in a
closed circuit, or a voltage potential in an open
circuit. Using VLS grown silicon nanowires, it
was established early in the lab that their thermal
conductivity can be significantly reduced from the
bulk value of 150 (at 300 K) to ~8 W/mK (Li et.
al, 2003). The size-dependent reduction in thermal
conductivity is a direct result of strong phonon
boundary scattering at the nanowire surface. It
has been demonstrated recently that the thermal
conductivity in Si-NWs can be further reduced
down to almost the amorphous limit through a
surface defect engineering process (Law et. al,
2004). As a result, these rough Si-NWs behave
Figure 11. Illustrative comparison of I-V characteristics of planar and core-shell NW PV devices.
Although the NW device has lower VOC the maximum power point is higher because of the greater collection efficiency
123

Si-NWs
totally differently from their bulk counterparts.

At room temperature, bulk silicon is considered
to be both a good thermal conductor and electron
conductor, while rough Si-NWs are thermal insulators and at the same time electron conductors,
making them good thermoelectric materials for
waste heat recovery and power generation at a
relevant temperature range.
A sensor is a device that produces some form
of a measurable signal in response to an external
stimulus. The properties of many materials are
influenced by their surroundings. Indeed, there is
a miniaturization effort in progress to reduce the
size and power consumption of various analytical
instruments using the advances in microelecromechanical system (MEMS), and nanotechnology. Nanotechnology offers advantages with
respect to some of the criteria of sensors; such
as, small package, low power consumption. First,
nanomaterials possess a large surface to volume
ratio, leading to large adsorption rates for gases
and vapors; high reactivity. These attributes of
nanomaterials aid with the criteria of increased

sensitivity and response. Certainly, a reduction in
size, weight, and power consumption is possible
due to the small amount of active materials used
in the sensor.

The main practical advantage for NWs in large
scale PV applications is that they can potentially
be made to lower cost. One of the possible future
research directions on nanotechnology is Si-NWs
can be grown on cheap substrates. For example
we have grown NWs on common Al foil (see
Figure 12) on reusable substrates. In this process
the NWs are grown on an expensive substrate that
can be reused after the nanowires are removed
(Kayes et al., 2005). In both of these cases the
cost of the substrate has the potential of being
much less than the cost of single crystal material. The efficiency can also be almost as good
Figure 12. (Left) A schematic representation of growing Si-NWs on a cheap substrate. Nanowires grow
on Al foil. (Right) ASEM micrograph of the grown Si-NWs on Al foil, the growth parameters are: 490
C/ 500 mTorr SiH4/ 30 min
124

Si-NWs
or even better in some particular thickness and

application range (Kayes et al., 2005). Thus it is
possible to save on the relatively high cost of the
single crystal substrates and produce cells with
reasonable efficiency. This may have an impact
on the cost per watt production metric.
Growth of NWs on Al foil is a good illustration
of how NWs can be grown, doped, and made on
cheap substrates. In this case the substrate can
also act as the back contact for the solar cell further enhancing the cost savings. In this case the
nanowires where grown with Al as the seed similar
to the procedure published earlier. A sample of
ordinary Heavy Duty aluminum foil approximately
2 cm2 was rinsed with Acetone, alcohol, and then
deionized water (dI). After which it was blown
dry. The substrate was then loaded into the load
lock of the CVD chamber and Al was evaporated
on top of the Al foil. The substrates where then
transferred into the main growth chamber where
they were treated at an annealing temperature
of 600C. The temperature was then lowered to
460C and Silane (SiH4) was introduced into the
chamber. The Si-NWssubsequently grew, as it is
presented in Figure 12. The growth characteristics
of these nanowires are similar to those grown on
Si except that they are not epitaxially oriented to
the substrate, which in this case was not expected
because the substrate is not single crystal.
Having demonstrated that many of the most
interesting discoveries to date relate to nanowire
properties not present in their bulk material counterparts, we can expect future research emphasis
to be increasingly focused on smaller diameter
nanowires, where new unexplored physical phenomena related to quantum confinement effects
are more likely to befound. We can also expect
the development of applications to soon follow.
CONCLUSION
Epitaxial growth of Si-NWs that grows freestanding from the substrate was the topic of this chapter.
With the remarkable progress in research on the

synthesis of Si-NWs over past few years in the
control growth which is accompanied by progress
templating techniques. Detailed analyses have
been presented of the innovative technique of
NCT using oxygen reactive materials. The main
advantages of NCT method are that it works for
reactive seed materials that can be more desirable
for many applications. This method can also have
fewer steps, not requiring lift-off of a metal layer or
removal of the mask. It is also amenable to standard
lithography techniques as well as self-assembled
patterning techniques like nanosphere lithography.
Patterning and growth parameters can be chosen
to achieve a high growth yield and fidelity, where
no NWs grow between openings, most openings
are occupied by one or more NWs and the majority is occupied by a single vertical NWs. We
believe that the methodology used in achieving
controlled placement of single NWs, seeded with
Al is only one example of this technique and that
other oxygen reactive materials such as Sn, Sb, In,
Ga, and Ti and others templated by NCT will have
applications in nanotechnology research as well as
3D CMOS devices(Complementary metaloxide
semiconductor). The production scale method
of high resolution AFM tips represents a direct
application of NCT technique. Nevertheless, for
more applications, an improvement of current
techniques of Si-NWs growth is still needed and/
or an innovative technology should be developed.
With the remarkable progress in research on the
synthesis of Si-NWs over recent years in the
control growth which is accompanied by progress
templating techniques. This is highly desirable to
future nano-manufacturing and applications, and
is in particular an essential step towards in situ
integration of well aligned Si-NWs into devices
with existing technologies. The chapter also covered some concerns and recent demonstrations for
using Si-NWs as solar cells and photonic devices.
There is no doubt that Si-NWs will create
countless new opportunities and hopefully in
technology. Many promising applications are now
125

Si-NWs
at the early demonstration stage, but are moving

ahead rapidly because of their promise for new
functionality, not previously available, to the fields
of electronics, optoelectronics, biotechnology, and
energy conversion and generation, among others.
Many exciting challenges remain in advancing
both the nanoscience and the nanotechnological
promise already demonstrated bythe Si-NWs
research described in this chapter.
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Roca Cabarrocas, P. (2008). In situ generation
of indium catalysts to grow crystalline silicon
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AFM: Atomic force microscope; which is one
of the foremost tools for imaging, measuring, and
manipulating matter at the nanoscale level. The
information is gathered by sensing the surface
with a mechanical probe or tip called a cantilever
with a sharp tip at its end that is used to scan a
sample surface. The cantilever is typically silicon
or silicon nitride with a tip radius of curvature on
the order of nanometers.
ALD: Atomic layer deposition method.
Bottom-Up: Building larger structures from
molecular building blocks.
CVD: Chemical vapor deposition method.
Epitaxy: A type of growth where the growing
crystal retains crystallographic information from
the substrate.
129

Si-NWs
LSMCVD: Liquid source misted chemical

vapor deposition.
MBE: Molecular beam deposition method.
Nanocrystal: Orderly crystalline aggregates of
10s to 1000s of atoms or molecules with diameters
in the range of approximately 100 nm.
Nanolithography: Writing in three dimensions in nanoscale.
Nanoscale Chemical Templating: A method
of fabricating semiconductor nanowires on a
surface of a semiconductor substrate in which the
spatial placement of the semiconductor nanowires
is controlled by using an oxygen reactive seed
material.
130
Nucleation: A term used in crystallography

to describe the process that occurs when two or
more atoms from the supply media chemically
bind to form a molecular unit.
PECVD: Plasma enhanced chemical vapor
deposition method.
PLD: Pulsed laser deposition method.
UHVCD: Ultra high vacuum chemical vapor
deposition method.
VLS: A growth method of semiconductor
nanowire which is based on different phases in
the system; vapor-liquid-solid mechanism.
131
Chapter 6
Principles of Raman Scattering

in Carbon Nanotubes
K. A. Shah
Govt. Degree College for Women, Anantnag, India
M. A. Shah
National Institute of Technology, Srinagar, India
ABSTRACT
Carbon nanotubes have attracted the scientific community throughout the world, and in the past decade,
a lot of work has been reported related with synthesis, characterization, and applications of carbon
nanotubes. This chapter is written for readers who are not familiar with the basic principles of Raman
spectroscopy in carbon nanotubes. The structure of carbon nanotubes, types of the carbon nanotubes,
Brillouin zone of carbon nanotubes, and band structure of carbon nanotubes are discussed at length,
which will serve as foundation for the study of Raman scattering in carbon nanotubes. The Density
of States (DOS) of single walled carbon nanotubes are illustrated by an example which will encourage readers to calculate the DOS of any type of carbon nanotube. The Raman modes of vibration are
discussed, and Raman spectroscopic analysis is presented by considering the typical spectra of singlewalled carbon nanotubes.
INTRODUCTION
For the past several years, great interest has
been devoted to nanosized materials of various
compositions and structures. For example, carbon nanotubes (CNTs) are promising for various potential applications. Precise and reliable
handling of these nanomaterials is important for
bottom-up assembly of nano-devices and considerable efforts employing a variety of approaches
have been made and reported. Characterization
of nanomaterials includes the determination not

only of size and shape, but also of the atomic and
electronic structures and other important properties. A theoretical treatment of Raman scattering
is essential for understanding, interpretation and
appreciation of the experimental Raman spectra
from any type of sample.
Usually the Raman spectra only involve phonons explicitly, being independent of the electronic
structure of the material and the laser energy used
to excite the Raman spectra. Furthermore, the
DOI: 10.4018/978-1-4666-5824-0.ch006

Principles of Raman Scattering in Carbon Nanotubes
usual Raman scattering signal is weak. However,

the scattering efficiency gets larger when the laser
energy (excitation energy) matches the energy between the optically allowed electronic transitions
in the material and this intensity enhancement
process is called resonance Raman scattering.
The resonance Raman intensity depends on the
density of states (DOS) available for the optical
transitions, and this property is very important
for one-dimensional (1D) systems. Raman spectroscopy is usually among the first experimental
techniques used for the characterization of carbon
nanotubes.
Since carbon nanotube is the most popular
material among the researchers, and is called
the wonderful material of 21st century, therefore
in this chapter we describe the Electronic and
vibrational properties of this nanomaterial. We
start with the electronic properties of carbon
nanotubes. The study is focused on difference
in electronic properties of semiconducting and
metallic nanotubes. Furthermore the vibrational
properties discussed, gives review as well as principles of Raman scattering which is an important
tool for the characterization of carbon nanotubes
and other nanomaterials.
STRUCTURE OF CARBON
NANOTUBE (CNT)
Carbon nanotubes are tubular carbon molecules
provided with very particular properties. Their
structure is similar to fullerenes, but while fullerenes molecules form a spherical shape, nanotubes
are cylindrical structures with the ends covered by
half of a fullerene molecule. Nanotube diameter
is of the order of few nanometers, while their
length is of the order of several millimeters. The
physical properties make them potentially useful
in nanometer scale electronic and mechanical applications. They show unusual strength, unique
electrical properties and extremely high thermal
conductivity. The chemical bonding between
132
carbon atoms inside nanotubes is always of sp2

type. Nanotubes align themselves into ropes held
together by the van der walls force and can merge
together under high pressure. Nanotubes can be
excellent conductors as well as semiconductors,
depending on their structure. The thermal conductivity of carbon nanotubes is also high in the
axial direction. The particular properties of carbon
naotubes make them of great interest for potential
use in biotechnology, since they can be opened
and filled with other molecules. The structure,
electrical conductance and transport properties
of carbon nanotubes has been discussed at length
by Saito, Dresselhaus, and Dresselhaus (1998).
The structure of carbon naotubes has been
explored by high resolution TEM and STM,
yielding direct confirmation that the nanotubes
are cylinders derived from honeycomb lattice
(graphene sheet). As stated earlier the structure of
a SWNT can be conceptualized by wrapping a oneatom-thick layer of graphite called graphene into a
seamless cylinder. The way the graphene sheet is
wrapped is represented by a pair of indices (n, m)
called the chiral vector (Ch) as shown in Figure 1.
The intersection of the vector OB (which is normal
to Ch) with the first lattice point determines the
fundamental one dimensional (1D) translation
vector T. The unit cell of the one dimensional
lattice is the rectangle defined by the vectors Ch
and T (Figure 1). The cylinder connecting the
two hemispherical caps ofthe carbon nanotube
(see Figure 1) is formed by superimposing the
two ends of the vector Ch and the cylinder joint is
made along the two lines OB and AB in Figure 1.
The vectors OB and AB` are both perpendicular
to the vector Ch at each end of Ch .
The integers n and m denote the number of unit
vectors along two directions in the honeycomb
crystal lattice of graphene. If m = 0, the nanotubes are called zigzag. If n=m, the nanotubes
are called armchair. Otherwise, they are called
chiral. In the zigzag conformation, two opposite
C-C bonds of each hexagon are parallel to the
tube axis, whereas in the armchair conformation

Figure 1. The (n,m) nanotube naming scheme can be thought of as a vector (Ch) in an infinite graphene
sheet that describes how to roll up the graphene sheet to make the nanotube. T denotes the tube axis,
and a1 and a2 are the unit vectors of graphene in real space.
Figure 2. Left: Different chiral vectors and chiral angle ; Right: a) (5,5) arm-chair-tube, b) (9,0) zigzag-tube and c) (10,5) chiral-tube with matching fullerenes (Dresselhaus, Dresselhaus, & Avouris, 2001)
the C-C bonds are perpendicular to the axis. In

all other arrangements, the opposite C-C bonds
lie at an angle to the tube axis, resulting in a so
called helical nanotube that is chiral (Figure 2).
The Chiral vector Ch is defined by two integers

(n,m) as well as two base vectors a1 and a2 (Dresselhaus, Dresselhaus, & Avouris, 2001; Reich,
Thomsen, & Maultzsch, 2004. The graphite layer
133

is bent in such a way that both ends of the vector

lie on top of each other.
Ch = na1 + ma2 = ( n, m )
(1)
These two integers (n, m) determine unambiguously the diameter dt and the chiral angle
of the tube. represents the angle between the
chiral vector Ch and the direction (n, 0) (Figure 2).
3
d t = a n 2 + m2 + nm

(2)
3m

= tan1
2n + m
(3)
where a = 1.44 A is C-C distance. In (n, m) notation for chiral vector, the vectors (n, 0) or (0, m)
denote zigzag nanotube ( = 00) and the vectors
(n, n) denote armchair nanotube ( = 300). All
other vectors (n, m) correspond to chiral nanotubes
(00<< 300). The shape of cross-section are trans
type, cis type and mixture of cis and trans type for
zigzag, armchair and chiral nanotubes respectively.
The unit cell length is given by
0
T= 3
dt

d
(4)
N = 2 (m + n + nm) / dR
2
(5)
where dR = d if n-m is not a multiple of 3d or dR

= 3d, if n-m is a multiple of 3d and d is defined
134
BRILLOUIN ZONE FOR A CNT

The general relationship between a direct lattice
vector, ai, and reciprocal lattice vector, bj, is given
by Brennan (1999):
ai b j = 2 ij
(6)
Here ij is the well known Kronecker delta function defined such that:
1 if i = j

ij =
0 if i j
(7)
Thus for a graphene unit cell, if a1 and a2 are

direct lattice vectors, we may define two indirect
or reciprocal lattice vectors b1 and b2. Figure
3 shows the four vectors. Now, the length of a
reciprocal lattice vector is, given by
bj =
where d greatest common divisor of (2n + m)

and (n + 2m).
The characteristic of semiconducing and metallic nanotubes depends precisely on the values
of m and n. A tube is metallic when (n-m)/3 is an
integer. The number of hexagons N per unit cell
of a chiral nanotube defined by (n, m), is given by
2
as the greatest common divisor of (n, m). Each

hexagon in the honeycomb lattice contains two
carbon atoms. The unit cell area of the carbon
nanotube is N times larger than that for a graphene
layer and consequently the unit cell area of the
nanotube in the reciprocal space is correspondingly 1 / N times smaller.
2

ai
(8)
Similarly if vectors Ch and T define a CNT unit

cell in 2-D, then we may assign two associated
reciprocal vectors K1 and K2 respectively. These
vectors are given by:
K1 =
and
2
Ch
= Ch

Figure 3. Direct (a), and indirect (b) lattice structure of graphene. Two atoms, A and B, define the unit
cell with unit vectors a1 and a2. b1 and b2are the reciprocal unit lattice vectors. The high-symmetry ,
K, and M points are also depicted in the reciprocal lattice structure.
K2 =
2
T
(9)
Thus K1 and K2 define a CNT reciprocal unit

cell in 2-D. It is also clear from the definition of
K1 and K2 that the larger the CNT unit cell, the
smaller the 2-D reciprocal unit-cell. For a CNT,
only K2 is the reciprocal lattice unit vector, corresponding to a single direct lattice vector.
The above picture is, however, not complete.
In a CNT, the vector Ch actually folds onto itself,
thus imposing periodic boundary conditions on
the wave function. This means that only certain
values of the component of wave vector k parallel
to K1, are allowed.
Consider the electron wave function for graphene:
( x ) = e ikx u ( x )
(10)
where u(x) is the Bloch function that contains

the periodicity of the lattice. Now by imposing
periodic boundary conditions on the wave function we imply that any translation by a distance in
multiples of |Ch|, and in the direction of Ch on the
graphene lattice should result in the same wave

function. Therefore,
k .Ch = 2 v
(11)
where is in an integer. Expanding out the above

equation in components of kx and ky, we obtain a
linear relationship between kx and ky. Therefore
the application of periodic boundary conditions
on Ch results in the appearance of discrete lines
in the CNT Brillouin zone (BZ) that represent
the allowed values of kx and ky and satisfy Equation 11. These lines are continuous along the K2
direction. The distance between each parallel line
along the K1 direction is 2 / | Ch|.,
The next step in determining the Brillouin zone
for a CNT is to determine the restriction on the
integer , if any. Since any point outside of the
first Brillouin zone of graphene is equivalent to
any point within the zone, we obtain:
y=
graphene reciprocal unit cell area

=N
K1 K 2

( N = Number of hexagons in CNT unit cell)

(12)
135

These N lines (0 to N-1, or (N/2 + 1) to N/2

represent the extended zone scheme for a CNT.
Since a CNT is essentially a 1-D material, each
line segment can be translated to the K1=0 line,
resulting in a reduced zone scheme. This is called
the zone folding method.
imposing strictly periodic boundary conditions

for translations by the roll-up vector that defines
the nanotube. In this section we first discuss the
method to obtain the band structure of a CNT from
a simple zone-folding scheme of the electron
band structure of graphene.
ELECTRONIC BAND STRUCTURE

OF CARBON NANOTUBES
BAND STRUCTURE OF
2-D GRAPHITE
The electronic band structure of a CNT depends

very strongly on its diameter and chirality (i.e.
chiral vector). CNTs may be metallic or semiconducting. Even within the broad category of
semiconducting CNTs, vastly different properties
are exhibited by different CNTs. A single wall
carbon nanotube is essentially a single 2-D layer
of graphite (a graphene sheet) rolled into a tube.
Graphene is a sp2 bonded network of carbon atoms
arranged in a hexagonal lattice with two atoms per
unit cell. A nanotube of a particular radius and
chirality may be specified by choosing a roll-up
vector known as Chiral vector Ch that maps two
given hexagons in the lattice on top of each other.
Since any vector connecting two hexagons in the
lattice is a Bravais lattice vector, it is a linear
combination of the primitive vectors with integer
weight. Thus, a given nanotube is associated with
two indices that specify these integers. However
this indexing scheme is one of convention as the
choice of primitive lattice vectors is not unique.
However, this scheme appears to be the most
commonly used in the literature.
For a very large radius tube, one might expect
that the properties of the tube are very similar
to that of graphene. It has been found that even
for very small diameter tubes (~1 nm) that the
basic electronic properties of nanotubes may be
deduced from the band structure of graphene. In
the simplest possible model, the band structure of
nanotubes can be derived directly from the band
structure of graphene. This is accomplished by
The -electron band structure for graphene may be

obtained from the application of the tight-binding
(TB) method (Dresselhaus et al., 2001; Reich et al.,
2004). Figure 3, as mentioned previously, shows
the direct lattice structure (a), and reciprocal or
indirect lattice structure (b) of graphene. Vectors
a1 and a2 define the unit cell, and b1and b2 define
the reciprocal unit cell. The symmetry points, , K,
and M, in the reciprocal lattice are also depicted.
By considering the orbital overlap between the
A and B atoms to be zero (i.e. no overlap), one
obtains a tight-binding (TB) formulation of the
band structure as:
136
3k x a
k a
k a
e ( k ) = 0 1 + 4cos 2 y + 4cos y cos
2
2
(13)
In the equation, 0 is the nearest-neighbor

transfer integral, also called the hopping matrix element, a is the lattice constant for the
graphene direct lattice structure, and e is the
electron energy.
Figure 4 depicts an illustration of the energy
dispersion for graphene over the entire Brillouin zone (BZ). This intersection gives rise to
the semi-metallic nature of graphene. If we do
not consider the overlap to be zero, we obtain
an asymmetric band structure around the Fermi
level. This is depicted in Figure 4, which shows
the band structure of graphene along the high
symmetry directions.

Figure 4. Illustration of the electron energy dispersion of the and * orbitals of graphene over the
entire Brillouin zone
BAND STRUCTURE OF
CARBON NANOTUBES
As was mentioned in the previous section, periodic
boundary conditions imposed by the chiral vector
Ch cause the wave vector K1, which is associated
with Ch, to be quantized in a CNT, while the wave
vector K2, which is associated with the vector T,
remains continuous. This gives rise to a set of k
vectors that are parallel to T. These k vectors will
result in cross-sections of the graphene electron
dispersion. These cross-sections result in the
appearance of various sub-bands in a CNT. The
band structure is obtained along the K2 vector.
Figure 4 shows the electron energy dispersion
relations for 2D graphene as a function of the
two dimensional wave vector k in the hexagonal
brillioun zone. The valance and conduction *
bands are seen to meet at the six high symmetry
K points, giving rise to the metallic nature of

graphene. The overlap integral is considered to
be zero. The energy dispersion along the high
symmetry lines between the , K, and M points
is shown in Figure 5. The band (upper part) and
the conduction * band (upper part) are degenerate
at the K points in the hexagonal Brillioun zone
which corresponds to the Fermi energy (EF = 0)
(Dresselhaus et al., 2001; Reich et al., 2004). Since
the energy dispersion near the Fermi energy is
linear, the density of states of metallic nanotubes
is constant at the Fermi energy and is inversely
prepositional to the diameter of the tube.
To distinguish metallic and semiconductor
nanotubes we introduce the Figure 6. In the direction of K1, discrete k values are obtained by
periodic boundary conditions for the circumferential direction of the carbon nanotubes, while in
the direction of K2 vector, continuous k vectors
137

Figure 5. Electron energy dispersion of graphene along the high symmetry lines between the , K, and
M points. The overlap integral is non-zero
are in the one dimensional Brillioun zone. If,

for a particular (n, m) nanotube, the cutting line
passes through a K point of the 2D brillioun zone
(Figure 6), where the and * energy bands of
the 2D graphite are degenerate by symmetry, then
one dimensional bands have a zero energy gap.
For metallic nanotubes, the bold line intersects
the K point (corner of the hexagon) at the Fermi
energy of graphite (Figure 6a), where the density
of states are finite as shown below. For the semiconducting nanotubes, the K point always appears
one-third of the distance between two bold lines
(Figure 6b), and thus a semiconducting nanotube
with a finite energy gap appears. For each bold
line, there is an energy minimum (or maximum)
in the valance and conduction energy sub-bands,
giving rise to energy difference Eii (dt). The rule
for being either a metallic or a semiconducting
nanotube is, respectively, that n-m = 3q or n-m
3q, where q is an integer (Dresselhaus, Dresselhaus, & Avouris, 2001).
It is to note that to obtain the band structure for
a CNT, we simply obtain allowed CNT Brillouin
zone K vectors and obtain the associated energy
for each k from the graphene band structure.
138
Figure 6. Wave vector k for one-dimensional

carbon nanotube shown in the two dimensional
Brillioun zone of graphite (hexagon) as bold lines
for (a) metallic and (b) semiconducting nanotubes.
The points K and K` are equivalent

ELECTRONIC DENSITY
OF STATES (DOS)
A quantity that enters critically in the experimental
study and the application of the electronic properties is the density of electronic states i.e, the number
of available electrons for a given energy interval.
The density of electrons is known to depend
dramatically on the dimension of a system. For
parabolic bands as found in most semiconductors
it rises as the square root of the energy above the
band gap in the three dimensional case, exhibits
a step like function in two dimensional solids,
diverges as the inverse of a square root in one
dimensional system, and finally, is a delta function in zero dimensions. Carbon nanotubes are
one-dimensional systems and around its minimum
and maximum a band can always be approximated
as parabolic. Thus the density of states varies as
square root of the energy above the band gap.
Some early tight binding and ab-initio calculations confirmed this for armchair nanootubes (Rao
et al., 1997; Mintmire & White, 1998). However it
was generally expected that the electronic density
of states is very different for achiral and chiral
tubes (Dresselhaus, 1998). However this view
changed when Mintmire and White (1998) published their derivation of a universal density of
states for carbon nanotubes Mintmire and White
(1998), given by
n(E) =
4a0
m =+
g(E, E
2d 0 m=
(14)
with density of states function

1
2
2 E > Em
E
/
(
E
E
)
2

g ( E , Em ) =
m
E
<
E
m
0
(15)
where a0 = 2.49 A0 is the lattice constant, 0 =

2.9 eV is the energy overlap integral, m is an
integer, d is the diameter of the tube and Em =

(ia00 31/2)/d is the points of energies of vanishing
slope for different electronic bands, with i = 1,
3, 6, for metallic and i = 1, 2, 4, 5, 7, . for
semiconducting nanotubes (Reich, Thomsen, &
Maultzsch, 2004).
For Em 0, g(E, Em) shows the divergence
at E= Em as expected for a critical point in a
one-dimensional system. For Em= 0, the density
of states functional g = 1, i.e., it is constant and
different from zero. Em= 0 refers to metallic tubes
and the bands that cross at the Fermi energy.
Three methods were successfully used in the
past to confirm the electronic density of states in
single-walled carbon nanotubes. Scanning tunneling spectroscopy (STS) (Wildoer et al., 1998;
Odom et Al., 2001), resonant Raman (Jorio et al.,
2001; Strano et al., 2003) and Optical absorption
and emission measurements OConnell et al.,
2002; Lebedkin et al., 2003). STS was the first
experimental technique that directly demonstrated
the existence of metallic and semiconducting
nanotubes and shows the presence of van-Hove
singularities (vHs). Raman scattering depends
strongly on the nanotube band structure and the
energies with a high density of electronic states.
Raman scattering do not directly measure the
electronic density of states as scanning tunneling
spectroscopy. They rather depend on joint density
of states (JDOS).
An example is given here, how to calculate the
density of states of a (5, 5) armchair nanotube using
Mintmire and White approximation (Mintmire &
White, 1998). Since n-m =0, it is a metallic tube
with diameter d = a/ (n2 + m2 + nm)1/2 =0.686
nm where a =0.249 nm is lattice constant. The
points of energies of vanishing slope for the first
electronic transition i = 1 is Em = 0.607 eV. Since
| E | >| Em |, therefore let us assume the electronic
energy E = 0.7 eV. With this value the density
of states function g(E, Em) =2.005. Substituting
this value along with other constant parameters
in equation (14) the value for density of states
calculated will be n(0.7) = 0.101.
139

Table 1. Calculated density of states for (5, 5)

nanotube
Em
g(E, Em)
n(E)
0.607
0.7
2.005
0.101
1.821
1.9
3.473
0.176
3.642
3.7
5.642
0.286
Table 1 demonstrates the calculated density

of states for first three electronic transition energies of (5, 5) nanotube using Mintmire and White
approximation Mintmire and White (1998). The
calculated electronic transition energy is shown
in first column of Table 1, however the calculated
electronic energy, density of states function and
the density of states are shown in second, third
and fourth column of Table 1 respectively. The
magnitude for the value of density of states in
the valence band will be equal to its value on
the conduction band. Therefore, by considering
other states in the valance and conduction band,
the density of states can be plotted as a function

of energy similar to as shown in Figure 7.
Figures 7ac shows the DOS for three different SWNTs. Since SWNTs are one dimensional
(1D) systems, their DOS is characterized by the
so-called van Hove singularities (vHSs). The
sharp vHSs define narrow energy ranges where
the DOS intensity becomes very large. Therefore,
in practice, a single carbon nanotube exhibits
a molecular-like behavior, with well-defined
electronic energy levels at each vHS. The three
DOS curves in Figures 7ac come from different
SWNTs as labeled by their (n, m) indices (see
caption). Each pair of indices defines a unique
way to roll up the graphene sheet to form the
nanotube, and each unique (n, m) nanotube has a
distinct electron and phonon structure.
An observable Raman signal from a carbon
nanotube can be obtained when the laser excitation
energy is equal to the energy separation between
vHSs in the valence and conduction bands (e.g.,
see ES11, ES22and EM11in Figure 7), but restricted to
Figure 7. DOS for a (a) armchair (10, 10) SWNT, (b) chiral (11, 9) SWNT and (c) zigzag (22, 0) SWNT
obtained with the tight binding model (d) Shows the electronic transition energies Eiifor all the (n, m)
SWNTs with diameters from 0.4 and 3.0 nm using a simple first-neighbor tight binding model
140

the selection rules for optically allowed electronic

transitions. Because of this resonance process,
Raman spectra at the single nanotube level allow
us to study the electronic and phonon structure
of SWNTs in great detail. When Raman spectra
of SWNT bundle samples are taken, only those
SWNTs with Eii in resonance with the laser excitation energy Elaser will contribute strongly to
the spectrum. From Figure 7 it is clear that the
metallic nanotubes (10, 10) has wider energy gapes
between spikes than semiconducting (11,9) and
(22,0) single-walled nanotubes.
For the characterization of nanotubes by Raman
spectroscopy, it is useful to consider plots of the
energies Eii versus the nanotube diameter, dt, as
shown in Figure 7d. Each point in this plot represents one optically allowed electronic transition
energy (Eii) from a given (n, m) SWNT. Crosses
come from semiconducting SWNTs, and circles
from metallic SWNTs. This plot should be considered as a guide for answering the question if
we use a given Elaser to excite our sample, which
(n, m) carbon nanotubes can be in resonance with
my laser line?. In other words, since the observable Raman spectra come predominantly from
tubes in resonance with Elaser, Figure 7 specifies
the nanotubes that will be observable for a given
laser line.
VIBRATIONAL PROPERTIES
OF CARBON NANOTUBES
Many common spectroscopic methods are used
for the study of vibrations in solids, like inelastic
light scattering, far-infrared spectroscopy, and
neutron scattering. Among all methods available,
Raman scattering has been far the most used for
the characterization of carbon nanotubes. However
it is very important to have a general knowledge
of the vibrational properties of carbon nanotubes
using Raman spectroscopy. Raman scattering insitu method is also available. The scattering signal
is so large compared to other spectroscopic meth-
ods that even isolated carbon nanotubes could be

investigated. The ever-growing interest in carbon
nanotube applications like mechanical enforcement, chemical sensor, electronically active and
passive devices etc, demands a thorough and robust
understanding of the vibrational properties. Combined with theoretical work the vibrational spectra
are intimately related to the electronic properties
of the tubes, it is as such that Raman scattering
became a straightforward in-situ non-destructive
tool for the characterization of carbon nanotubes.
From vibrational spectroscopy of carbon
nanotubes one can derive the tube diameter, tube
orientation, metallic or semiconducting nature,
and even attempts to derive tubes chirality has
been reported. Therefore an in-depth analysis of
the spectra is necessary to derive such specific
and important qualities from the spectra. Some
properties of carbon nanotubes indeed follow from
simple analogy to graphite, while others require
more detailed understanding of the nanotubes.
The zone folding approach is widely applied
in work on nanotubes. The folding is obtained by
slicing the graphite Brillouin zone in the appropriate direction. The phonons where the vertical
lines cut the graphite dispersion become -point
phonons in nanotubes. However zone-folding approach has some systematic shortcomings. Firstly
simple zone folding does not yield four acoustic
modes, one of them is the new twiston mode,
where the nanotube performs a twisting type
vibrations. Secondly the out of plane translation,
an acoustic mode in graphene, transforms into the
radial breathing mode (RBM) in carbon nanotubes
with non-zero frequency at the -point. This mode
is an exception to carbon nanotubes and is most
important for determining the tube diameter.
The main features in the Raman spectra of
carbon nanotubes are: the radial breathing mode
(RBM), which is a totally symmetric (in the ring
plane) vibrational mode with A symmetry; the
disorder-induced D-band, also with A symmetry,
and its corresponding second-order G-band;
and the tangential G-band, which is made up of
141

a mixture of symmetric and asymmetric in-plane

modes (A and E1 symmetry), and asymmetric
out-of-plane modes (E2 symmetry). We will now
describe each mode by considering typical spectra
of a single walled nanotube.
TYTICAL SPECTRA OF SINGLEWALLED CARBON NANOTUBES

The first order spectra are divided into regions
where the entire tube deforms at low frequency
and where neighboring carbon atoms vibrate out
of phase at higher frequency. The low frequency
range of the radial breathing mode (RBM) is between 100 and 400 cm-1, the intermediate range
with the defect induced vibration (D-mode), which
involves phonons from the graphite K-point, lies
between 1200 and 1400 cm-1, and the high energy
range, (1500-1600 cm-1) belongs to the so-called
high energy mode (HEM). A typical Raman
spectrum of a sample of single-walled nanotube

bundles excited at = 488 nm is shown in Figure
8, the RBM and HEM are very strong.
It is remarkable to note that most Raman spectra
look remarkably similar when excited with Elaser>
2.0 eV, however when excited with lower energy
around 1.9 eV the spectra in the high energy region
broaden, change their shape, and shift somewhat
to lower wave numbers, the maximum intensity
being around 1550 cm-1.
The two types of line shapes are traditionally
referred to as semiconducting and metallic, a notation related to the electronic density of states of
semiconducting and metallic nanotubes believed
to cause corresponding Raman resonances. Hiura
et al. (1993) were the first to publish Raman spectra of nanotubes in (1993). The spectrum looked
exactly like graphite with a single peak at ~1580
cm-1. Holden et. al (1994) reported for the first
time the group of broad Raman peaks just below
~1600 cm-1, which is typical for single-walled
Figure 8. Typical Raman spectrum of single walled nanotubes excited with 488 nm. The RBM, K-point
related D mode and HEM are shown
142

nanotubes. A tentative assignment of all Raman

modes to calculated frequencies was made by Rao
et al. (1997). This assignment is still considered
partly correct.
One of the most curious aspects of Raman scattering in nanotubes actually goes back to graphite.
There, the vibrational mode in the region 1200 to
1400 cm-1 has the unusual property that it changed
its energy in the Raman spectrum with excitation
energy (Vidano et al., 1981; Pocsik et al., 1998).
The corresponding mode in nanotubes showed a
very similar behavior (Thomsen, 2000; Kastner
et al., 1999) and so a common explanation was
called for. Raman scattering experiments have
given the impetus to improve the understanding
of both electronic and vibrational aspects of carbon nanotubes. When analyzing Raman spectra
the splitting of electronic joint density of states
can be detected.
The carbon nanotube samples whether single
walled, multi walled, double walled or a bundle
carbon nanotubes often consists of un-oriented
tube ensembles where only the average tube diameters can be controlled by growth conditions,
however the chirality cannot be controlled and
therefore all chiral angles will be present in the
sample. As such the Raman signal is averaged over
different polarizations, diameters and chiralities.
Therefore, the correct interpretation of the Raman
spectra, in particular of the high-energy mode,
posed quite serious challenge.
CONCLUSION
This chapter starts with the discussion of the
structure of carbon nanotubes, so that the readers should understand the types of the carbon
nanotubes and the various parameters which are
necessary for foundations of the subject. Brillouin
zone and band structure of carbon nanotubes is
presented in detail, which will serve as backbone
for studying the vibrational properties of carbon

nanotubes. Density of states of carbon nanotubes
are also discussed with an illustrative example.
The new method presented will help to calculate
the density of states of any type of single wall
carbon nanotube. The importance of the various
modes of Raman spectra are also presented by
considering the typical spectra of single-walled
carbon nanotubes excited with 488nm. In short
this chapter provides a complete background of the
study of vibrational properties of carbon nanotubes
and gives new dimensions to the characterization
of carbon nanotubes by Raman spectroscopy.
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Band Structure: Band structure describes the
ranges of energy that an electron within a solid
may have or ranges of energy that it may not have.
It provides electronic levels in crystal structure
which are characterized by a Bloch vector k and

a band index n. The band theory can be used to

explain many electrical, optical, magnetic, and
physical properties of crystals.
Brillouin Zone: The Brillouin zone is defined
as the set of points in k-space that can be reached
from the origin without crossing any Bragg plane.
Equivalently it can be defined as the Wigner-Seitz
Cell of the reciprocal lattice. In case of single
walled carbon nanotubes the first Brillouin zone
is given by irreducible set of equidistant lines
whose length and spacing are dependent on the
values of two integers n and m.
Carbon Nanotubes: Carbon nanotube can
be thought as a rolled sheet of graphene in the
form of cylinder with diameter of the order of a
nanometre varying from 0.5 to 3nm. The carbon
nanotubes can be metallic or semiconducting depending upon the value of two integers n and m.
They have unique electrical, mechanical, thermal,
optical and magnetic properties.
Density of States: The Density of States (DOS)

of a system can be defined as the number of states
per interval of energy at each energy level that are
available to be occupied by electrons. For a system
a high DOS at a specific energy level means that
there are many states available for occupation and
zero DOS means that no state can be occupied at
that energy level.
Raman Spectroscopy: Raman scattering is
the inelastic scattering of light that provides the
chemical and structural information of a liquid
or crystal. A Raman spectrum is a plot of the
intensity of Raman scattered radiation as a function of its frequency difference from the incident
radiation. This difference in frequency is called
Raman shift. Raman spectroscopy is widely
used for studying carbon nanotube - length and
diameter, whether nanotubes are single- walled or
multi-walled, isolated or bundle, conduction type
of semiconducting or metallic and even chirality.
145
146
Chapter 7
Pharmacokinetics of
Polymeric Nanoparticles at
Whole Body, Organ, Cell,
and Molecule Levels
Mingguang Li
Wayne State University, USA
ABSTRACT
Polymeric nanoparticles have been increasingly studied and applied in a variety of areas, most commonly
in biomedicine. The efficiency and toxicity are two aspects that need to be considered for nanoparticles,
and both are closely related to the pharmacokinetics of nanoparticles. In this chapter, the pharmacokinetics
of polymeric nanoparticles were introduced at the whole body level (including absorption, distribution,
metabolism, and excretion), organism level (transportation within organs and pass through physiological barriers), cell levels (binding to cell surface, endocytosis, intracellular transition, and exocytosis),
and molecule level (protein binding and ligand-receptor binding). Examples were also given to illustrate
the modeling of the pharmacokinetics of polymeric nanoparticles at different levels. A comprehensive
understanding of the pharmacokinetics of polymeric nanoparticles will facilitate the applications in
various areas such as drug delivery and disease diagnosis.
1. INTRODUCTION
Nanoparticles, according to their chemical compositions, could be classified into three categories:
polymeric, non-polymeric, and hybrid particles.
Non-polymeric nanoparticles are commonly
used for imaging and diagnosis in medicine, but
they are very limited to modifications. Polymeric
nanoparticles are very flexible, and could be
prepared using numerous polymers to achieve

very complicated properties and functions, which
make them very advantageous for drug delivery.
Hybrid nanoparticles contain both polymeric and
non-polymeric materials with the purpose to retain
the advantages and functions of both.
It is difficult to distinguish polymeric nanoparticles from non-polymeric and hybrid nanoparticles in terms of pharmacokinetics, although there
DOI: 10.4018/978-1-4666-5824-0.ch007

Pharmacokinetics of Polymeric Nanoparticles
are certainly some differences such as degradation.

However, it is not in the scope of this chapter to
compare the pharmacokinetics of nanoparticles
with different chemical composition. This chapter
will focus on the pharmacokinetics of polymeric
nanoparticles, while research about non-polymeric
and hybrid nanoparticles will be mentioned only
when they are helpful in understanding the pharmacokinetics of polymeric nanoparticles. On the
other side, most general statements in this chapter
also apply to non-polymeric and hybrid nanoparticles, unless indicated specifically.
Polymeric nanoparticles are increasingly used
in diverse areas, such as cosmetics, foods, and
especially medicine (Nitta & Numata, 2013).
There are two aspects of nanoparticles that need
to be understood thoroughly before they can be
used on human body: how efficient they are for
the purposes and what is the toxicity. Both aspects
are closely related to the fate of nanoparticles
in the human body, which could be generally
described as ADME (absorption, distribution,
metabolism, and excretion). ADME of polymeric
nanoparticles, similar as those of small molecules,
are dynamic processes, involving numerous interactions between the nanoparticles and the human
body. Mathematical description of the kinetics of
these processes enhances our understanding of the
interactions between polymeric nanoparticles and
human body, and further promotes the designation
and optimization of nanoparticles with higher
efficiency and low toxicity (M. Li, Al-Jamal,
Kostarelos, & Reineke, 2010).
The pharmacokinetics of polymeric nanoparticles depends on their properties including
size, surface charge and modifications, chemical composition, and shape. There are a few
comprehensive reviews have discussed this in
full detail (Duan & Li, 2012; Owens & Peppas,
2006). Many studies have been done to show the
relationships between nanoparticle properties and
their ADME within animal bodies and interaction
with cells (Duan & Li, 2012; Moghimi, Hunter,
& Andresen, 2012; Yue et al., 2011). These stud-
ies significantly advanced the understanding of

nanoparticle pharmacokinetics within the human
body. Based on these studies, mathematical models were established or improved to describe and
illustrate the kinetic processes of these particles
inside the living systems.
2. PHARMACOKINETICS OF
POLYMERIC NANOPARTICLES
2.1 The Pharmacokinetics
at Whole Body Level
Nanoparticles entering the human body can be
classified by two ways of exposure: unintentional
and intentional. The former includes airborne
pollutants and nanomaterials in working environments, or in food and cosmetic products. Intentional exposure is mostly for medical applications,
especially drug delivery and imaging. In most
cases, polymeric nanoparticles were engineered
and intentionally given to human for designed
applications such as drug delivery and diagnosis. Nanoparticles may be given through various
routes, such as through the respiratory tract,
gastrointestinal tract, and skin. Nanoparticles can
also be injected into the body, mostly for medical purposes. Numerous studies have shown that
the properties of nanoparticles have complicated
influences on the pharmacokinetics (Figure 1).
2.1.1 ADME of Polymeric Nanoparticles

The most common route is through the respiratory tract, especially for pollutants (Yue et al.,
2011). Due to the physiological structures of the
lungs, pharmacokinetics of inhaled nanoparticles
is very complicated and under numerous studies,
as discussed later in this chapter. According to
the physiological structures, the lungs could be
divided into the airways (trachea, bronchi, and
bronchioles) and the alveoli. Particles could deposit in the airway surface, and then be cleared
147

Figure 1. A general view of the influence of nanoparticle physicochemical characteristics (size, shape,
and surface properties) on ADME (absorption, distribution, metabolism, excretion). Abbreviation: RES,
reticuloendothelial system. (Reproduced with permission; Moghimi, Hunter, & Andresen, 2012)
away from the lungs by mucociliary movement,

diffuse through the mucus layer to reach the epithelium cells, or captured by macrophages cells. The
large surface area of the alveoli and the intimate
airblood contact has been taken advantages to
deliver nanoparticles into the blood or lymphatic
system. As part of the respiratory tract, the olfactory region could also allow nanoparticles to pass
through into the central nerve system, as shown
in some animal studies.
148
Nanoparticles enter through the digestive tract

reach the stomach and then transit to the intestine.
The small intestine is the primary location of
nanoparticle absorption, while absorption may
also happen in stomach and colon. While in the
digestive tract, nanoparticles are also cleared out
the body by the movement of the intestines. There
were studies showing that nanoparticles (50 nm
to 200 nm) can pass through Peyers patches in
the wall of small intestine (Yue et al., 2011). In-

testinal enterocytes could be another absorption

routes (Florence, Hillery, Hussain, & Jani, 1995).
After that, nanoparticles then further distributed
into other organs and tissues through the blood
and local lymphatic system.
Other route of nanoparticle entrance into human body include the penetration through the
skin, injection directly into the blood circulation
or local tissues. Exposure to the skin has also
drawn increasing attention during the past years
(Pegoraro, MacNeil, & Battaglia, 2012). Studies
have shown that a variety of nanoparticles could
penetrate through the epidermis. For medical applications, nanoparticles could also be given to
the body by injections. No absorption process is
needed for intravenously administered nanoparticles, but nanoparticles administered through
other injection sites still need to be absorbed into
the blood circulation (Maincent et al., 1992).
After the absorption into the blood circulation,
nanoparticles could distribute into all organs and
tissues in the body as shown in many research
works. The concentrations in different tissues or
organs may be much different depending on the
properties of nanoparticles and their interaction
with the living system.
After nanoparticles enter the blood circulation,
they interact with the blood components immediately, including plasma proteins, platelets, red and
white blood cells (Oberdorster, Oberdorster, &
Oberdorster, 2005). Protein binding to nanoparticle surfaces (opsonization) almost instantaneously
once the particle enters a biological medium, and
subsequently change nanoparticle properties and
following interaction with the biological systems
(Aggarwal, Hall, McLeland, Dobrovolskaia, &
McNeil, 2009). Opsonization was reported to be
the major step to facilitate the recognition and
further phagocytosis of nanoparticles by macrophages. The binding kinetics of proteins to the
surface of nanoparticles is further discussed later
in this chapter. Nanoparticle distribution could also
be influenced by the blood supply of tissues. Tissues are divided into two groups by blood supply:
quickly and slowly perfused. The effect of blood

supply depends on the tissue blood supply and the
transportation rates of nanoparticles from blood
into tissues. When the blood supply is very limited,
or nanoparticles distribute into tissues very fast,
the blood flow may become the limiting step of
nanoparticle distribution.
As mentioned before, nanoparticle could
have distribution into almost all organs and tissues, although in most cases not as significant
as into the liver and spleen. A well known factor
that influences distribution of nanoparticles is
the reticuloendothelial system (RES, also called
mononuclear phagocyte system). The RES is composed of a group of cells having the ability to take
up nanoparticles (Otsuka, Nagasaki, & Kataoka,
2003). This includes macrophages, macrophage
precursors, specialized endothelial cells lining
the sinusoids of the liver, spleen and bone marrow, and the reticular cells of the lymphatic tissue
(macrophages) and bone marrow (fibroblasts).
Nanoparticle biodistribution studies have shown
that nanoparticles are accumulating and retained
by the organs compromising of the RES.
Lungs and GI tract could have relatively high
accumulation when they acted as the administration sites (Hillyer & Albrecht, 2001). In most
cases nanoparticles were found at very low levels
or missing in the brain due to the blood-brain barrier (BBB) (Hillyer & Albrecht, 2001). Although
showing low accumulation of nanoparticles
in most cases, the heart is routinely tested for
nanoparticles distribution due to its physiological
importance. The particle distribution into muscle
may be low, but the absolute amount may be quite
high due to the mass of muscles. Unless under
specific circumstances, other organs and tissues,
such as the reproductive tract, skin, and glands are
seldom tested separately, because low distribution
of nanoparticles.
As expected, the metabolism of nanoparticles
depends on their composition and properties. Different particles go through different metabolism
routes. Nanoparticles may be broken down in the
149

macrophage cells of RES after being internalized.

The hepatocytes of the liver could also capture
nanoparticles by phagocytosis and digest them.
Nanoparticles prepared using polymers are under
mostly commonly used for drug delivery purposes.
The metabolism of these polymeric nanoparticles
is through the degradation of the matrix polymers.
Biodegradation of natural polymers is generally
faster than that of synthesized ones. One of the
advantages of polymeric nanoparticles is that
their biodegradation rate can be controlled by
modifying the polymer composition and molecular
weight (Shive & Anderson, 1997). Nanoparticles,
especially polymeric ones, could also change their
physical properties which results in the loss of
their original form. Particles could swell, shrink,
dissolve, or break in the biological environment
(M. Li, et al., 2010). These physical changes could
result in removal of nanoparticles from the living system or drifting of their ADME behaviors.
The most studied polymers are PLGA and PLA,
which are approved by FDA to be used in human
body. The degradation of PLGA and PLA is well
documented as depending on molecular weight
and composition. Natural polymers are frequently
chemically modified to obtain certain properties
that may alter their metabolism kinetics within
the body.
Besides metabolism, nanoparticles are also
eliminated out of the body through excretion,
which is also depending on their properties. Studies showed that liver and kidneys are the major
organs for nanoparticle excretion. Nanoparticles
may also be removed from the body through other
excretion routes such as the lungs, the breast milk,
and sweat. In the kidneys, nanoparticles could
enter the urine by glomerular filtration or tubular
secretion. The clearance was shown to be closely
size-dependent, and most studies were done using
inorganic particles. Choi et al,(2007) studied the
renal clearance of Quantum Dots depends on the
size of nanoparticles. Nanoparticles with size less
than 5.5nm showed efficient and complete renal
clearance. Renal clearance of larger nanoparticles
150
could be very slow, but still possible. Liver is

another major organ for nanoparticle clearance
through excretion (Yamago et al., 1995 ;Cho et
al., 2009). The excretion occurs across hepatocytes through the biliary production pathway.
For example, polystyrene nanoparticles were
excreted through hepatic route (Furumoto et al.,
2001). after intravenous administration in rats.
After being taken up by the liver, there particles
were excreted in the bile, about 4% of the dose
after 24 hours.
2.1.2 Pharmacokinetic Modeling

of Polymeric Nanoparticles
at Whole Body Level
Pharmacokinetics has been traditionally applied
to study the ADME of drug molecules. In the recent years, it is also used for nanoparticles. Most
recently, some scientist used other terms such as
particokinetics, or nanokinetics, in the place of
pharmacokinetics for the same type of study for
nanoparticles. The principles of pharmacokinetics
for drug molecules are generally applicable for
nanoparticles, and have been reported in many
studies.
However, as discussed before, ADME of
nanoparticles are very different from that of
drugs especially small molecules. Methods for
drug pharmacokinetics may need to be modified
to be used for nanoparticles. For example, some
nanoparticles have very long retention time in the
body, up to several years. This is very uncommon
for drugs. More importantly, most medical applications of nanoparticles need to understand the
distribution in particular tissues, in most cases, the
diseased ones such as the tumor. Toxicity study
also requires the knowledge of nanoparticles in
those crucial organs such as liver, heart, lungs,
and kidneys. Traditional PK modeling could not
provide sufficient information.
To serve the needs of nanoparticle studies,
physiologically based pharmacokinetics modeling
(PBPK) has been applied to nanoparticle PK stud-

ies. PBPK modeling has been widely and successfully applied for drug pharmacokinetics prediction,
as illustrated comprehensively in the review by
Nestorov (2003). These models separate a living
system into compartments based on physiological
information. Time-dependent concentrations of
drugs and metabolites in these compartments are
described by mathematical equations.
The PBPK models have just found application
for nanoparticle during the past several years.
Although only very limited works available
in the literature, they covered various aspects.
Nanoparticle formulations of the same composition or different composition were compared
in the same model. Models were based on data
from both animal models and human. Several
of administration routes were covered including
intravenous, inhalation, and intradermal injection.
Both whole body and region PBPK models
were reported.
Application of PBPK modeling on polymeric
nanoparticles is still at the beginning stage. A very
successful example among a few works in this area
is from Li and coworkers who developed a PBPK
model to simulate the effect of nanoparticle properties on their distribution in the rats (Figure 2). The
biodistribution profiles of PLGA nanoparticles
with various PEG content were mathematically
described by a PBPK model. The model simulated
the experimental results of tissue concentrationtime curves quite well. The model also provided
insights into the kinetics of nanoparticle in vivo
distribution and the influence of multiple properties. The correlation between nanoparticle properties and biodistribution parameters enabled the
relatively accurate prediction of biodistribution
for another nanoparticle formulation. This is the
first work using PBPK modeling to interpret the
effects of multiple nanoparticle properties on their
biodistribution. This illustrates the significance
of a PBPK modeling approach for the building of
nanoparticle property-distribution relationships in
vivo. The applications of this work are far-reaching
including, but not limited to, nanoparticle toxicity
assessment, rational carrier design for drug delivery and imaging, and data interpretation from in
vivo bioimaging/biomarker systems.
Figure 2. A. Schematic diagrams of the membrane-limited PBPK model. Arrows indicate the transportation
of nanoparticles. Triangles represent the intravenous administration. Abbreviation: GI, gastrointestinal
tract. B. Exemplarys imulation of experimental data using the membrane-limited model. (Reproduced
with permission; Li et al, 2012)
151

2.2 The Pharmacokinetics at

Organ and Sub-Organ Level
In traditional pharmacokinetics studies and PBPK
studies, most organs and tissues can be considered
as homogeneous in terms of nanoparticle transport
and distribution, without considering the kinetic
processes within the organs and tissues. However,
there are certain organs and tissues in which the
distribution of nanoparticles are not homogeneous
and there are particle transportation and relocation within the same organ or tissue. Lungs and
lymphatic systems are the most significant ones
in this meaning among others.
2.2.1 The Lungs

The kinetics of nanoparticles inhaled into the lungs
remained one the mostly studied topics, in most
cases for the toxicity (Kendall & Holgate, 2012).
The deposition, distribution, retention, and clearance of nanoparticles in the lungs have been in
extensive research and complicated computational
models have been developed to simulate these
processes. Computational modeling of kinetics
of inhaled particles is well developed. Such as
the free public software Multipath Model of
Particle Deposition, MPPD for particle deposition and clearance estimates in humans and rats.
The Human Respiratory Tract Model (HRTM)
of the International Commission of Radiological
Protection (ICRP) provides deposition data of
inhaled particles from 1 nm to 10 m of healthy
adult female and male human subjects, at different
breathing patterns and physiological activities.
The mechanisms, the pattern and the efficiency
of particle deposition in the respiratory tract largely
depend on the aerodynamic or thermodynamic
diameter of the inhaled particles. Nanoparticles
deposit with high efficiency in the entire respiratory tract due to diffusion. Most particles could
be cleared with 48 hours, but prolonged retention
of both micro- and nanoparticles in small airways
of humans were also reported (Wilkey et al.,
152
1980), the probability being inversely correlated

to particle size.
The major pathway for particle clearance from
conducting airways is by mucociliary transport.
The clearance rate depends on both the cilia and
the lung lining layer; faster in the central airways
and slower with increasing airway generation in
rodents. Kinetic studies using iridium nanoparticles showed that about 30% of the deposited
particles were cleared within the first 24 h after
aerosol inhalation. In some cases, a small portion
of nanoparticles could be also cleared from the
lymphatic system or enter the systemic blood
circulation.
2.2.2 Physiological and

Biological Barriers
There are also numerous philological barriers to
nanoparticle transportation, including blood walls,
blood brain barrier, and placental barrier (Pietroiusti, Campagnolo, & Fadeel, 2012). To distribution into other organs, nanoparticles need to pass
through these barriers. The capability for penetrating these biological barriers is mainly determined
by particle size and surface functionalization.
The BBB is a physical and physiological barrier
that regulates the passage of molecules from the
systemic circulation to the brain parenchyma. To
date, efforts to achieve polymeric nanoparticles
that can enter into the brain tissue have provided
promising results (Beduneau, Saulnier, & Benoit,
2007). Surface functionalization with a specific
ligand or cell penetrating peptides facilitates BBB
delivery (Newton, 2006). Biodegradable polymers
are preferred for nanoparticles targeting the brain
due to toxicity concern.
The placental barrier is of particular interest
in terms of protecting the developing fetus during
pregnancy. Only a few studies available in this
area and most of them use inorganic nanoparticles. In one study, it was found that fluorescent
polystyrene particles with a diameter of up to
240 nm were able to cross the placenta in an ex

vivo human placental perfusion model (Wick et

al., 2010). These studies show that under certain
circumstances, it is possible for nanomaterials to
penetrate this biological barrier. However, more
studies are needed for better understanding of the
mechanism, extent and consequences of maternofetal transfer of nanoparticles.
Another factor that influences nanoparticle
distribution into tissues from the blood compartment is the blood vessel endothelium. Endothelia
composing the blood vessels have been classified
as continuous, fenestrated, or discontinuous, depending on the morphological features of the endothelium (Gentile, Ferrari, & Decuzzi, 2008). The
fenestrated endothelium exists in glands, digestive
mucosa, and kidneys and has an octagonal symmetry with radial fibrils interweaving in a central
point forming fenestrae of approximately 60 nm.
Discontinuous endothelium is a characteristic of
the liver, spleen, and bone marrow with pores of
50-100 nm. Nanoparticles with different sizes
may selectively diffuse through blood vessel of
different tissues. For example, nanoparticles less
than 60 nm may have easier access into tissues
with fenestrated or discontinuous endothelium.
The higher permeability of tumor vessels has
been taken advantage of for drug delivery using
nanoparticles.
2.2.3 The Tumor

Of special interest is the nanoparticle pharmacokinetics in tumors, because much attention has
been paid to chemotherapy using nanoparticles
(Bhagat, Halligan, & Sofou, 2012). Nanoparticles
have been extensively used for treatment and diagnosis of tumors. Tumors are abnormal organs
and consist of unique physiological features which
may be taken advantage for targeting nanoparticles
into the tumor. Both passive and active targeting
approaches have been investigated. Nanoparticles
can be passively targeted to tumor tissues, taking advantage of their abnormal physiological
features. Tumors are generally divided into two
types for transportation and kinetics studies: avascular and vascular tumors. Avascular tumor has
no blood vessels and the transportation is mainly
by diffusion of particles driven by concentration
gradient. Vascular tumor has blood vessels and the
transportation is influenced by the blood supply.
Avascular model is relatively simple, and
commonly represented using in vitro cultured
3-D tumor cell cluster termed spheroids. Studies
have shown the penetration of nanoparticles into
avascular tumors depends on time, concentration,
particle properties, and tumor properties (Ma et
al., 2012). In general, longer time and higher
concentration lead to more penetration into tumors. Because diffusion depends on the size and
the porosity of the tumor, smaller particles could
penetrate deeper. Nanoparticles within the tumor
could be located in interstitial space, bound to the
cell membrane, or internalized into cells. Binding
and internalization into cells deplete nanoparticle
in the interstitial space and reduce the concentration gradient which drives the particle to penetrate
deeper. The tumor cell density, extracellular matrix
(ECM), and necrotic stage all affect nanoparticle
penetration.
Diffusional model has been applied to simulate
and predict the diffusion of nanoparticles into avascular tumors. Pun et al developed a computational
model to describe the penetration of nanoparticles
into tumor spheroid based on experimental data
(Goodman, Chen, Matveev, & Pun, 2008). The
model accounts for radially dependent changes in
tumor architecture, as represented by the volume
fraction of tissue accessible to nanoparticle diffusion. Parameters such as nanoparticle binding,
internalization rate constants, and accessible
volume fraction were determined experimentally.
Unknown parameters of nanoparticle binding
sites per cell in the spheroid and pore shape factor
were determined by fitting to experimental data.
The model could help to understand how particle
properties and tumor properties could influence
particle penetration into tumor.
153

For vascular tumors, the distribution is much

more complicated than avascular ones. The
transportation of nanoparticles could be driven
by particle extravasation, convection, hydraulic
pressure, and diffusion. Tumor blood vessels are
leaky, tortuous, and dilated, and their endothelial cells lining have aberrant morphology with
the basement membrane often being abnormal.
Their high vascular density, vascular leakiness,
and impaired lymphatic recovery lead to an enhanced permeability and retention (EPR) effect
for nanoparticles. At the same time, hydraulic
pressure inside tumor is reported to be higher due
to hindered lymphatic drainage, which may reduce
the diffusion of particles. Convection is another
factor that is not clearly understood in terms of
particle transport in tumors.
2.3 The Pharmacokinetics at

Cellular and Subcellular Level
The kinetics of nanoparticle transportation
within the living system is very complicated and
still poorly understood. The most basic process
nanoparticles experience within the body is interaction with various types of cells, including
epithelium, endothelium, tissue cells, and macrophages. The kinetics of the nanoparticle-cell
interaction (adhesion, endocytosis, intracellular
transport, and exocytosis) depends on the properties of both nanoparticles and individual cells
(Mailander & Landfester, 2009; Rivera-Gil, Clift,
Rutishauser, & Parak, 2012). There are multiple
pathways for nanoparticles entering the cells as
indicated in Figure 3, although the knowledge in
this area is expanding daily.
Figure 3. Model of endocytic mechanisms and intracellular transport. EE, early endosomes; MP, phagosomes or macropinosomes; MVB, multivesicular bodies/late endosomes; Lys; lysosomes; RE, recycling
endosomes. (Reproduced from with permission; Iversen, Skotland, & Sandvig, 2011)
154

2.3.1 Binding to the Cell Surface

Binding to cells is necessary for endocytosis of
nanoparticles into cells. The binding kinetics
to cells surface depends on the properties of
nanoparticles and the cells. In general, there are
specific and nonspecific binding. Specific binding
depends on certain receptors on the cells surface
while nonspecific binding is proportional to the
extracellular nanoparticle concentration. After
binding to the surface, nanoparticles could be
internalized into cells. Due to the importance of
this step, many studies have been done to control
the binding of nanoparticle to cell surface, and
the most common method is modify the particle
surface with targeting ligands which have high
affinity to specific receptor on certain types cells
(Holgado, Martin-Banderas, Alvarez-Fuentes,
Fernandez-Arevalo, & Arias, 2012). The strength
of interaction between the surface ligand and
membrane receptors can be controlled by various
parameters, including the type of ligand (i.e., affinity) and by changing the surface ligand density
(i.e., avidity) (Tassa et al., 2010).
Research has been done to use mathematical
modeling to predict the optimal design of nanoparticles for cell binding. A stochastic approach for
predicting the adhesion strength of nanoparticles
to a cell layer under flow has been coupled to a
mathematical model for the receptor-mediated
endocytosis of nanoparticles (Decuzzi & Ferrari,
2008). The study examined the main geometrical,
biophysical and biological parameters governing
both binding and endocytosis and analyzed their
relative importance. Based upon the geometrical
and biophysical properties of the particle and the
biological conditions at the site of adhesion, the
model predicted that there are three different situations for particle-cell interaction: no adhesion,
adhesion with no endocytosis, and adhesion with
endocytosis. Based on the model, nanoparticles
could be designed for better binding and entering cells.
2.3.2 Cellular Uptake

(Endocytosis) Kinetics
Nanoparticles can enter cells through either
endocytic dependent or endocytic-independent
(direct penetration) pathways. There are five
pathways reported in literature for nanoparticle
endocytic-dependent internalization by mammalian cells: phagocytosis, macropinocytosis,
clathrin-mediated, caveolin-mediated, and clathrin/caveolin-independent endocytosis (Mailander
& Landfester, 2009). Cellular uptake mechanisms
of nanoparticles are mainly influenced by their
hydrophobicity/hydrophilicity, surface charge,
surface functionalization, size and shape. Hydrophobic nanoparticles generally have short circulating half-lives and low bioavailability in vivo. The
hydrophobic surfaces are not physically stable and
do not remail well-dispersed in the bloodstream,
thus tending to agglomerate formation and are
therefore recognized by macrophages and removed
from circulation by the reticuloendothelial system.
Besides the surface properties, size and shape
are also shown to affect cellular uptake of nanoparticles. Many studies have indicated that size and
shape are crucial parameters in both specific and
non-specific cellular-uptake processes. Particles
larger than 500 nm could be recognized and
taken up by phagocytosis, whereas smaller ones
may escape from phagocytosis. Internalization of
larger particles by non-phagocytic cells is mainly
through macropinocytosis via hydrophobic and
electrostatic interactions. Direct cell penetration
could also happen for very small sized cationic
nanomaterials (such as metal nanoclusters and
dendrimers) by passing through cell membranes
without disrupting the integrity of the membrane
barrier.
Nanoparticle-cell interaction kinetics was
mostly studied using non-polymeric nanoparticles
due to their easy detection and stability. Based on
the results of pharmacokinetic models, the halflives of internalization for nanoparticles could
155

be from minutes to hours. Chithrani et al. studied

kinetics of both endocytosis and exocytosis using
gold nanoparticles with sizes from 14 to 74 nm
(Chithrani & Chan, 2007). They reported that
the internalization half-lives were from 1 to 3 h,
depending on the nanoparticle sizes and the cells
tested. The half-lives of removal of the internalized
gold nanoparticles were faster (from 0.33 to 0.75
h). Serda et al.99 studied the internalization of
silica nanoparticles by vascular endothelial cells
and reported the half-life to be 15.7 min.
Mathematical models were also applied to
simulate the endocytosis kinetics (Y. Li, Yue,
Yang, & Zhang, 2012). An N-varied dissipative
particle dynamics (DPD) simulation technique
is developed for endocytosis kinetics for ligandcoated nanoparticles with different shapes. The
results indicate that the rotation of nanoparticles
regulates the competition between ligand-receptor
binding and membrane deformation. There are
two stages of particle internalization including
membrane invagination and nanoparticle wrapping. The kinetics of the first wrapping stage is
mainly dominated by the part of nanoparticles
with the largest local mean curvature, at which
the membrane is most strongly bent. The study
showed that nanoparticles with various shapes
have different favorable orientations for these two
stages, and one or two orientation rearrangement
may be necessary for endocytosis.
lysosomes contain proteases and other enzymes

that degrade most biological substances.
Metabolism and biotransformation of nanoparticles may happen during all the dynamic processes
of nanoparticles cell interaction. Biotransformation of nanomaterials leads to continuous changes
of physicochemical properties and subsequently
alters their interaction with the biological environments.
After particle wrapping in the sorting endosomes, acidification occurs maintaining a slightly
acidic environment (pH 6.2-6.5) within the early
endosomes and a more strongly acidic environment in the late endosomes and in lysosomes (pH
4.5-5.5). This process is always accompanied by
recruitment of digestive enzymes into the vesicle
to digest the vesicular contents.
Polymeric nanoparticles are frequently surface
modified such as conjugated with targeting ligands
or other function groups. These ligands or function
groups may be cleaved off in early endosomes.
For biodegradable polymers, such as PLGA and
PLA, the hydrolytic degradation is accelerated
in the endosomal or lysosomal environment. The
metabolic products of PLGA are lactic acid and
glycolic acid, and those of PLA are lactic acid,
which can be incorporated into cell metabolic
pathways. The biodegradation rate is determined
by the particle size, composition and molecular
weight and ultrastructure of the shell polymer.
2.3.3 Intracellular Traffic and

Biotransformation Kinetics
2.3.4 Exocytosis Kinetics
Nanoparticles internalized into cells through the

formation of early endosomes (EE), phagosomes
or macropinosomes (MP). These vesicles with particles then mature down the degradative pathway
and become multivesicular bodies/late endosomes
(MVB) which fuse with lysosomes (Lys). Alternatively, the nanoparticles may be transported
back to the cell surface either directly from EE
or through the recycling endosomes (RE). The
156
Most of those studies about exocytosis of nanomaterials used inorganic particles, due to their
stability and easy detection. However, research on
polymeric nanoparticle exocytosis has increased
in the past several years due to high interests in
their biomedical applications. The physicochemical properties which regulate the exocytosis of
nanoparticles are still not clear, but appear to be
impacted by size, shape, surface functionalization
and cell type.

In general, exocytosis depends clearly on

particle size, surface properties, and geometry. In
general, nanoparticle exocytosis is much slower
than endocytosis. For particles of 20-50 nm,
the rate of endocytosis seems to be faster, and
the rate of exocytosis decreases with increasing
particle size . Chithrani and Chan reported that
the fraction of endocytosed nanoparticles varied
for different cell lines and that the percent of cellular nanoparticles being exocytosed within 1 h in
HeLa cells was approximately 35, 10 and 5% for
nanoparticles of 14, 50 and 74 nm, respectively.
One study showed that exocytosis of PLGA
nanoparticles occurred with about 65% of the
internalized fraction undergoing exocytosis in
30 minutes. Exocytosis of nanoparticles was
slower than the exocytosis of a fluid phase marker,
Lucifer yellow. Furthermore, the exocytosis of
nanoparticles was reduced after the treatment
of cells with the combination of sodium azide
and deoxyglucose, suggesting that exocytosis of
nanoparticles is an energy-dependent process (Panyam & Labhasetwar, 2003). It is also possible that
polymeric ones may be break down within cells,
and would not be exocytosed in the same form.
Mathematical models were also developed to
describe the kinetics of exocytosis of nanoparticles. Hong Jin and coworkers investigated
the endocytosis and exocytosis rates of lengthfractionated single-walled carbon nanotubes
(SWNT) (Tassa, et al., 2010). Interestingly, the
endocytosis rate constant of SWNT is found to be
nearly 1000 times that of Au nanoparticles but the
recycling (exocytosis) rate constants are similar
in magnitude for poly(d,l-lactide-co-glycolide),
SWNT, and Au nanoparticles across distinct cell
lines. They also develop a quantitative model
to correlate endocytosis rate with nanoparticle
geometry that accurately describes this data set
and also literature results for Au nanoparticles.
The model asserts that nanoparticles cluster on
the cell membrane to form a size sufficient to
generate a large enough enthalpic contribution
via receptor ligand interactions to overcome the
elastic energy and entropic barriers associated

with vesicle formation.
2.4 The Pharmacokinetics

at Molecular Level
2.4.1 Protein Binding
Once in the blood vessels, nanoparticles interact
with the proteins (termed opsonization). Protein
binding leads to the recognition of nanoparticles
by the immune cells and subsequently captured
and cleared from the circulation. The formation
of a protein corona could significantly alter the
nanoparticle surface properties, and subsequently
influence the uptake, biotransformation and biocompatibility of the particles. The composition
of the protein corona may vary over time due to
continuous protein association and dissociation as
well as local environmental changes. The composition of the protein corona also depends on particle
surface characteristics (primarily hydrophobicity
or charge), particle size, and composition.
Characterization of the protein binding kinetics
onto nanoparticle surface is important for understanding the fate of nanoparticles in the body.
Rates of protein binding to and dissociation from
nanoparticles are critical parameters determining
their interaction with receptors, and biological effects. A tightly associated protein that exchanges
slowly may follow the particle into intracellular
locations, whereas a protein with fast exchange
will be replaced by an intracellular protein during or after such transfer. The biological outcome
may also differ depending on the relative protein
exchange rates between nanoparticles and cellular
receptors.
Depending on the protein and particle properties, the association and dissociation rates
may vary significantly (Cedervall et al., 2007).
Proteinprotein complexes may have lifetime for
microseconds to weeks, while proteinligand
complexes may last microseconds to days. Studies using silica, polymer and TiO2 nanoparticles
157

Figure 4. Numerical simulation of the time evolution of the interaction between three human plasma
proteins and nanoparticles. The concentrations of NP (black-dotted), NP HSA (red), NP HDL (blue) and
NP Fib (green) as a function of time are shown. (Reproduced with permission; DellOrco et al., 2010)
showed the exchange of adsorbed proteins may

take 100 s to many hours (Cedervall et al., 2007).
The highest mobility proteins arrive first
and are later replaced by less motile proteins
that have a higher affinity for the surface, in a
process that may take several hours. DellOrco
et al. (2010) developed a mathematical model
to describe the kinetics of the corona formation
around a copolymer nanoparticle. Nanoparticle
interaction with three proteins were simulated:
high density lipoprotein (HDL) which has low
mobility by high affinity; human serum albumin
(HSA) which has high mobility by low affinity;
and fibrinogen (Fib) which has low mobility and
low affinity. The results indicated that the temporal
development of the corona strongly depends on
the association/dissociation rates of each protein.
The simulation showed that the time required to
reach equilibrium, which depends on the association/disassociation rates, is determined by size of
protein and particles. (see Figure 4)
By understanding the binding kinetics and
mechanisms of proteins on nanoparticles, scientist
may be able to control the binding kinetics for
particular purposes. Looking into the fundamental
influencing factors of nanoparticle-protein interactions, it also was demonstrated that increased
158
hydrophobicity favors blood protein binding. When

nanoparticles were more densely coated with
polyethylene glycol (PEG), less protein was bound.
Thus, surface modifications like PEG coating are
widely applied to prolong the circulating half-life
and to allow escape from phagocytosis. It has been
reported (Hoshino Y, Nakamoto M, Miura Y, 2012)
that temperature-responsive binding kinetics was
used to monitor the association/disassociation
rates of protein-nanoparticle binding, which may
be applied in targeting nanoparticles to certain
tissues by temperature control.
2.4.2 Ligand-Targeting
There is increasing interests in using Nanoparticles with surface-conjugated targeting ligands
for a variety of biomedical applications. The
main purpose of applying targeting ligands is
to enhance nanoparticle binding to the desired
tissues or organs, which express higher levels of
corresponding receptors. For example, Carlos
Tassa and coworkers (Tassa, et al., 2010) used
surface plasmon resonance (SPR) to directly
and quantitatively study the affinity and binding
kinetics of nanoparticles with small molecules
conjugated to their surface. They studied the

interaction between a single protein target and a

series of targeting ligands whose intrinsic affinity varies over a 4500-fold range and performed
SPR at protein densities that reflect endogenous
receptor densities. The results showed that even
weak small molecule targeting ligands can significantly enhance target-specific avidity through
multivalent interactions.
While ligand-receptor binding kinetics has
been under study for many years, the binding
kinetics could be different when the ligands were
conjugated on the particle surface, instead of being free ones. The interaction between conjugated
ligands and receptors on cells surface is still far
from well understood. Multiple factors contribute
to the complexity of the interaction, including the
chemical structures and density of ligands, the size
and shape of particles, and expression levels of
receptors, binding entropy, and others.
For example, nanoparticle size may affect
the ligand/antibody to nanoparticle ratio, surface
ligand conformation, ligand binding capacity,
surface curvature, and relative orientation of
ligands during nanoparticle membrane docking.
It is assumable that the spatial position of ligands
on the particle surface will is a major factor affecting binding with receptors on cells surface.
Ligands connected with chains to the particle
surface have flexibility and may be more effective in binding to receptors. One study showed
(Wang & Dormidontova, 2012) that the onset of
nanoparticle adsorption has a universal character
for a range of nanoparticles: the onset receptor
density decreases exponentially with the energy
of ligand-receptor binding and inversely with the
ligand density. The same study also showed that a
bimodal tether distribution, which permits shielding ligands by longer nonfunctional tethers, leads
to extra loss of entropy at the adsorption onset,
enhancing the selectivity.
While ligant-targeting is very promising, it is
not always effective in vivo due to much more complicated environments. Ligands may be cleaved
off and the targeting ability will be weakened.

Another possibility is that biological molecules
such as plasma proteins may bind to the ligands
or the particle surface and block the binding of
ligands to their receptors. For example, one study
has shown that transferrin-targeted nanoparticles
lose their targeting capabilities when a biomolecule corona adsorbs on the surface (Salvati A,
Pitek AS, Monopoli MP, Prapainop K, Bombelli
FB, et al., 2013).
3. CONCLUSION
Understanding the controlling pharmacokinetics
of polymeric nanoparticles will lead to improvements in biomecial applications such as drug
delivery and diagnosis, and lower toxicity. The
pharmacokinetics of polymeric nanoparticles
should be viewed at multiple levels for clear understanding, including whole body, organ, cell,
and molecule levels. The experimental findings
and computational models for understanding polymeric nanoparticle pharmacokinetics will have
significant impact in designation, optimization,
and administration of these particles for clinical
applications.
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Biodistribution: The determination of compounds of interest travel and retaining in organs
and tissues of an animal or human subject.
Computational Model: A mathematical

model that simulates the behavior of a complex
system based on knowledge of that system.
Ligand: A substance (usually a small molecule), that forms a complex with a biomolecule
to serve a biological purpose.
Nanoparticles: Solid particles that have at least
two dimensions within 100 nm. In broad meaning,
solid or semi-solid particulate materials with at
least two dimensions within 1000 nm.
Opsonization: The process by which nanoparticles are altered by opsonins so as to become
more readily and more efficiently engulfed by
phagocytes.
PBPK Modeling: Physiologically based pharmacokinetic (PBPK) modeling is a mathematical
modeling technique for predicting the absorption,
distribution, metabolism and excretion (ADME)
of substances animals or human beings.
Pharmacokinetics: The determination of the
fate of substances administered externally to a
living organism.
163
164
Chapter 8
Applications of Nanomaterials
in Construction Industry
Salim Barbhuiya
Curtin University of Technology, Australia
ABSTRACT
The application of nanomaterials in various applied fields has gained worldwide recognition. Nanomaterials
have the ability to manipulate the structure at nano-scale. This leads to the generation of tailored and
multifunctional composites with improved mechanical and durability performance. Recognizing this, the
construction industry recently has started to use a variety of nanomaterials. The use of these materials is
found to improve various fundamental characteristics of construction materials including the strength,
durability, and lightness. In this chapter an attempt is made to review the use of various nanomaterials
in cementitous system. This is followed by a discussion of the challenges related to their use. Finally, the
strategies for using nanomaterials in construction industry for the next ten years are identified.
INTRODUCTION
When the physicist and Nobel laureate Richard
Feynman presented, in late 1959 at the California
Institute of Technology, USA the lecture There is
plenty of Room at the Bottom (Feynman, 1960),
he outlined what today is known as Nanotechnology. He stated that when we have some
control of the arrangement of things on a small
scale we will get an enormously greater range of
possible properties that substances can have, and
of different things that we can do,. Years later,
the chemist and Nobel laureate Roald Hoffman, at
Cornell University, stated that: Nanotechnology
is the way of ingeniously controlling the buildDOI: 10.4018/978-1-4666-5824-0.ch008
ing of small and large structures, with intricate

properties. It is the way of the future, a way of
precise, controlled building, with incidentally,
environmentally benignness in by design. The
physics and chemistry of nanomaterials are fundamentally different from those of their micro-scale
counterparts. Dramatic changes and improvements
are brought about not only by size reduction, but
also by new properties only apparent at the nanoscale. In fact, nanotechnology has changed and
will continue to change our vision, expectations
and abilities to control the materials world.It is
for these reasons, nanotechnology has recently
become one of the hottest areas in Research and
Development worldwide, and attracted considerable attention in the media and as well as in the
investment community.

Applications of Nanomaterials in Construction Industry
The advances in productivity of the construction industry in the 20th century were slow, and
development of its technology lagged behind that
of other industry sectors. Nanotechnology is a
route to achieving real competitive and sustainable
growth and innovation within the construction
industry. This scientific approach is essential if the
potential for a new generation of materials which
are of both high performance and more economically viability is to be realised. Nanomaterials are
defined as those materials which have at least one
dimension (length, width or thickness) below
100 nanometer (1nm), 1nm being s thousand of
a micron, or about 100,000 times smaller than a
human hair.
One of the challenges in the field of construction
materials has been, and still is, the development
of concrete with improved durability. Concrete
is a complex multi-phase composite material.
The properties, behaviour and performance of
concrete are dependent on the nano-structure of
the cementitious matrix that glues together and
provides integrity. Therefore, the study of the
structure of the cement pastes and phenomena
in the nanoscale is crucial for the development
of new construction materials and applications
(Beaudoin, 1999). However, the common approach for the development of durable concrete
has mostly consisted of varying the macroscopic
parameters which are used to produce concrete.
i.e., basically working on the concrete mix design
and using different types of SCMs (Mehta, 2000;
Mehta & Manmohan, 2006; Concrete Centre,
2007). To a great extent, this approach, motivated
mostly by the inertia of the construction industry
itself, has slowed down the advance in the deep
understanding of construction materials. Within
the new paradigm of Nanoscience and Nanotechnology this can no longer continue. Construction
materials must be investigated within a scientific
approach if a new generation of materials that are
both of higher performance and more economically viable is to be created.
NANOMATERIALS IN
GENERAL APPLICATIONS
Nano particles are the cornerstones of Nano science and nanotechnology. Nano materials bridge
the range of micro and nano scales and their
presence enhances the mechanical properties of
the material. Over the years nanomaterials have
seen widespread acceptance and utilization in
various fields of science and technology. Owing
to its nano size, this technology has allowed us to
fabricate enormous products having advantages
over conventional ones; ranging from the materials
(nano-fuel cells, catalyst, lubricant, aeronautics,
automobiles, telecommunications, energy production, mechanics, biology, medicine etc.
Epoxy resins embedded with nanomaterials are
now being developed for better mechanical characteristics. Researchers are also trying to analyze
the changes in properties of epoxy-based coatings
filled with nanoparticles.Shi et al. (2009) added
nanoparticles of Zn, SiO2, Fe2O3 and halloysite clay
in a commercial epoxy resin and found enhanced
mechanical and chemical properties.In another
study Woo et al. (2008) investigated the residual
mechanical properties of epoxy organoclay composites after they were exposed to moisture and
UV light. Li et al. (2008) analyzed epoxy resin
containing various percentages of coiled carbon
nanotubes and single-walled carbon nanotubes.
The coating formulations were prepared by reacting diglycidyl ether of bisphenol-A (DGEBA) and
isophoronediamine. The coating was modified
with nanoalumina, silanizednanoalumina and
organo-modified montmorillonitenanoclay. It was
found that the Youngs modulus and hardness
increased considerably on addition of nanomaterials.The wear resistance of nanocomposite coating containing nano-TiO2 and other fillers were
studied by Chang et al. (2007). The authors found
that the addition of TiO2 reduces the coefficient
of friction but increased the wear resistance and
load bearing capacity.
165

Gold nanoparticles are used in numerous biomedical applications. A review article by Khan et
al. (2013) discusses the biomedical applications
of gold nanoparticles in drug delivery, imaging
and treatment of major life threatening diseases.
Iron oxide nanoparticles are also used in various
biomedical applications. Nano TiO2 is finding
applications in cosmetics, sunblock creams and
self-cleaning windows. A number of nanoparticles
are now being explored for developing dental
fillings and artificial bones.Various memory
chips are now being manufactured using nanoparticles. Silicon nanocrystal memory and nanowire
memory are used in devices with flash memory
applications. Nanomaterials are also used for
energy applications. Nanostuctured metal-oxide
thin films are receiving a growing attention for
the realization of gas sensors (NOx, CO, CO2,
CH4 and aromatic hydrocarbons) with enhanced
sensitivity and selectivity. Nanostructured MnO2
finds application for rechargeable batteries for
cars or consumer goods. Nanomaterials are also
explored for use in environment friendly energy
sources and emission control.
NANOMATERIALS IN
CEMENTITIOUS SYSTEMS
While talking about the use of nanomaterials in
a cementitious system, it is not always easy to
span the bridge between the modern advanced
technology and know-how that exist for the last
2000 years. From nanotechnology point of view,
cement itself is clearly a nanomaterial without
any modification. This is because it has a hierarchical structure ranging from sub-millimeter
dimension down to nanometer scale. Moreover,
it is also well established that most of its material
properties mainly depend on the microstructural
development below 100nm (Taylor, 1997). In
a cementitious system, it is expected that the
strength and durability properties should improve
if the overall porosity and capillary pore sizes in
166
cement paste are reduced or the diffusion of pore

solution and aggressive chemicals are hindered
by the incorporation of some additives having a
similar range of sizes. Nanomaterials have the
potential to reduce the pore size of cement paste
and, hence, improve the strength and durability
of the system. They have a high surface area to
volume ratio (Figure 1). Therefore, they have
the potential for tremendous chemical reactivity
within a cementitious system.
In cement matrix, most of the research works
to date was conducted on nano-silica (nano-SiO2)
(Bjornstromet et al., 2004; Ji, 2005; Jo et al., 2007;
Li et al., 2004,2006; Qing et al., 2007; Lin et al.,
2008; Sobolev et al., 2009; Qing et al., 2008) and
nano-titanium oxide (nano-TiO2) (Li et al., 2006;
Li et al., 2007). A few studies on the incorporation if nano-iron (nano-Fe2O3) (Li et al., 2004),
nano-alumina (nano-Al2O3) (Li et al., 2006) and
nano-clay particles (Khuo et al., 2006; Chang
et al., 2007) in cement matrix are also reported.
Research (Sobolevand Ferrada-Gutirrez,
2008; Li et al., 2004) showed that nano-SiO2
(Figure 2) improves the workability and strength
of concrete. They are also found to increase the
resistance to water penetration of concrete (Ji,
2005). Gaitero et al. (2008) have demonstrated that
use of nano-SiO2can help to control the leaching
of calcium leaching in concrete. It is also reported
that nano-SiO2 is more effective than microsilica
in enhancing the strength properties of concrete
(Jo et al., 2007; Qing et al., 2007). According to
Jo et al., (2007) particles of nano-SiO2not only act
as a filler material, but also they act as an activator to promote the pozzolanic reaction. Li (2004)
reported that significant increase in compressive
strength at early age can be obtained using nanoSiO2 in high volume fly ash concrete, which is
one of the drawbacks of this type of concrete.
However, in order to achieve good performance
and to use nano-SiO2in economical way, it is better to use nano-SiO2in a combination of fly ash
and microsilica.

Figure 1. Particle size and specific surface area related to concrete materials (Sobolev and FerradaGutirrez, 2005)
The addition of nano-Al2O3 was found to be

very effective to increase the elastic modulus of
mortar. With the addition of 5% nano-Al2O3having
size in the range of 150 nm, Li, et al., 2006 found
that there was an increase of 143% in the elastic
modulus. However, the authors reported that they
had a limited effect on the compressive strength.
Nano-Fe2O3 is reported to provide concrete the
self-sensing capacity (Li et al., 2004). Their inclusion also improves the compressive and flexural
strength of concrete. The sensing capabilities
of concrete are invaluable not only for real time
structural health monitoring, but also for the
construction of smart structures. This is simply
because they do not invoke the use of embedded
or attached sensors.
Nano-TiO2 has been identified as a potential
nanomaterial with wide range applications. This
is mainly because of its strong oxidizing capacity
under U-V radiation, chemical stability, chemical

inertness in absence of U-V light and absence of
toxicity. Studies (Jayapalam et al., 2009) have
shown that nano-TiO2 can accelerate early age
hydration of Portland cement. They are also found
to improve the compressive and flexural strengths
of concrete (Li et al., 2007). The authors alsofound
that the abrasion resistance of concrete containing
Nano-TiO2is better than that containing the same
amount of nano-SiO2. Nano-TiO2has proven to
be very effective to produce self-cleaning and
depolluting concrete (Murata et al., 1999; Vallee et al., 2004). Nano-TiO2based self-cleaning
concrete products are commercially available. Figure 3 shows the Church Dives in Misericordia,
Rome, Italy, which was built using self-cleaning
concrete. In Tokyo (Figure 4) several areas of
roads have been coated with nano-TiO2 in order
to reduce the pollution.
167

Figure 2. Spherical nano-SiO2 particles of uniform distribution observed using TEM
Figure 3. Church Dives in Misericordia, Rome, Italy
168

Figure 4. Use of nano-TiO2 on roadway for pollution reduction: left coating application; right finished
road showing a lighter colour
CARBON NANOTUBES/
NANOFIBRES IN
CEMENTITIOUS SYSTEMS
Carbon nanotubes/nanofibres (CNTs/CNFs) are
potential candidates for use as nano-reinforcements in cement-based materials. CNTs/CNFs
exhibit extraordinary strength with moduli of
elasticity on the order of TPa and tensile strength
in the range of GPa, andthey have unique electronic
and chemical properties (Ajayan, 1999; Thomson
et al., 1999; Srivastava et al., 2003). CNTs/CNFs,
thus, appear to be among the most promising
nanomaterials for enhancing the mechanical
properties of cement-based materials and their
resistance to crack propagation while providing
such novel properties as electromagnetic field
shielding and self-sensing (Makar et al., 2005;
Li et al., 2007). Single-wall CNTs (SWCNTs),
multi-wall CNTs (MWCNTs), and CNFs are
highly structured graphene ring-based materials
with very large aspect ratios (of 1000 or more)
(Xie, 2005) and very high surface areas. SWCNTs
are single graphene cylinders and MWCNTs are
multiple, concentric graphene cylinders coaxially
arranged around a hollow core. Unlike CNTs,
CNFs present numerous exposed edge planes
along the surface that constitute potential sites

for advantageous chemical or physical interaction.
While CNTs/CNFs have been extensively studied
in polymeric composites (Coleman et al., 2006;
Lau et al., 2006; Hammel et al., 2004), their use
in cement has, to date, remained limited. One
of the main challenges is the proper dispersion
of CNTs/CNFs into cement paste, partly due to
their high hydrophobicity and partly due to their
strong self-attraction. Incorporating the unique
mechanical properties of CNTs/CNFs in cement
composites has proven to be rather complex and to
date mixed results have been obtained. A number
of methods have been investigated to improve
dispersion and to activate the graphite surface in
order to enhance the interfacial interaction through
surface functionalization and coating, optimal
physical blending, and/or the use of surfactant
and other admixtures.
Researchers (Baoguo et al., 2009) have developed a self-sensing nanotechnology composite
material for traffic monitoring by using piezoresistive multi-walled carbon nanotubes (CNTs) as
an admixture. The authors studied the response
of the piezoresistive properties of this composite
to compressive stress and they investigated with
vehicular loading experiments the feasibility of
169

Figure 5. Illustration of self-sensing concrete pavement for traffic flow detection
using self-sensing CNT/cement composite for

traffic monitoring. The results indicate that there
are good corresponding relationships between
compressive stress and the electrical resistance of
the self-sensing CNT/cement composite (Figure
5). The self-sensing CNT/cement composite also
presented remarkable responses to vehicular loadings. These findings indicate that this self-sensing
nano-composite cement has great potential for
traffic monitoring use such as in vehicle detection,
weigh-in-motion measurement and vehicle speed
detection. An interesting aspect of this work is
that, from the eventual traffic applications point
of view, the pavement itself would become the
traffic detection, thus eliminating the need for
separate traffic flow detection sensors.
CHALLENGES RELATED TO THE

USE OF NANOMATERIALS
The primary challenge related to the use of
nanomaterials is to manufacture the nanomaterials itself. The second challenge is the heat of
hydration. Due to many folds increase in specific
170
surface areas the nanoparticles are very reactive

and results in enormous amount of heat of hydration. Special organic and inorganic additives are
needed to be developed to control the setting and
heat of hydration. For the nano-coatings, the properties of the coatings themselves need extensive
investigation. Durability of coatings under various
exposure conditions, abrasion resistance, friction
resistance, high temperature resistance, failure
modes and electrical characteristics need to be
proven by using exhaustive experiments.
Huge amount of expenditure is needed for the
equipment to study the behaviour of nanoparticles
and nano-additive in cement based materials.There
are issues concerning the potential toxicity of
nanomaterials as well. Investigationsshowed that
nanoparticles can cause symptoms like the onescaused by asbestos fibres. Grassian et al. (2007)
studied the effects relatedto the inhalation of TiO2
particles with a primary particle sizebetween
2 and 5 nm, reporting lung inflammation for a
concentrationof 8.8 mg/m3. These symptoms have
been confirmed by otherauthors (Yu et al., 2008;
Liu et al., 2008; Poland et al., 2008; Donaldson
& Poland, 2009; Pacurari & Castranova, 2010).

Hallock et al. (2008)recommend that the use

ofnanoparticles should be made with the same
care already used in Universities for materials
of unknown toxicity, i.e., by using airextraction
devices to prevent inhalation and gloves to prevent
dermalcontact. Singh et al. (2009) mentioned the
possibility of DNA damage resulting in later cancer
development. Some authors (Dhawan et al., 2009)
believe that the nanotoxicity risk depends on the
nanoparticlestype, concentration volume superficial characteristics. Others (Tyshenko & Krewski,
2008) suggest that several categories and new
parameters must beformulated to better analyze
this subject. Some questions that deserve further
investigation are presented elsewhere (Hirano,
2009; Walker & Bucher, 2009).BystrzejewskaPiotrowska et al., (2009)have recently carried out
an extended literature review on this subject. These
authors mentionedthat Environment Protection
Agency has considered that carbon nanotubes are a
new form of carbon that must be treatedunder the
toxic products Act. These authors also mentioned
that nanoparticles may be responsible for a new
kind of problem, the appearance of nano-wastes.
They suggest that products containing nanoparticles should be labelled in order to facilitate future
separation and recycling procedures.
STRATEGIES FOR USING

NANOMATERIALS FOR
THE NEXT TEN YEARS
The filed encompassed by the term nanomaterials has changed dramatically over the past 10
years. While it was useful, 10 years ago, to describe
nanomaterials on the sole basis of our ability to
understand and to control matter at the nanoscale
where material properties possess a distinct sizedependence, the filed has now grown well beyond
that earlier definition. For example, it is evident
now that additional factors beyond constituent
nanoparticles are also playing major roles. The
past decade has seen an evolution in scientific

understanding and capabilities, from working with
isolated nanoparticles, nanotubes and nanowires
to working with hybrid nano-composites whose
particles are controlled not only by the constituentnanomaterials, but also by their morphology,
spatial anisotropy and relative proximity with
respect to one other and the host matrix.
Over the next ten years, nanoscience researchers will focus on a range of issues to improve the
performance, multi-functionality, integration and
sustainability of nanomaterials in a variety of
emerging and converging technologies. In particular, methods are required for nanomaterials and
nano-systems by design; scaling up high-quality
and mono-disperse nanomaterial production;
for rapidly measuring and characterizing quality
and reproducibility of manufacturing processes
incorporating nanomaterials and for manufacturing nanostructures into bulk materials, coatings
and devices while retaining enhanced nanoscale
properties. Through controlled assembly of
nano-constituents that have distinct properties,
the next generation nano-composite materials
are expected to have the unique and powerful
attribute of independent tunability of previously
coupled properties. For example, bulk materials
with high electrical conductivity typically possess high thermal conductivity, whereas these
properties have the potential of being decoupled
in next-generation nano composites. This specific
example has broad implications for thermoelectric devises that convert waste heat into useful
electricity. Similarly, the decoupling of electrical
conductivity and optical reflectivity would enable
a new class of transparent conductors that could
serve as the basis of improved photovoltaic and
display technologies. Ultimately, the rational assembly of nanomaterials into nano-composites
will yield high-performance materials with new
combinations of properties, thusunderpinning
the development of previously unrealizable applications.
171

CONCLUSION
Nanotechnology application in construction
industry is still a very small, fragmented pursuit and unknown outside the scientific circle.
Nanoparticles are not cost-efficient materials,
and this prevents their commercial applications
in a near future. However, some nano-based
materials & products are now used or ready to
be adopted by the industry, and many others are
coming to the market. Photo catalytic applications
of nanomaterials are already a reality, still more
research efforts are needed in order to find other
semiconductors apart from TiO2 and conductors
that can be activated with visible light. Huge
potential has been predicted for nanotechnology
application in construction. This is because even
minor improvements in materials and process
could bring large accumulated benefits. However,
further research is also needed in the field of
nanotoxicity, be there as it may, extreme caution
must be used when using nanoparticles. While
nano-engineering of cement-based materials is
seen as having tremendous potential, nonetheless,
several challenges will need to be solved to realize
its full potential, including the proper dispersion
of the nanoscale additives, scale-up of laboratory
results and implementation on larger scale, and a
lowering of the cost benefit ratio.
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KEY TERMS AND DEFINTIONS

Carbon Nanofibre: Cylindric nanostructures
with graphene layers arranged as stacked cones,
cups or plates.
Carbon Nanotubes: Allotropes of carbon
with a cylindrical nanostructure.
Nano-Fe2O3: Oxide Particles typically 20-40
nanometers with specific surface area in the 3050 m2/g range.
Nanomaterials: Describe in principle materials the single units of which is sized in at least
one dimension between 1 and 1000 nanometers
(109 meter).
Nano-SiO2: Single particles of silica dioxide,
an inorganic metal oxide, with a diameter less
than 100 nm.
Nano-TiO2: Spherical or faceted high surface
area oxide magnetic nanostructure particles, typically 20-80 nanometers with specific surface area
in the 10-50 m2/g range.
Pozzolanic Reaction: Chemical reaction that
occurs in Portland cement containing pozzolans.
175
176
Chapter 9
Silicon NanostructuresGraphene Nanocomposites:

Efficient Materials for Energy
Conversion and Storage
Chaitanya Krishna Kamaja
National Chemical Laboratory (CSIR), India
M. Rajaperumal
Rabah Boukherroub
Universit Lille 1, France
Manjusha V. Shelke
ABSTRACT
Global demand of energy is increasing at an alarming rate, and nanotechnology is being looked at as
a potential solution to meet this challenge (Holtren, 2007). Although the efficiency of energy conversion and storage devices depends on a variety of factors, the overall performance strongly relies on the
structure and properties of the component materials (Whitesides, 2007). Compared to conventional
materials, silicon (Si) nanostructures and graphene nanosheets possess unique properties (i.e. morphological, electrical, optical, and mechanical) useful for enhancing the energy-conversion and storage performances. Graphene can enhance efficiency of nano-Si based solar cells and battery due to its
high electronic conductivity, ultrahigh mobility, high transparency, and strong mechanical property.
This chapter provides a comprehensive review of recent progress and material challenges in energy
conversion (solar cells) and storage (batteries/supercapacitors) with specific focus on composites of Si
nanostructures-graphene nanosheets.
DOI: 10.4018/978-1-4666-5824-0.ch009

Silicon Nanostructures-Graphene Nanocomposites
INTRODUCTION
The increasing energy demand due to increase in
population, industrial activity, etc. led to decrease
in fossil fuel. According to US energy information
administration (EIA), for the year 2011, energy
consumed for electricity generation from fossil
fuel is about 87% and 13% from renewable energy
(Figure 1) [http://www.eia.gov/electricity].
Among renewable energy sources, solar energy is the most important because the amount
of energy that reaches the earth surface in one
hour is about 18TW, and the global consumption
of energy per year is about 15TW (Kalyanasundaram, 2012). Solar energy has to be converted
to different convenient forms of energy and the
conversion efficiency is the measure of practicality of this energy source. Materials and devices to
convert solar light energy into electrical energy

efficiently are the immediate concerns. Most of
the conventional solar cells in the market are based
on Si p-n junction diodes and their efficiency
had reached 25% (Green, 2009). Advantages of
Si are high abundance (second most abundant
element in the earth crust), non toxic, and long
term stability. But the main disadvantage of Si is
that the process of making ultrapure crystalline Si
is very costly, but also it is an indirect band gap
semiconductor, so for absorbance of sunlight a
very thick layer of Si is required. To reduce the
cost of the solar cell, researchers started to evaluate
heterojunctions of Si. Among the heterojunctions,
Schottky diode holds advantage over p-n junction diode. In Schottky diode the thickness of Si
layer can be decreased, that eventually decreases
the cost of the device. The condition for Schott-
Figure 1. The percentage of electrical energy generation from different resources (Source: U.S. Energy
Information Administration, Annual Energy Outlook 2013 Early Release, December 5, 2012)
177

kydiode is that the semiconductor should have

moderate doping (high doping results in electron
flows from semiconductor to metal and forms
ohmic contact). When metal and semiconductor
brought too close to each other, electrons flow
from the conduction band of the semiconductor
to metal until thermal equilibrium is reached i.e.
the Fermi level becomes the same for both metal
and semiconductor. This forms a depletion region
with the absence of electrons at the junction, and
results in barrier for further electron transition at
the junction (Lutz, 2011). The Schottky barrier
height (SBH) is given by:
b = M
where b = Schottky barrier height, M = metal
work function and = electron affinity of the
semiconductor. The built in potential separates
the electron hole pair by the incident light photon.
The net current density (j) in the solar cell is
given by:
j = jlight jdark
j =jsc jo e
qV / nk B T
1
where jsc = short circuit current density, n=

diode ideality factor, V = voltage across the diode,
q = elementary charge, kB = Boltzmanns constant,
T = absolute temperature and jo = reverse current, corresponding to thermal generation of
carriers, which can be expressed as:
(qb / kBT )
jo = Aeff A**T 2e
The efficiency of the solar cell depends mainly

on the series resistance and shunt resistance. The
series resistance includes the contact resistance
between the metal and top electrode, the contact
178
resistance between Si and bottom electrode and

the bulk resistance of both Si and metal. For better
efficiency, the solar cell should have low series
resistance and high shunt resistance.
In the conventional Schottkydiode a thick
metal layer is required, which results in absorbing most of the radiation and thus limits the
efficiency of the cell. In order to increase the
absorbance of the semiconductor a thin layer of
indium doped tin oxide (ITO) is used. However
due to less abundance and high cost of indium,
it became less usable (Ye, 2012). So, in order to
decrease the cost of device, new materials have
to be developed in such a way to replace indium.
Si and graphene form Schottky junction. In this
chapter, we will discuss the strategies reported to
increase the efficiency of Si-graphene Schottky
junction solar cell.
As solar energy source is climate dependent,
effective energy storage systems are also essential. The electrochemical energy storage systems
are one of the clean, green, economically valuable methods. In this respect, electrochemical
supercapacitors (ECs), batteries and fuel cells
are considered as important key components
of modern electronic devices/tools. These three
electrochemical devices critically depend on the
electrochemistry at the electrode material and
electrode/electrolyte interface. For real applications, the performance of these electrochemical
devices are evaluated in terms of energy and power
density. Figure 2 shows the comparative performance of these devices with combustion engine.
Moreover, energy and power density of ECs and
batteries covered a large area in the Ragones plot,
which clearly states their significant technological
importance (Yu, 2013; Padbury, 2011).
Supercapacitors are electrochemical devices
that can provide high power for a short time period. The typical energy density is 5 Whkg-1 and
power density is 5-10kWkg-1(Miller, 2008). The
power density of a supercapacitor is two orders of
magnitude higher than the current Li ion battery.

Figure 2. Ragones plot comparison of various electrochemical devices and (a) internal combustion
engine, (b) schematic diagram of Li ion battery, and (c) supercapacitor
The energy storage mechanism of a supercapacitor is near surface charge storage. Therefore,
only slight structural change is observed in the
active materials during cycling. Hence, the life
time of a supercapacitor may exceed more than
50,000 cycles and better heat management could
be achieved. Based on the storage mechanism,
supercapacitors can be classified into two types.
One is double layer capacitor (EDLC) that can
store the energy in the form of non faradic reaction and the other is pseudo capacitor which stores
the energy in the form of faradic reaction. Based
on the device fabrication, supercapacitors can be
further classified as symmetric supercapacitors,
wherein both electrodes store the energy in same
mechanism, or as asymmetric supercapacitors
where one electrode can store the energy in form
of EDLC and the other electrode is used to store
faradic energy.
In contrast to supercapacitors, batteries are high

energy density devices, which utilize almost all
active material present in the electrode. Hence,
large structural changes are observed during the
cycling, as a result the power density and cycle
life of batteries are lower than those of supercapacitors. Among many batteries, Li Ion Battery
(LIB) has been successfully commercialized and
extensively used in portable electronics due to
their high energy, power density, rate capability
and better cycle life.
BACKGROUND
Since the discovery of graphene in 2004, it became
the hot topic in current research because of its
wide applications in different fields (Novoselov,
2004; Guo, 2011; Luo, 2012). A graphene is a
179

two dimensional hexagonal crystal of carbon atoms with high transparency, approximately zero
band gap, low sheet resistance, high mechanical
strength, flexibility and highly stable. Because of
its high transparency, it can be used as electrode
in photoelectric devices and it can also separate
electron-hole pair at the junction. It is mostly
synthesized by CVD (Kim,. 2009) or solution
process methods and transferred to the Si surface
(Hernandez, 2008).
In the year 2007, carbon nanotubes (CNT)Si heterojunction concept was first introduced
in solar cells (Wei, J. 2007). Later on, the same
group modified the device structure and compared
the efficiencies of multi-walled carbon nanotubes
(MWCNT) and double-walled carbon nanotubes
(DWCNT) (Jia, 2008). There are two main disadvantages of CNT-Si heterojunction: first they
form both Schottky and p-n junctions because
CNT exist as both metallic and semiconducting
nanotubes, and second the conductivity of CNT
is low because of the space between the bundles

of CNT network.
Graphene has advantages over CNT because of
its high surface coverage over Si surface (100%),
the conductivity of the film is high because it consists of multiple layers of Graphene Sheets (GS)
which are overlapped and interconnected; it also
acts as an antireflective layer. In 2010,grapheneSiheterojunction concept was used for solar cell
application (Li, X. 2010). GS were coated on
patterned n-Si/SiO2 substrate with a Si window,
the front and back contacts were made by sputtering of Au on SiO2 and Ti/Pd/Ag on n-Si. The
band structure and schematic representation of
the device are shown in figure 3a, b. Si absorbs
light and the photo generated holes and electrons
are separated by built in potential, the holes move
to the graphene and electrons diffuse to the Si
surface. Two cells are demonstrated with an area
of 0.1 and 0.5 cm2 with efficiencies of 1.65 and
1.34%, respectively.
Figure 3. a) The band structure of graphene with n-Si, b) Schematic representation of the device. Bottom
left inset shows that at the junction holes and electrons are separated, and bottom right inset displays an
optical image of the device (Reproduced from Li, Zhu, Wang, Cao, Wei, Li et al., 2010 with permission
from WILEY-VCH Verlag GmbH & Co. Weinheim)
180

In case of materials for energy storage, currently graphite is used as anode material in commercial lithium ion batteries and has quite low
capacity of 372mAhg-1, which is insufficient to
satisfy certain high energy requirements (Dimov,
2007). Si is considered as one of the most promising substitutes for graphite; it has a capacity of
4200 mAhg-1 due to Li22Si5 alloy formation and
relatively low working voltage (0.5 V vs Li/Li+)
(Kasavajjula, 2007). In order to improve the cycle
life of Si-based anode, many strategies have been
proposed. The most attractive strategy is to reduce
the host size and form a Si-carbon nanocomposite.
It has been reported that Si nanowires (SiNWs)
and nanotubes possess better capacity retention
over many hundredth of cycles (Chan, 2008; Park,
2009; Cui, 2009; Wu, 2012). Although, this kind
of morphology has better cycle life, it requires
quite expensive synthetic methods which limit
their practical utility. At the same time, the energy density of grapheme based supercapacitors
showed to be enhanced up to 85Wh/kg, which is
comparable to that of nickel metal hydride batteries
(Liu, C. 2011).This enhancement is attributed to
the unique morphology of curved graphene sheets,
which maintain their high surface area even after
reduction thereby reducing the restacking tendency
of graphene sheets. Graphene enhances Li storage
capacity of Si nanostructures when grapheme is
used as conducting agent (Wang, X. L. 2010).In
this chapter, we will review the recent progress
in the cost effective synthesis of various Si and
graphene composites for energy production and
storage. Even though fuel cells will fall into the
energy production area, this will be out of the
scope for this composite material. So only solar
cells, photoelectrochemical water splitting, batteries and supercapacitors are discussed throughout
this chapter.
MAIN FOCUS OF THE CHAPTER

1. Graphene-Si Nanocomposites
for Energy Conversion
An untreated Si solar cell only absorbs 67.4%
of sunlight shone upon it, meaning that nearly
one-third of that sunlight is reflected away and
thus unharvestable. From an economical and
efficiency perspective, this unharvested light is
wasted potential and a major barrier hampering
the proliferation and widespread adoption of solar
power. In conventional solar cells, anti-reflective
coatings are used to trap the light and to increase
the efficiency. To further address this problem,
researchers started to use patterned Si pillar arrays
(SPA). The advantage of SPA is that they provide
more surface area for light harvesting and also act
as an anti-reflective coating. The highest reported
efficiency for only Si nanostructures is 18.2%(Oh,
J. 2012).The other factor that can enhance the efficiency of Schottky junction solar cell is coating
with p-type graphene. The p-doping increases
the work function of graphene, which results in
enhanced conductivity of GS and increases the
built in voltage of graphene-Si junction. However,
the performance of Si/graphene composite is low
because of the high density of defects present at the
interface of Si and graphene hetero junction, which
increases the electron-hole recombination rate,
leading to a decrease of the solar cell efficiency.
So far, various approaches have been developed
to increase the work function of GS by p-doping.
AuCl3 acts as p-type dopant for most of organic
semiconductors because it takes electrons from the
semiconductor and forms Au particles, so it can be
used for p-doping of graphene. The efficiency of
AuCl3 doped graphene with Si heterojunction is
about 0.08% (Shi, 2010). When graphene is doped
with thionyl chloride (SOCl2) vapor and the device
181

is made with SiNWs, the efficiency increased

up to 2.86% (Fan, 2011). Doping graphene with
HNO3 vapor for integration in solar cell device
with both Si and n-Si SPA raised efficiencies to
3.55% and 4.35%, respectively (Feng, 2011,2012).
It was found that after doping, the series resistance of solar cell decreases from 6.11 to 4.07
cm-2. It was concluded that with the increase of
doping time the efficiency and fill factor of solar
cell increase to certain limit and then decrease.
Indeed, prolonged doping causes degradation of
GS, built up the series resistance of the solar cell
and oxidation of the Si surface. In order to have
better understanding of the device performance,
theoretical and experimental studies on the effect
of doping on graphene and the number of graphene
layers that influence the efficiency of G-Si solar
cell have been carried out (Lin, 2013). From the
simulation results, it was proposed that a maximum
conversion efficiency of 9.2% can be achieved.
Figure 4a suggests that increasing the number
of grapheme layers decreases the transmittance
linearly; this indicates that the graphene will
harvest the sunlight and the amount of sunlight
absorbed by the Si decreases, which will decrease
the performance of the solar cell. Figure 4b shows

that the sheet resistance of graphene decreases
with increasing the number of graphene layers.
So for a good solar cell efficiency, the number of
graphene layers has to be optimized in such a way
that it should have low series resistance and high
optical transmittance. Finally experiments showed
that the G-Si solar cell with 2-3 layers of graphene
and HNO3 doping achieves efficiency of 7.72%.
Ihm et al. studied how the open circuit voltage of
the device changes with the number of graphene
layers (Ihm, K. 2010).Li et al. synthesized borondoped graphene (BG) and made a device with
n-Si to achieve an efficiency of 2.3%. To further
improve the device performance, they doped BG
with HNO3 vapor and achieved 3.4% efficiency (Li,
X. 2012). Recently, an efficiency of graphene/n-Si
solar cell of 8.6% was reported by doping graphene with bis-(trifluorometanesulfonyl)amide
(TFSA). As seen in Figure5, the Jsc, Voc, FF and
all increased from 14.2 to 25.3mA/cm2, 0.43 to
0.54V, 0.32 to 0.63, and 1.9 to 8.6%, respectively
and the series resistance decreased from 14.9 to
10.3 cm-2 upon doping (Miao, 2012).
Figure 4. Theoretical calculation dependence of the number of grapheme layers with a) transmittance,
b) sheet resistance (Reproduced from Lin, Li, Xie, Feng, Chen, Song et al., 2013 with permission from
182

Figure 5. a) The J-V characteristics of pristine and bis-(trifluorometanesulfonyl)amide (TFSA) doped

graphene under AM1.5 illumination at 100mW/cm2, b) the sheet resistance values of pristine and TFSA
doped graphene(Reproduced from Miao, Tongay, Petterson, Berke, Rinzler, Appleton, & Hebard, 2012
with permission from American Chemical Society)
In the future, nanoscale power devices will play

a vital role in nano-electronics. Xie et al. (2012)
prepared a solar cell with grapheme and multiple
SiNWs and achieved an efficiency of 1.47%.
Although Si can be effectively used for photoelectrical conversion, the real problem arises when
Si is applied for the conversion of solar energy
to chemical energy, because it forms an insulator layer by oxidation in the electrolyte solution.
Hence, the protection of Si surface is essential.
Generally, noble metals, wide gap semiconductors
and polymers are employed as protective layers.
The high cost of noble metals, low conductivity
of wide band gap metal oxides and low stability
of polymers restrict the practical application for
photo-electrochemical water splitting.
Graphene alone cannot generate hydrogen
because its work function lies below the reduction potential of water. However when it forms
a heterojunction with p-Si, the electrons from
Si flow to the graphene and the Fermi level of
graphene moves upwards in such a way that it
generates hydrogen. In 2010 Hongtao et al. inves-
tigated macroporous Si/graphene composite for

photo-electrochemical water splitting (Hongtao,
2010). The nanocomposite was produced through
electrodeposition of graphene on macroporous
Si substrate and the photoelectrochemical measurements were performed in 0.05M H2SO4. The
onset potential of pristine macroporous Si was
-0.24V, which is shifted to 0.3V for macroporous
Si/graphene composite. These results indicate
that using the composite material the graphene
Fermi level shifted upper wards for easier hydrogen evolution. Wu et al. (2011) studied pristine
Si/graphene composite for hydrogen evolution
and found that without annealing the composite
material, the photocurrent density was low. This
has been attributed to weak adhesion between
graphene and Si, which is responsible for Si oxidation due to electrolyte diffusion. Huang et al.
synthesized SiNWs by using Ag assisted chemical etching and grapheme by two steps, first they
synthesized grapheme oxide (GO) by Hummers
method, followed by the reduction of GO in hydrazine. The obtained graphene was dispersed in
183

Figure 6. a) Schematic representation of SiNWs and grapheme heterojunction device for photoelectrochemical water splitting, b) photo electrochemical behaviour of SiNWs and SiNWs/graphene composite.
(Reproduced from Huang, Zhong, Wang, Zhang, & Zhang, 2013 with permission from American Chemical Society)
ethanol and spin coated on SiNWs and the photo

electrochemical measurements were performed
in aqueous H2SO4 containing K2SO4 (pH=1.8).
Figure 6a shows the schematic representation of
the device for hydrogen generation. From figure
6b, it was found that both SiNWs and SiNWs/
graphene exhibited larger light current when
compared to the dark current. The photo current
density was 4 times greater than pristine SiNWs
alone and 600 times larger than SiNWs/graphene
composite compared to planar Si/graphene composite at -0.05V.The open circuit potential of
SiNWs/graphene composite was shifted positively
by 20mV in comparison to that of SiNWs. The
enhanced photo current density was due to fast
electron transfer from Si to graphene and from
graphene to electrolyte (Huang, 2013).
In order to decrease the number of recombination sites and thus enhance the efficiency of the
solar cell, surface passivation of Si is required. For
example, a thin layer of SiO2, formed by keeping
the Si wafer in air for 2 h, enhances the device
performance due to oxygen passivation of dangling
bonds on the Si surface. The preparation of SPA
and SiNWs from Si wafer introduces roughness
184
on the Si surface, while acting as recombination

sites. Nearly 15% efficiency is reported for planar
Si-CNT hetero-junction solar cell by using TiO2
as an antireflection coating (Shi, E. 2012). Conclusively, the efficiency of planar Si-graphene
solar cell can be increased by using the concept
of antireflective coating. Even after doping, the
sheet resistance of grapheme remains quite high.
In order to decrease the sheet resistance, new
dopants have to be employed. To optimize the
number of GS layers, layer by layer removal of
grapheme can be used (Dimiev, 2011). Finally, the
device fabrication should be improved in order to
expand the device area.
2. Graphene-Si Nanocomposites
for Energy Storage
The successful commercialization of Si-based
energy storage devices is handicapped because
Si anodes experience large volume change upon
battery operation, leading to pulverization of electrode materials and fast capacity fading. Cheaper
synthesis techniques need to be developed for Si
nanostructured anodes.

As mentioned earlier in the text, the capacity

fading in Si based Li-ion battery can be surpassed
by the use of Si nanostructures, which can tolerate
the strain induced during the use of Li ion batteries due to the better mechanical properties of the
nanostructures. The electronic conductivity and
mechanical stability can be further enhanced by
preparing graphene composites. In this section,
first we will discuss varieties of nanostructured
Si and graphene or tailored graphene composites for Li-ion battery followed by discussion on
nanostructured Si as electrode for supercapacitor
applications.
2.1 Si Nanostructures and Graphene

Composites for Li-Ion Battery
2.1.1 Si Nanoparticles (Si NPs) and Graphene
Composite in Powder Form
For the practical application of Si-based anode,
it remains a key challenge to achieve favorable
structure beneficial to both high capacity and
long-term cyclability. To alleviate these problems,
Zhou et al. (2012) prepared silicon nanoparticles/
graphene composite using a simple and straightforward method combining freeze-drying and
thermal reduction. The Si NPs intercalated into
the graphene sheets form a typical hierarchical
micro-nanostructure in which graphene plays the
roles of both electronically conducting network
and an elastic buffer for the silicon nanoparticles.
Figure 7aillustrates the synthesis process of Si NPs
inserted into graphene sheets. Figure 7b shows
the X-ray diffraction (XRD) patterns of Si NPs
inserted into thermally reduced grapheme composite, Si NPs and thermally reduced graphene
(TRG). The XRD pattern of the composite is
similar to that of pure Si NPs, indicating that the
Si nanocrystals are not destroyed during the high
temperature heating process. The XRD pattern of
TRG displays a characteristic peak at 2 = 26.4,
corresponding to d-spacing of 0.338 nm, close to
the d-spacing of graphite (ca. 0.335 nm). This peak
is absent in the XRD pattern of the composite,

suggesting that the Si NPs are nicely dispersed
within the micrometer graphene sheets. These
results are corroborated by transmission electron
microscopy (TEM) analysis (figure 7d), revealing
micrometer sized aggregates made of Si NPs and
graphenesheets. HRTEM analysis shows a single
Si crystal intercalated between graphene sheets
(figure 7e).The electrochemical performance
of the Si NPs inserted in graphene and pristine
Si NPs was investigated through cyclic voltammetry and discharge/charge profiles (figure 7c).
This composite material showed initial discharge
capacity of 3060mAhg-1with a reversible charge
capacity up to 1866 mAhg-1. After 100cycles,
the reversible capacity dropped to 1153 mAhg-1
at a current density of 200 mAg-1, which is more
than 3 times than that of the theoretical specific
capacity of currently used graphite anode (LiC6,
372 mAhg-1), while that of pristine Si NPs is as
low as 13 mAhg-1. The composite displayed also
an improved rate capability with stable and reversible capacities of 1304, 1014, and 803 mAhg-1 at
current densities of 1000, 2000 and 4000 mAg-1.
The capacity is calculated based on the total
composite weight.
Reassembled graphene-platelets encapsulated
Si NPs, prepared in large scale, have been evaluated as an anode material for lithium ion battery
(Yoon, T., 2011). The incorporation of SiNPs into
graphene platelets was performed by using simple
solution dispersion method. Robust electrical integrity provided by the flexible graphene sheets
led to improved electrochemical performance. This
electrode exhibited reversible lithiation capacity
of 802 mAhg-1 with excellent capacity retention
up to 30 cycles.
2.1.2 Si NPs/SiNWs-Graphene Composites
as Free Standing Flexible Film
A free standing Si nanoparticles-graphene composite flexible film was prepared by simple filtration technique and used as anode material without
185

Figure 7. Schematic illustration of the synthesis of Si NPs inserted into graphene (a), XRD patterns of
Si NPs inserted into thermally reduced graphene composite and their pristine constituents (b), Anode
performance of Si NPs/graphene composite and pristine Si NPs versus lithium (c), TEM images of the
composite at low magnification (d), and high magnification (e) (Reproduced from Zhou, Yin, Wan, &
Guo, 2012 with permission from Royal Society of Chemistry)
current collector. Interestingly, the absence of

current collector reduces the total weight of batteries. Hence, the performance of the full device
significantly increased. Recently, many research
groups reported flexible film anode materials.
Graphene oxide (GO) sheets were first prepared
from natural graphite and then mixed with commercial Si powder followed by vacuum filtration
to obtain flexible film. Then thermal reduction
was performed at different temperatures to yield
the final anode material. The anode film prepared
from reduced GO and Si NPs showed discharge
capacity of 708 mAhg-1 after hundred cycles at a
current density of 50 mAg-1 (Wang, 2010). The
anode film thermally reduced at 700C showed
186
charge capacity of 1500 mAhg-1 after 300 cycles

in the case of constant current-constant voltage
(CCCV) cycling mode (Lee, 2010). However, the
powder form of the same composite exhibited
quite low capacity in the constant current mode.
Similar free standing film anodes prepared by
thermal reduction at 700C displayed discharge
capacity of 768 mAhg-1after 300 cycles at a current density of 50 mAg-1 (Tao, H. C., 2011).Very
recently, SiNWs-graphene composite prepared
by the same simple filtration technique was used
as anode film (Chockla, 2012). The authors attributed the better capacity at very high current
to graphene present in the composite rather than
only SiNWs. SiNWs-graphene film anode was pre-

pared by simple filtration of SiNWs and grapheme

oxide, followed by heat treatment at 600C.The
SiNWs-rGO electrode delivered a significantly
higher specific capacity of about 3350 mAhg-1 at
840 mAg1 and retained relatively same capacity
up to 20 cycles (Wang, 2013).
2.1.3 Electrostatic Self-Assembly of Si NPs/
SiNWs and Grapheme Sheets
Electrostatic self-assembly of nanoparticles provides intimate contact between oppositely charged
nanoparticles. Figure 8 shows the schematic portray of electrostatic self-assembly of Si NPs on
graphene sheets. GO sheets are negatively charged
due to the presence of many oxygen containing
functional groups. The presence of native oxide
on the Si surface provides a negative charge for Si
NPs. Positively charged Si NPs are prepared via
functionalization with poly (diallyldimethylammomium chloride) (PDDA).After functionaliza-
tion with PDDA, the Si NPs surface charge changed

from original negative (zeta potential = 33 mV)
to positive (zeta potential = + 41 mV).Positively
charged Si-PDDA nanoparticles assemble with
negatively charged GO sheets by electrostatic
attraction. Subsequently, the aqueous dispersion
was freeze-dried and thermally reduced, followed
by HF treatment to produce graphene encapsulated
Si nanoparticles composite (Zhou, 2012). This
new synthetic strategy of graphene encapsulated
Si nanoparticles composite is supported by TEM
analysis (figure 8a,b), revealing the small size Si
NPs completely encapsulated within micrometer
size graphene sheets. HRTEM image clearly
shows a single Si NP completely encapsulated
by graphene sheets (figure 7c). Survey spectra
of Auger electron spectroscopy (AES) analysis
of single Si NPs graphene composite shows that
absence corresponding signal for silicon suggest-
Figure 8. Schematic diagram of the formation of Si nanoparticles encapsulated in graphene sheets and
TEM images of the resulting composite (Reproduced from Zhou, Yin, Wan, & Guo, 2012 with permission
from WILEY-VCH Verlag GmbH & Co. Weinheim).
187

ing that Si NP was completely encapsulated by

graphene sheet.
This nanocomposite material exhibits initial
discharge capacity of 2920 mAhg-1 with a reversible capacity of 1720 mAhg-1. The reversible
capacity of the nanocomposite is maintained as
high as 1205 mAhg-1 even after 150 cycles at a
current density of 100 mAhg-1, which is more
than 3.2 times higher than that of the theoretical
specific capacity of commercial graphite anode.
A similar approach, based on self-assembly of
positively charged Si NPs and negatively charged
GO, was applied for the preparation of SiNWs and
graphene composite (Zhu, Y., 2012). Here, the
positive charge on the SiNWs was acquired through
chemical functionalization with (3-aminopropyl)triethoxysilane (APTES). Electrostatic interaction
between NH2-SiNWs and GO leads to their self
assembly. Subsequent heat treatment reduces GO
to graphene in the composite. As synthesized
SiNWs/graphene composite showed a discharge
capacity of 2142 mAhg-1 initially and after 80
cycles the capacity was still maintained above
1000 mAhg-1.
anchoring of Si nanoparticles onto the surface

of graphene sheets via phenyl linkers. This was
achieved by successively diazotizing two amines
of p-phenylenediamine, and the in situ generated
aryl radicals grafted spontaneously to the graphene
sheets and Si nanoparticles. The resulting SiPhG
nanocomposite exhibited delithiation capacity of
1079 and 828 mAhg1 in the initial and 50th cycle
at a current density of 300 mAg1.This graphene/
SiNPs composite showed better performance
because Si was well connected with the conductive matrix. Carbon coated Si on graphene was
recently prepared (Evanoff, 2011). First, a few
layers of graphene was synthesized from natural
graphite and uniformly coated with Si via SiH4
decomposition at 500C followed by coating with
a thin amorphous carbon by thermal decomposition of propane. Carbon coating was deposited to
reduce Si oxidation and improve anode stability.
High reversible discharge capacity of 2300 mAhg1
was obtained for this composite at a low current
density of 140mAg-1. This reversible capacity is
six times greater than the commercial graphite.
2.1.4 Direct Attachment of Si Nanostructures

onto Graphene
Effective 3D conductive network was built by the

combination of graphene, carbon nanoparticles
and SiNPs to achieve better performance anode
material (Zhou, 2012).The capacity fading of
graphene, carbon and Si nanoparticles tertiary
composite is lower than any binary composite
of graphene and Si or carbon nanoparticles. This
might be the result of effective 3D conductivity
and low aggregation in the tertiary composite.
3D porous architecture of SiNPs/grapheme was
prepared by thermal reduction of SiO2 coated GO
by magnesium (Xin, 2012). This 3D porous SiNPs/
grapheme nanocomposite maintained reversible
capacity of ~900 mAhg1at charge rates up to
1000 mAhg1whereasthe Si/graphene composite
delivered a capacity below 100mAhg1at a 1000
mAg1 charge rate.
Recently, SiNWs are synthesized in situ on graphene sheets (Lu, Z., 2012). Graphene prepared
from GO, was decorated with gold nanoparticles
and used for catalytic growth of SiNWs. Thermal
decomposition of diphenysilane in hexane was
utilized for simultaneous growth of SiNWs and
reduction of GO to graphene. The first insertion
of lithium gave a discharge capacity of 3506
mAhg1 and a subsequent charge capacity of
2009 mAhg1. Acoulombic efficiency of about
57.3% was obtained at the rate of 0.1C in the
first cycle. Similarly, Si nanoparticles were attached onto functionalized graphene by covalent
functionalization (Yang, S., 2012). In this study,
a novel nanocomposite was fabricated by covalent
188
2.1.5 3D Si NPs/Grapheme Nanocomposite

2.1.6 Tailored Graphene and Si NPs/SiNWs

Composite
2.1.7 Si NPs/Graphene Composite Prepared

by Mechanical Blending
Plane vacancy present on the graphene/Si NPs

composite shows excellent rate capability. The
plane vacancy present in the graphene allows
lithium ion transport throughout the structure
thereby reducing the diffusion length as confirmed
by impedance spectroscopy. Electrochemical impedance spectroscopy is one of the better-known
techniques used to quantify the solution and charge
transfer resistance of electrode materials. The
charge transfer resistance and Warburg coefficient
of plane defective graphene/Si NPs composite
was lower than their counterpart of non plane
vacant graphene (Zhao, 2011).Thin film of this
plane defective graphene/Si NPs composite was
subjected to the anode performance evaluation.
It displayed better performance, suggesting that
the defective graphene still has better conductivity and mechanical stability. The solid electrolyte
interface can be controlled by forming crumpled
graphene-Si NPs composite (Luo, 2012). The
coulombic efficiency of this crumpled grapheneSi NPs composite reached up to 95% during the
second cycle and 99% after the fifth cycle. The
coulombic efficiency of the electrode with only
Si particles reached up to 95% at the tenth cycle,
but the capacity was completely lost after the
twentieth cycle. Recently, nitrogen doped graphitic
layer, prepared by thermal CVD of CH4/H2/NH3,
was coated as shell on vertically aligned SiNWs
synthesized by Ag metal assisted chemical etching
(Cho, 2012).It was found that by increasing the
thickness of the nitrogen doped graphitic layer on
SiNWs, high charge capacity of 1260mAhg1could
be achieved as compared to undoped graphitic
layer where it is initially 2100 mAhg1and further
drops to 1040mAhg1after 45 cycles. This reveals
that doping of graphitic layers on SiNWs can be
effective for lithium ion battery performance,
which eventually increases the charge storage
capacity and cycle life of a battery.
Xiang et al. reported that Si NPs (50 nm)-graphene

(prepared from thermal expandable graphite)
composite gave better performance than graphene prepared by chemical method (Xiang, H.,
2011). Pristine Si NPs anodes showed highest
charge capacity of 3170 mAhg1 in the first cycle.
However, it drops to 434 mAhg1 after 30 cycles.
Even though Si NPs-graphene composites have
lower capacity than the pristine Si NPs, the cycle
life was improved significantly. In this study all
of the Si NPs and chemically derived graphene
composites have reversible capacity less than
2000mAhg1. SiNPs and thermally expanded
graphene composites display initial reversible
capacity of about 2753mAhg1. They retained
83% of the initial capacity after 30cycles. The
entire cycling test was performed at 300mAg1.
This was attributed to the low density of defects
of graphene obtained from thermal expandable
graphite, which enhances the conductivity of the
composite therefore exhibits better performance.
Chou et al. prepared graphene-Si NPs composite
by mechanical mixing of graphene prepared by
solvo thermal method and Si NPs (40nm) (Chou,
2010).They demonstrated that the composite
had a discharge capacity of about 2158 mAhg1.
After 30 cycles, the charge capacity dropped to
1168mAhg1.
2.1.8 SiNPs/Grapheme Electrode as a BinderFree Anode
Ethanol suspension of Si NPs-graphene oxide
was spin coated on copper foil; subsequent heat
treatment at 700C yields the binder-free anode.
The resulting composite displays initial discharge
capacity of 2813mAhg1at a current density of
1A/g(ref. 68:Zhou, X. 2012).After 200cycles it
retains a capacity of 1611mAhg1 and also exhibits
better rate performance at various current densities. Another group developed a new synthetic
189

route for Si/graphene composite film on Cu foil

using simple electrophoretic deposition of grapheme sheets followed by RF sputtering of Si (Zhang,
Y. Q., 2012).The anode film showed capacity of
2204mAhg1, and after 150 cycles it retained a
capacity of about 87.7% of initial capacity.
2.2 Si-Based Supercapacitors

Although considerable research is dedicated for
designing micro-supercapacitors with electrode
materials like carbon and metal oxides, their integration in microelectronics is still a challenge.
Si plays ubiquitous role in electronic and microelectronic devices, and supercapacitors based on
Si can facilitate its integration in microelectronic
devices. In this regard, SiNWs are subjected to
Li-battery cycles to generate porous SiNWs as
excellent supercapacitor electrodes at high power
operations (Choi, J. W. 2010). The porous SiNWs
based supercapacitor device displayedenergy and
power densities of ~20 Wh/kg and ~22 kW/kg,
respectively. The symmetrical electrochemical
capacitor based on porous Si (PS) electrodes was
demonstrated to giving the highest series capacitance of 320 F/cm2(Desplobain, S. 2007). In this
study, surface electrical conductivity of PS was
increased by metallization with gold. Chemical
vapor deposition (CVD) grown SiNWs-based
electrodes display a promising cycling stability
in an organic electrolyte and a quasi-ideal pure
capacitive behavior (Thissandier, 2012). The same
research group investigated the influence of SiNWs length on symmetrical micro-ultracapacitor
devices (Thissandier, 2013). They demonstrated
that the capacitance increases with the length of
the SiNWs electrode and has been improved up
to 10 Fcm2 by using 20 mSiNWs, i.e.10-fold
bulk Si capacitance. This device exhibits promising galvanostatic charge/discharge cycling stability with a maximum power density of 1.4 mW
cm2.Sihollow nanostructures are recently used as
electrode material for supercapacitors (Liu, M.P.,
2012). Nanostructured Si hollow spheres with a
190
thin shell have been synthesized by magnesium

reduction of silica spheres. The electrode showed
maximum specific capacitance of 193 F g1 in the
neutral Na2SO4 aqueous solution at a scanning
rate of 5 mV s1, comparable to carbon capacitors. Alternatively, SiNWs coated with NiO (Lu,
2011; Tao, 2010), or SiC (Alper, 2012) have been
studied as potential materials for supercapacitor
electrodes, but so far no research work has been
demonstrated with Si and graphene composite
supercapacitor electrode.

As we know that solar energy plays a vital role
for the sustainability of the world. In order to
increase the solar cell efficiency, new materials
have to be developed and among them graphene
plays an important role. Because of its optical
properties and highly conducting nature, it can be
used as transparent electrodes in solar cell and will
replace other electrodes due to its low cost and ecofriendly. Entirely different optical and electronic
properties of graphene and Si provided interesting
platforms for exploring structure-activity relations of Si/grapheme nanocomposites. Surface
modifications of these materials to incorporate
organic linkers with fast charge transfer rates or
strategies to couple with plasmons can enhance
photocurrent generation in these composites.
In the future, graphene/Si composites might
replace the graphite anode thereby electric vehicle
dream may be possible. Graphene/Si composites
for lithium ion batteries are still in the infant
stage so more active research is required in this
area. New strategies and synthetic routes to develop graphene-Si based multilayer structures
can provide several advantages for Li-ion battery
electrode. Chemically modified graphene-Si
nanocomposites can be synthesized to tailor the
end application of the specific composite. Also
more detailed studies are expected using molecular
dynamic simulations for better understanding.

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Energy Density: Total energy available from
per unit weight of the system.
Open Circuit Voltage: Maximum voltage at
zero current in the solar cell.
Power Density: Total energy available per unit
time from per unit weight of the system. It refers
to the rate of energy transfer.
Schottky Diode: Metal/semiconductor heterojunction diode.
Short Circuit Current: Current at zero voltage in the solar cell.
195
196
Chapter 10
Metal Oxide-Graphene
Nanocomposites:
Synthesis to Applications
Ponchami Sharma
CSIR-North East Institute of Science and
Technology, Jorhat, India
Ashvini B. Deshmukh
CSIR-National Chemical Laboratory, India
Najrul Hussain
Manjusha V. Shelke
CSIR-National Chemical Laboratory, India
Manash R. Das
Sabine Szunerits
Institut de Recherche Interdisciplinaire
Rabah Boukherroub
Institut de Recherche Interdisciplinaire
ABSTRACT
Graphene is one of the most interesting materials in the field of nanoscience and nanotechnology. Metal
oxide nanoparticles exhibit unique physical and chemical properties due to their reduced size and high
density of corner or edge surface sites. The metal oxide-graphene nanocomposites not only possess
favorable properties of graphene and metal oxide, but also greatly enhance the intrinsic properties due
to the synergistic effect between them. These composites are used for catalysis, supercapacitors, lithium
ion batteries, solar cells, sensors, removal of pollutants from water, etc. There is a very broad scope of
further research for the development of metal oxide-graphene nanocomposites with enhanced properties for different applications. This chapter deals with a comprehensive review of the current research
activities from the viewpoint of chemistry and materials science with a special focus on the synthesis,
characterization, and applications of metal oxide-graphene nanocomposite materials.
DOI: 10.4018/978-1-4666-5824-0.ch010

Metal Oxide-Graphene Nanocomposites
INTRODUCTION
In the recent years, graphene the mother of all
the graphitic materials has drawn the attraction
of researchers worldwide (Geim & Novoselov,
2007). Graphene is a single layer of carbon atoms
closely packed into honeycomb two dimensional
(2D) lattice with a carbon-carbon distance of
0.142 nm. The sp2 hybridized carbon network
as well as its high electron mobility at room
temperature (250,000 cm2/Vs), exceptional thermal conductivity (5000 W m-1K-1) and superior
mechanical properties with Youngs modulus of
1 TPa make it the material of choice for a wide
range of applications in the field of materials
science, physics, chemistry and nanotechnology
(Novoselov, Geim, Morozov, Jiang, Katsnelson,
Grigorieva, et al., 2005; Li, Wang, Zang, Lee, &
Dai, 2008; Stankovich, Dikin, Dommett, Kohlhaas, Zimney, Stach, et al., 2006; Schedin, Geim,
Morozov, Hill, Blake, Katsnelson, et al., 2007;
Singh, Singh, Nayak, Kumari, Grcio & Dash,
2011). Two dimensional, atom-thick graphene can
be considered as the ideal substrate for the synthesis of hybrid composites with three-dimensional
(3D) architectures with unique chemical, physical and structural properties (Zhao, Song, Song,
Yin, Wu, Zhou, et al., 2010). The fabrication of
metal and metal oxide-graphene/graphene oxide
(GO) nanocomposites has drawn special interest
in this regard. The presence of metal and metal
oxide nanoparticles (NPs) on reduced graphene
oxide (rGO) sheets prevents the restacking of
the individual graphene sheets which arises due
to strong Van der Waals interactions between
the sheets (Zhao et al., 2012). Metal oxide NPs
exhibit unique physical and chemical properties
upon a decrease of their particle size and structural
geometry. The decrease of the particle size has
a direct influence on the band gap of the oxide
particles and is reflected on their conductivity
and chemical reactivity. However, these properties are greatly affected by the aggregation of the
NPs. Therefore, prevention of such aggregation

is necessary when synthesizing metal oxide NPs.
Graphene or GO nanosheets can effectively stabilize such NPs to prevent their aggregation, and
the properties of the NPs could be enhanced by
anchoring them onto the graphene sheets (Bai &
Shen, 2012). Therefore, current research trends
are focused on the preparation and application of
metal oxide-graphene nanocomposites. A number
of research activities have been carried out in
this area in recent years. This chapter consists of
a comprehensive review of current research activities in the synthesis and applications of metal
oxide-graphene nanocomposites.
BACKGROUND
Recently, many efforts have been focused on the
preparation of metal oxide-graphene nanocomposites using different strategies such as precipitation
from a mixed solution, hydrothermal/solvothermal
method, microwave-assisted synthesis, photoassisted synthesis, sol-gel method, atomic layer
deposition, electrostatic interaction, layer-bylayer self- assembly, covalent interaction, etc.
(Yao, Miao, Liu, Ma, Sun & Wang, 2012; Yang,
Zhang, Ma, Huang, Wang & Chen, 2009; Zhang,
Dwivedi, Chi, & Wu, 2010; Chandra, Park, Chun,
Lee, Huwang, & Kim, 2010; Ji, Wu, Shen, Zhou
& Xi, 2011; Seo, Lee, Kim & Kim, 2013; Wu,
Feng, Wang, & Wan, 2013; Xu, Wang, Zhu,
Yang & Lu, 2008; Zhu, Zeng, Nie, Xu, Chen,
Han, et al., 2010; Zhang, Chen, Zhang, Huang,
Chen. Yang, et al., 2010; Wu, Shen, Jiang, Wang
& Chen, 2010; Chang, Lee, Hu, Chang, Liu &
Yang, 2010; Wu, Ren, Wen, Gao, Zhao, Chen, et
al., 2010; Zhang, Lei, Yin, Chen, Li, Wang, et al.,
2010; Zou, Zhu, Sun & Wang, 2011; Wu, Wang,
Wang, Ren, Zhao, Zhou, et al., 2010; Zhou, Zhu,
Yang, Jiang & Li, 2011; Zhou, Zhu, Yang, &
Li, 2011; Liu, Pan, Zhao, Liu, Zhu, Chen, et al.,
2012; Li, Zhang, Wang, Han, Liu, Zheng, et al.,
197

2010; Ng, Iwase, Bell, Kudo & Amal, 2011; Hu,

Zhao, Zhou, Gogotsi & Qiu, 2011; Zhang, Li,
Cui & Lin 2010; Yan, Fan, Wei, Qian, Zhang &
Wei, 2010; Chen & Wang, 2010; Meng, Geng,
Liu, Li & Sun, 2011; Alles, Aarik, Aidla, Fay,
Kozlova, Nilisk, et al., 2011; Yang, Feng, Ivanovici
& Mullen, 2010; He, Fan, Ma, Zhang, Leung &
Chan, 2010; Bai & Shen 2012; Li, Cao, Shao, Li,
Qu & Yin, 2011; Li, Wang, Liu, Liu, Ou & Yang
2011; Ren, Huang, Fan & Liu, 2011; Sreeprasad,
Shihabudheen, Maliyekkal, Lisha & Pradeep,
2011; Zhou, Zhu, Cheng, Liu, Yang, Cong, et al.,
2011; Nethravathi, Rajamathi, Ravishankar, Basit
& Felser, 2010; Liu, Meng, Hu, Geng, Banis, Cai,
et al., 2013; Wu, Zhou, Yin, Ren, Li & Cheng,
2012; Xue, Chen, Yu, Wang, Yardeni, Dai, et al.,
2011). Each of these techniques possesses some
unique characteristics, which lead to the formation
of functional metal oxide-graphene nanocomposites. In this chapter, different synthesis processes
commonly applied for the production of metal
oxide-graphene nanocomposites are described
in detail. The resulting metal oxide-graphene
nanocomposites have found a wide number of
applications in various fields such as Li-ion battery, supercapacitors, photovoltaic cell, water
purification, biomedicine, etc. which are also
discussed in this chapter.
Preparation of Metal OxideGraphene Nanocomposites

A number of procedures are available for the synthesis of metal oxide-graphene nanocomposites.
Broadly, they can be classified into two categories:
in situ and ex situ methods. The in situ process
involves the formation of nanomaterials in the
presence of pristine or functionalized graphene or
GO nanosheets, while the ex situ approach involves
prior synthesis of nanomaterials in the desired
dimensions and morphology, and subsequently
connected to the surface of pristine or functionalized graphene or GO nanosheets.
198
In Situ Process
The in situ process is the most commonly used
strategy for the synthesis of metal oxide-graphene
nanocomposites. This process has the advantage
of avoiding the use of protecting surfactants or
extra linker molecules, which may imply a tedious experimental procedure and may also affect
the properties of the nanocomposites. Another
advantage of this process is that a variety of
chemical and physical synthesis techniques can
be used, including solution chemistry methods,
direct decomposition of precursors, hydrothermal/
solvothermal techniques, gas-phase deposition,
solgel processing, template method, and so on.
Precipitation of Metal OxideGraphene Nanocomposites

from a Mixed Solution
A variety of metal oxide-GO nanocomposites have
been synthesized by precipitating the mixed solution of metal salts and GO, followed by subsequent
reduction to metal oxide-graphene nanocomposites. The general procedure for the synthesis of
metal oxide-graphene nanocomposites can be
schematically represented as in Figure 1.
Synthesis of Fe3O4-graphene nanocomposites
by precipitation of Fe3+/Fe2+ ions and GO in an
alkaline solution followed by reduction with
hydrazine hydrate is reported in a number of
studies (Yao et al., 2012; Yang et al., 2009; Chandra et al., 2010). Independently, CuO-graphene
nanocomposites were obtained by addition of
CuSO4.5H2O, NH4OH, and NaOH to an aqueous
solution of dispersed graphene nanosheets followed by hydrazine reduction (Seo et al., 2013).
Similarly NiO/graphene nanocomposites were
also synthesized using nickel chloride and graphite
oxide as starting materials and hydrazine hydrate
as a reducing agent in a basic pH range (Ji et al.,
2011). However, the use of hydrazine hydrate as
reducing agent is often not preferred due to its
toxicity. Ethylene glycol was thus investigated

Figure 1. Schematic representation of the synthesis of metal oxide-graphene oxide/graphene nanocomposites by the precipitation approach
as an alternative reducing agent for the synthesis

of Fe3O4-graphene nanocomposites with FeCl3 as
iron source (Wu et al., 2013). Typically, FeCl3 was
mixed with GO followed by addition of sodium
acetate. The mixture was autoclaved at 200 C
for 8 h to yield Fe3O4-graphene nanocomposites.
Co3O4-graphene (Xu et al., 2008), CuO-graphene
(Zhu et al., 2010), SnO2-graphene (Zhang, Jiang,
Yan, Wang, Wang, Song, et al., 2010), and RuO2graphene (Wu et al., 2010b) nanocomposites were
synthesized using a similar approach. A two step
strategy for the synthesis of metal oxide-graphene
nanocomposites was reported by Chang, Lee,
Hu, Chang, Liu & Yang (2010). It is based on
precipitating hydroxides onto GO nanosheets
followed by microwave-assisted hydrothermal/
solvothermal annealing (Chang, 2010) to produce
a number of unitary and binary metal oxides
(Mn3O4, TiO2, SnO2, NiCo2O4, Zn2SnO4)-graphene
nanocomposites.
Teo, Kim, Huang, Chia & Harrison (2012)
described a green and energy efficient method for
the synthesis of Fe3O4-graphene nanocomposites
based on the redox reaction between Fe2+ ions and
GO nanosheets at room temperature in basic medium. The pH of the GO suspension was adjusted
to 11-12 using 25% NH4OH solution followed by
a slow addition of FeSO4 as iron precursor under
magnetic stirring. The resulting Fe3O4-graphene
nanocomposite was collected by centrifugation
and washed with water to remove excess of ammonia. The probable reaction mechanism for the
formation of metal oxide-graphene nanocomposites in alkaline medium can be described as follows.
Mx+ + xOH- M(OH)x
M(OH)x + xOH- M2Ox + xH2O + xeGO + xe- Graphene

The formation of Fe3O4-graphene nanocomposite was confirmed by SEM-EDX analysis.
The SEM image of GO nanosheets displayed a
smooth surface with a distinctive layered appearance (Figure 2a), while that of Fe3O4 nanoparticles
showed agglomeration of the particles (Figure
2b). The SEM image of Fe3O4-graphene nanocomposite showed uniform distribution of the
nanoparticles over the graphene surface (Figure
2c). The elemental mapping of C, O, and Fe using
energy dispersive X-ray (EDX) analysis clearly
indicated the presence of Fe in the nanocomposite
(Figure 2d).
Zhao et al. (2012) investigated the synthesis
of CuO-graphene nanocomposites by such redox
reaction in alkaline solution. The CuO-graphene
nanocomposites were characterized by XRD,
FTIR, Raman spectroscopy, TGA, SEM and TEM
analysis. The structural features of CuO-graphene
nanocomposites were thoroughly identified using
Raman spectroscopy (Figure 3). Graphite oxide
exhibits two characteristic peaks at about 1581 cm-1
(G band), corresponding to an E2g mode of graphite,
related to the vibration of the sp2-bonded carbon
atoms in a two-dimensional hexagonal lattice, and
at about 1333 cm-1 (D band) related to the defects
and disorder in the hexagonal graphitic layers.
The G band peak was blue shifted to 1594 cm-1
after formation of CuO-graphene nanocomposite
which may be due to a decrease of the number
of layers in the solid state. In addition to the Gand D-bands, three extra weak peaks at 281, 342
and 612 cm-1 corresponding to one Ag and two
199

Figure 2. SEM images of (a) graphene nanosheets, (b) Fe3O4 nanoparticles, (c) Fe3O4-graphene nanocomposites, (d) EDX of Fe3O4-graphene nanocomposite. ( 2012 Elsevier Ltd. Reprinted with permission
from Teo, Lim, Huang, Chia, & Harrison, 2012)
Figure 3. Raman spectra of (a) GO, (b) CuO-graphene nanocomposite ( 2012 The Royal Society of
Chemistry. Reprinted with permission from Zhao, Song, Song, & Yin, 2012)
200

Bg modes of CuO were observed in the Raman

spectrum of the CuO-graphene nanocomposite.
The Raman ID/IG ratio was increased from 1.14
for GO to 1.24 for CuO-graphene nanocomposite,
indicating that more defects have been introduced
into the CuO-graphene nanocomposite. At the
same time, the change of D/G intensity ratio for
CuO-graphene nanocomposite as compared with
GO nanosheets suggests partial reduction of the
GO nanosheets.
The thermal stability of the CuO-graphene
nanocomposite was further investigated by using TGA. Figure 4 displays the thermal behavior
of the CuO-graphene nanocomposite, GO and
graphene, respectively. The TGA curve of the
CuO-graphene nanocomposite shows 3% weight
loss from 50 to 150 C, which is due to the loss
of water or some organic solvent. Increasing the
temperature resulted in 10% weight loss around
200 C and 20% weight loss around 450 C, at-
tributed to the decomposition of residual oxygencontaining functional groups and carbon skeleton
from graphene, respectively. As can be seen, the
weight loss of the CuO-graphene nanocomposite
in the removal of residual oxygen functional group
process is much lower than that of GO (29.5 wt%),
which indicates the oxygen-containing functional
groups are largely eliminated during the reduction process. Compared to GO and graphene,
which show a complete decomposition of carbon
at about 650 C, full carbon decomposition of
CuO-graphene nanocomposite occurred at a lower
temperature (450 C), indicating that the thermal
stability of graphene was decreased after forming
a composite with CuO nanoparticles.
The morphology of the resulting nanocomposite was investigated using TEM and SEM.
Figure 5a and b display TEM and SEM images
of rGO (prepared by chemical reduction of GO
with hydrazine) sheet, respectively. It can be seen
Figure 4. TGA curves of (a) CuO-graphene nanocomposite, (b) GO nanosheets, (c) reduced GO nanosheets
(prepared by hydrazine reduction of GO) in air (2012 The Royal Society of Chemistry. Reprinted with
permission from Zhao, Song, Song, and Yin, 2012)
201

Figure 5. TEM (a) and SEM (b) images of graphene nanosheets; TEM (c) and SEM (d) images CuOgraphene nanocomposite (2012 The Royal Society of Chemistry. Reprinted with permission from Zhao,
Song, Song, & Yin, 2012)
that the rGO sheet exhibits a typical rippled and

crumpled morphology and paper-like structure
with single or very thin layers. TEM and SEM
analysis of CuO/rGO nanocomposite show that
the CuO nanoparticles are homogeneously distributed on the rGO surface without any apparent
aggregation. The inset in Figure 5c corresponds to
a high magnification image of CuO/rGO, in which
spindle-like CuO nanoplates (30 nm in diameter
and 60 nm in average length) are visible.
SolGel Method
The solgel process is a cheap and low-temperature
technique, which undergoes a series of hydrolysis
and polycondensation reactions and its use for the
synthesis of metal oxide-graphene nanocomposites
202
is widely adopted. However, the product obtained

by this method consists typically of an amorphous
phase rather than defined crystals and therefore
it requires crystallization and post-annealing
steps. Wu et al. (2010b) applied this method for
the synthesis of RuO2-graphene nanocomposites.
Zhang et al. (2010c) synthesized in this manner
TiO2graphene nanocomposites using tetrabutyl
titanate and GO nanosheets as starting materials.
They first dispersed GO nanosheets in ethanol by
ultrasonication and then reduced it to graphene
using NaBH4. The as-synthesized graphene was
again dispersed in ethanol and tetrabutyl titanate
was added dropwise followed by addition of glacial
acetic acid and water. The mixture was stirred and
dried at 80 C for 10 h to yield the precursor. The
TiO2-graphene nanocomposites were produced by

Figure 6. Schematic illustration of the synthesis of TiO2-graphene nanocomposites by sol-gel method

(2010 The Royal Society of Chemistry. Reprinted with permission from Zhang, Li, Cui, & Lin, 2010d)
annealing the precursor at 450 C. The synthetic

route is schematically represented in Figure 6.
Hydrothermal/Solvothermal
Technique
Hydrothermal and solvothermal techniques are
other frequently used strategies for the synthesis
of metal oxide-graphene nanocomposites. In
this fabrication process, the synthesis is generally carried out in an autoclave under high vapor
pressure and high temperature. Nanocomposites
can be obtained by this process without the need
of post-annealing and calcination. However, the
requirement of high temperature and long reaction
times are the two major drawbacks of this process
when compared to other energy efficient and short
term processes. In spite of such drawbacks, a
number of metal oxide-graphene nanocomposites
such as ZnO (Zou et al., 2011; Wu et al., 2010a),
TiO2 (Zhou et al., 2011a; Fan, Shi, Wang, Shi,
Wang, Xu, et al., 2011; Shen, Shi, Yan, Ma, Li
& Ye, 2011; Shen, Yan, Shi, Ma, Li & Ye, 2011),
Fe3O4 (Zhou et al., 2011b; Wang, Zhong, Wexler,
Idris, Wang, Chen et al., 2011; Shen, Wu, Bai &
Zhou, 2010; Shi, Zhu, Sim, Tay, Lu, Zhang, et al.,
2011), SnO2 (Huang, Zhou, Zhou, Qian, Wang,
Liu et al., 2011; Jung, Myung, Cho, Shon, Jang,
Kim, et al., 2010), Co3O4 (Li et al., 2011a), Bi2O3
(Wang, Hu, Chang, Chen, Lei, Zhang, et al., 2010),

Fe2O3, CoO (Zhu, Zhu, Zhou, Zhang, Lou, Chen,
et al., 2011) have been prepared by this approach.
Hwang, Lee, Kim, Han, Kim, Park, et al. (2011)
prepared transparent ZnO nanowires on graphene
sheets by this method. The GO nanosheets were
synthesized by the Hummers method and then
transferred onto a flexible PDMS substrate to
constitute a mechanically flexible/stretchable,
electro-conductive, and optically transparent
substrate. Vertical ZnO nanowires were then
grown by hydrothermal/solvothermal process on
the flexible substrate, as illustrated in Figure 7.
Photo-Assisted Reduction
Photo-assisted reduction is another green process,
which provides a uniform reducing environment in
solution without the need of any additional reducing agent. Semiconductors with large band gaps
are photo-catalytically active under UV-visible
light irradiation and can be used to reduce GO
through a photogenerated electron transfer process
to produce semiconductor-graphene nanocomposites. TiO2 and ZnO are used to generate metal
oxide-graphene nanocomposites by this process.
Williams, Seger, & Kamat (2008) reported the
photocatalytic reduction of GO nanosheets with
TiO2 nanoparticles (NPs) in an inert atmosphere at
203

Figure 7. A schematic illustration of the fabrication process of ZnO nanowires on graphene film/PDMS
substrates (2011 The Royal Society of Chemistry. Reprinted with permission from Hwang, Lee, Kim,
Han, Kim, Park, No, & Kim, 2011)
room temperature using ethanol as hole scavenger

for TiO2 photocatalyst. Under UV irradiation,
TiO2 NPs were excited to generate electronhole
pairs. The holes are scavenged by ethanol to
produce ethoxy radicals leaving the electrons to
accumulate within TiO2 particles (reaction 1).
The accumulated electrons serve to reduce the
GO sheets into graphene (reaction 2).
C2 H 5OH
TiO2 + hv TiO2(h e ) TiO2(e )

+
+ C2 H 4OH + H +
TiO2(e) + GO TiO2 + Graphene
(1)
(2)
Photo-assisted production of TiO2-graphene

nanocomposites without any scavenging agent was
also investigated (Li et al., 2010). The photogenerated holes react with surface adsorbed water to
204
generate oxygen and protons, whereas the electrons

are efficiently captured by the sp2 regions of GO
nanosheets. The electrons delocalized in the sp2
regions of GO nanosheets may initiate the reactions
to dissociate oxygenated functional groups at the
boundary of sp2 regions, together with protons, as
shown in Equations (3) and (4) (Li et al., 2010).
4h+ (TiO2) + 2H2O O2 + 4H+
(3)
4e (TiO2) + GO + 4H+ Graphene + 2H2O

(4)
This photocatalytic reduction was carried in
air atmosphere although the dioxygen in air competes with GO nanosheets for electron capture. In
a similar manner, ZnO-graphene nanocomposites
were successfully prepared (Liu, Pan, Zhao, Lv,
Zhu, Chen, et al., 2012).

One of the greatest advantages of the photoassisted reduction of GO nanosheets is that it allows
the preparation of patterned graphene areas by
UV irradiation. Since UV irradiation has a little
thermal effect, the shapes of the graphene patterns
can be well controlled by limiting the thermal
diffusion effect (Li et al., 2010). Photo-assisted
reduction using visible light is carried out for
WO3-graphene and BiVO4-graphene nanocomposites (Ng et al., 2011). However, this process
only applies for semiconductors with narrow band
gaps i.e. absorbing visible light.
Microwave-Assisted Synthesis
Microwave irradiation is widely used as a green
and efficient technique for the production of
metal oxide-graphene nanocomposites. Unlike
photocatalytic reduction, this method can be
utilized as a general procedure for all types of
metal oxides. Microwave energy is transformed
into heat energy upon absorption by the substrate,
which is believed to be the driving force for the
reduction of GO nanosheets and metal salts (Hu
et al., 2011). However, the exact mechanism is
not yet clearly understood. Microwave synthesis
has the advantages of very short reaction time
and production of small particles with narrow
size distribution in comparison to conventional
methods. Zhang et al. (2010b) generated Fe3O4graphene nanocomposites by microwave heating
a Fe(NO3)3/GO mixture in the presence of urea
and ascorbic acid under reflux condition for
1 h. A similar reaction was performed by the
same group for the synthesis of SnO2-graphene
nanocomposites, starting with GO nanosheets,
tin chloride and urea with variable concentrations (Zhang, Lei, Yin, Chen, Li, Wang, et al.,
2011). Yan, Wei, Qiao, Shao, Zhao, Zhang, et al.
(2010) prepared Co3O4-graphene nanocomposites
by microwave irradiation of a mixture of cobalt
nitrate hexahydrate and GO nanosheets in the
presence of urea in a domestic microwave oven
for 10 min. Similarly, Co3O4- (Chen, 2010a) and
ZnO-graphene nanocomposites (Liu et al., 2011)

have been synthesized by this method.
Atomic Layer Deposition (ALD)

While the solution-based methods offer potentially
low cost and scalability, they have the disadvantage in precisely manipulating the deposition of
metal oxides (Meng et al., 2011). Atomic layer
deposition (ALD) is a layer-by-layer technique
of gassolid synthesis route having two sequentially cyclic self-limiting half-reactions. Metal
oxide-graphene nanocomposites with excellent
uniformity and conformity can be obtained by
precisely controlling the deposition parameters
at the atomic level. Meng et al. (2011) have prepared TiO2-graphene nanocomposites by ALD
method. Graphene nanosheet powders were
first loaded into a commercial preheated ALD
reactor. Then, titanium isopropoxide (TTIP) and
deionized water were introduced into the ALD
reactor in an alternating sequence to perform
ALD of TiO2. TiO2-graphene nanocomposites
were produced in six sequences at three growth
temperatures namely 150, 200 and 250 C, as the
phase change, morphology and deposition rate
of the TiO2 nanoparticles deposited on graphene
sheets depend on the growth temperature. From
the SEM images in Figure 8 of a TiO2-graphene
nanocomposite grown at 150 C, the deposited
layer is uniform and smooth. At 200 C, the layer
is smooth except the presence of some nanoparticles of around 15 nm, while at 250 C this layer
becomes totally rough and bumpy.
The absence of diffraction peaks in the XRD
spectrum of TiO2-graphene nanocomposites deposited at 150 C suggests that the as-deposited
TiO2 is amorphous. However, the sample grown
at 200 C exhibits a clear peak at 25.28o as well
as two weak but uncertain peaks at 38.58o and
48.05o, corresponding to the (101), (112), and
(200) planes of anatase TiO2, respectively. Furthermore, more peaks are visible in the XRD spectra
of the sample grown at 250 C with increased
205

Figure 8. High-magnification SEM images of (a) pristine graphene nanosheets, and ALD-TiO2 on graphene nanosheets at 150 C (b), 200 C (c), and 250 C (d). ( 2011 IOP Publishing Ltd. Reprinted with
permission from Meng, Geng, Liu, Li, & Sun, 2011)
intensities, corresponding to different characteristic planes of anatase TiO2 as denoted in Figure

9. Such observations in XRD spectra prove the
phase transitions in the growth of ALD-TiO2 with
temperature.
Alles et al. (2011) also found a similar trend
in surface morphology during the synthesis of
HfO2-graphene nanocomposites. Smooth nanocomposites were prepared at 180 C, while nanocomposites with comparatively rougher surface
were obtained by a two-step (170/300 C) growth
process as evidenced from the AFM imaging. This
is due to crystallization of HfO2 during the film
growth at higher temperature.
Meng, Geng, Liu, Li & Sun (2010) adopted
this approach to prepare amorphous and crystalline SnO2-graphene nanocomposites.
206
Ex Situ Method
In the ex situ approach, metal oxide NPs are synthesized separately and then attached to the surface
of graphene nanosheets via linking agents that
utilize covalent or noncovalent interactions such
as Van der Waals interactions, hydrogen bonding, stacking or electrostatic interactions. In
this approach, either the metal NPs or graphene
nanosheets or both are modified with functional
groups. This self-assembly based method can
overcome the incompatibilities between metal
oxide and graphene nanosheets. Compared to
in situ growth, better control of the distribution,
size, and feeding amount of the metal oxide NPs
on graphene nanosheets can be achieved by this
method (Bai & Shen, 2012).

Figure 9. XRD spectra of ALD-TiO2-graphene nanocomposites prepared at 150, 200, and 300 C. (
2011 IOP Publishing Ltd. Reprinted with permission from Meng, Geng, Liu, Li, & Sun, 2011)
Non-Covalent Interactions
Metal oxide-graphene nanocomposites can be
synthesized by non-covalent interactions such as
electrostatic interactions, layer-by-layer assembly
between the metal oxide NPs and the graphene or
GO moiety (Yang et al., 2010a; He et al., 2010;
Bai & Shen, 2012; Li, Wang, Liu, Liu, Ou &
Yang, 2011; Zhang, Chen, Zhang, Huang, Chen,
Yang, et al., 2011).
Electrostatic Interactions
Electrostatic interactions between metal oxide and
GO/graphene nanosheets are utilized for the preparation of metal oxide-graphene nanocomposites.
GO and graphene are negatively charged due to
ionization of the oxygen functional groups present
on their surface. The net negative charge is used
to assemble them with positively charged metal

oxide NPs through electrostatic interactions. Yang
et al. (2010a) have synthesized Co3O4-graphene
nanocomposites by this method. They have first
modified the oxide NPs by surface grafting of
3-aminopropyltrimethoxysilane (APS) to make
the oxide surface positively charged. The modified oxide NPs were assembled with negatively
charged GO by electrostatic interactions. Under
optimal conditions, almost all the GO and modified oxide NPs co-assembled to give a transparent
aqueous solution. Finally, the resulting aggregates
were reduced with hydrazine hydrate to give
Co3O4-graphene nanocomposites. The overall
procedure for the synthesis of Co3O4-graphene
nanocomposites can be schematically represented
as in Figure 10.
However, precise control of the size of the
NPs is still a challenge using this method. An-
207

Figure 10. Fabrication of Co3O4-graphene nanocomposites including (1) modification of the Co3O4 by
grafting aminopropyltrimethoxysilane (APTS) to render the oxide surface positively charged, (2) hybrid
assembly between positively charged oxide nanoparticles and negatively charged graphene oxide by
electrostatic interactions and (3) chemical reduction (2010 Wiley-VCH Verlag GmbH & Co. KGaA,
Weinheim. Reprinted with permission from Yang, Feng, Ivanovici, & Mullen, 2010a)
other disadvantage of this process is that since

the metal oxide NPs are attached to the GO or
graphene nanosheets by electrostatic interaction,
they may be easily leached out during application
(He et al., 2010).
Layer-by-Layer (LBL) Self-Assembly

LBL self-assembly is also an effective method
for the synthesis of metal oxide-graphene nanocomposite films. Such films are generated by
alternating layers of graphene nanosheets with
the metal oxide component. The simplicity and
thickness controllability at the nanoscale range are
the major advantages of this process. Moreover,
the blending of two components into composites
and the fabrication of composites into films can
208
be carried out simultaneously by this method

(Bai & Shen, 2012). Yao, Wu, Cui, Fang & Yu
(2010) applied this technique for the preparation
of GO/PDDA/TiO nanocomposite films (PDDA:
poly[diallyldimethylammonium], TiO: Titania)
through photothermal and photocatalytic reduction
of GO to graphene nanosheets by TiO nanosheets.
First, a high quality GO/PDDA/TiO hybrid film
was fabricated on glass substrate through alternating LBL self-assembly of GO and TiO nanosheets
with PDDA. The obtained hybrid film was then
illuminated under the 300 W Xe lamp through
a shadow mask for desired time intervals. The
photoconductive patterns were formed at the area
where it was exposed to the light illumination due
to the photodegradation of PDDA and reduction
of GO nanosheets. The graphene nanosheets acted

Figure 11. Schematic illustration of the fabrication procedure of LBL assembled multilayered composite
films consisting of PDDA/GO/PDDA/TiO (DIW: deionized water). (2011 The Royal Society of Chemistry. Reprinted with permission from Yao, Wu, Cui, Fang, & Yu, 2010)
as electrodes on the glass substrate due to their

high electronic conductivity, the TiO nanosheets
acted as photo conversion medium in the hybrid
films and ultrafast photocatalytic electron transfer
took place between TiO nanosheets and graphene
nanosheets to yield GO/PDDA/TiO nanocomposite films. A schematic illustration of this synthetic
procedure is summarized in Figure 11.
Li et al. (2011a) synthesized 3D multilayer
architectures of (PDDA/PSS-graphene/PDDA/
MnO2)10 using negatively charged species of
poly(sodium-4-styrenesulfonate) (PSS) modified graphene, negatively charged MnO2 sheets
and positively charged PDDA as building blocks
(Figure 12).
However, as this method is also based on noncovalent interaction of oppositely charged species,
the problem of leaching out during application
time still persists.
Covalent Interactions
In covalent interactions, GO nanosheets rather than
graphene is preferred in immobilizing metal oxide
NPs due to its large amount of oxygen containing
groups that facilitate the linkage with other functional groups. The main advantages of this technology are its capability of pre-defining the loading
amount of metal oxide and the metal oxide NPs
that can be grafted on graphene surface firmly by

covalent bonding. He et al. (2010) have synthesized
Fe3O4-graphene nanocomposites by this method.
They have first functionalized Fe3O4 NPs sequentially with tetraethyl orthosilicate (TEOS) and
3-aminopropyltriethoxysilane (APTES). Fe3O4
NPs tended to form nanoscale aggregates during
surface functionalization because of the magnetic
dipolar interaction among the magnetite NPs. With
the aid of N-hydroxysuccinnimide (NHS) and
1-ethyl-3-(3-dimethylaminopropyl) carbodiimide
(EDC), a GOFe3O4 hybrid was obtained from the
condensation reaction between amino groups of
APTES-modified Fe3O4 and carboxylic groups
of GO nanosheets through amide bond formation
(He et al., 2010). The functionalized Fe3O4 NPs
and GO nanosheets were then mixed together and
stirred for 1 h at 80 C. The Fe3O4-graphene nanocomposites were isolated by magnetic separation
and washed with water (Figure 13).
The functionalization of GO nanosheets with
magnetic Fe3O4 NPs was confirmed by FTIR
spectroscopy (Figure 14). The peak at 1723 cm-1
corresponds to C=O stretching in carboxylic acid
and carbonyl moieties terminating GO nanosheets.
After amidation reaction, three new characteristic peaks of the amide carbonyl group for GO
Fe3O4 hybrid at 1647 (CONH amide band I),
1533 (NH amide band II), and 1455 cm-1 (CN
209

Figure 12. A schematic view of the synthesis of multilayer films on substrate (2011 The Royal Society
of Chemistry. Reprinted with permission from Li, Wang, Liu, Liu, Ou, & Yang, 2011b)
Figure 13. Schematic illustration of the synthesis of Fe3O4-graphene nanocomposites by covalent interaction
stretching of amide) appeared, suggesting that

Fe3O4 nanoparticles were linked to GO surface
by covalent bonding.
To confirm the covalent bonding between
Fe3O4 NPs and GO nanosheets via amidation
210
reaction, GO nanosheets were mixed with NH2terminated Fe3O4 NPs at 80 C for 1 h in the
absence of NHS and EDC and the mixture was
subjected to an external magnetic field. The
solution remained brown colored even though it

Figure 14. FTIR spectra of (a) GO and Fe3O4-GO nanocomposites with different ratios of Fe3O4 to GO:
(b) 1:9 and (c) 1:1 (2010 Elsevier Ltd Reprinted with permission from He, Fan, Ma, Zhang, Leung,
& Chan, 2010)
had been influenced by a magnet for a long time.

In the presence of NHS and EDC, the resultant
Fe3O4-GO nanocomposites could be immediately
separated from the reaction mixture once a magnet was placed nearby and the solution became
colorless, indicating the formation of chemical
bonding between Fe3O4 NPs and GO nanosheets
through amide bond. They have further reduced
Fe3O4-GO nanocomposites by NaBH4 to form
Fe3O4-graphene nanocomposites. The chemical
changes brought by NaBH4 reduction were investigated by X-ray photoelectron spectroscopy (XPS).
The C1s XPS spectrum of GO with peak-fitting
curves is displayed in Figures 15a and b. The
peaks at 284.9, 287.0, 288.3, and 289.3 eV were
assigned to carbon atoms in C=C/CC, CO, C=O
and OC=O, respectively. This result suggested
that GO nanosheets contained large numbers of
functional groups on their surface. In comparison
to GO nanosheets, the C1s XPS spectrum of Fe3O4-
graphene nanocomposite obviously exhibited

a decreased intensity for peaks corresponding
to GO functional groups, indicating effective
deoxygenation of GO nanosheets. Besides, an
additional component at 286.1 eV was observed
for Fe3O4-graphene nanocomposites resulting
from the formation of CN bonding during the
amidation reaction. The reduction of Fe3O4-GO
nanocomposites to Fe3O4-graphene nanocomposites was also evidenced by UVVis absorption
spectra (Figure 15c). GO nanosheets exhibit a
characteristic peak at 224 nm corresponding to
* transitions of aromatic CC bonds. For
Fe3O4-graphene nanocomposite, the absorption
peak blue-shifted to 213 nm, suggesting that the
covalent attachment of Fe3O4 onto the GO surface
by the amidation reaction changed the structure
of GO nanosheets. After reduction, the Fe3O4graphene absorption peak red shifted to 248 nm
211

Figure 15. C1s XPS spectra of (a) GO, (b) Fe3O4-graphene nanocomposites, and (c) UVVis spectra of
GO, Fe3O4-GO nanocomposites and Fe3O4-graphene nanocomposites. (2010 Elsevier Ltd. Reprinted
with permission from He, Fan, Ma, Zhang, Leung, & Chan, 2010)
as the electronic conjugation in the graphene was

restored by the reduction with NaBH4.
Zhang et al. (2011a) reported another route
to synthesize Fe3O4 graphene nanocomposites
by covalent bonding. Fe3O4 nanoparticles were
modified with hydrophilic 2,3-dimercaptosuccinnic acid (DMSA), followed by assembling
them onto polyethylenimine (PEI)-grafted GO
nanosheets via the formation of amide bonds
between COOH groups of DMSA molecules and
amine groups of PEI.
Applications of Metal OxideGraphene Nanocomposites

Graphene and graphene-based nanocomposites
are the most appealing matrices because of their
unique properties and potential applications as
electronic and photonic devices (Du, Skachko,
Barker & Andeei, 2008; Wang, Ang, Wang, Tang,
Thong & Loh, 2010; Eda, Fanchini & Chhowalla,
212
2008; Xia, Muller, Lin, Garcia & Avouris, 2009),

sensing platforms (Schedin et al., 2007; Jung,
Cheon, Liu, Lee & Seo, 2010; He et al., 2010)
and clean energy systems (Wang, Zhi & Mullen,
2008; Yin et al., 2010). In particular, graphene or
a few-layers graphite decorated with metal oxides
including titania, cobalt oxide, zinc oxide or tin
oxide have been intensively investigated, and
have shown promising applications in capacitors,
batteries, catalysis, and biomedicine. Moreover,
graphene and its metal oxide nanocomposites have
also found applications in wastewater purification
(Chandra & Kim, 2011; Sun, Cao & Lu, 2011).
Li-Ion Battery
Currently for Li ion battery (LIB), there is a great
demand to provide high efficiency, low cost and
green solution for energy storage devices. Graphite
with a theoretical capacity of 372 mAhg-1 is commonly used as anode material for LIB (Winter,

Besenhard, Spahr & Novak, 1998). Graphene has

great potential as anode for Li-ion battery due to
its special Li ion storage mechanism i.e. lithium
can be stored on both sides of graphene sheets
and also on the edges of graphene sheets, which
eventually leads to larger practical capacity than
that of graphite. Even though graphene shows
higher capacity, it fails after a few cycles due to
restacking of graphene sheets. To overcome this
issue, metal oxide-graphene nanocomposites e.g.
SnO2-graphene (Kim, Kim, Park, Gwon, Seo, Kim,
et al., 2010; Wang, Choi, Li, Yang, Nie, Kou, et
al., 2009) and Fe3O4-graphene (Zhou, Wang, Li,
Zhang, Li, Wu, et al., 2010) electrodes have been
applied in LIB. Among these, SnO2-graphene
nanocomposites, prepared by hydrothermal
method, shows the first reversible specific capacity of 729 mA h g1 at a current density of 50 mA
g1, and remains at 646 mA h g1 after 30 cycles
at a current density of 100 mA g1 (Fan, 2013).
In these type of hybrid electrodes, incorporation
of graphene helps to maintain the conductivity.
Moreover, direct growth of metal oxide NPs on
graphene sheets improved the contact between the
NPs and the 3D network of graphene; this comprehends efficient conduction of charge carriers.
capacitors, commonly used electrode materials

are metal oxides and conducting polymers which
offer higher specific capacitance compared to the
porous carbon based EDLC electrode. But the
high cost and low conductivity of these materials
have restricted their applications. Therefore, metal
oxide-graphene nanocomposites are efficiently
being used as hybrid materials for supercapacitors. Recently, many research groups reported
nanocomposites of graphene with metal oxide
such as ZnO (Zhang, Chen, Zhang, Huang, Chen,
Yang, et al., 2009), SnO2 (Li et al., 2009), Co3O4
(Yan, Wei, Qiao, Shao, Zhang & Fan, 2010), MnO2
(Chen, Zhu, Wu, Han & Wang, 2010; Yan, Fan,
Wei, Qian, Zhang & Wei, 2010), and RuO2 (Kim,
Luo, Cruz-Silva, Cote, Sohn and Huang, 2010)
as electrodes for supercapacitors. MnO2-graphene
composite electrode shows a high specific capacitance of 310 F g-1 at 2 mV s-1 (228 F g-1 at
even 500 mV s-1), about 3 times higher than that
given by pristine graphene or MnO2 (Figure 16).
Higher specific capacitance is achieved for this
metal oxide-graphene composite as compared to
pure graphene electrode.
Supercapacitors
Waste water generated by industrial, domestic

and agricultural activities can be purified by technologies like adsorption, precipitation, membrane
separation, amalgamation, and ion-exchange.
To remove the pollutants from dilute solutions,
adsorption which is economical and efficient
over other technologies is widely used. Graphene
and its composites have large surface area and
present surface functional groups, which make
them an attractive adsorbent candidate for water
purification. Due to difficulty large scale synthesis, graphene materials have limited applications
in water purification. To avoid these problems,
several attempts have been made to synthesize
graphene and its nanocomposites (Stankovich et
al., 2006; Zhou, Huang, Qi, Wu, Xue, Boye, et al.,
2009). Recent literature survey reveals that, for the
Supercapacitors are alternative energy storage

devices with high rate capability, low cost and
long cycle life. There are two types of supercapacitors based on their charge storage mechanism: 1)
electrical double layer capacitor (EDLC), which
stores energy via electrostatic process, 2) pseudocapacitors, which store energy through surface
redox reaction.
Generally in EDLC, porous carbon materials
are used as electrode materials but this restricts
their applications in high power density supercapacitors due to their low conductivity. Graphene
is one of the best candidates with high electrical
conductivity and large surface area to replace the
porous carbon materials for EDLCs. In pseudo-
Water Purification
213

Figure 16. Graphene-based supercapacitor. (2013 American Chemical Society. Reprinted with permission from He Chen Li Zhang Fu Zhao & Xie 2013)
removal of arsenic from water, magnetite-graphene

and ferric hydroxide-GO nanocomposites were
successfully used (Chandra et al., 2010; Zhang
et al., 2010a). Zhang, Liu, Zhang, Wei, Jang, &
Oh (2012) synthesized high crystalline Fe3O4graphene composite via one-step thermolysis
reaction which proved to be a promising sorbent
material for wastewater treatment. The zero band
gap of graphene helps to display high catalytic
activity for the degradation of organic pollutants
when traditional photocatalysts, such as ZnO,
TiO2, and CdS, are incorporated with graphene.
Photovoltaic Cells
In the dye sensitized solar cells (DSSC), graphene
and its composites with metal oxide NPs are used
to enhance the interface area of dye/electrolyte,
to increase the loading of dye molecules and
to improve the conductivity of electrons at the
semiconductor layer to compete with charge
recombination. In TiO2-graphene, the band gap
of graphene is about 4.4 eV situated between the
214
conduction band of TiO2 (anode) and the work

function of ITO (cathode), which allows for the
fast collection of electrons at the anode to suppress charge recombination (Tang, Lee, Xu, Liu,
Chen, He, et al., 2010). Under visible light irradiation, valence electrons are directly excited from
graphene into the TiO2 conduction band at the
TiO2-graphene interface giving rise to separated
electronhole pairs. Moreover, the enhancement
of light scattering at the photoanode is achieved by
forming TiO2-graphene porous network. A TiO2
graphene nanocomposite based dye sensitized
solar cell is depicted in Figure 17. By using TiO2
rGO nanocomposites as photoanode, a photo
conversion efficiency (PCE) of about 47% is
obtained, which is at least 39% higher as compared
to the commercial P25 TiO2 (Yang, Zhai, Wang,
Chen & Jiang, 2010). Ng, Iwase, Bell, Kudo &
Amal (2010) and Ng et al. (2011) achieved higher
photoelectrocatalytic efficiencies by fabricating
the composites of graphene and TiO2, WO3, or
BiVO4 via a one-step UV or visible light inducedphotocatalytic reduction process.

Figure 17. Metal oxide-graphene nanocomposite

based dye sensitized solar cell. (2010 American
Chemical Society. Reprinted with permission from
Yang, Zhai, Wang, Chen, & Jiang, 2010c)
Biomedicine
Nanostructured metal oxides have recently attracted much attention due to their high surfaceto-volume ratio, high surface reaction activity,
high catalytic efficiency, and strong adsorption
ability. Great efforts have been devoted to explore
potential applications of metal oxide-graphene
nanocomposites in biomedicine. The graphene
nanosheets act as an advanced support with large
surface area for immobilizing different target biomolecules. Moreover, it effectively promotes the
electron transfer between electrode and analytes.
Iron oxide-graphene nanocomposites are widely
studied for magnetically targeted drug delivery,
photothermal therapy, and magnetic resonance
imaging (Yang et al., 2009). Yang, Zhang, Ma,
Huang, Wang & Chen (2009) reported the use
of iron oxide-graphene nanocomposites as drug
carriers. Recently, Chen, Zhang, Zhang, Deng
& Zhang (2011) demonstrated the use of magnetic aminodextran coated iron oxide-graphene
nanocomposites as the T2-weighted magnetic
resonance imaging (MRI) contrast agent for in
vitro cell labeling. Taking advantages of the su-
perparamagnetic properties, high drug loading

capacity, and strong optical absorption of iron
oxide-graphenePEG (PEG=polyethylene glycol)
nanocomposites, they demonstrated magnetically
targeted drug delivery and photothermal therapy
(PTT) in vitro to selectively destroy cancer cells
in highly localized regions.
SiO2-graphene nanocomposite was successfully used for highly selective and sensitive detection of cancer biomarkers (Myung, Solanki, Kim,
Park, Kim & Lee, 2011).
Copper and copper oxide-based nanomaterials were of great interest for their extensive applications in gas sensing and biosensing. Qian,
Ye, Xu & Le (2012) demonstrated the excellent
electrocatalytic activity of Cu2O-graphene nanocomposites towards glucose. The electrocatalytic
activity of Cu2O-graphene nanocomposites was
compared with graphene and Cu2O alone as
electrode modifying material for oxidation of
glucose in 50 mM NaOH solution (Figure 18). The
nanocomposites exhibited typical current response
for the oxidation of glucose (curve 3), while no
obvious oxidation peak for glucose can be found
at the graphene (curve 2) and Cu2O nanoparticles
(curve 1) modified electrodes. Such excellent
electrocatalytic activity of the Cu2O-graphene
nanocomposites may be attributed to high catalytic
active sites for the glucose oxidation provided by
the Cu2O nanoparticles and increase of the efficient
electroactive surface area due to introduction of
graphene, which also provides conductive bridges
for accelerating the electron-transfer.

Metal oxide-graphene nanocomposites are promising materials for a number of applications in
many fields. The properties and efficiency of the
composites are dependent on a number of factors
such as size, shape, distribution of the NPs, thickness of the GO/graphene nanosheets, purity of the
215

Figure 18. Linear sweep voltammetry of Cu2O (curve 1), graphene (curve 2), and Cu2O-graphene composites (3) modified GC electrodes in 50 mM NaOH solution containing 2 mM glucose at a scan rate of
50 mV s1 ( 2012, ESG. Reprinted with permission from Qian, Ye, Xu, Le, 2012)
material, etc. Though a number of methods have

already been reported for the synthesis of metal
oxide-graphene nanocomposites, the development
of a method bridging several aspects such as cost
effectiveness, eco-friendly, control of properties,
etc. is still a challenge. The development of a
process that can fulfill all these requirements and
which can be utilized for large scale production of
such composites is a promising research area. The
interaction mechanism and structural-properties
relationship between the metal oxide NPs and
graphene sheets need to be studied from both
theoretical and experimental aspects so as to help
future developments in this area. The composites
are studied for applications in a number of fields.
However, there may be some more fields in which
they have the possibility of potential applications.
Proper study in this regard may open up a new
window for practical applications of these composites in different fields.
216
CONCLUSION
GO and graphene nanosheets have been utilized
as a very good support for incorporating metal
oxide NPs. A number of procedures are studied
for the synthesis of metal oxide-graphene nanocomposites. These composites have applications
in various fields. Further proper and systematic
studies in this area will open up new directions
for large scale production of such nanocomposites
for practical applications and new fields in which
these composites can be efficiently used.
ACKNOWLEDGMENT
The authors thank the DST New Delhi, the CNRS,
the Universit Lille1 and Nord Pas de Calais
region for financial support and also the Director, CSIR-North East Institute of Science and

Technology Jorhat, India for the interest in this

work. PS acknowledges CSIR, New Delhi, India
for Senior Research Fellowship grant.
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Aggregation of Nanoparticles: Nanoparticles
bind each other to form larger aggregates.
Ex Situ Method: A method in which different
precursors are generated separately and then mixed
together to generate the final product.
Graphene Oxide: Oxidized form of grapheme.
Graphene: A single layer of sp2 hybridized
carbon atoms closely packed into a two dimensional honeycomb lattice.
In Situ Method: A method in which all the
reactions take place in the same reacting vessel
to give the product.
Metal Oxide: Compounds of metal with
oxygen.
Metal Oxide-Graphene Nanocomposites:
Hybridized form of metal oxide nanoparticles
and graphene nanosheets.
225
226
Chapter 11
In2X3 (X=S, Se, Te)

Semiconductor Thin Films:
Fabrication, Properties, and Applications

Mahieddine Emziane
Masdar Institute of Science and Technology, UAE
Rahana Yoosuf
ABSTRACT
Indium chalcogenide thin film semiconductor compounds In2X3 (with X being a chalcogen atom, i.e., S,
Se, or Te) are important materials in many current technological applications such as solar cells, microbatteries, memory devices, etc. This chapter reviews the recent progress in In2X3 (X = S, Se, or Te) thin film
research and development, with a particular attention paid to their growth and processing methods and
parameters, and the effects that these have on the films microstructure. The intimate relationship between
their fabrication conditions and the resulting physico-chemical and functional properties is discussed.
Finally, results pertaining to the fabrication and characterization of these thin film materials, as well
as the main devices and applications based on them are also highlighted and discussed in this chapter.
INTRODUCTION
Remarkable advances have taken place during the
past few decades in semiconductor materials and
devices. The semiconductor compounds of In2X3
family, where X is S, Se or Te have attracted particular interest in recent years due to their promising technological applications including a wide
variety of devices. Among the important In2X3
devices that have been developed are solar cells
(Yu et al, 1998), dry cells (Dalas & Kobotiatis,
1993), photochemical cells (Hara et al, 2000), solid

state batteries (Julien et al, 1985), phase change
memory devices (Lee & Kang, 2005; Lee & Kim,
2005; Hirohata et al, 2006), thin film strain gauge
(Desai et al, 2005a), gas sensors (Desai, et al,
2005b), etc. Some In2X3 compounds can be used
in Schottky diodes, capacitors, heterojunctions,
and micro batteries (Kobbi, B., et al, 2001), and
they also have a potential application as passivating layer for III-V semiconductor devices (Barron
DOI: 10.4018/978-1-4666-5824-0.ch011

In2X3 (X=S, Se, Te) Semiconductor Thin Films
1997). Many of the devices based on In2X3 have

already found their way into industry.
A number of books, book chapters, and
topical reviews are dedicated to semiconductor
compounds such as II-VI, III-V and group IV
(Adachi, 2005; Ahrenkiel, 1993; Chu & Chu,
1995; Shay & Wernick, 1975). However there is
no review on In2X3 semiconductor compounds
available in the literature. This article reviews the
status of research on In2S3, In2Se3 and In2Te3 thin
films, and focuses on their fabrication methods
and functional properties. It also summarizes the
recent advances in their relevant applications in
many devices.
The interest in In2S3 thin films has increased
during the last decade or so because of the high
potential demonstrated by this material. With
optimal physical properties, this material can meet
the requirements for use as a window material or
a buffer layer for photovoltaic device structures
(Barreau et al, 2003). In2S3 can be used as an
effective replacement for CdS in Cu(In,Ga)Se2
(CIGS) based solar cells (Spiering et al, 2003).
Though the highest conversion efficiency in thin
film solar cells has been reported for CIGS with
CdS buffer layer, it is desirable to replace CdS
with cadmium free buffer layers for environmental reasons (Hariskos et al, 2005; Naghavi et al,
2003a; Naghavi et al, 2003b; Sakata, 2000; Lee,
et al, 2007).
Indium selenide (In2Se3) is another promising
In2X3 material. In thin film form, it has valuable
optical and electrical properties and is thus of
interest for low-cost photovoltaic applications
(Sahu, 1995; Lakshmikumar & Rastogi, 1994;
Brahim-Otsmane et al, 1994; Hasehawa & Abe,
1982; Jayakrishnan et al, 2008). This is because
of its high absorption coefficient as well as optimum energy band gap, suitable for solar energy
conversion (Former et al, 1985; El-Sayed, 2004;
Lee, et al, 2008; Bernede & Marsillac, 1997;
Segure, et al, 1983; Qasrawi, 2007; Konagai et
al, 1996). In2Se3 can also be used as a precursor
for the growth of CuInSe2 absorber layer (Kim et
al, 2005). The hexagonal layered structure of this

material allows the change of the physical properties without destroying the initial structure. This
characteristic makes it feasible to use this material
in batteries (Balkanski, 1998; Julien, et al, 1989).
In2Te3 is also drawing attention due to its photoconducting properties (Guettari et al, 2003; Bose
& De Purkayastha, 1981) and for its switching and
memory effects (Balevicius et al, 1975; Balevicius
et al, 1976; Afifi et al, 1996). The research and
development of highly sensitive In2Te3 as gas
detector and thin film screw gauge have attracted
growing interest (Desai et al, 2005a; Afifi et al,
1995; Lakshminarayana et al, 2002; Hussein &
Nagat, 1989).
FABRICATION PROCESSES
The properties of In2X3 thin films usually show
a strong dependence on the film deposition
technique and conditions as well as on the postdeposition heat treatment. The deposition method
also has an impact on the overall fabrication cost.
In2S3 Thin Films

Deposition Methods
A wide range of methods exist for growing In2S3
thin films. In2S3 thin films are deposited using
both wet and dry processes. Prominent among
them are low pressure metal-organic chemical
vapor deposition (MOCVD) (Horley et al, 1999),
atomic layer chemical vapor deposition (ALCVD)
(Spiering et al, 2003), spray pyrolysis (Jayakrishnan et al, 2005; Bhira et al, 2000; Pai et al, 2005),
chemical bath deposition (CBD) (Barreau et al,
2002), atomic layer epitaxy (ALE) (Yousfi, et
al, 2000a; Yousfi et al, 2000b; Asikainen et al,
1994), photochemical deposition (Kumaresan et
al, 2002), annealing of elemental layers (Barreau
et al, 2000a; Barreau et al, 2001), physical vapor
deposition (PVD) (Barreau et al, 2002; Trigo
227

et al, 2008; Timoumi et al, 2006), sulfurisation

of metallic electrodeposited indium (Herrero &
Ortega, 1988; Data et al, 2008), etc.
CBD method which uses chemical reactions in
solution as the driving force for the film growth
is a low-cost method which can operate at low
processing temperature and provides large area
deposition (Bernede et al, 2002). CBD involves
the controlled precipitation from the solution of
a compound on a suitable substrate. The method
consists of a complex metal ion of interest, a source
of chalcogen ions, and a stability equilibrium that
provides a concentration of ions small enough for
controlled homogenous precipitation of material
in thin film form on the substrate. Various reports
on the deposition of In2S3 thin films from a bath
containing In salt and thioacetamide as sulfide
ion source were published (Yahmadi et al, 2005;
Yamaguchi et al, 2003). The most common In
salt used for the preparation was indium chloride
(InCl3) (Asenjo et al, 2004). Indium sulfate was
another alternative (In2(SO4)3) (Lokhande et al,
1999). Nanoporous network of In2S3 platelets
were grown by CBD method on ITO substrates
(Puspitasari et al, 2008).
Attempts were made to deposit In2S3 thin films
by using successive ionic layer adsorption and
reaction (SILAR) method (Kundakci, 2008). This
method is mainly based on the immersion of the
substrate into separate cation and anion precursor
solutions and rinsing between every immersion
with ion exchanged water. Indium chloride could
be used as cationic precursor and sodium sulfide
could be used as anion source (Ranjith, et al, 2007).
Utilization of triethanolamine and hydrazine
hydrate complexed indium sulfate and sodium
sulfide as precursors resulted in nanocrystalline
In2S3 thin films (Pathan, et al, 2005).
A systematic study of -In2S3 thin films grown
by ALCVD was carried out by various groups.
ALCVD is based on the surface reaction of the
precursors. The main advantage of this deposition
method is that it allows the deposition of highly
homogenous thin films with controlled layer
228
thickness. The non metal precursors used in the

preparation were usually hydrides like H2S for S
and metal halides (especially chlorides) or alkyls
were used as In precursors (Naghavi, 2004). A
recent result showed that -deketonate precursors such as indium acetylacetonate gave better
results and seemed to be more favorable for low
temperature deposition (Yousfi et al, 2001).
MOCVD, a chemical vapor deposition process
based on metal organic precursors, is the most
advantageous method for the thin film growth of
In2S3. MOCVD provides a single in-line process
without interruption for device fabrication, independent control of III/VI ratio, and easy mass
production. The synthesized dimeric indium
thiolates were used as single source precursors
for MOCVD, while trimethyl-indium and t-butylthiol were applied as precursor sources in another
work (Spiering et al, 2009). Thin films of -In2S3
were deposited using low pressure MOCVD with
air stable precursors In(S2CNMenButyl)3 and
In(S2CNMenHexyl)3 (OBrien et al, 1998).
Better quality In2S3 films can be obtained by
electrochemical synthesis, where the deposition
of In and S may take place by direct electronic
exchange with the substrate. Electrochemical
methods have demonstrated the possibility of obtaining In2S3 films by electrodeposition followed
by a sulfurisation process (Herrero & Ortega,
1988), one-step cathodic deposition (Asenjo et
al, 2005), and two-step electrodeposition (Tacconi & Rajeshwar, 1998). Electrodeposition is
a liquid phase method with the advantage of
up-scaling feasibility to large substrate areas for
production. In2(SO4)3 was used most commonly
as the In source and Na2S2O3 as the S source
(Abdel Haleem & Ichimura, 2008). Tacconi &
Rajeshwar (1996) reported another approach for
the electrosynthesis of In2S3 films over a sulfurmodified gold substrate by an alternating use of
two baths; one contained sulfide ions and the other
contained In ions (Tacconi & Rajeshwar, 1998).
Electro chemical synthesis gives a wide range of
parameters that can be changed independently to

Figure 1. Schematic showing the different phases of In2S3
obtain better quality films (Pandey et al, 1996).

(see Figure 1)
With respect to industrial integration, the high
vacuum growth techniques are attractive and their
main advantage is the easy control of the growth
rate through various process parameters. There
were a number of reports on the preparation of
In2S3 by PVD either by sequentially evaporating In
and elemental S (Nagavi et al, 2003b; Barreau et
al, 2000; Robles et al, 2005) or by co-evaporation
(El-Nahass et al, 2006; Gall et al, 2005; Barreau
et al, 2009). Single source vacuum evaporation
using pre-synthesized powder of In2S3 was also
employed for thin film preparation (Timoumi
et al, 2005; Timoumi et al, 2006). However, an
additional annealing step was required to form
high-quality In2S3 (Spiering et al, 2004; Yoosuf
& Jayaraj, 2005).
It is possible to use spray pyrolysis to deposit
In2S3 with good uniformity, which also allows the
production of large area films. In this method, gas
atomizes the solution containing the constituents
into a fine mist with a spray nozzle. The reactant
in the droplets is pyrolysed on the heated substrate.
Ideally, a pyrolysis reaction leads to the deposition of films of the desired compound while other
products evaporate as gaseous species. In2S3 thin
films prepared by the spray pyrolysis technique
showed optoelectronic properties that depend
on the deposition parameters. By controlling the
deposition parameters, In2S3 thin films could be
produced with optimized optoelectronic properties (John et al, 2003). Most of the research
works on In2S3 prepared by spray pyrolysis were
carried out by using InCl3 and thiourea as start-
ing materials but there were reports on the use of

other precursor materials as well. Indium acetate
and thiourea were used as precursor compounds
(Calixto-Rodrigueza et al, 2005) for the In rich
In2S3 thin films that are optimal for application
as a window material in photovoltaic structures.
Indium nitrate and thiourea were used as precursor
solutions in the preparation of In2S3 thin films in
another work (John et al, 2005).
Reports of In2S3 thin films successfully synthesized by other techniques like spray ions layer
gas reaction (ILGAR) (Allsop et al, 2005), RF
sputtering (Hariskos et al, 2004), modulated flux
deposition (MFD) (Asenjo et al, 2007; Sanz et
al, 2006), etc. are also available in the literature.
Kumaresan et al. reported the growth of In2S3
thin films by photochemical deposition from an
aqueous solution by means of UV illumination
(Kumaresan et al, 2002).
Post-Deposition Annealing
The annealing temperature is a critical parameter
for In2S3 window layers, as excessive temperature
results in copper diffusion and decreased solar
cell performance (Gall et al, 2005; Spiering et
al, 2004; Bedir & Oztas, 2008). Several groups
have optimized the annealing conditions that
are favorable for the good crystalline growth of
In2S3 for PV applications. Timoumi et al. (2006).
optimized the annealing temperature and duration
in nitrogen and air atmospheres (Timoumi et al,
2006). The as-deposited films were amorphous
in nature and the annealing treatment induced the
crystallization of the layers, but showed additional
229

In6S7 phase for higher annealing temperature. For

different annealing times, the chemical analysis
showed the presence of these same elements, but
with less S content. The film annealed in air was
found to be optimum for PV applications.
The structural and electrical properties of
In2S3 films prepared using the spray pyrolysis
technique were shown to improve considerably
through annealing at 400C. The films showed
good homogeneity with 80% transmission (John
et al, 2006). Annealing at 500C led to the phase
transition from InS to In2S3 in the films grown
by photochemical deposition (Bedir & Oztas,
2008). For the In2S3 thin films prepared by thermal
evaporation, the as-deposited In2S3 thin films were
non-crystalline, while they were found to have a
polycrystalline nature after being annealed for
1 h at both 150C and 200C (El-Shazly et al,
1998). Similar characteristics were observed for
the films prepared by the MFD procedure. After
being annealed for one hour at 150C, the films
showed the polycrystalline -phase, which had
amorphous nature while as-deposited (Guillen
et al, 2004).
A two-stage process consisting of the evaporation of In in the first step followed by an annealing
in S atmosphere in the second step for the growth
of In2S3 was reported (Yoosuf & Jayaraj, 2005).
In2S3 films synthesized by solid-state reaction of
sequentially deposited In and S thin layers were
followed by annealing in argon atmosphere for
30 minutes and it was observed that in order to
obtain the films with the best crystalline properties
and the best purity, the optimum temperature was
400C (Barreau et al, 2000a). The same results
were obtained for studies carried out on different
substrates such as glass coated with SnO2, In2O3
and ZnO transparent conductive oxides (TCOs)
(Barreau et al, 2000b). The effect of annealing
on CBD grown In2S3 films was studied under
nitrogen (Yahmadi et al, 2005) and argon atmospheres (Sandoval-Paz et al, 2005). In both cases
all annealed thin films showed an improvement
in their structural and morphological properties.
230
Ranjith et al. (2007) observed a color change

from yellow for the as prepared sample to reddish
black after annealing due to the formation of In
rich phases (Ranjith et al, 2007). The color was
changed from yellow to orange after annealing
in nitrogen atmosphere for electrodeposited In2S3
films (OBrien et al, 1998).
Effect of Deposition Parameters

The processing parameters such as deposition
temperature, deposition time, pH of the solution,
thioacetamide (TA) concentration, and the nature
of substrates have strong influence on the properties of thin films grown by CBD method. The
deposition temperature between 50C and 70C
was found optimum for the growth of good quality films (Barreau et al, 2002; Trigo et al, 2008;
Lokhande et al, 1999). The studies showed that well
crystallized films with good surface homogeneity and roughness were deposited on glass slides
using [TA] = 0.10 M, pH = 2.35 and tD = 60 min
as deposition conditions (Bernede et al, 2002).
However the films grown on SnO2/glass substrate
under the same deposition conditions contained
the unwanted In6S7 phase even after annealing
treatment. Kamoun et al. (2001) claimed that they
obtained the best crystalline -In2S3 films on SnO2/
glass substrate out of the different substrates they
used for the spray pyrolysis deposition (Kamoun
et al, 2001). Na free lime glass could be used to
prevent diffusion of Na in the films during the
synthesis process (Barreau et al, 2002b).
The substrate temperature (Ts) has a significant
influence on the stoichiometry of the grown In2S3
films. The films deposited at Ts < 300C were S
rich, whereas the films deposited at Ts > 300C
were rich in In (Revathi et al, 2008). It was proved
that the rate-determining step for the film growth
at the higher substrate temperature was not identical to that at lower temperature (Yamaguchi et
al, 2003). The best deposition rate for ALD films
was obtained at a deposition temperature of 180C
with a source temperature of 135C (Naghavi

et al, 2004). The studies on the variation of Ts

during the deposition of In2S3 as the buffer layer
in a CIGSe/In2S3 solar cell structure showed that
the chemical nature of the interface was changed
as Ts varied (Gall et all, 2005). The increase of
Ts resulted in a higher Cu content in the buffer
layer thus affecting all of the solar cell parameters
and decreasing its overall conversion efficiency.
The preparation temperature, i.e., the temperature of the deposition bath (Tp) also has influence in the film growth. It was found that films
prepared by spray pyrolysis at Tp > 400C were
either amorphous or nanocrystalline, whereas
those prepared at Tp 400C were polycrystalline
(Calixto-Rodrigueza et al, 2005). Prolongation of
reaction time in CBD process led to the formation of nanocrystalline In2S3 films together with a
slight increase in the crystallite size (Yamaguchi
et al, 2003).
In2Se3 Thin Films

Deposition Methods
A number of deposition methods for growing
single-phase In2Se3 thin films have been reported,
and the popular ones are evaporation techniques
such as elemental evaporation, (Thomas, 1992;
Watanabe et al, 1989), evaporation of indium
selenide powder (Kenawy et al, 1990), electron
beam evaporation (Manno et al, 1995), flash
evaporation (Persin et al, 1972), but also pulsed
laser deposition (PLD) (Ye et al, 1998; Hrdlicka
et al, 2007), spray pyrolysis (Bouzouita et al,
2002), molecular beam epitaxy (MBE) (Emery
et al, 1992; Ohtsuka et al, 1999), chemical vapor
deposition (Park et al, 2003), MOCVD (Gysling
et al, 1992; Gordillo & Calderon, 2003), etc.
The growth of In2Se3 by the evaporation of
In2Se3 powder or co-evaporation of In and Se
was a classical deposition method. Single-phase
-In2Se3 with a preferential orientation along (113)
plane was obtained by the evaporation of In2Se3
powder (Marsillac et al, 1995). Single-phase
-In2Se3 oriented along (004) plane was grown by

the evaporation of -In2Se3 crystals at a substrate
temperature of 200C (Qasrawi, 2006). The films
deposited by the co-evaporation of In and Se
showed (006) as the preferred oriention (Amory
et al, 2003a; Amor et al, 2003b). Clavijo et al.
(2009) prepared -In2Se3 thin films with a band
gap of 1.47 eV by co-evaporation and they could
convert it into -In2Se3 films with a band gap of
2.11 eV by thermal annealing in Se atmosphere
(Clavijo et al, 2009).
The formation of In2Se3 thin films by solidstate reaction induced by annealing of vacuum
deposited In-Se stack layers was reported (Marsillac et al, 1996; Bernede et al, 1997; Emziane
et al, 1997). Promising IV characteristics were
obtained with TCOs such as SnO2 and ZnO for
-In2Se3 grown by a similar method (Marsillac
& Bernede, 1998). Bindu et al. (2002) obtained
polycrystalline -In2Se3 with a band gap of 2.09
eV by annealing stack layers consisting of amorphous Se and In, where Se was deposited by
CBD and In by vacuum evaporation (Bindu et
al, 2002). Negative conductivity was observed
at room temperature in In2Se3 films prepared by
annealing In/Se bilayer at 100C (Sreekumar et
al, 2006). The films produced by the evaporation of In2Se3 powder and by solid-state reaction
between In and Se sequentially deposited were
compared, and it was indicated that the best films
were obtained by the solid-state reaction followed
by annealing (Marsillac et al, 1995). The growth
of In2Se3 polycrystalline thin films by electron
beam evaporation was also reported (Manno et
al., 1995; Micocci et al, 2006).
The most common chemicals used for the preparation of In2Se3 thin films by CBD were indium
chloride (InCl3), tartaric acid, hydrazine hydrate
and sodium selenosulphate (Lincot et al, 1999;
Ortega-Borges, 1993; Gorer & Hodes, 1994). The
reaction between these chemicals in an aqueous
alkaline medium at room temperature gave In2Se3
(Asabe et al, 2008). Pathan et al. (2005) reported a
modified chemical bath deposition (M-CBD) for
231

the growth of In2Se3 thin films. In M-CBD, each

reaction was followed by rinsing, which enabled
the heterogeneous reaction between the solid phase
and the solvated ions in the solution (Pathan et al,
2005). They obtained nanocrystalline films with
a band gap of 2.5 eV higher than the usual band
gap obtained by CBD (2.35 eV). The resistivity
of M-CBD prepared films also showed a higher
value of electrical resistivity of 106 cm, while
the CBD films had a typical resistivity of the order
of 102 cm (Asabe et al, 2008).
Electrodeposition technique is another lowcost, simple and low-temperature liquid phase
method used for the growth of In2Se3. The lowtemperature deposition minimizes the inter diffusion of the materials at the grain boundaries
(Park et al, 1998) so that the films of high quality
can be produced for device applications such as,
heterojunctions devices, switching devices, etc.
(Massaccesi et al, 1996; Valdes et al, 2008). Highly
crystalline films were obtained by the electrodeposition technique from a mixture of InCl3 and
SeO2 in an aqueous solution (Gopal et al, 2005). A
TiO2/In2Se3/CuInSe2 heterojunction was reported

with electrodeposited In2Se3 (Valdes et al, 2008).
Nathan et al.(2003) developed an electrochemical
method analog to atomic layer deposition allowing
the formation of one atomic layer at a time. In2Se3
thin films and nanostructures were fabricated by
this method (Vaidyanathan et al, 2003).
Spray pyrolysis was chosen by several authors
to prepare In2Se3 thin films due to its simplicity
and versatility. It was observed that the properties of In2Se3 sprayed films depended mainly on
Se/In molar concentration ratio in the solution
(Bouzouita et al, 2002). Spray pyrolysis was
also used as a first step of a low-cost two-stage
process for preparing In2Se3 thin films. The spray
pyrolysed In203 thin films were allowed to react
with elemental Se vapor at atmospheric pressure
in nitrogen ambient to yield In2Se3. (see Figure 2)
The most important aspect of MBE is the slow
deposition rate, which allows the films to grow
epitaxially. In2Se3 epitaxial films were successfully
grown on (001) GaAs substrates by MBE. From
the studies carried out by Ohtsuka et al. (2000),
Figure 2. Raman scattering spectrum of -In2Se3 thin films (Emziane et al, 1997)
232

it was revealed that the crystallinity of the films

was improved by using slightly disoriented (001)
GaAs substrates (Ohtsuka et al, 2000). In2Se3
epitaxial films with zincblende structure were
successfully grown on (001) GaAs substrates at
low substrate temperatures and polycrystalline
In2Se3 films with defect wurtzite structure were
grown at high substrate temperatures (Okamoto
et al, 1997).
Polycrystalline In2Se3 films with a columnar
structure were grown by different groups (Huang
et al, 2008; Lyu et al, 2010) using MOCVD.
Homogeneous -In2Se3 thin films with a band
gap of 1.87 eV were reported using single source
MOCVD. Afzaal et al. (2005) fabricated In2Se3 by
low pressure (LP) MOCVD and aerosol assisted
(AA) CVD processes using a single source approach (Afzaal et al, 2005). By employing AACVD
they were able to reduce the growth temperature
to a few hundred degrees below that needed for
the growth by LP MOCVD. The growth of In2Se3
by AACVD was also reported (Park et al, 2003).
The MOCVD growth of In2Se3 films using the
volatile In[SeC(SiMe3)3]3 as the single-source
precursor was also reported (Cheon, J., et al,
1995). Another MOCVD method proposed to
prepare single-phase In2Se3 films was by using
dual-source precursors, trimethylindium (TMI),
and hydrogen selenide (H2Se) (Chang, 2007).
The flow rate of these two precursors could be
adjusted independently to obtain a different VI/
III ratio (Chang, 2007).
There were also reports of the growth of In2Se3
thin films by PLD, but the prepared films were
found to be amorphous in nature (Hrdlicka et al,
2007). Beck et al. (2007) reported the growth of
vacancies ordered in screw form (VOSF) and
layered In2Se3 thin films by laser back ablation
(LBA), which was analog to PLD (Beck et al,
2007). The growth by electron beam evaporation of polycrystalline -In2Se3 with a band gap
of 1.41 eV [111], and the growth of -In2Se3 by
flash evaporation of powdered single crystals of
In2Se3 [110] were reported.
The difficulty with the deposition of In2Se3 is often the coexistence of more than one InSe phase
and the amorphous nature of the as-deposited
films. Indeed, most of the deposition methods
yield amorphous thin films, and a heat treatment
of the as-deposited films is necessary to obtain
polycrystalline In2Se3 thin films. Such an annealing also helps eliminate the unwanted phases and
favors the existence of single-phase In2Se3.
The already mentioned evaporation techniques
and solid state reaction between the sequentially
deposited In and Se were completed by a postdeposition annealing treatment. The In-Se stacked
layers deposited were subjected to an annealing
treatment in vacuum in closed ampoules to obtain
single-phase -In2Se3 with a good texture. The
optimized annealing conditions were found to be
300C for 24 hours to obtain nearly stoichiometric
-In2Se3 thin films (Gordillo & Calderon, 2003;
Marsillac et al, 1996; Bernede et al, 1997). But an
annealing under a dynamic vacuum at 250C for
6 hours was necessary at the end of the process
to sublimate the Se deposited on the sample surface during the annealing. In a subsequent work
(Emziane et al, 1997), an open reactor was used
with an argon atmosphere during the annealing
process and the excess Se left was removed from
the samples following this process. The optimum
annealing temperature was 400C for a duration
of 30 minutes. It was also proved from studies
carried out by Emziane et al. (1999) that a higher
annealing temperature was needed to start the
crystallization for the films deposited with Se/In
ratio greater than 1.5 (Emziane & Le Ny, 1999).
Studies were carried out using nitrogen as a substitute for argon as the annealing atmosphere and
resulted in good crystalline quality -In2Se3 thin
films with the same annealing conditions, i.e.,
400C and 30 minutes (Marsillac et al, 1999).
Single-phase -In2Se3 films were obtained using
the same technique for an annealing temperature
of 587C for 40 minutes followed by quenching
233

to room temperature instead of a slow cooling

(Emziane et al, 2000c). The temperature was high
enough to obtain the single-phase which can
be kept at room temperature due to the quench
(instead of changing to the room temperature
stable -phase).
The post-deposition annealing was essential
for the process of preparation of -In2Se3 thin
films from InSe stacked layer also (Bindu et al,
2002), and the best crystalline films obtained for
an annealing temperature of 400C. The postdeposition annealing treatment also resulted in the
conversion of as-deposited -In2Se3 into -In2Se3
(Amory et al, 2003b). The -In2Se3 phase grown
by co-evaporation of In and Se was converted
into the -In2Se3 phase through thermal annealing at 550C in Se atmosphere. Sreekumar et al.
(2006) observed a phase transition from -In2Se3
to -In2Se3 upon annealing of In-Se stacked layers
at 400C (Sreekumar et al, 2006). Single-phase
-In2Se3 was formed on annealing at 200C with
grain orientations along (410) and (500), and
annealing at 400C resulted in the formation of
highly crystalline -In2Se3 having grains oriented

along (110) and (006). (see Figure 3)
The preparation of -In2Se3 thin films by
electron beam evaporation also necessitated
post-deposition annealing treatment in argon
atmosphere at a temperature of 427C (Manno et
al, 1995). Herrero et al. studied the (1987) effects
of post-deposition annealing on the properties of
the films prepared by alternate electrodeposition
of In and Se from separate baths. They observed
that when the temperature ranged between 300C
and 500C, the films were of -phase. At 600C
the thin films lost some Se and the ratio Se/In
decreased (Herrero & Ortega, 1987).
Effect of Deposition Parameters

The substrate temperature usually influences the
phase in which the In2Se3 films grow. At lower
substrate temperatures around 300C, the deposition of the -phase occur, while temperatures
higher than 500C resulted in the -phase. It was
also found that the samples deposited at tempera-
Figure 3. XRD patterns of -In2Se3 thin films (Emziane et al, 2000c)
234

tures ranging from 300C to 550C grew with a

mixture of -In2Se3 and -In2Se3 phases (Clavijo
et al, 2009).
The study of Julien et al. (1986) showed that
In2Se3 thin films grew with a good stoichiometry
at a substrate temperature around 187C in the
-phase, but were seen remained in the -phase
above 207C (Julien et al, 1986). The influence
of the substrate temperature and post-deposition
vacuum heat treatment on the properties of the
films was examined by Persin et al. (1972) for
films prepared by flash evaporation. Large agglomerates of defects were present in the films
formed at lower substrate temperatures, which
could not be removed by post-deposition heating
(Persin et al, 1972).
From the studies of In2Se3 prepared by electrodeposition from indium sulfide and selenious
acid solutions at 22 and 82C, it was found that
the higher deposition temperature caused a better
crystallization while the as-grown films showed a
small excess of elemental Se (Valdes et al, 2008).
(see Figure 4)
Figure 4. Cross-section of -In2Se3 thin films grown

on (a) glass substrate, (b) SnO2-coated glass, and
(c) gold-coated glass (Marsillac et al, 1999)
In2Te3 Thin Films

Deposition Methods
Techniques such as thermal evaporation, electron
beam evaporation, molecular beam epitaxy, and
flash evaporation are some of the methods used
for the growth of In2Te3 polycrystalline thin films.
Most of the researches on In2Te3 were done
on thin films grown by evaporation technique
(Rousina & Yousefi, 1990; Barua & Goswami,
1970; Peranantham et al, 2007; Mathur, 1981).
-In2Te3 thin films were grown by the sequential
evaporation of In and Te layers (Emziane et al,
1999) and by co-evaporation (Guettari et al, 2003).
-In2Te3 thin films were obtained by annealing the
films prepared by thermal evaporation (Hegab
et al, 1998). Balevicius et al. (1975) studied the
nanosecond switching and memory behavior
of In2Te3 thin films prepared by direct thermal
evaporation (Balevicius et al, 1975; Balevicius et

al, 1976). The films deposited by the electron beam
evaporation technique were found to be of -In2Te3
phase and no -In2Te3 phase could be observed
(Balevicius et al, 1976). Golding et al. reported
235

the studies of the molecular beam epitaxial growth

of In2Te3 (Golding et al, 1989), and the formation of In2Te3 thin films by the evaporation from
independent sources of elementary components
in a quasi-closed volume on InAs substrates was
also reported (Bezryadin et al, 1998). Thin films
of In2Te3 were prepared by the conventional flash
evaporation method onto freshly air cleaved single
crystal surfaces of NaCl (Desai et al, 2005). In2Te3
for use in thin film screw gauge (TFSGs) and gas
sensors was grown by flash evaporation (Desai et
al, 2005a; Desai et al, 2005b).
The depositions of In2Te3 by electrodeposition from propylene carbonate solutions containing InCl3 and tri-n-butyl phosphine telluride
(Wynands & Cocivera, 1988), and -In2Te3 by
the direct synthesis of this compound from In
and Te in a calorimetric bomb with an electrical
micro-furnace, were also reported (Lavut et al,
1997). Pure cubic In2Te3 films were deposited by
AACVD of a single-source precursor, {In(m-Te)
[N(iPr2PTe)2]}3 (Shivram et al, 2006).
Deposition Parameters and

The influence of the annealing conditions on
vacuum evaporated In2Te3 thin films was studied. The as-deposited indium telluride films had
an amorphous structure but annealing at 200C
resulted in the -phase polycrystalline structure
(Hegab et al, 1998), whereas the as-deposited
amorphous films showed InTe phase only on annealing at 250C in another study (Peranantham et
al, 2007). From the compositional analysis it was
observed that the films annealed at 400C were
In rich In2Te3 films due to the re-evaporation of
Te at elevated temperature. Similar observations
were also made by Emziane et al. (1999) where
the films subjected to a post-deposition annealing
at 390C resulted in Te deficient films. The results
were the same regardless of the annealing atmosphere (i.e. argon or nitrogen), and an annealing
236
temperature higher than 420C resulted in surface

oxidation (Emziane et al, 1999).
The effect of substrate temperature on the
preparation of thin films of In2Te3 was studied and
a substrate temperature of 180C was found to be
optimum for the preparation of In2Te3 thin films
(Balevicius et al, 1976). The growth of -In2Te3
at 227C was reported by Guettari et al. (2003).
It was also reported that a substrate temperature
of 200C favored the growth of -In2Te3 on glass
substrates, while -In2Te3 thin films were obtained
at 250C on NaCl substrates (Bezryadin et al,
1998).
PROPERTIES OF In2X3 THIN FILMS

An understanding of the fundamental properties
of thin films is an important prerequisite for the
fabrication of device quality materials. The film
functional properties depend on its chemical
composition and structure and the way it interacts
with its environment: light, electric and magnetic
fields, chemicals, mechanical force, heat, etc. This
section deals with the various properties of the
In2X3 thin films.
In2S3 Thin Films

Structural Properties
In2S3 is one of the In2X3 materials that crystallize
in cubic or hexagonal closed packed structure,
similar to II-VI compounds upon the replacement
of the divalent cation by the trivalent In. As one
third of the cation site remains empty, it causes a
defect structure (Becker et al, 1986). Three major
crystal modifications are known for In2S3 (Joint
Committee on Powder Diffraction, cards 5-731,
32-456, 25-390, 33-623). The low temperature
metastable -phase has a cubic structure with a
lattice constant a of 5.358 . It is a cubic closed
packed structure of sulfur, where 70% of the In
atoms are randomly distributed on octahedral

sites and the rest remain in tetrahedral sites (Diehl

& Nitsche, 1973). The -phase transforms irreversibly at 360 C to the -phase having a defect
spinal lattice (a = 10.73 ) in which eight of the
tetrahedral sites are occupied by In, and four are
randomly left empty (Kambas et al, 1985). Thus
the chemical formula of -In2S3 can be written
as [In(t)2/31/3]In2(o)S4 where (t), (o) and ()
represent the tetrahedral, octahedral and vacant
sites, respectively. Under certain conditions, a
high ordering of this vacancy at the tetrahedral
sites occurs, establishing a tetragonal super cell
containing spinel blocks along the c-axis (Kambas et al, 1981). This phase transition from the
tetragonal structure to the less ordered -phase
takes place at 420 C (Diehl & Nitsche, 1973;
Gilles et al, 1962). At a temperature of 754 C
-In2S3 is reversibly transformed to the -In2S3,
which has a layered structure with a hexagonal
unit cell (a = 3.85 , c = 9.15 ). The following
relation can be suggested for the phase transition
of In2S3.
Beside these phases, there is a high pressure
-phase, which is rhombohedral (a = 6.0561
and c = 17.5 ) (Joint Committee on Powder
Diffraction, card 33-624). Several reports were
published regarding the growth of different phases
of In2S3. The higher temperature cubic -phase
was observed in chemically deposited films onto
glass substrates as a mixture with the cubic -phase
(Gillen et al, 2004; Bayon & Herrero 2000). The
transmission electron microscopy (TEM) studies of CBD films showed that the initial growth
on glass corresponded to the -phase of In2S3
while the films deposited on FTO coated glass
substrate corresponded to the -phase (Lokhande
et al, 1999).
Among the different phase modifications,
-In2S3 is the stable form with a tetragonal structure
(Rooymans, 1959). Various groups studied the
structures of -In2S3 thin films by X-ray diffraction
(XRD) and scanning electron microscopy (SEM).
Cubic structures were reported for the CBD thin
films annealed under nitrogen atmosphere (Ber-
nede et al, 2002) and for films grown by SILAR

method (Kundkei et al, 2008). Films were found
to be composed of a mixture of the cubic and
-In2S3 phases for films grown by CBD technique
(Bayon & Herrero, 2000). The investigations of
films prepared by closed vapor evaporation showed
a combination of tetragonal and cubic structures
of -In2S3 phases at lower substrate temperatures
of less than 200 C (Revathi et al, 2008). XRD of
thermally annealed In2S3 films deposited by CBD
revealed that the thermal annealing on the films
produced the conversion of the cubic crystalline
phases to the tetragonal -phase and a crystalline reorientation of the latter phase (Gillen et
al, 2004). Similar characteristics were observed
for In2S3 prepared by annealing In in S pressure
(Benchouk et al, 2009).
Most of the as-deposited PVD films were noncrystalline and they were found to have polycrystalline nature belonging to the tetragonal -phase after
annealing (Timoumi et al, 2005; El-Shazly et al,
1998; Lee et al, 2009). Same trends were observed
for films obtained by some SILAR (Ranjith et al,
2007) and CBD (Bernede et al, 2002). Electrodeposition also required a subsequent annealing step
for best results (OBrien et al, 1998; Tacconi &
Rajeshwar, 1998), and it was also found that the
degree of crystallinity increased as the temperature
of annealing increased (Barreau et al, 2002; Barreau et al, 2000a; Yoosuf & Jayaraj, 2005; Revathi
et al, 2010). Indeed, the crystallinity increases
with increasing the annealing temperature as
well as the film thickness for -In2S3 deposited by
thermal evaporation (El-Nahass et al, 2006). The
increase of S concentration in the spray pyrolysis
also caused an increase in crystallinity.
In general, the (103) peak is the preferred
orientation for most of -In2S3 films that grow
in the tetragonal structure (Barreau et al, 2003;
Naghavi, 2003b; Sanz et al, 2006). But different
preferential orientations were observed by various
researchers depending on the method and substrate
used for the growth. The (109) preferential orientation was observed for films deposited by CBD
237

on TCO and glass substrates. The films prepared

by MFD presented different preferential orientations depending on the substrate used. On glass,
the films had a (103) preferential orientation, and
the films on TCO substrate exhibited the (109)
preferential orientation (Asenjo et al, 2007). The
preferential orientation was observed along (220)
plane for films prepared by spray pyrolysis (Pai
et al, 2005; John et al, 2005; John et al, 2006).
Guillen et al. (2004) reported that the (103) preferential orientation was achieved only when the S
source temperature was adjusted in a narrow range
between 220 and 230 C (Guillen et al, 2004).
Substrate temperature has a strong impact on
the film morphology and grain size. The surface
topology studies carried out by atomic force microscope (AFM) measurements on close spaced
evaporated films showed that the granularity was
improved by 25 nm with an increase in substrate
temperature (Revathi et al, 2008). A similar observation of variation in grain size with substrate
temperature was reported for the spray pyrolysed
films (Pai et al, 2005). The variation in grain size
by 20 nm was reported also by post-deposition
annealing (Revathi et al, 2010). A decrease in a
and c lattice parameters with substrate temperature
was observed for the films grown by close spaced
evaporation (Sotelo-Lerma et al, 2006).
The surface studies of In2S3 prepared by CBD
at room temperature showed a cauliflower-like
morphology, while the films deposited at a higher
temperature resulted in a fibrous structure (Yamaguchi et al, 2003). The film deposition at lower
reaction temperature was by the sedimentation of
particles formed in the bath, and the film growth
was by the heterogeneous precipitation on the
substrate at higher temperature. A microcrystalline
morphology was observed in the sample deposited by plasma-assisted co-evaporation (PACE)
at 350 C with an average grain size around 100
nm, while a nanocrystalline film morphology was
observed at lower temperatures with a reduction
in grain size to 10 nm at 100C (Sahu, 1995). A
238
significant variation in surface morphology with

the reaction temperature was also reported.
Deposition time also affects the morphology
of the films. The films prepared by CBD were
composed of nanometric round shape grains for
lower deposition time, whereas the films deposited
were composed of a porous layer formed by larger
and irregular agglomerates for higher deposition
time (Yahmadi et al, 2005). Similar growth stages
were reported by some other authors as well. The
layer grown at a shorter deposition time was constituted by rectangular-shaped crystallites whose
growth was combined with the sticking of large
colloidal agglomerates formed in the reaction
solution at longer deposition times. The number
and size of the agglomerates on the film surface
increased with deposition time (Asenjo et al,
2009). The presence of In6S7 phase caused some
fibre structures along with large lumps (Bernede et
al, 2002). Irregular shaped platelet-like structures
were obtained for films grown by CBD (Asenjo
et al, 2004) and different film morphology was
observed depending on the substrate used. On
glass the films were composed of large nanometric
round shape grains, whereas the films deposited
on PET and Arylite were composed of irregular
agglomerates (Bouguila et al, 1997).
The composition of the films usually depends
on the growth process. It was generally observed
that when the deposition was based on chemical
methods, the residual precursor elements were
found within the films. Typically, chlorine was
frequently detected in the films grown by ALD
with InCl3 precursor (Asikainen et al, 1994),
ILGAR (Allsop et al, 2005), and spray pyrolysis
(Hariskos et al, 1996; Vaidynathan et al, 2003). In
the case of CBD and electrodeposition, the layers
contained In(S, OH) compound (Bayon & Herrero,
2000; Kim & Kim, 1986; Datta et al, 2008). Sulfur
composition in excess of the stoichiometric value
in spray pyrolysed In2S3 films caused an increase
in the lattice parameters a and c (John et al, 2005).
Similar observations were reported with EDX studies for the films grown using a two-stage process

(Yoosuf & Jayaraj, 2005) with a suggestion that

the expansion of the lattice parameters was due
to the occupation by sulfur of the interstitial sites
of defect spinal structure.
Optical Properties
-In2S3 thin films exhibit a direct optical transition
with a band gap energy (Eg) around 1.98-2.3 eV
(Naghavi et al, 2003b; John et al, 2003; Guillen et
al, 2004; Nomura et al, 1991; George et al, 1998).
An indirect optical transition (with Eg = 2.2 eV)
was also reported (Kim & Kim, 1986; Timoumi et
al, 2006; Sterner et al, 2005). Several values greater
than 2.3 eV have been reported in the literature.
A higher band gap of 2.84 eV was obtained for
CBD grown films (Asenjo et al, 2004), and similar
values were reported for -In2S3 films deposited
on several kinds of TCO by PVD. A band gap
energy of ~2.6 eV was obtained for -In2S3 thin
films deposited onto glass substrates by CBD and
SILAR (Kundakci et al, 2008; Sanz et al, 2006).
Several authors studied a widening in the
band gap by an increase in oxygen content in the
films (Barreau et al, 2002c; Tacconi & Rajeshwar, 1998; Barreau et al, 2002b). An increase in
band gap was observed due to Na content in the
films, and this was explained by the fact that Na
increased the ionicity of the tetrahedral cationic
sulfur bonds which increased the optical band
gap. Some authors attributed the gap broadening
to an excess of S (Naghavi et al, 2004). The blue
shift of the optical transmission was interpreted
by the broadening due to an excess of S in the
bulk (Kim & Kim 1986). But contrary to these
reports, John et al. observed a decrease in band
gap when the S concentration increases (Pai et al,
2005). Some authors explained the broadening
of the optical band gap of In2S3 by quantum size
effect induced by the small grain size (Yasaki et
al, 1999). The higher band gap obtained for the
spray pyrolysed films was explained both by the
presence of oxygen and the quantum size effect
(Pai et al, 2005). The broadening or shift of the
short wavelength absorption of In2S3 thin films

was also explained by the presence of secondary
phases and disordered structure (Kamoun et al,
1998).
Higher band gaps were generally observed in
vacuum deposited In2S3 thin films after annealing (Timoumi et al, 2006; El-Nahass et al, 2006).
The band tails observed in the optical spectra of
vacuum deposited In2S3 thin films after air annealing were interpreted as defects introduced
by the thermal evaporation process (Timoumi
et al, 2006). In contrast, there were reports of a
decrease in band gap on annealing (Yousfi et al,
2001; Revathi et al, 2010). The sharp decrease of
energy band gap at higher annealing temperatures
could be explained by structural defects.
A strong effect of the film thickness on the
optical absorption coefficient and the band gap
energy was observed for films grown by MFD
where values above 3.0 eV were obtained for very
thin In2S3 films (Guillen et al, 2004).
A broadening of the band gap of the films
with the increase of substrate temperature up to
300 C was observed for evaporated films, and
further increase in substrate temperature caused a
reduction in band gap. The initial bad gap increase
was explained by the decrease of mid band gap
defects while the subsequent decrease was thought
to be due to the larger compositional deviations
in the films as indicated by the compositional
analysis. The band gap of the films deposited by
PACE was reduced by the increase in substrate
temperature (Sahu, 1995) and a red shift in band
gap was observed for In2S3 thin films on swift
heavy ion irradiation (Kumar et al, 2006).
Electrical Properties
The electrical properties of -In2S3 phase were
studied by Rehwald et al. (1965). They found it
to have a n-type electrical conductivity, however,
the conductivity strongly depended on the S concentration. A deficiency in S relative to the In2S3
stoichiometry increased the electron density, and
239

thus the n-type nature. It was also observed that

the annealing of In2S3 films in air or vacuum at
temperatures around 150 C for 2 hours resulted
in an increase in conductivity by more than an
order of magnitude.
The large increase in conductivity observed
for the spray pyrolysed films on annealing was
explained by the modification of the properties
of the grains or their boundaries by the presence
of oxygen (John et al, 2006).
For photovoltaic device applications, it is
essential to know the photosensitivity of the
material. The processing parameters such as
substrate temperature, reaction temperature, and
S/In concentration in the reaction solution have
influence on the film photosensitivity. The photosensitivity was found to be decreasing by an
increase in substrate temperature. The increase in
S concentration caused an increase in photosensitivity, while the increase in In concentration had
a negative impact (Pai et al, 2005). The increase
in reaction temperature during the sulfurisation of
In films to obtain In2S3 films showed an increase
in photosensitivity (Yoosuf & Jayaraj, 2005). The
post-deposition annealing of the spray pyrolysed
films led to the reduction in photosensitivity (John
et al, 2006).
The Presence of Other Elements

Recent investigations dealt with the effect of the
introduction of foreign atoms within In2S3. The
presence of Al atoms in the compound noticeably contributed to the growth and structure of
the deposited films. The presence of Al caused
an increase in adsorption of oxygen in the spray
pyrolysed films (Kamoun et al, 2001). The study
of Na containing -In2S3 films proved that the
introduction of Na in the -In2S3 crystalline matrix induced an increase of the lattice parameter
a and an increase of InS and NaS bond lengths
(Barreau et al, 2002d). Ag and Cl doping resulted
240
in samples with enhanced crystallinity and photosensitivity (Mathew et al, 2009; Cherian et al,
2010). The substitution of a third element also
helped in stabilizing the phases. The stabilization of -In2S3 at room temperature was achieved
through replacing about 510% of In atoms by
As, Sb or Bi (Pandey et al, 1996).
The partial substitution of In by another element like Al (Bhira et al, 1998; Couzinie-Devy
et al, 2010), or a partial substitution of S by O
(Hariskos et al, 1996; Brauger et al, 1996), were
widely accepted methods of making wide band gap
In2S3 films. Sn doping investigated by introducing Sn into the spray solution also resulted in a
widening of the optical band gap through oxygen
incorporation (Mathew et al, 2010).
The presence of a third element can lead to
drastic changes in the electrical properties. Indeed,
the conductivity was found to increase with Na
content. When Na was introduced in the crystalline
matrix, it created a disorder by the non-periodic
occupation of the tetrahedral sites and this could
explain the increase in electrical conductivity
(Barreau et al, 2002a). But reportedly when the Na
content was increased above a particular value, a
total filling of the tetrahedral sites resulted, leading
therefore to a perfectly ordered material having
a very low electrical conductivity (Barreau et al,
2003). The introduction of oxygen in the thin films
could modify the properties of grain boundaries,
which induced an increase in conductivity of the
films approximately by two orders of magnitude
(Barreau et al, 2002b). The effect of the substitution of S by O in -In2S3 films also induced an
increase in conductivity (Bessergenev et al, 1996).
The conductivity of the samples was enhanced
by five orders of magnitude through Sn doping
done by thermal diffusion for the films grown by
spray pyrolysis (Mathew et al, 2010). Sn doping of
In2S3 films also increased the conductivity of the
films prepared by chemical vapor phase transport
(Becker et al, 1986).

In2Se3 Thin Films

In2Se3 is an interesting material because of its
polymorphism and related metal-ion defect structure. Though there are relatively five well known
phases , , , , and , there are only two basic
phases for this compound. One is the -phase that
crystallizes in a layer structure and is metastable at
room temperature but stable at temperatures higher
than 550 C, and the other is the -phase which is
stable phase at room temperature and crystallizes
in a defect wurtzite-like structure with one third of
the cation sites being vacant (Emery et al, 1992;
Ohtsuka et al, 1999; Ye et al, 1998b; Popovic et al,
1979; Pfitzner & Lutz, 1996; Manolikas, 1988).
Such structural vacancies behave as one atomic
species and should be arranged in a screw form
along the c axis (Ye et al, 1998a). (see Figure 5)
-In2Se3 with a rhombohedral structure is
metastable and can be obtained by heating
-In2Se3, that will transform back to -In2Se3 at
room temperature. -phase can be stabilized by Sb
doping which makes it stable (Eddike et al, 1998).
The -phase is found to be stable above 750 C
(Marsillac et al, 1995). The different phases and

their properties are given in Table 1.
The -In2Se3 phase with an anistrophic structure was reported by De Groot et al. (2001) and
Jasinky et al. (2002). Although the conditions of
deposition are similar to that of the -phase, doping is necessary to obtain and stabilize -In2Se3
thin films at room temperature. However, the
-phase transforms to -phase on annealing at
higher temperatures (Eddike et al, 1998). -In2Se3
has a flake like structure, whereas -In2Se3 has a
columnar structure (Huang et al, 2008).
There were studies carried out to understand the
phase transition during the preparation. Annealing
In/Se bilayer films at lower temperature resulted in
the formation of In6Se7 and -In2Se3 phases. The
growth of the -phase with a good stoichiometry
was observed at a substrate temperature around
187 C and shown to remain in the -phase above
187 C (Julien et al, 1986). The suitable annealing
temperature for the growth of single-phase -In2Se3
was found to be 200 C by another study, and a
phase transformation from -In2Se3 to -In2Se3 as
well as a structural re-orientation of planes was
also observed at an annealing temperature of 400
C (Sreekumar et al, 2006). A high Se/In ratio in
amorphous multilayers or a high Se overpressure
Figure 5. Photoluminescence spectra of a -In2Se3 thin film at different temperatures [Marsillac et al,
1999].
241

Table 1. The characteristic phases of In2Se3 films

Phase
a ()
c ()
Structure
Characteristic
4.025
4.025
19.235
Hexagonal
Stable
28.762
Rhombohedral
Stable
4.0157
28.33
Rhombohedral
Metastable
7.1286
19.382
Hexagonal
Stable
8.09
19.8
Hexagonal
metastable
hexagonal
Stable at higher
temperatures
4.014
during the annealing of amorphous films was

found to promote the formation of the singlephase -In2Se3 (Emziane et al, 2000a; Bernede
et al, 1997). A high Se overpressure during hot
depositions resulted in the -phase (Emziane et
al, 1999; Ohtsuka et al, 2001). At substrate temperatures ranging from 300 to 550 C, the In2Se3
films grew with a mixture of the -In2Se3 and
-In2Se3 phases (Amory et al, 2003b).
XRD studies showed that the -In2Se3 films
were highly orientated along the (006) plane
(Afzaal et al, 2005; Afifi et al, 2001). To improve
the crystallinity, it was suggested to remove the
excess of Se by the heat treatment of the asdeposited films at temperatures above 300 C in
flowing nitrogen (Emziane et al, 1999). The same
observations were reported for films prepared by
vacuum evaporation of InSe crystals (Ates et al,
2008). The solution temperature was found to
influence the crystallinity for the electrodeposited
films (Valdes et al, 2008). Another suggestion for
improving the crystallinity of the films prepared
by electrodeposition was to increase the concentration of InCl3 in the reaction solution (Gopal et
al, 2005). A similar observation was reported by
another group that improved the crystallinity of
In2Se3 films by increasing the In concentration
during the fabrication process of In2Se3 films by the
stacked elemental layer (SEL) technique (Deepa
et al, 2006). The growth of In2Se3 films on AlN
buffer layers also resulted in a better crystallinity
(Chang et al, 2007).
242
9.646
The morphology of the In2Se3 films depends

on the deposition parameters and the substrate
on which the film is grown. Investigations using reflection high-energy electron diffraction
(RHEED), Raman spectroscopy, and SEM showed
that low growth temperatures (500 C) resulted
in the formation of a zincblende structure, and at
high temperatures (> 540 C) the films grew in a
defect wurtzite structure on GaAs (001) substrates
(Okamoto et al, 1997). Similar structural characteristics were observed for MOCVD films grown
at different temperatures. XRD analysis revealed
that In2Se3 had a wurtzite structure at a growth
temperature below 450 C, while a rhombohedral
structure was obtained above 450 C (Huang et al,
2008). SEM showed a vertical columnar structure
of -In2Se3 on Si (111) substrates (Huang et al,
2008; Chang et al, 2007), and a horizontal lamellar
structure on Si (100) substrates (Chang et al, 2006).
The film morphology was observed to improve
by introducing an AlN buffer layer for the films
grown by MOCVD (Chang et al, 2007). The CBD
grown films appeared to be made of small grains
with an average size of 21nm (Asabe et al, 2008).
AFM measurements showed that the phase of
the In2Se3 thin films and their thickness significantly affect their morphology. The and phases
grown by the same method showed different visual
appearances, and it was found that the increase
of the film thickness affected both the average
roughness and the average grain size (Amory et
al, 2003b). Furthermore, the grain size and the

growth rate were drastically increased with the

increase in substrate temperature (Lyu et al, 2007).
Optical Properties
In2Se3 films have a high optical absorption coefficient and a direct band to band type optical
transition. The band gap of -In2Se3 at room
temperature is estimated to be in the range 1.7-2
eV (Lyu et al, 2010; Lyu et al, 2007), while the
band gap of -In2Se3 is in the range of 1.2-1.3 eV
(Qasrawi et al, 2001; Emziane et al, 2000c). A
direct band gap of 1.55 eV was obtained for the
-phase (Julien et al, 1986) and 1.75 eV for the
-phase (Eddike et al, 1998).
A higher band gap of 2.35 eV was reported
for all the films prepared by CBD at room temperature showing a n-type conduction mechanism
(Asabe et al, 2008; Hankare et al, 2008). A band
gap of 2.5 eV was observed for indium selenide
compound formed with InSe, In2Se3 and In6Se7
phases (Pathan et al, 2005), and oxygen was also
present in the films. The annealing resulted in an
increase in optical band gap with temperature due

to the formation of the -In2Se3 phase (Afzaal et
al, 2005; Ates et al, 2008). A maximum band gap
of 2.08 eV was obtained for evaporated films annealed at 400 C. Contrarily, the band gap energy
of In2Se3 thin films prepared by SILAR seemed
to decrease with increasing temperature (Astam
et al, 2007).
A decrease in optical band gap was reported
by the substitution of Te for Se (Hrdlicka et al,
2007). A decrease in optical band gap was also
shown for electrodeposited In2Se3 films with an
increase in the concentration of InCl3 which, in
turn, caused an increase in the In content in the
films (Gopal et al, 2005).
The optical studies of In2Se3 films showed that
in the films grown in the -phase the transmittance was caused by photon absorption via states
within the gap, which contributed to the absorption process simultaneously with the fundamental
absorption. Whereas, in -In2Se3 films the photon
absorption was mainly through the fundamental
absorption mechanism (Amory et al, 2003b).
Figure 6. Photocurrent spectra of a 1m thick -In2Se3 film with the beam incident on the film (a), and
on the substrate (b) [Marsillac et al, 1999].
243

Photoluminescence spectra of single-phase

-In2Se3 films prepared by AP-MOCVD showed
an exciton emission at 580 nm (Lyu et al, 2010;
Lyu et al, 2007). Strong emissions were observed
at around 580 nm for films grown by MBE. The
emission consisted of three well-resolved lines
that were identified with a free exciton (Ex) and
bound excitons (Ix0, Ix1) at 579.2 nm (Ex), 579.8
nm (Ix0) and 580.2 nm (Ix1), respectively (Ohtsuka et al, 1999).
Photoluminescence investigation of films
prepared by annealing In/Se bilayer system at 100
C showed that as the In concentration increased
the intensity of the emission decreased sharply.
A strong emission with a maximum intensity was
observed at 802 nm, i.e. and energy of 1.55 eV
(Sreekumar et al, 2006).
It is reported that the type of conductivity of In2Se3
thin films depends on the annealing temperature.
Low temperature annealed films showed n-type
conductivity due to the presence of undiffused
In, while films annealed at higher temperatures
showed a p-type conductivity (Bindu et al, 2002).
Qasrawi et al. (2001) reported p-type -In2Se3 by
thermal evaporation followed by annealing at 200
C. The annealing increased the conductivity for
electron beam evaporated and vacuum evaporated
films (Manno et al, 1995; Afifi et al, 2001). The
conductivity was controlled by the grain boundaries and was very sensitive to oxygen contamination
(Bernede et al, 1997). The increase in the electrical
conductivity of the -phase after thermal treatment above 200 C and its irreversibility were
explained in terms of structural changes at high
temperatures (Julien et al, 1986).
The dark and photoconductivity were found to
be decreasing with temperature when annealing Se
and In stacked layers to obtain In2Se3 thin films.
The films synthesized by annealing the layers at
100 C resulted in a maximum photoconductivity,
244
while those formed at 450 C showed a minimum

photoconductivity (Bindu et al, 2002).
Negative photoconductivity in -In2Se3 thin
films was reported at room temperature (Sreekumar et al, 2006). The trapping of photo excited
carriers, recombination of minority carriers, and
capture of conduction band electrons ultimately
resulted in negative photoconductivity at room
temperature. The same work also revealed that
the photoconductivity of the films decreased
gradually and became negative upon increasing
In concentration.
The Presence of Other Elements

Doping with a third element helped in stabilizing
the -phase of In2Se3. Indeed, Zn doping was found
to stabilize -In2Se3 thin films at room temperature
(De Groot & Moodera, 2001). A small addition
of Ag also resulted in stabilizing the -In2Se3
phase formed both with and without capped films
(Eddike et al, 1998). Mn doping of -In2Se3 was
implemented by depositing a Mn layer of ~ 10
nm thickness prior to the co-evaporation of In and
Se, and the insertion of Mn in the film strongly
influenced its crystallization (Amory et al, 2006).
Doping of p-type -In2Se3 thin films by Cd
was observed to significantly alter their structural, electrical, and photoconductive properties
(Qasrawi et al, 2002). The hexagonal structure of
-In2Se3 was transformed to hexagonal InSe due
to a change in the lattice parameters, reflection
lines, and stacking orders upon Cd doping. The
values of the room temperature dark electrical
conductivity, carrier concentration, and Hall
mobility increased when the samples were doped.
However, the activation energy and the barrier
height at the grain boundaries were decreased
by Cd incorporation due to a higher density of
traps in the band gap and at the grain boundaries.
The temperature dependence of the electrical
conductivity and Hall mobility of S and Li doped
In2Se3 films were studied by Julien et al. (1986).

In2Te3 Thin Films

A systematic XRD investigation of In2Te3 has
shown that there are two phases and , and the
former transforms to the latter at a temperature of
about 620 C. The high temperature disordered
-In2Te3 has a zinc blende structure (Hahn &
Klinger, 1949) with a lattice parameter of a =
0.6158 nm, whereas the low temperature -In2Te3
phase has a defect antifluorite structure with a
lattice parameter of a = 1.6548 nm. It has been
reported that the to transition is fully reversible.
These two phases are characterized by one-third
or two-thirds, respectively, of the In sub-lattice
sites being vacant.
The electron microscopic studies revealed that
the ordered -In2Te3 phase was actually composed
of two different ordered phases, namely -In2Te3-I
and -In2Te3-II (Karakostas & Economou, 1975).
The -In2Te3-II was a super structure of the
-phase with a high density of stacking faults.
The -In2Te3-I was of a hyper-stoichiometric

type, whereas the -In2Te3-II was of a hypostoichiometric type.
Different phase growths were observed with
respect to the substrate on which the films are
deposited. In2Te3 thin films grown on glass substrates were of -phase, whereas those formed
on crystalline NaCl substrates were of -phase
(Desai et al, 2005). The annealing of amorphous
In2Te3 films at 300 C resulted in polycrystalline
-In2Te3 films (Hegab et al, 1998).
Optical Properties
The direct band gap values reported in the literature for In2Te3 vary between 1.03 and 1.23
eV (Rousina & Yousefi, 1990; Peranantham et
al, 2007; Emziane et al, 1999; Afifi et al, 2000).
The transmittance and the band gap were found
to increase with the annealing temperature for
the vacuum evaporated films (Peranantham et al,
2007). (see Figure 7)
Figure 7. Absorption coefficient and band gap determination for a typical -In2Te3 thin film [Emziane
et al, 1999].
245

A band gap of 1.02 eV was reported for

-In2Te3, and the effect of annealing on the
band gap was interpreted by the density of states
(Hegab et al, 1998). A band gap of 0.8261 eV
for as-deposited films increased to 1.1480 eV
for films annealed at 250 C (Peranantham et
al, 2007).
A band gap of 1.19 eV was observed at room
temperature for -In2Te3 grown by MBE, and
the refractive index was found to be 2.85 at a
wavelength of 1100 nm (Bezryadin et al, 1998).
The electrical measurements show that In2Te3
films are p-type semiconductors (Matheswaran
et al, 2010). An irreversible change in electrical
conductivity was observed above 252 C hinting to the possibility of decomposition (Mathur
et al, 1981). DC electrical conductivity and
Hall effect measurements were carried out for
-In2Te3 thin films obtained by direct thermal
evaporation on sapphire substrates (Afifi et al,
2000). The variation of the DC electrical conductivity of In2Te3 thin films with temperature
was studied at different substrate temperatures
(Desai et al, 2006). The AC and dielectric
properties were also studied for In2Te3 films
grown by vacuum evaporation (Seyam, 2001;
Matheswaran et al, 2010). Both the dielectric
constant and the dielectric loss increased with
temperature and decreased with frequency in
the investigated range.
The junction studies showed that Ag, Sn, In
and Zn provided good ohmic contact for In2Te3
thin films (Desai et al, 2006). Finally, it was
shown that the thermoelectric power of -In2Te3
was temperature independent (Lakshminarayana
et al, 2002).
246
APPLICATIONS OF In2X3 THIN FILMS

In2S3 Thin Films
In2S3 is among the interesting candidates for the
replacement of CdS as buffer layer in Cu(In,Ga)
Se2 (CIGS) as well as in CdTe based solar cells
due to the possible gains in efficiency associated
with an increase in the short circuit current. To
avoid the toxic heavy-metal Cd containing waste
in the module production, a Cd free buffer layer
is desirable. Wide band gap (>2.5 eV) In2S3 thin
films have the potential to be used as a better
buffer layer with an improved light emission in
the blue region compared to CdS that has a band
gap of 2.4 eV.
The development of Cd free devices started in
1992 with an efficiency of about 9% and intensively
continued to the current efficiency level of 16.4%
(Naghavi et al, 2003a) for CIGS solar cell prepared
with atomic layer chemical vapor deposited In2S3
as a buffer layer. Comparing the results with those
using a CdS buffer layer, the initial difference was
about 4% absolute and became almost negligible
following more investigations (Hariskos et al,
2005). The ALD process for the In2S3 deposition
was up-scaled to a substrate size of 3030 cm2 with
best efficiencies up to 10.8% (Brahim-Otsmane
et al, 1994) and 12.9% (Spiering et al, 2004) for
such a CIGS sub-module. The cell parameters of
some CIGS modules with In2S3 buffer layers grown
by different methods are summarized in Table 2.
The best cell efficiencies obtained so far with
In2S3 buffer layers by PVD as an in-line compatible dry vacuum deposition method are: 15.2%
(Pistor et al, 2009) by depositing the buffer layer
on industrially developed Cu(In,Ga)Se2 absorber,
and 14.8% (Strohm et al, 2005) by depositing the
buffer and absorber layers in the same chamber
without vacuum breaking.
An efficiency of 7.9% was reported for the
buffer layer with a mixed ZnS-In2S3 composition
(Sakata, 2000), with the introduction of Zn in
proportion around 1% in the reaction mixture. The

Table 2. Performance of some CIGS modules of different sizes with In2S3 buffer layer grown using different methods
Deposition method
Efficiency (%)
JSC (mA.cm-2)
VOC (V)
FF (%)
Area (cm2)
ALCVD
16.4
31.5
0.665
78
0.1
ALCVD
14.9
30.8
0.648
74.7
0.5
PVD
15.2
29.8
0.667
75.6
0.528
PVD
14.8
31
0.65
71
0.48
Ultrasonic CSP
12.4
34.7
0.502
71
Not specified
CSP
9.5
48.2
0.588
33.5
0.009
ALCVD
12.9
45.7
0.278
72.6
714
ALCVD
10.8
29.5
0.591
62
724
Zn introduction favored the JV characteristics

of the cells, open circuit voltage (Voc), fill factor
(FF), and efficiency (). The deposition of a small
amount of zinc sulfide (ZnS) at the absorber/buffer
interface was also used to improve the performance
of CIGS solar cells. ZnS helped increase Voc of
the cell by approximately 20 mV and raised its
overall efficiency (Allsop et al, 2007).
An annealing step (~ 5-10 min at 200 C in air)
of the complete cell was shown to be beneficial
for the cell performance (Todorov et al, 2008;
Buecheler et al, 2009). An efficiency of 12.3%
was reported after annealing the laboratory cells
with CIGS/MOCVD indium sulfide structure,
although the composition of the In2S3 buffer layer
was not specified. A cell efficiency of 12.4% was
achieved with an ultrasonically sprayed In2S3 buffer layer on a CIGSSe absorber after heat treatment
(Buecheler et al, 2009).
The substrate temperature during the deposition of the In2S3 buffer layer turned out to be a
crucial parameter with regard to CIGSe/PVD-In2S3
solar cell efficiency (Barreau et al, 2009). The
chemical nature of the interface changed as the
substrate temperature varied, which affected all
the solar cell parameters and caused a decrease
of its efficiency.
In2S3 thin films can also be used as precursors
for the preparation of CuInS2, which is one of the
most widely used absorber layers in solar cells

(Sakata et al, 2000).
The surface sulfurisation by sequential evaporation of In2S3 after CIGS deposition improved by
1% the performance of ZnO:Al/CdS/CIGS/Mo/
glass solar cell without antireflection coating
(Ohashi et al, 2001).
The possibility of using n-type In2S3 in photoelectrochemical cells (PECs) also attracted some
interest recently. In a PEC using In2S3 and In2O3
multilayer composite, single walled carbon nanotubes (SW-CNTs) led to an increase in power
conversion efficiency by reducing the recombination rate (Lee et al, 2007). The polymer-sensitized
PECs based on In2S3 nanorods in thin film form
were recently reported (Lee et al, 2008), where
the PECs were prepared by the adsorption of
acetylene-polymer photosensitizers on In 2S3
nanorods in aqueous solution which demonstrated
a power conversion efficiency of 1.63%.
In2S3/TiO2, In2S3/ZnO, and In2S3/ZnS photoelectrode structures were fabricated using In2S3
colloidal thin films grown by spin coating. A
photocurrent sensitized by In2S3 was observed for
ZnO and TiO2, but not for ZnS (Yasaki et al, 1999).
The use of In2S3 in polymer heterojunction solar
cells was reported (Dalas et al, 1993; Tang et al,
2008), and the effect of each layer thickness in an
inverted polymer solar cell using spray pyrolysed
In2S3 and MEH-PPV polymer was carried out.
247

The optimum layer thickness was found to be

200 nm for In2S3 and 100 nm for MEH-PPV, and
the maximum efficiency obtained was 0.075%
(Menon et al, 2010).
In2Se3 Thin Films

In2Se3 can be used as a window layer (Former et
al, 1985) in CIS/In2Se3 solar cells as well as an
absorber layer (El-Sayed, 2004; Lee et al, 2008) in
CdS/In2Se3 solar cells depending upon the optical
band gap of the film. -In2Se3 with a wider band
gap of 2.15 eV (Clavijo et al, 2009) can be used
as window layer, while -In2Se3 having a band gap
of 1.3 eV (Segure et al, 1983) can be used as an
absorber layer in solar cells. Its cleaved surfaces
do not need any additional treatment for pn
junction formation and are chemically inert under
ambient conditions (Qasrawi, 2007). In2Se3 has a
low surface recombination velocity resulting from
its low density of dangling bonds on the surface.
An efficiency of 13% was reported for CIGS
based solar cells with In2Se3 window layers grown
by co-evaporation (Konagai et al, 1996), while a
Mo/CIS/In2Se3/ZnO solar cell with an efficiency
of 8.3% was reported using the co-evaporated
In2Se3 as a the window layer (Gordillo et al, 2003).
The composition effect on the JV characteristics of -In2Se3 based diodes was investigated
for Mo/-In2Se3/ZnO:Al diode structures. When
-In2Se3 was doped with Mn there was no photovoltaic effect that is seen for pure -In2Se3,
which could be attributed to the presence of a
band of localized states present in the band gap
of Mn-doped -In2Se3 (Morsli et al, 2007). The
rectifying contact SnO2/In2Se3 was investigated
using n-type -In2Se3 with a band gap of 1.8 eV
(Bernede et al, 1997).
The formation of CuInSe2 from a migration
enhanced MBE deposited In2Se3 was reported
(Kim et al, 2005). The complex layered structure of
In2Se3, which makes it possible for ions to diffuse
and alter its physical properties without changing
its structure, allows this material to be used as
248
cathode in micro-batteries and as solid solution

electrodes in micro-capacitors (Balkanski, 1998).
The phase change characteristics and the
wider variation in electrical resistivity associated
with the crystallization of In2Se3 films have an
advantage in the multi-bit per cell operation of
PRAM devices (Lee & Kang, 2005; Ahrenkiel
et al, 1993; Segure et al, 1983). An In2Se3 based
PRAM device switching between amorphous and
crystalline states was fabricated and exhibited a
switching dynamic range as high as 100 (Lee &
Kang, 2005).
In2Te3 Thin Films

The gas sensing feature of In2Te3 thin films with
respect to CO2 was investigated and they were
found to be useful in monitoring the CO2 concentration (Desai et al, 2005b). With increased
CO2 concentration, the sensitivity of the sensor
increased.
The application of In2Te3 as a possible thin
film screw gauge (TFSG) was also studied, and
the resulting TFSGs had a high gauge factor and
a good temporal stability. They exhibited a linear
response for both tensile and compressive strains
and a negligible hysteresis (Desai et al, 2005a).
The study of the switching behavior in amorphous In2Te3 thin films revealed that it was typical
for a memory switch. The thickness dependence
of the mean value of the switching voltage Vt was
linear in the investigated range, and Vt decreased
exponentially with a temperature rise from 25 to
100 C. The switching voltage activation energy
was about 0.25 eV and the conduction activation
energy was 0.51 eV (Afifi et al, 1996).
In2Te3 was also found to be of interest as a radiation stable particle due to its suitable direct band
gap and large stopping power as a consequence
of high atomic mass and low defect migration
energy (Afifi et al, 1995).

TERNARY COMPOUND THIN

FILMS BASED ON In2X3
In addition to the binary compounds, there are
also some ternary phases of group In2X3, such as
In2(Se,Te)3, (In,Ga)2X3 that have band gaps and
photoconductive properties suitable for solar cell
absorber layer applications. (see Figure 8)
Thin films of In2Se3-xTex (x = 01.5) were prepared by pulsed laser deposition (PLD) however
the obtained films were amorphous (Hrdlicka
et al, 2007). The growth of -In2(Se2.5Te0.5)3 by
alternate thermal evaporation of In and (Se, Te)
layers on glass substrates was reported. Although
the as-deposited films were amorphous, the postdeposition annealing treatment resulted in their
Figure 8. XPS spectra of In2(Se1xTex)3 (x~0.11) films. In 3d: from top to bottom, respectively, after 0, 1,
3 and 6 min of sputtering. Se 3d and Te 3d: from bottom to top, respectively, after 0, 1, 3 and 6 min of
sputtering (Emziane & Le Ny, 2001)
249

Figure 9. The spectral distribution of the transmittance of In2(Se1xTex)3 (x~0.17) films with 600 nm
thickness in the visible and near-infrared (a). The transmittance of -In2Se3 films with 900 nm thickness
is also shown for comparison (b) (Emziane & Le Ny, 2001).
crystallization. A band gap of 1.45 eV was obtained

for the -In2(Se2.5Te0.5)3 films, and the substitution
of Se atoms by Te improved the photocurrent
intensity. The photocurrent was increased about
three orders of magnitude when the Te substituted
Se (Emziane & Le Ny, 2000a; Emziane & Le Ny,
2001; Emziane & Le Ny, 2000b). The growth
of In2x,Ga2(1-x)Te3 layers on InAs substrates by
evaporation from independent sources of elementary components in a quasi-closed volume was
proposed (Bezryadin et al, 1998).
Ternary indium sulfide compounds like CuInS2
with an improved photosensitivity and In2-xGaxS3
offering the possibility to tailor the band gap are
attractive materials for photovoltaic and optoelectronic devices (Naghavi et al, 2003b). (see Figure 9)
250
SUMMARY AND OUTLOOK

In2X3 compound semiconductor thin films, with
X being a chalcogen atom S, Se, Te, are promising candidates for applications in a variety of
devices. The different deposition and processing
methods used for the growth of these thin films
were reviewed, and various effects of fabrication
parameters, such as temperature, heat treatment,
doping, etc. were presented. The structural,
physico-chemical and functional properties of
these thin films were also extensively reviewed and
discussed in light of the many device applications
that such thin film have demonstrated.
A particular attention was paid to the intimate
relationship between their fabrication conditions

and the resulting microstructure and functional

properties, with an emphasis on the obvious use of
these materials in a variety of thin film solar cells.
We have shown the wide spectrum of compound
materials (i.e. binary, ternary and quaternary) that
can be synthesized based on the In2X3 semiconductor group, and the many devices and applications
that can be achieved by using them.
It is hoped that our review will contribute to
a better understanding of these thin film materials and help further investigate them in order to
improve the performance of the existing devices,
but also the demonstration of more efficient and
cost-effective devices in many areas of technology.
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Characterization: The study and analysis
of a material or a device in order to determine
its characteristics and properties. These can be
physical, chemical, electrical, optical, magnetic,
mechanical, catalytic, thermal, etc.
Functional Properties: The properties that
some materials can have and that make them useful
for specific applications such as electrical, optical,
magnetic, thermal, mechanical, etc.
Growth: It is often referred to the process of
depositing or growing a layer on a given material
used as a substrate.
Indium Chalcogenides: Compound semiconductor materials that have indium as well
as chalcogen atoms (like S, Te and Se) in their
chemical composition.
Junction: The physical contact of a semiconductor material with another material that
may be a semiconductor or a metal. The typical
example is the p-n junction used as the basis for

many devices.
Microstructure: The physic-chemical structure of a material at the microscopic level.
Photovoltaics: The process of converting light
directly into electricity using the photovoltaic
effect.
Processing: Treating a material thermally
or chemically or mechanically or otherwise in
order to alter its microstructure and, ultimately,
its functional properties.
Solar Cell: A device based on a typical semiconductor p-n junction and that converts photons
directly into electricity. Solar cell can be made
using a variety of semiconductor materials.
Thin Films: Materials with a thickness in
the nanometer or micrometer range, grown or
deposited on a substrate using a given physical or
chemical method. They are used as active layers
in devices or as coatings.
267
268
Chapter 12
Carbon Nanotubes
for Photovoltaics
Ayoola Brimmo
Mahieddine Emziane
ABSTRACT
Recent developments show that the exceptional physical, optical, and electrical properties of Carbon
Nanotubes (CNTs) have now caught the attention of the Photovoltaics (PV) industry. This chapter provides an updated and in-depth review of some of the most exciting and important developments in the
application of CNTs in photovoltaics. The chapter begins with a discussion of the underlying properties
of CNTs that make them promising for PV applications. A review of the literature on the application
of CNTs in the photoactive layer of Silicon (Si)-based heterojunctions, as anchors for light harvesting
materials in Dye Sensitized Solar Cells (DSSCs) and as components of other organic solar cells (OPVs),
is then presented. Findings portend the promise of CNTs in bridging the gap between the two classes of
solar cells currently in the market. Since the technology is in its early stages, it is generally limited by a
general lack of understanding of CNTs and their adequate growth mechanisms.
INTRODUCTION
The PV effect in simple words refers to the creation of voltage and electric current by a diode
upon exposure to light. In an ideal case, light
(photons) absorbed by a photovoltaic material
excite electrons into a higher state of energy, allowing them to act as charge carriers for electric
current. However, the efficiency of this process
is highly dependent on the materials ability to
successfully absorb photons in the light sources
spectrum, allow excitation of its electrons/holes

and then safe guard the delivery of these electrons/
holes to the electrodes before recombination
occurs. In reality, ensuring the success of these
processes is very difficult hence the relatively low
efficiencies of most commercial solar cells today.
Over the years, Si has proven to be the leading
material used in the PV industry with crystalline
Si wafer based PV responsible for the majority
of the worlds annual solar cell production (Mller, Ghosh, Sonnenschein, & Woditsch, 2006;
DOI: 10.4018/978-1-4666-5824-0.ch012

Carbon Nanotubes for Photovoltaics
Laird, 2010). This is the case as the Si wafer

based PV has long been a proven and robust PV
technology. The cost of high efficiency Si wafer
PV devices, limits this technologys potential of
performing well in the energy market; traditional
mono crystalline Si PV and the most efficient
multijunction PV (performing at about 40.7%
under 240 sun illumination) can cost upwards
of several dollars per installed watt (Kammen
& Pacca, 2004; King et al., 2007; Camacho et
al., 2007), with kWh cost several times higher
than energy from traditional fossil fuel sources.
In contrast, due to greatly reduced semiconductor material consumption and the ability to (i)
fabricate the solar cells on inexpensive largearea foreign substrates and (ii) to monolithically
series-connect the fabricated solar cells, thin-film
PV has the potential of achieving module costs
of well below $1.4 per W (Aberle, 2009). As
thin film materials are typically polycrystalline
or amorphous, they experience a high reduction
in efficiency due to interface recombination and
degradation under light illumination (StaeblerWronsky effect) (Galloni, 1996), making them
less efficient than their wafer based counterparts.

Evidently, the present trend in the PV industry
divides cells into two categories: cells which
are affordable but of relatively low efficiency
and cells which are of good efficiency but very
costly. Figure 1 shows the efficiency and cost
projection of these categories of cells. As it is
expected that the PV market will continue to
rise, it is of great interest to the PV industry to
bridge the gap between these two categories of
cells currently available and produce units which
are not only of decent efficiency but also affordable enough to compete with other sources of
secondary energy. Approaches in this line aims
to decrease the cost to well below the $1/W
level of the second-category PVs potentially to
$0.20/W or better, by significantly increasing
efficiencies but maintaining the economic and
environmental cost advantages of thin-film deposition techniques (Conibeer, 2007). In order
to establish a third category of PV devices, a lot
of methods have been explored to bridge this
and CNT unsurprisingly has been a well cited
candidate in the field.
Figure 1. Efficiency and cost projections for first- (I), second- (II), and third category (III) PV technologies (wafer based, thin film and advanced technologies respectively) (Green, 2001)
269

The abundance of carbon and the unique properties of its nanostructures which include high
transparency (Kaempgen, Duesberg, & Roth,
2005), excellent electrical conductivity (Sarno
et al., 2013), outstanding thermal properties
(Balandin et al., 2008), direct band gap (Avouris,
Freitag, & Perebeinos, 2008) and high predicted
mobility (Durkop, Getty, Cobas, & Fuhrer, 2004),
make it attractive for solar energy conversion.
Unfortunately, CNTs are currently extremely
expensive, making them unviable for applications in commercial PV devices (Baughman,
Zakhidov, & De-Heer, 2002). However, recent
advances in synthesis techniques, in particular
Chemical Vapor Deposition (CVD) methods,
show promise for being scalable (ton/day), low
cost (<$100/kg), and able to produce high purity
CNTs (Sinnott & Andrews, 2001). This prospect
coupled with the remarkable properties of CNT
has made it difficult to neglect CNTs as a candidate for facilitating the production of affordable
and efficient PV devices.
The aim of this study is to review major works
that have attempted to integrate CNTs in PV
devices. The next section briefly discusses the
CNTs properties which have enticed professionals in the PV field. This is followed by the main
focus areas of this review which includes: CNT
applications in the photoactive layer in Si based
heterojunctions; as anchors for light harvesting
materials in DSSCs and as components of other
OPVs. The roles played by CNT in these PV
cells are discussed and criticized in these sections. As the cost of resulting solar cells largely
depends on the fabrication technique applied,
the fabrication of CNT based PV devices are
highlighted. Finally, general technical challenges
and prospects in the field of CNT applications
in PV are discussed.
270
BACKGROUND
Physical, Electrical and
Optical Properties of CNTs
CNTs have a unique pseudo-one dimensional
tubular structure which can be envisaged as rolled
single sheets of graphene. They form spontaneously and efficiently under well-defined conditions either as single-wall nanotubes (SWNT) or
nested multi-wall nanotubes (MWNT). Contiguous carbon nanotubes exhibit a high degree of
atomic scale perfection (Jorio, G. Dresselhaus,
& Dresselhaus, 2008). The nanotubes are constructed with a length-to-diameter ratio of up to
132,000,000:1 (Wang et al., 2009), significantly
larger than that of any other material. The quantum
size nature of this material makes it possible to
exhibit special physical configurations which are
largely responsible for its outstanding properties
(Zhu, Klein, Schmalz, Rubio, & March, 1998).
Since their discovery by Iijma (1991) CNTs have
incited a great number of researches due to their
fascinating properties; Figure 2a shows that the
strength of an individual MWNT is about 100
times that of typical structural steel (Brimmo,
Hassan, Ibrahim, & Shatilla, 2013) and Figure 2b
shows that the electrical resistivity of a SWNT is
about an order of magnitude lower than that of a
copper nanowire (Liu et al., 2012). Also, CNTs
exceptional mechanical (Coleman, Khan, Blau,
& Gunko, 2006; Yu et al., 2000; Ciurea et al.,
2009; Treacy, Ebbesen, & Gibson, 1996), electrical (Venema et al., 1999; Jishi, Bragin, & Lou,
1999; Durkop, Getty, Cobas, & Fuhrer, 2004;
Gao, Chen, Fuhrer, Glattli, & Bachtold, 2005)
and optical properties (Movlarooy, Kompany,
Hosseini, & Shahtahmasebi, 2010; Chen, 2010;
Zhao & Mazumdar, 2005; Shan & Bao, 2006; Fa,
Yang, Chen, & Dong, 2004; Chen, Lee, Chang,
Lue, & Lin, 2006; Kataura et al., 1999) are well
cited in the literature as such, it is of no surprise
that CNTs are considered ideal for a wide range of
applications (Baughman, Zakhidov, & De-Heer,

Figure 2. (a) Plot of stress versus strain curves for an individual MWNTs(Yu et al., 2000); (b) I-V characteristics of a SWNT at 20K and 298K (Ciurea et al., 2009)
2002) and a test bed for fundamental science (Cao,

Wang, Rolandi, & Dai, 2004).
CNTs are electronically distinguished by how
the combination of the rolling angle and radius
decides if the resulting individual nanotube shell
is metallic or a semiconductor. Electron transport
in CNTs is described as ballistic, i.e. the resistance
of the nanotube does not depend on its length as
the mean free path m is longer than the nanotube
itself (Brown, Hao, Gallop, & Macfarlane, 2005).
The electrical resistivity of individual CNTs has
been measured to be as low as 106 cm (McEuen,
Fuhrer, & Park, 2002; Gao, Chen, Fuhrer, Glattli,
& Bachtold, 2005) for SWNTs and 3105 cm
(Bachtold, et al., 1998; Berger, Yi, Wang, & deHeer, 2002) for MWNTs. Semiconducting CNTs
are, unlike Si, direct band gap materials that have
the same effective mass for holes and electrons
which suggests their great potential in photonics
and related applications (Kuo, Tzolov, Straus, &
Xu, 2009).
The unusual and potentially useful optical
characteristics of CNTs can be traced back to the
nanotubes electronic structure (Weisman & Subramoney, 2006). A typical feature of the high aspect
ratio, quasi one-dimensional CNT is their discrete

density of state (DOS): their DOS as a function of
energy depicts a curve with discontinuous spikes as
shown in Figure 3. The sharp peaks as observed by
scanning tunneling spectroscopy (Li et al., 2001),
typically in one-dimensional materials, are called
the Van Hove singularities (Kataura, et al., 1999;
Kim, Odom, Huang, & Lieber, 1999). The peaks
signify discrete energy sub-bands which fall within
the broad visible-near-IR range (Bachilo, et al.,
2002; OConnell et al., 2002), with the band gap
magnitude depending on the nanotubes physical configuration (Rao, et al., 1997; Faga, et al.,
2007). This opens up the possibility of tuning the
optical properties of CNTs. Such fine tuning has
been experimentally demonstrated (Iakoubovskii
et al., 2006), often leading to innovative optical
applications of CNTs (Murakami, Einarsson,
Edamura, & Maruyama, 2005).
The optical properties of CNTs usually mentioned in the literature are absorption (Kataura,
et al., 1999; Sinnott & Andrews, 2001), photoluminescence (PL) (Iakoubovskii, Minami, Ueno,
Kazaoui, & Kataura, 2008; Iakoubovskii et al.,
2006; Tan et al., 2007; Oyama et al., 2006), and
271

Figure 3. Schematic density of electronic states

pattern in a semiconducting SWNT. The sharp
maxima are van Hove singularities. Arrows show
the dominant optical absorption and emission
transitions (in a one-electron model) (Weisman
& Subramoney, 2006).
Raman spectroscopy (Dresselhaus, Jorio, Hofmann, Dresselhaus, & Saito, 2010; Hennrich et
al., 2005; Zdrojek, Gebicki, Jastrzebski, Melin,
& Huczko, 2004) with the isolation of individual
nanotubes cited as critical for decoupling the
optical response of one nanotube from another
(Hartschuh et al., 2005). Typical SWNTs absorption spectra show perturbations (Naumov,
Ghosh, Tsyboulski, Bachilo, & Weisman, 2011)
as opposed to an absorption threshold followed by
an increase in absorption, as experienced by most
3-dimensional materials. The absorption spectra
of SWNT bundles contain three broad absorption
regions corresponding to the first and second allowed transitions for semiconductor SWNTs, and
the first allowed transition for metallic SWNTs
(Hartschuh et al., 2005). This trend can be seen
in Figure 4a which is the absorption spectra of
SWNTs produced by the laser-oven method. In
Figure 4a, the peaks at 1700 and 950 nm are due
272
to semiconducting nanotubes while the peak at

650 nm is due to metallic nanotubes (Hartschuh
et al., 2005).
PL of CNTs is a process whereby CNT absorb photons and then re-radiates them almost
immediately, with a light emission effect. This
phenomenon only occurs in semiconducting CNTs
as the hole created in metallic CNTs, by an excited
electron, is immediately filled up by one of the
large number of high energy electrons available
in the metallic material. Also, the luminescence
efficiency of SWNTs has been shown to increase
with decreasing temperature (Lauret et al., 2004).
The observation of structurally dependent PL
from SWNTs represented a major breakthrough
(Bachilo et al., 2002), as the electronic transition
energies was shown to depend on the nanotubes
description matrix ((n, m) values) explicitly and
not simply on the SWNT diameters (Hartschuh
et al., 2005). PL in CNT occurs within a wide
wavelength range (Iakoubovskii et al., 2006) and
has been observed in both isolated (OConnell et
al., 2002) and bulk (Lebedkin, Hennrich, Skipa,
& Kappes, 2003) SWNTs. While ensemble measurements are complicated by the superposition
of many PL peaks from many different species,
single nanotube spectra clearly isolate a single
peak and are thus simpler to interpret (Lefebvre,
Fraser, Finnie, & Homma, 2004). It has also been
reported that the PL of SWNTs is affected by the
nanotubes environment with an average of 28 meV
blue shift emission peak for the suspended nanotubes as compared to the encapsulated nanotubes
cited in reference (Lefebvre, Fraser, Homma, &
Finnie, 2004).
Raman spectroscopy is a spectroscopic technique based on inelastic scattering of monochromatic light, usually from a laser source. It has been
used extensively in studying the electrical and
optical properties of CNTs (Dresselhaus, Jorio,
Hofmann, Dresselhaus, & Saito, 2010; Hennrich
et al., 2005; Zdrojek, Gebicki, Jastrzebski, Melin,
& Huczko, 2004). The Raman spectra present
different features such as the radial breathing

Figure 4. Optical properties of CNTs (a) Optical absorption spectrum of SWNTs spun coat from toluene
onto quartz (Hartschuh et al., 2005); (b) Raman spectra of SWNT obtained from red laser (785 nm) and
green laser (514nm) (Doorn et al., 2005).
mode (RBM) where all the carbon atoms are

moving in-phase in the radial direction, the Gband where neighboring atoms are moving in
opposite directions along the surface of the tube
as in 2D graphite, the dispersive disorder induced
D-band and its second-order related harmonic
G-band (Costa, Borowiak-Palen, Kruszyska,
Bachmatiuk, & Kaleczuk, 2008). The frequency
of the RBM mode is dependent on the nanotube
diameter (Fantini et al., 2004; Souza-Filho et al.,
2004) and can therefore be used to deduce the
diameter of the nanotubes, indicate single versus
multiwalled structures and hence distinguish individual CNTs in bulk samples (Costa, BorowiakPalen, Kruszyska, Bachmatiuk, & Kaleczuk,
2008). Raman spectroscopy has also been cited
as a powerful tool for intra-molecular junctions
studies on isolated CNTs (Doorn et al., 2005). The
G-mode is diameter-sensitive in multiwall and the
nature of its complex structure in SWNTs is an
indicator of conductive properties (Dresselhaus,
Dresselhaus, Saito, & Jorio, 2005). The small
particle size, as well as the structural disorder in
the small particles (dia. -200 A), activates the Dband Raman scattering near 1350 cm-1 (Eklund,
Holden, & Jishi, 1995). The intensity ratio (ID/
IG) of D and G modes is conventionally used to

quantify the structural quality of CNTs (Nguyen
et al., 2011). The spectral position of G mode
depends on the diameter, so it can be used roughly
to estimate the SWNT diameter (Iakoubovskii,
Minami, Ueno, Kazaoui, & Kataura, 2008).
For more details on the physical, optical and
electrical properties of the CNT, refer to the references R.Saito, Dresselhaus, and Dresselhaus
(1999), Ajiki (2012) and Kong and Javey (2009).
CNT-Si HETERO-JUNCTION
SOLAR CELLS
The ideal CNT-Si junction i.e. the connection
between a 3-D Si system and a quasi-one-dimensional CNT system is in itself fascinating, all the
more so when combined with the space-charge
transfer across the hetero-junction barrier and the
long screening length in a 1-D system (Tzolov,
Kuo, Straus, Yin, & Xu, 2007). Because semiconducting SWNTs and double-walled nanotubes
(DWNTs) are naturally p-type semiconductors,
when interfaced with n-type Si, they form pn
hetero-junctions, exhibiting typical diode IV
273

characteristics (Ong, Euler, & Levitsky, 2010).

In the CNT/n-type Si hetero-junction, CNTs
serve as an active photo-sensing material directly
involved in the photon absorption process as well
as contributing to the charge separation, transport
and collection (Ong, Euler, & Levitsky, 2010). In
addition, the use of strong, environmentally benign
CNTs provides an excellent structural stability of
the PV devices (Jia Y. et al., 2012).
It has since been established that the metalsemiconductor junctions exhibit a Schottky barrier effect as such, it came as no surprise that the
possibility of achieving this with CNT interested
researchers in the field. At the close of the 20th
century, various theoretical studies on contact
between metal electrodes and CNTs had been
reported (Nakanishi, Bachtold, & Dekker, 2002;
K. Kong, S. Han, & J. Ihm, 1999; Rochefort,
Ventra, & Avouris, 2001; Anantram, Datta, &
Xue, 2000; Nakanishi & Ando, 2000; Odintsov,
2000; Leonard & Tersoff, 2000). One of the early
experimental reports in this field is that of Jin et
al (Hu, Ouyang, Yang, & Lieber, 1999) where
semiconducting Si nanotubes were coupled with
metallic CNTs via a controlled catalytic growth
of metallic CNTs and Si. Their results suggested
that these junctions exhibit a reproducible rectifying behavior. However, at the time, methods had
not been developed to synthesize the proposed
nanotube junction structures (Hu, Ouyang, Yang,
& Lieber, 1999). A few years later, similar studies on arrays of heterojunction between CNTs
and Si were reported, establishing the junction
to be photosensitive (Tzolov et al., 2004), with
a temperature-related change in I-V dependence
(Kuo, Tzolov, Straus, & Xu, 2009) and demonstrating feasible syntheses methods (Kawano,
Christensen, Chen, Cho, & Lin, 2006).
In 2007, the application of a highly ordered
array of parallel identical CNTs in PV was reported by Straus et al (Straus, Tzolov, Kuo, Yin,
& Xu, 2007). An SEM image of this type of
aligned CNT arrangements is presented in Figure
5a. Their approach was to perform the growth
274
non-lithographically in a bottom-up fabrication

method, forming a hetero-junction with a Si
substrate. Evidence of a space-charge separated
region at the nanotube-Si interface was observed
in the form of diode rectification and a closedcircuit, zero-bias photocurrent in response to
infrared (IR) light. In the same year, Tzolov et
al. (2007) reported a periodic array of CNTs-Si
heterojunctions, this time functioning as an IR
detector (Figure 5a and b). The mid-IR photocurrent response achieved at room temperature (as
well as cryogenic temperatures) in their CNT-Si
heterojunction system represented a significant
advance of CNT technology into the broad area
of photonic devices and sensor applications. Other
works on the use of CNT as IR sensors include
(Zhang, Xi, Chan, & Li, 2006; Chen et al., 2013).
Generally, these results suggest a suitability of
CNT as an affordable replacement for the Germanium layer (IR absorber) in multijunction PV cells
and in thermal PV applications. As about 50% of
the radiant energy reaching the earth lies within
the IR region (Qiang, 2003), CNT multijunction
PV cells may be used in tapping into that unused
resource, in a potentially affordable manner.
Arena et al (Arena et al., 2008) reported the
use of MWNTs grown by catalytic chemical
vapor diffusion (CCVD) over Fe supported on
alumina catalyst, in CNT-Si heterojunctions.
The developed MWNTs/n-Si heterojunction cell
displayed an energy conversion efficiency of 3%,
higher than that of heterojunctions consisting of
doped Si coated with composites of conjugate
polymers and CNTs. Later that year, Jia et al.
(2008) reported CNT-on-Si heterojunction solar
cells, with efficiencies of 57% under one sun
illumination (100 mW/cm2). In the device, the
nanotubes served as a heterojunction component
for charge separation, as a highly conductive
percolated network for charge transport and as a
transparent electrode for charge collection (Jia et
al., 2008). By simply coating thin nanotube films
onto Si wafers about 7% efficiency and negligible
degradation of current density after hundreds

Figure 5. (a) SEM image of aligned nanotube array samples used for Si/CNT heterojunctions (Tzolov, Kuo,
Straus, Yin, & Xu, 2007) (b) Dark current-voltage characteristic of Si/CNT device at room temperature.
The insets illustrate the device structure and the lineup of the energy levels at the Si/CNT heterojunction
(Tzolov, Kuo, Straus, Yin, & Xu, 2007). Dark current measurements are well explained by assuming that
the charge transport is controlled by tunneling between carbon nanostructures and Si (Tinti et al., 2011)
Figure 6. (a) Hybrid heterojunction/PEC solar cell composed of SiNW arrays, the DWNT film, and the
redox electrolyte. (b) Side view of the hybrid structure. (c) SEM image of the SiNW arrays cross section. (Shu et al., 2009)
of hours of exposure to air was achieved. The

manufacturing process demonstrated in this study
is simple and scalable, involving solution transfer
of a porous, single-layer film of DWNTs to Si
surface to form heterojunctions with Si, and did

not include any separation of metallic and semiconducting nanotubes. Although, both metallic
and semiconducting nanotubes are able to gener-
275

ate eh pairs in this type of cell (Castrucci et al.,

2011), further studies on the use of homogenous
nanotubes might prove beneficial. In 2009, Shu
et al. (2009) proposed and characterized a hybrid
solar cell comprising a heterojunction cell and
a photoelectrochemical (PEC) cell. In this cell,
a thin film of DWNTs formed a heterojunction
with Si nanowire (SiNW) array and also acted
as the transparent counter electrode of the PEC
cell (Figure 6). It was reported that the cell performance could be readily tuned by controlling
the SiNW density. Under AM 1.5G illumination,
a power conversion efficiency of 1.29%, higher
than those reported for SiNW array-based PEC
cells, was obtained (Shu et al., 2009). Schematics
of the hybrid heterojunction and an SEM image
of the SiNW array is presented in Figure 6.
Li et al. (2009) achieved PV conversion from
high-density pn heterojunctions between SWNTs
and n-type crystalline Si produced with a simple
airbrushing technique. Chemical modification of
the SWNT coating films by thionyl chloride was
found to significantly increase the conversion efficiency by more than 50% through adjusting the
Fermi level and increasing the carrier concentration and mobility. Initial tests showed a conversion
efficiency of above 4%, proving the suitability
of a SOCl2 treated-SWNT/n-Si configuration for
light-harvesting, at relatively low cost.
In Si-CNT heterojunction PV devices, two digit
conversion efficiencies have been obtained with
a metal-insulator-semiconductor heterojunction
solar cell produced by depositing a CNT film
onto Si substrate, followed by acid oxidation of
the Si surface to form a thin oxide layer at the
junction interface (Jia et al., 2011). The nanotubeoxide-Si solar cells with polymer encapsulation
demonstrated stable efficiencies of about 10%,
and a good stability in encapsulation. Using
the same synthesis method, a 13.8% efficiency
solar cell was obtained by combining CNTs
with Si and doping with dilute HNO3 (Jia et al.,
2011). It was suggested that acid infiltration of
nanotube networks significantly boosted the cell
276
efficiency by (1) reducing the internal resistance

which improves the fill factor (FF); (2) forming
photoelectrochemical units that enhanced charge
separation and transport and; (3) encapsulating the
previous cell with a polymeric cover to further
reduce reflection (Jia et al., 2011). The device
performance might be further improved by tailoring the electrical property and the film porosity
of CNTs. However, for practical applications,
stability issues related to Si photo corrosion and
acid storage have to be addressed. This might
be circumvented by the introduction of an oxide
layer or mild acid electrolytes and a better device
encapsulation. Compared to conventional Si cells,
the fabrication process in this study is greatly simplified; simply involving the transfer of a porous
semiconductor-rich nanotube film onto an n-type
crystalline Si wafer followed by acid infiltration
(Jia et al., 2011)
Recently, Jia et al. (2012) showed a relation
between enhancement in cell characteristics and
oxide layer thickness at the interface between a
CNT film and Si substrate. The cell efficiency
increased steadily from 0.5% without interfacial
oxide to 8.8% with an optimal oxide thickness of
about 1 nm. Jia et al (Jia et al., 2012) also reported
PV properties of SWNT fibers and n-type Si
heterojunctions. Their results showed that when
the SWNT fibers allow photo-generated holes to
transport along the axis of the fiber, a nominal
efficiency of up to 10.6% was observed. The PV
devices also showed excellent structural stability
due to the use of strong, environmentally benign
CNT fibers.
Over the years, computer simulations have
proven to be a reliable and cost effective way of
modeling materials and devices, and these tools
have also been exploited in this field. Xia et al.
(2012) used molecular dynamics (MD) simulations to demonstrate that the SWNTs and Si
nanotubes (SiNTs) with different chirality and
diameters can coaxially assemble into C/Si nested
heterojunction nanotubes by inserting the smaller
diameter CNTs into the larger diameter SiNTs. A

stepwise demonstration of this assembly procedure

is presented in Figure 7. The van der Waal-driven
assembly approach in this report provided a fascinating and efficient way to fabricate the complex
structures with targeted properties from a set of
given nanostructures. The possibility of using such
a coaxial assembly presents a means of producing
Si based PV wires with the possibility of powering
portable devices.
Besides Si, CNTs have also been shown to
form a rectifying heterojunction with n-GaAs.
Liang and Roth (2008) found that the p-doped
GaAs forms an ohmic contact with a nanotube
but in the n-doped GaAs/nanotube heterojunction, a strong rectifying behavior was observed.
PV effect was also observed in n-GaAs/nanotube
Figure 7. Snapshots of stepwise assembly of CNT
and SiNT into C/Si nested MWNT. Snapshots of
the initial and final configurations of (a and b)
assembling a CNT (16, 3) and an armchair SiNT
(10, 10) into a double-walled C/Si nanotube, (c and
d) assembling the formed CNT (16, 3) and SiNT
(10, 10) and a CNT (22, 20) into a triple walled
C/Si/C nanotube, and (e and f) assembling the
resulting CNT (16, 3) and SiNT (10, 10) and CNT
(22, 20) and a SiNT (17, 17) into a tetra walled C/
Si/C/Si nested nanotube (Xia, Xue, Zhang, Chu,
& Dong, 2012).
junction with the illumination of a green laser or

desk lamp. Zhang et al. (2010) demonstrated a
way to develop large-area, Schottky junction solar
cells by coating CNT films on individual CdSe
nanobelts and recorded modest power-conversion
efficiencies (0.450.72%) under AM 1.5G, 100
mW/cm2 light conditions.
CNT IN DSSC
DSSC is a solar cell which mimics the workings
of a plant during photosynthesis. Upon receiving
sufficient energy photons from an incident light,
the dye based absorber solar cell ejects an electron
into the cells conductive layer. This brings about
the existence of an extra electron in the conductive
layers conduction band. The electron diffuses to
the transparent anode material placed on top of it
after which it is collected by the external circuit.
Meanwhile, the electron ejected by the dye is replaced by an electron stripped from the electrolyte
directly below. The counter electrode below then
re-introduces the electron which has flown through
the external circuit, into the electrolyte. Detailed
descriptions and a schematic of the workings of this
device can be found in reference (Gratzel, 2003)
and Figure 8, respectively. The anode, conductive
layer, electrolyte and counter electrodes of the
DSSC in their most common forms are, fluoride
doped tin dioxide (SnO2: F), tin dioxide (TiO2),
iodide and platinum, respectively.
Gratzel et al. (1991) first demonstrated this
PV cell created from low to medium-purity
materials through low-cost processes, with commercially realistic energy-conversion efficiency.
The device was based on a 10-m-thick, optically
transparent film of titanium dioxide particles a
few nanometers in size, coated with a monolayer
of a charge-transfer dye which sensitizes the film
for light harvesting. The overall light-to-electric
energy conversion yield was between 7.1-7.9% in
simulated solar light and 12% in diffuse daylight.
However, this 3rd generation PV technology is still
277

Figure 8. Schematic of the dye sensitized solar

cell (Ahmad et al., 2010)
not widely commercial due to costly components

(ruthenium based dye and platinum catalyst
(Huang et al., 2012), electrolyte instabilities
(Chung, Lee, He, Chang, & Kanatzidis, 2012) and
dye degradation (Koo et al., 2006). This section
presents progress in line with the application of
CNTs in remedying these issues in an attempt to
facilitate the commercialization of this technology.
CNT as Counter Electrode for DSSCs

The noble platinum (Pt) is an expensive material
which remarkably increases the cost of the DSSC.
In addition, the best Pt counter electrode of the
DSSC is produced by a high-temperature hydrolysis process which presents an adverse condition
for depositing Pt on a flexible plastic substrate
required for producing flexible DSSCs (Fan, Mei,
Sun, & Ouyang, 2008). As such, a replacement
for the platinum counter electrode which does
not deteriorate the conversion efficiency was the
impetus of several researches in the early years
of applying CNTs in the development of DSSCs.
Suzuki et al (Suzuki, Yamaguchi, Kumagai, &
Yanagida, 2003) is one of the earliest citations
on the examination of SWNTs as electrodes
in DSSCs. A cell with a conversion efficiency
of 4.5% was reported in this study. This value
278
is comparable to Grtzel-type DSSC (counter

electrode: platinum-sputtered fluorine-doped tin
oxide) under the same experimental condition
(Suzuki, Yamaguchi, Kumagai, & Yanagida,
2003) depicting a minimal effect of CNTs on the
Pt based cell conversion efficiency.
Agglomeration and entanglement of CNTs
have been shown to negate benefits associated
with the nanoscopic dimension of these CNT
structures (Choi et al., 2010) and this effect on
the efficiency of CNT counter electrode DSSCs
have also been examined. Lee et al (Lee, Lee, Park,
Kim, & Park, 2011) prepared vertically aligned
nitrogen doped CNTs on a rigid glass substrate
and a flexible plastic substrate via a growthdetachment-transfer process. A schematic of
the preparation process and SEM images of the
synthesized nanotubes are shown in Figure 9. The
vertically aligned N-doped CNT arrays were employed as counter electrodes for DSSCs, resulting
in a power conversion efficiency of 7.04%, while
that of a reference DSSC with a conventional Pt/
TCO counter electrode was 7.34%.
The study demonstrated that the growthdetachment-transfer method is useful for constructing flexible DSSCs, offering a promising
route to low-cost and substrate-independent Ptfree counter electrodes for this PV device. Better
spatial distribution and improved solubility of
CNTs on electrodes and solvents were mentioned
as key requirements to harvesting the desirable
properties of CNTs (Choi et al., 2010). Nath et
al. (2012) examined three different electrode
structures with different spatial arrangements of
CNTs in the mesoporous TiO2 of DSSCs. This
was aimed at studying the effect of surface states
at the interface formed by the incorporation of
CNTs. It was found that the decay of open circuit
voltage (Voc) was significantly minimized by
avoiding the direct contact of nanotubes with the
conducting substrate by introducing a thin buffer
layer of TiO2 while maintaining the superior electron collection efficiency from the incorporation
of nanotubes. To improve the performance of a

Figure 9. (a) Schematic diagram of the procedure used for preparing the vertically aligned N-CNTs on
various substrates. (b) Low- and high (inset)-magnification SEM images showing cross-sectional views
of the synthesized vertically aligned N-CNT arrays (Lee, Lee, Park, Kim, & Park, 2011).
well distributed and aligned CNT film, Huang et

al (Huang et al., 2012) general drying approach
can be adopted. The CNT film produced from
this method was used as a counter electrode for
DSSCs applications and an energy conversion
efficiency of 9.05% was attained.
Clearly, the magnitude of CNT induced cost
reduction in this field is highly dependent on the
cost of fabricating CNT based electrodes. As such,
it comes as no surprise that various methods of
synthesizing CNT based counter electrodes have
been investigated. Ramasamy et al. (2008) fabricated a counter electrode for tri-iodide reduction in
DSSCs by spray coating MWNT film on SnO2:F
glass substrate. The FF of the resulting DSSC
showed a strong dependency on the spraying time
of MWNTs. The device displayed a maximum
energy conversion efficiency and FF of 7.59%
and 0.62, respectively. Electrochemical impedance
spectroscopy analysis revealed a decrease in the
charge transfer resistance of the MWNT coated
counter electrode with increase of spraying time
leading to an improvement in the PV parameters.
Choi et al (Choi et al., 2010) reported using the
screen printing method on FTO glass employing
pastes containing CNT. The pastes were then
thermally treated at 350C for 10 min followed by
the treatment at 430C for 20 min. Cell efficiency
of 5.94% was recorded in this study demonstrating

the performance of CNT based counter electrodes
can be improved through surface modification
and dispersion control of CNTs. Fan et al. (2008)
reported the fabrication of DSSCs with a thin film
of MWNT/conducting poly(3,4 ethylenedioxyt
hiophene):poly(styrenesulfonate) composite as
the counter electrode. The composite thin film
was fabricated by a low-cost solution processing
at room temperature; spin coating. The devices
exhibited high performance with the energy conversion efficiency of 6.5%, short-circuit current
density (Jsc) of 15.5mA/cm, Voc of 0.66V, and
FF of 0.63. Gagliardi et al. (2009) deposited carbon
nanoparticles and MWNT on an optically transparent electrode (OTE) and applied it as a counter
electrode for DSSC applications. Electrochemical
Impedance Spectroscopy (EIS) was used to evaluate the behavior in the I-3/I- electrolyte solution.
Their results showed that MWNTs have a charge
transfer resistance and an ohmic resistance lower
than commercial Pt counter electrodes. Chou et
al. (2010) also applied the deposition technique
of fabricating these electrodes. They investigated
the applicability of SWNTs deposited on the
FTO-glass (Fluorine doped tin oxide, SnO2: F)
substrate of the counter electrode for DSSC applications. The power conversion efficiency of
279

their DSSC was measured using an IV measurement system, and the incident photo conversion
efficiency (IPCE) of the DSSC was obtained
using the phase-locked loop optical chopper. The
film of SWNT/Ag markedly increased the IPCE
from 3.9% (conventional DSSC with a thin film
of platinum on the FTO-glass substrate of the
counter electrode) to 15.3% (DSSC with SWNT/
Ag/acetylacetone), at a light wavelength of 380
nm. Furthermore, as the wavelength of the light
was increased to 550 nm, the IPCE of the DSSC
with SWNT/Ag/acetylacetone (6.8%) becomes
nearly equal to that of conventional DSSC (7.2%).
Most interestingly, this study shows that the power
conversion efficiency of the DSSC with SWNT/
Ag/acetylacetone (1.3037%) is not inferior to
that of DSSC with a thin film of platinum on the
counter electrode (1.25%).
The deposition technique has been predominant as various deposition techniques have been
explored in synthesizing CNT based electrodes for
DSSC applications. Zhu et al. (2011) fabricated
CNT films by an economical and versatile deposition technique; electrophoretic deposition (EPD)
for applications in DSSCs as counter electrodes.
The CNTs counter electrodes consisted of a large
number of bamboo-like structures with defect-rich
edge planes exhibiting a highly interconnected
network structure with high electrical conductivity and a good catalytic activity. A high PV
conversion efficiency of 7.03% was achieved for
DSSCs with CNT based counter electrodes. The
results suggest that the synthesis strategy applied
provides a potential for the fabrication of low-cost
flexible counter electrodes of DSSCs using a facile
deposition technique from an environmentally
friendly solution, at low temperatures. The PV
conversion efficiency of DSSCs with CNT counter
electrodes was further improved by Balamurugan
et al. (2013) catalyst synthesized CVD produced
CNTs. A detailed description of the CVD deposition of CNTs can be found in reference (Fahlman,
2002) and a detailed review on advances in the
use of CVD for CNT deposition is available in
280
reference (Meyyappan, 2009). Balamurugan et

al. (2013) synthesized well-ordered mesoporous
Fe incorporated SBA-15 (Fe-SBA-15), Fe-Cr
incorporated SBA-15 (Fe-Cr-SBA-15) and Cr
incorporated SBA-15 (Cr-SBA-15) catalysts for
the production of CNTs by CVD. These catalysts
were tested systematically, and then used to synthesize CNTs used as counter electrode material for
DSSCs. The CNT counter electrode showed good
chemical stability, lower charge-transfer resistance
and higher electro catalytic activity towards I3 /
I redox reaction than that of platinum (Pt) counter
electrode. The study reported an energy conversion efficiency of the CNT counter electrode
based DSSCs of 8.86% under irradiation with a
simulated solar light intensity of 100 mW cm2.
Hydrothermal deposition has also been reported
as a sustainable, simple and low cost method of
synthesizing nanostructure carbon materials (Zhao
et al., 2010; Yu et al., 2004; Titirici, Antonietti, &
Thomas, 2006). Siriroj et al. (Siriroj et al., 2012)
explored this technique in DSSCs application by
coating a conductive glass with MWNTs by a
hydrothermal method. The MWNTs films were
subsequently used as DSSC counter electrodes.
The performance of hydrothermal MWNT DSSC
was about 2.37%. After film annealing in an Ar
atmosphere, the annealed-hydrothermal MWNT
(AHT-CNT) DSSC efficiency was significantly
increased to about 7.66%. Improvement of cell
efficiency was attributed to the reduction of
impurities and counter electrode charge-transfer
resistance (RCE), as well as exposure of more
CNT surface area.
Some studies have compared different methods of fabricating CNT based counter electrodes.
Nam et al. (2010) investigated the performance
of DSSCs by coating the FTO glass substrate
counter electrode with CNT using two different methods: screen-printing MWNT paste and
growing relatively well-aligned CNTs directly by
CCVD. Figure 10 (a and b) shows SEM images
of CVD grown CNT layer and a screen printed
CNT paste, respectively. With the application

of CNTs coated counter electrode, a conversion

efficiency 10.04% was recorded for the DSSC.
The CNT-deposited counter electrode showed
higher photo conversion efficiency than CNTprinted electrodes under the same experimental
conditions. While all three PV parameters were
affected by an aligned CNT counter electrode,
the variation in FF in particular had a significant positive impact on the overall conversion
efficiency. Also the thermal CVD approach to
synthesizing a CNT electrode produced cells with
electron conduction path between the electrolyte
and the FTO glass significantly improved, with
a large surface area. Huang et al. 2012) reported
high-efficient fibrous DSSC (F-DSSC) with CNT
thin films as counter electrodes. The CNT films
were fabricated by two ways: brush coating CNT
paste and spraying CNT suspension solution on Ti
wires. Fluorine tin oxide-coated CNT under layer
was used to improve the adherence of the CNT
layer on Ti substrate for sprayed samples. The best
efficiencies obtained from F-DSCs using brush
coated and sprayed CNTs as counter electrodes
are 4.14% and 4.18%, respectively, both reaching
80% of the efficiency of the cell with Pt counter
electrodes indicating the promise of both of the

explored fabrication techniques.
Other carbon materials as counter electrodes
have been compared with CNT counter electrodes
for DSSC applications. One of these studies includes Hsieh et al. (2011) examination on DSSCs
equipped with 1-D CNTs and 2-D graphene nano
sheets (GNs) counter electrodes. When compared
with the GN-based counter electrode, CNT-based
counter electrodes showed a better improvement
in the incident photon-to-current efficiency and
power conversion efficiency of the cells (i.e., =
2.19% for GN and 2.91% for CNT). This enhancement of cell performance was attributed to the
combination of the CNT network and spherical
graphite bottom layer, favoring dye adsorption,
catalytic redox activity, and 1-D charge-transfer
path length. However, this has not stopped other
carbon materials (mostly graphene) from being
jointly implemented with CNTs as DSSC counter electrodes. One of the earliest works using
carbon counter electrode to achieve a conversion
efficiency close to that of a Pt counter electrode
DSSC is that of Imoto et al. (Imoto et al., 2003). In
their study, carbon electrode made from activated
Figure 10. (a) Cross-sectional SEM image of CVD grown CNT layer on soda lime glass (Nam, Park,
Kim, & Lee, 2010). (b) Cross-sectional SEM images of a screen printing CNT paste (Nam, Park, Kim,
& Lee, 2010).
281

carbon powder with a cell efficiency of 3.89%

was reported. In as much as this was superior to
a Pt sputtered counter electrode available at the
time, this conversion efficiency was inferior to the
activated Pt counter electrode (4.3%) (Imoto et
al., 2003). Choi et al (Choi et al., 2011) reported
graphene-based multiwalled carbon nanotube
(GMWNT) electrodes synthesized by CVD.
Graphene was grown on a SiO2/Si substrate and
then CNTs were grown on top of the graphene.
The DSSC with the GMWNT counter electrode
exhibited a conversion efficiency of 4.46% indicating that the high FF of the cell with GMWMT
electrode is due to the enlarged reaction area at
the interfaces between GMWNT and electrolyte,
which has well-aligned lateral and vertical structures. Battumura et al. (2012) fabricated counter
electrodes for DSSCs with varying compositions
of MWNTs and graphene using the doctor blade
method. The composite electrode containing 60%
MWNTs and 40% graphene showed a high conversion efficiency of 4% which is comparable to
that of the cell using a sputter coated Pt counter
electrode under the same conditions. Velten et al.
(2012) demonstrated the use of a dry spun MWNT
nano-composite with graphene flakes (Gr-F) as

DSSC counter electrodes. The effectiveness of
this counter electrode on the reduction of the
tri-iodide in the iodide/tri-iodide redox (I/I3)
redox reaction was studied in parallel with the use
of the dry spun carbon MWNT sheets alone and
graphene flakes used independently. The MWNT
deposited onto fluorinated tin-oxide-coated glass
showed improved catalytic behavior and power
conversion efficiency (7.55%) beyond the use
of the MWNTs alone (6.62%) or graphene alone
(4.65%), for the tri-iodide reduction reaction in
DSSCs. (see Figure 11)
Modification of CNTs applied as counter
electrodes have also been explored to further
improve power conversion efficiency. Choi et al.
(2010) investigated the effect of MWNT surface
modification on the fabrication and performance
of CNT based counter electrodes. Pyrene functionalized poly(p-hydroxystyrene) block copolymers
(HSPM) (poly(maleic acid-co-p-hydroxystyrene)block-poly(p-hydroxystyrene)) was prepared
through living radical polymerization technique.
A paste was prepared employing the modified
CNT and used to fabricate a counter electrode
Figure 11. Schematic of a dye-sensitized solar cell with a carbon MWNT/graphene composite. The expansion of the counter electrode portion of the scheme is to show the placement of the graphene to act
as a conducting bridge and as a space to offer the sharp atomic edges for catalysis (Velten et al., 2012).
282

for DSSC applications. Figure 12 is an illustration of the preparation process adopted in this
study. Their results showed that the FF and solar
energy conversion efficiency of the DSSC were
improved when CNTs were modified with HSPM
demonstrating that the performance of CNT based
counter electrodes can be improved through surface modification and dispersion control. Wang et
al. (2011) modified MWNTs by the substitution
of poly (acrylic acid) (PAA) and inorganic acids
(H2SO4 and HNO3), as hydrophilic MWNTsPAA
and MWNTsAcid, dispersed the modified MWNTs
in an ethanol solution containing 3, 4-ethylenedioxythiophene (EDOT), deposited Pt nanoparticles (nps) on the MWNTs to form MWNTsPAAPEDOT-Pt(nps) and MWNTsAcid-PEDOT-Pt(nps)
and used these composite materials to fabricate
counter electrodes for DSSCs.
The authors suggested that the electrostatic
interactions between carboxyl groups on the
MWNTs and EDOT monomers allowed the
Pt(nps) to be adsorbed onto the MWNTs. Also,
the quantity of Pt(nps) associated with the MWNT-PEDOT-Pt(nps) composite was greater than
sPAA
that with the MWNTsAcid-PEDOT-Pt(nps) com-
posite, due to the substitution of the carboxyl

group in MWNTsPAA. DSSCs incorporating the
MWNTsPAA-PEDOT-Pt(nps) and the MWNTsAcid
-PEDOT-Pt(nps) electrodes showed impressive
efficiency enhancements of 4.78% and 2.71%,
respectively. However, the ISC and VOC values of the
MWNTsAcid-PEDOT-Pt(nps) electrode cells were
much higher than that of the MWNTsPAA-PEDOTPt(nps) electrodes.
Nano particles were not left out of the search
for enhancing materials for CNT in DSSC electrodes applications. Charinpanitkul et al. (2011)
showed that hybridized materials of titanate
nanoparticles and CNTs could be synthesized
by the hydrothermal treatment process and used
as thin film electrodes of DSSCs. In their study,
a comparison was made between DSSCs with
working electrodes fabricated from commercial
anatase titania, titania nanoparticle-CNT (TNTCNT) and rice shaped titanate nanoparticleCNT
(rice-CNT). DSSCs with electrodes fabricated
from Rice-CNT hybridized material exhibited
the highest photo conversion efficiency of 3.92%
while the DSSC with working electrodes made
of TNT had the lowest efficiency of 2.39%. The
Figure 12. Illustrating sketches of the preparation process of tri-elements composite electrode (Wang
et al., 2011).
283

authors suggested that the TNT-CNT electrodes

could help increase the photo conversion efficiency
of DSSCs to 2.73% but this is still lower than the
DSSC with electrodes fabricated from anatase
titania (2.93%). Dang et al. (2011) reported a
cell fabricated by the synthesis of SWNTTiO2
nanocrystal coreshell nano-composites using a
genetically engineered M13 virus as a template.
In this study, a cell efficiency of 10.6% was attained. Results showed that both the electronic
type and degree of bundling of the nanotubes in
the nanotube/TiO2 complex are critical factors in
determining the device performance. By using the
nano-composites as photo anodes in the DSSC,
it was demonstrated that nanotubes improve the
power conversion efficiency by increasing the
electron collection efficiency. The device of
best performance in this study was a DSSC 0.1
wt% SWNTs and 99% semiconducting electrode
component.
Investigations on the use of a hybrid catalytic
layer of Pt/MWNT on the counter electrodes of
DSSCs have also been cited (Mathew, Rao, &
Munichandraiah, 2011). In Mathew et al. (2011)
study, MWNT decorated with Pt as a catalytic
layer for the reduction of tri-iodide ions in DSSCs
was employed. The performance of DSSC with
Pt/MWNT catalytic layer on the counter electrode was studied and compared with a counter
electrode made of sputtered platinum. MWNTs
were prepared by a simple one step pyrolysis
method using ferrocene as the catalyst and xylene
as the carbon source while Pt decorated MWNTs
were prepared by chemical reduction method.
In combination with a dye adsorbed TiO2 photo
anode and an organic liquid electrolyte, the Pt/
MWNT catalytic layer cell showed an enhanced
Jsc of 16.12 mA/cm2 leading to a cell efficiency
of 6.50%, which is slightly higher than that of the
cell with only Pt as a catalytic layer (6.32%). In
examining the I-V characteristic curves of both
cells, a decrease in FF is observed in the cell of Pt/
MWNT composite electrodes. This was attributed
to the difference in series resistance (Rs) of Pt/
284
MWNT and Pt counter electrodes, which could

be attributed to the inherently high conducting
property of metallic platinum. The Voc values
are almost the same for both electrodes.
As mentioned earlier, another major delay of
the DSSCs commercialization is its performance
stability. The efficiency of DSSC often rapidly
drops with time in the initial several days after
manufacturing due to the degradation of dye
molecules and the reaction of electrolyte with
sealing materials or counter electrode (Nakade,
Kanzaki, Kambe, Wada, & Yanagida, 2005; Ke et
al., 2010). In view of a remedy to this drawback,
Koo et al. (2006) studied the time dependent
characteristics of the DSSCs having different
counter electrodes. In their study, three different
types of counter electrodes CNT were considered: a MWNT film coated by the Doctor Blade
method, a Pt-sputtered film (500 nm) and a Pt
electroplated film ( 5 nm). Results showed that
DSSC having CNT counter electrode has higher
efficiency and more stability than those in the
case of two Pt counter electrodes. Electrochemical
Impedance Spectroscopy (EIS) was used to study
the aging effect of the three counter electrodes
through measuring electrochemical properties of
counter electrode/electrolyte interface as a function of time. In the EIS experiment, there was no
significant change of impedance characteristics
in CNT electrode even after 5 days. However, in
the case of Pt electrode, a three times increase in
the value of series resistance was observed. It is
suggested that this increase of resistance comes
from the degradation of the adhesion between Pt
(or CNT) and TCO layers.
Recently, a promising disulfide/thiolate (T/
T2) redox couple as a replacement for the corrosive I-/I3- redox couple was reported (Wang et
al., 2010). However, conventional planar platinum
counter electrode showed poor catalytic activity
towards this iodine-free redox couple, thus resulting in a poor FF and relatively moderate power
conversion efficiency (Hao et al., 2012). To this
effect, Hao et al. (2012) attempted to use CNT

based counter electrodes as a replacement for Pt

counter electrodes in the iodine free DSSC. In
their work, it was reported that vertically aligned
SWNTs (VASWNTs) were transferred onto transparent conducting oxide glass and implemented
as efficient low-cost, platinum-free counter electrode in sulfidemediated DSSCs. Device with
VASWNTs counter electrode demonstrated a high
FF of 0.68 and power conversion efficiency up to
5.25%, which are significantly higher than a FF
of 0.56 and power conversion efficiency of 3.49%
recorded for a similar cell with conventional Pt
electrode. Furthermore, VASWNTs counter electrode produced a charge transfer resistance of only
21.22 towards aqueous polysulfide electrolyte
commonly applied in quantum dots-sensitized
solar cells (QDSCs), which is lower than that of
a typical Pt electrode. (see Figure 13)
CNTs as Electron Transport

Layer in DSSCs
In as much as efficiencies in parity with commercial
Si based PVs have been achieved by DSSCs (Yella
Figure 13. Literature overview of CNTs application in DSSCs as counter electrodes. Vertical axis- power
conversion efficiency
285

et al., 2011), room for improvements in the intricate

efficiency of the DSSC still exists (Gratzel, 2005).
Loss in efficiency is usually experienced during
the electron transport across the semiconductor
particle network (Brown, Takechi, & Kamat,
208), as grain boundaries encountered during
the transit can result in electron recombination,
inhibiting efficient collection at the electrodes
surface (Gratzel M. J., 2004; Heimer, Heilweil,
Bignozzi, & Meyer, 2000). An approach to cut
these losses using CNTs involves incorporating
CNT networks in the cells conducting electrode
to promote charge transport in the TiO2 layer. Lee
et al. (2007) attempted this by fabricating a DSSC
using TiO2 coated MWNTs (TiO2-CNTs). Results
showed that the value of the short circuit current
density (Jsc) of DSSCs tested was increased by this
process. To prevent leakage current in the device,
a thin passivated layer was prepared between the
transparent conducting (FTO) glass substrate and
the porous TiO2 film. Compared with a conventional TiO2 cell, the modified TiO2 cell (0.1 wt. %
TiO2-CNTs) showed 50% increase in the value
of conversion efficiency. The enhancement in Jsc
was attributed to the improved interconnectivity
between the TiO2 particles and the TiO2-CNTs in
the porous TiO2 film.
Other studies on the incorporation of CNTs in
the TiO2 layers include Chen et al. (Chen et al.,
2012) report which suggested that stable, ultra
strong, and highly flexible aligned CNT fibers
can be used as conductive materials to support
dye-loaded TiO2 nanoparticles in DSSCs. A
schematic of a wire-shaped DSSC fabricated
from two CNT fibers, as described in this study,
is presented in Figure 14. This fiber solar cell was
shown to achieve a power conversion efficiency of
2.94%. The authors suggest that the flexible CNT
fiber solar cell can act as woven fabrics to make
textiles by a conventional weaving technology,
which enables a wide variety of applications in
portable devices, e.g. power regeneration for space
aircraft and clothing integrated photovoltaics.
Khamwannah et al. (2012) demonstrated that an
286
incorporation of DWNTs into a TiO2 photo-anode

layer results in a significant improvement in the
DSSC overall energy conversion performance.
Compared to the standard TiO2 anode, the CNTcontaining TiO2 anode with 0.2 wt. % DWNTs
boosted the Jsc by 43%. The DSSC power conversion efficiency was also improved from 3.9%,
in the case of CNT-free TiO2 anode, to as high as
6.4% with the addition of DWNTs and optimized
anode annealing. The observed enhancement in
the solar cell performance, with the presence of
the CNTs, was attributed primarily to the noticeable reduction in micro cracking and associated
robust electrical conduction.
Brown et al. (2008) investigated the use
of SWNT on TiO2 layers as conducting scaffolds. In this study, SWNT networks were created on conducting glass electrodes and TiO2
nanoparticles were dispersed on this conducting
scaffold of SWNT and then modified with the
Ru(bpy)2(dcbpy)2+ complex. Both transient
absorption and emission measurements indicated
that the film SWNT network has no noticeable
influence on the charge injection process from
the excited Ru(II) trisbipyridyl complex into TiO2
particles, however it plays an important role in
improving the charge separation, as the rate of back
electron transfer between the oxidized sensitizer
(Ru(III)) and the injected electrons becomes slower
in the presence of the SWNT scaffold.
CNT as TCO Layer in DSSC

The use of a TCO layer in the DSSC seemed a
somewhat indispensable approach as front glass
requires light-harvesting and electron-collecting
properties. However, this specialized glass is
expensive and restricts DSSCs to flat shapes. In
comparison to traditional TCOs, carbon-based
materials may allow for substantially reduced
costs because of the abundant material source
and potentially scalable fabrication from solution
process (Dan, Irvin, & Pasquali, 2009). However,
when carbon based materials are used as a work-

Figure 14. Schematic of a wire-shaped DSSC fabricated from two CNT fibers.(a) Two CNT fibers twined
into a cell. (b) Top view of a cell. (c) Working mechanism (Chen et al., 2012)
ing electrode their catalytic property allows the

collected electrons at the working electrode to
recombine with I3- in the electrolyte by the reaction
I3- + 2e 3I-, at the electrolyte/working electrode
interface. Hence, in as much carbon based materials have been successfully applied as counter
electrodes in DSSC to replace the expensive Pt, it
is difficult to integrate carbon-based materials as
a working electrode in liquid-type DSSC. Kyaw
et al. (Kyaw et al., 2011) were one of the first
groups to demonstrate a transparent CNT film
as the working electrode in a DSSC containing
iodide/ tri-iodide redox couples. This implementation was realized by inhibiting the charge-transfer
kinetics at CNT/redox solution interface with the
aid of thin titanium oxide film that facilitates the
unidirectional flow of electrons in the cell while
maintaining the electrical and optical properties
of CNT, as shown in Figure 15. A power conversion efficiency of only about 1.8% was realized
in this study.
Kyaw et al. (2012) reported, in a more recent
publication, a DSSC with a pair of carbon-based
electrodes, using a transparent, conductive CNTs
film modified with ultra-thin titanium-sub-oxide
(TiOx) as the working electrode and a bilayer of
conductive CNTs and carbon black as the counter electrode. However, this DSSC gave an even
Figure 15. Schematic of (a) recombination of

electrons with I3- at the CNT/electrolyte interface
in the case of bare CNT electrode, (b) inhibiting
the charge-transfer kinetics at the interface by
using a thin TiOx layer, (c) unidirectional flow
of electrons in the liquid-type DSSC with the
TiOx-modified-CNT working electrode, showing
the energetics of the individual components used
in the cell (Kyaw et al., 2011).
287

lower power conversion efficiency of 1.37%. The

use of CNTs as both the working electrodes and
counter electrodes has also been cited (Cai, Chen,
& Peng, 2012). In Cai et al. (2012) study, CNTs
were spun into macroscopic wires, in which CNTs
were highly aligned along the axial direction,
providing excellent mechanical and electrical
properties capable of producing a desired PV effect. Two CNT fibers were used in this wire with
one adsorbed with dye molecules functioning as
the working electrode, and the other used as the
counter electrode. This PV wire was reported to be
capable of being woven into textiles or integrated
into various flexible equipments which remains
challenging to the conventional planar solar cells.
Certainly, these are just initial attempts towards
the direction of DSSCs with all carbon-based
electrodes and the authors cited room for improvements in the Jsc and Voc of their cells.
Compared with inorganic PVs, OPVs suffer from

insufficient light absorption due to their low carrier
mobility and very thin active layer of about 10nm
(restricted by the short excitons diffusion length
of organic materials) (Blom, Mihailetchi, Koster,
& Markov, 2007; Shrotriya, Wu, Li, Yao, & Yang,
2006). CNTs have been identified as a potential
solution to some of these problems: high electric
field at CNTpolymer interface effectively splits
excitons; CNT charge carrier high mobility and
ballistic conductivity improves charge transport
and collection (Somani, Somani, & Umeno, 2008);
this nanomaterial displays a more homogeneous
charge collection and; SWNTs are expected to be
less corrosive towards the ITO electrode (Kymakis
et al., 2012). Progress in the implementation of
CNTs in OPV devices are presented in the following paragraphs. (see Figure 16)
CNT IN ORGANIC PV DEVICES (OPV)
The application of CNT in OPVs can be traced

back to 1999 when Ago et al. (1999) explored the
advantages of combining CNTs with conjugated
polymers for high-efficiency PV devices. In this
study, they obtained a good quantum efficiency
(1.8% at 2.9-3.2 eV), about twice that of the standard ITO device, but a drastic reduction of the PL
efficiency caused by MWNTs. The authors suggested that the quantum efficiency increase was
partly due to a complex interpenetrating network
of polymer chains and MWNTs while the reduction in PL efficiency could be a result of energy
transfer and partial hole transfer from the polymer
chains to MWNTs, together with scattering and
absorption by MWNTs. A year later, Ago et al
(Ago, Shaffer, Ginger, Windle, & Friend, 2000)
again studied the electronic interaction between
photo excited poly (p-phenylene vinylene) (PPV)
and MWNTs. Their study revealed an interaction
between MWNTs and the photo excited PPV, with
no significant interaction in the ground state. The
authors concluded from their findings that the predominant electronic interaction is the non radiative
Studies on OPVs date back to 1959 when Kallman and Pope (1959) reported a PV device made
of anthracene, producing a Voc of 0.2V with an
energy conversion efficiency of only 0.0002%.
In these devices, PV conversion is based on
the separation of photo generated charges at an
interface between electron donor and electron
acceptor materials (Ratier, Nunzi, Aldissi, Kraft,
& Buncel, 2012). OPV has been the focus of
many studies due to their prospective as a low
cost route to solar energy conversion, however
its efficiency and lifetime are considered too
low for commercial viability. An overview on
the status of OPV and its different production
technologies can be found in reference (Hoppe &
Sariciftci, 2004). A fundamental drawback of bulk
heterojunctions OPVs is the lack of congruence
in achieving simultaneous high efficiencies for
light absorption, excitons dissociation, and charge
carrier collection (Miller, Hatton, Chen, & Silva,
2007; Sun & Sariciftci, 2005; Li & Liu, 2011).
288
Early Period

Figure 16. Schematic drawings of an organic PV (P3HT:PCBM organic material) device structures
with the SWNTs acting as the hole transport layer.(b)Energy level diagrams of PV device components
referenced to the vacuum level (Kymakis et al., 2012)
energy transfer of singlet excitons from the PPV

to the MWNTs. Ago et al. studies were followed
by Kymakis and Amaratunga (2002) investigation
on the application of CNTs as acceptor materials
in OPVs. The author reported blending SWNTs
with poly (3-octylthiophene) (P3OT) to fabricate
a diode (Al/polymer-nanotube composite/ITO)
which exhibited a PV behavior at a low nanotube
concentration (<1%). SWNTs doping was found
to dramatically improve the PV performance
of P3OT devices, revealing a photocurrent two
orders of magnitude larger compared to that of
the pristine diodes, and a doubling of Voc. The
power conversion efficiency of the blended device
was dramatically increased with respect to the
pristine device however the efficiency obtained
by this device was still only 0.04%. From Kymakis and Amaratunga (2002) results, it was clear
that only a small percentage of CNTs is required
in the polymer blend to improve the OPV conversion efficiency. Suggestions (Kymakis et al.,
2007) had been made but no salient reason had
been attributed to this behavior. Liu et al. (2009)
investigated the performance drop at high CNT
percentages in OPV made from blended films of
regioregular poly 3-hexylthiophene and methanofullerene. As expected, excessive SWNTs in the
active layer of OPVs had a detrimental effect.
An intensity dependent photocurrent measurement showed that the decreased performance at

higher concentration of SWNTs can be attributed
to bimolecular recombination in the presence
of metallic SWNTs, as the presence of metallic
CNTs significantly suppresses the effective carrier mobility (Ago, Shaffer, Ginger, Windle, &
Friend, 2000). Another major limitation of CNT
incorporated OPV is the non-homogeneity of
available CNT arrays. Also, it has been showed
that the optoelectronic properties of SWNT based
OPV can be tuned by selecting different sources
of CNTs (Kazaoui, Minami, Nalini, Kim, &
Hara, 2005), different SWNTs diameters (Landi,
Raffaelle, Castro, & Bailey, 2005) and various
CNT alignment level (Berson, Bettignies, Bailly,
Guillerez, & Jousselme, 2007). (see Figure 17)
Role of CNT in OPV

Right from the pioneering studies, it was evident
that CNTs have the potential of improving OPV
cells efficiencies, however different perspectives
on the actual role of CNTs in the photoactive layers
of OPV were reported. Bhattahryya et al. (2004)
suggested that the main reason for the increase
in short circuit current and efficiency of their
functionalized SWNT-conjugated polymer OPV
289

Figure 17. Comparison of (a) Voc (b) short circuit current for homo junction, nonaligned heterojunction,
and aligned heterojunction SWNT in a bulk heterojunction OPV (Rud, Lovell, Senn, Qiao, & Mcleskey,
2005)
was partly due to the rapid transfer of the generated electrons to the SWNTs at the dye/nanotube
interface. This study was closely followed by
Kymakis and Amaratunga (2005) report on an
OPV behavior of 0.1% conversion efficiency, with
CNTs attributed as electron acceptor materials in
the polymer based PV cell. Geng et al. (2006) suggested that the work function of CNTs modulated
by electron transfer from poly(3-hexylthiophene)
P3HT to SWNTs explains the high Voc obtained
from the OPV devices based on a SWNTs/P3HT
system. Pradhan et al. (2006) reported an increase
in Voc and Jsc in their polymer-CNT/C60 devices
as compared to the polymer/C60 and attributed
this increase to CNT role as excitons dissociation
sites and hopping centers for hole transport. It
was also suggested in their report that polymerCNT composite and C60 layers acted as donor
and acceptor, respectively. Kymakis et al. (2007)
reported a 1% optimum SWNT concentration, in a
poly(3-octylthiophene) (P3OT)/ SWNT composite
PV cell, producing a 500 time increase in photo
response as compared to the pristine poly(3octylthiophene) (P3OT). This improvement was
attributed partly to the increase (50 times) in
effective hole mobility, due to the reduction of
localized states of the pristine P3OT matrix, and
290
partly to the enhanced excitons extraction at the

polymer/nanotube junctions. Li et al. (Li et al.,
2007) reported that their 0.57% efficient OPV
based on an immobilized fullereneSWNT (C60
SWNT) complex, takes advantage of SWNT high
electron transport capability and SWNT induction
of morphology change in the system. Kymakis
et al. (2008) (1.4% conversion efficiency) and
Stylianakis et al. (2010) (1.78% conversion efficiency) also suggested that high electron transport
capability of SWNT was partly responsible for the
improvement of their CNT based OPV devices
conversion efficiency, in comparison with their
respective pristine devices.
By 2010, there was still a controversy in the
literature regarding the fundamental role of CNTs
in bulk heterojunction OPVs. Considering the
ability of CNTs to provide percolation pathways
for the photo generated charges in PSCs, there
remained an important question about what type
of charge will be carried by these nanoparticles
(Ratier, Nunzi, Aldissi, Kraft, & Buncel, 2012).
Some reported CNT worked as an acceptor (hole
rich) (Bhattacharyya, Kymakis, & Amaratunga,
2004; Kymakis, Kornilios, & Koudoumas, 2008;
Geng & Zeng, 2006; Kymakis et al., 2007; Li et
al., 2007; Stylianakis, Mikroyannidis, & Kymakis,

2010) while others reported it worked as a donor

(electron rich) (Pradhan, Batabyal, & Pal, 2006;
Ulbricht et al., 2007). This controversial role incited Liu and Li (Liu & Li, 2010) to investigate
the electrical role (donor or acceptor) of SWNTs
in OPVs, using the Kelvin probe force microscope
(KPFM). As the KPFM affords the ability of a
surface work function to be observed at atomic
or molecular scales (Nonnenmacher, OBoyle, &
Wickramasinghe, 1991), Liu and Li (2010) used
this technology to investigate SWNTs on P3HT
films as well as on P3HT and methano-fullerene
blended films. In their study, SWNT bundles were
deposited on the active layer in order to expose
CNTs to the probe. Figure 18(a) is the topography
of SWNTs on top of P3HT: PCBM blended film
in the dark. The surface potential images in the
dark (Figure 18(b)) and under illumination (Figure
18(c)) as well as their surface potential values of the
cross section (Figure 18(d)) indicate that surface
potential contrast between SWNTs and P3HT/
PCBM under illumination almost disappeared
(Liu & Li, 2010). The authors suggested that
significant decrease of surface potential contrast
between SWNTs and P3HT/PCBM under illumination can only be explained when more holes are
transported from the active layer (P3HT/PCBM)
to SWNTs due to the built-in potential generated
by the heterojunction between CNTs and P3HT/
PCBM blend, as shown in Figure 18(e). Therefore,
a conclusion was drawn that introducing CNTs
into the active layer of OPVs primarily increases
the hole mobility.
CNT Electrodes in OPV

In most PV devices, the TCO layer is usually
indium tin oxide (ITO). Recent studies (Xue,
Uchida, Rand, & Forrest, 2004) have pointed out
that the conductivity of ITO is a source of series
resistance which decreases the fill factor and
hence decreasing the power conversion efficiency,
especially in large area devices. Compared with
ITO-coated glass by vacuum sputtering, it would
be much easier to fabricate transparent SWNT
electrodes to reduce the PV fabrication cost in the
near future (Miller, Hatton, & Silva, 2006). Also
the work function of SWNTs has been reported
Figure 18. (a) Topography of SWNT bundles on top of P3HT/PCBM film. (b) Surface potential (SP) image
in the dark. (c) SP image under illumination (d) both SP values of the cross section (e) Heterojunction
formed between CNT and P3HT/PCBM (Li & Liu, 2011).
291

to be between 4.5 and 5 eV, which is in the same

range as ITO, making it very well suited for hole
collection (Van-De-Lagemaat et al., 2006). Other
advantages of transparent CNT electrodes include
their relatively flat surface (10-nm roughness),
mechanical flexibility (Miller, Hatton, & Silva,
2006) and raw material abundance.
Undoubtedly, the promise of CNTs as PV
electrodes has been widely explored and OPV
has not been left out in its application. One of
the early works in this line is that of Pasquier et
al. (2005) which comprised the application of
CNT as transparent electrodes in OPVs. In their
study, they reported the use of SWNT thin films
as transparent and conducting electrodes for hole
collection in poly(hexyl)thiophene-[6-6]phenylC61-butyric acid methyl ester (P3HT-PCBM)
OPVs, with a power conversion efficiency of
0.99%, FF of 0.3, Jsc of 6.5mA/cm2 and a Voc
of 500 mV. A year later, Van de Lagemaat et al.
(2006) reported two viable organic excitonic solar
cell structures where the conventional In2O3:Sn
(ITO) hole-collecting electrode was replaced by
a thin SWNT layer. The first structure included
poly(3,4-ethylenedioxythiophene) (PEDOT) as a
hole selective contact while the second did not.
These cells displayed efficiencies of 1.5% and
0.47%, respectively. Interpenetrating electrode
which extends into the active organic layer, extracting charge carriers close to the point of generation,
have been explored as a solution to the low hole
mobility in OPVs. Miller et al. (2006) showed
that low concentrations of MWNTs (1wt%)
uniformly distributed within the donor layer of
a heterojunction OPV is an effective means of
greatly reducing the cell series resistance without
compromising the shunt resistance. By chemically functionalizing MWNTs with polar surface
moieties, the possibility of manipulating the device Voc was demonstrated. The findings of this
study demonstrated that MWNTs have excellent
potential as a versatile interpenetrating electrode
material for OPVs. Crucially, interpenetrating
MWNT electrodes can be incorporated into the
292
device structure without complicating the process of device fabrication. Ulbricht et al. (2007)
demonstrated that combining 3-D t-CNT network
with planar ITO (hybrid CNT-ITO electrode) can
lead to a 200% increase in photocurrent in bulk
heterojunction OPVs. Jsc of 11 mA/cm2, FF of
0.49, and an efficiency of 1.74% were obtained in
this study, which is a significant increase compared
to only 5.5 mA/cm2 of photocurrent in the sole
ITO device. Ulbricht et al. (2007) suggested that
this enhancement is due to a combined effect of
an enhanced hole collection by 3-D t-CNT and
improved transport via planar ITO part. This claim
is substantiated by reports on the replacement
of both the hole transport layer (HTL) and the
ITO electrode with a SWNT network transparent
electrode, with promising performances (Stylianakis & Kymakis, 2012). More recently, Kim
et al. (2012) reported a semi-transparent nip
OPV with free-standing MWNT (f-CNT) sheets
as transparent top electrodes. The cells displayed
high FFs, efficiencies of up to 1.5% and a greater
long-term stability compared to the device having
a metal electrode.
By 2006, the applicability of CNT as electrodes in OPV was established as such, works
on fabricating the electrodes started to surface.
Notable methods of fabricating OPV transparent
electrodes, with CNT incorporated, includes the
printing method (Rowell et al., 2006) and direct
growth via CVD (Miller, Hatton, Chen, & Silva,
2007). Both methods produced electrodes with
encouraging performances but OPV efficiencies
less than their corresponding control devices
(ITO/glass electrodes) have been cited for both
techniques (Rowell et al., 2006; Miller, Hatton,
Chen, & Silva, 2007). However, as little was done
to control detrimental effects like the non-homogeneity of nanotubes, non-alignment of nanotubes
and inappropriate electron injection buffer layer,
it is envisaged that the use of CNTs as electrodes
in OPVs is a promising path to enhancing the efficiency of bulk-heterojunction OPVs.

Trends in Efficiency Improvement

In 2009, an OPV with a power conversion efficiency of 6% was reported (Hou et al., 2009).
Meanwhile, bulk heterojunction CNT based
OPVs were still demonstrating relatively poor
efficiencies. Tanaka et al. (2009) explored the
multijunction approach to boost efficiencies and
demonstrated a MWNT anode OPV with a monolithic tandem structure in parallel connection. The
Jsc recorded for the parallel tandem cell was larger
than the currents of each individual cell, however
an unimpressive maximum conversion efficiency
of 0.31% was recorded. (see Figure 19)
After 2009, the understanding of the CNTorganic material junctions further improved (Ham
et al., 2010) hence a trend depicting a steady
rise of this device efficiency began. This trend
can be observed starting from Kim et al (2010)
report on bulk-heterojunction solar cells using
thin-film SWNT anodes deposited on glass. In
this study, two types of SWNT films were investigated: spin-coated films from dichloroethane
Figure 19. Schematic device structure of the monolithic parallel tandem OPV cell. (a) Cross section
view of stacked layers. (b) Top view of a typical
tandem OPV cell. (c) Equivalent circuit. Three
electrodes are accessible for an external circuit
connection independently (Tanaka et al., 2009).
(DCE), and spray-coated films from deionized

water using sodium dodecyl sulphate (SDS) or
sodium dodecyl benzene sulphonate (SDBS) as
the surfactant. The resulting PV devices displayed
a maximum power conversion efficiency of 2.3%
which was at a virtual parity with reference devices using ITO-coated glass as the anode (2.3%).
Ham et al. (Ham et al., 2010) achieved a higher
efficiency by fabricating a planar nano-heterojunction comprising well-isolated millimeter-long
SWCNT underneath a poly(3-hexylthiophene)
(P3HT) layer. The resulting junctions displayed
PV efficiencies per nanotube ranging from 3% to
3.82%, exceeding those of polymer/nanotube bulk
heterogeneous junctions by a factor of 50100.
The authors suggested that this increase is due
to the absence of aggregate formation in this
planar devices geometry. Radbeh et al. (2010)
reported that transport optimization can be obtained via orientation of CNTs perpendicular to
the electrodes of solar cells with an active layer
of poly(3-hexylthiophene)CNT(6,6-phenyl C61
butyric acid methyl ester) (P3HTCNTPCBM)
composite. In order to achieve this preferred orientation, a high AC electric field was applied on the
device electrodes. The electric field was applied
continuously on the electrodes during annealing
at a temperature near the glass transition of the
polymer matrix and it was demonstrated that a
significant increase in cell performance (i.e. Voc
= 0.61 V, efficiency = 4.53%, FF= 0.46) can be
achieved, which may signify a better path created
by the oriented nanotubes for carrier transport
to the electrodes. Lee et al. (2011) reported that
N- and B-doped CNTs uniformly dispersed in
the active layer of P3HT/PCMB (poly (3-hexylthiophene/[6,6]-phenyl-C61-butyric acid methyl
ester) bulk-heterojunction solar cells enhances
carrier collection. Specifically, the incorporation
of 1.0 wt% B-doped CNTs results in balanced
electron and hole transport and accomplishes a
power conversion efficiency improvement from
3.0% to 4.1%.
293

So far, the study which has suggested the most

promising efficiency, although somewhat theoretical, is that of Li et al. (2011). In their report, an
inverted structure of OPV cells with interdigitated
bulk heterojunctions was proposed (Figure 20 (a))
to be implemented by vertically aligned CNTs
(VACNTs). The structure comprised a layer of
semiconducting polymer (polythiophene) which
was electrochemically polymerized on VACNTs
to block electrons. The donoracceptor blend
was infiltrated into the gaps between these polymer coated VACNTs and a layer of TiOx on top
of the blend was deposited to block holes and
absorb ultraviolet light. Based on simulations,
it was reported that the interdigitated structure
effectively decoupled the light absorption length
and the charge collection length such that both
can be tuned independently for obtaining the best
device performance. For example, by maintaining the spatial distance between VACNTs, the
effective collection length can be fixed, while
the effective absorption length can be increased
by simply increasing the length of the VACNTs

(i.e. device thickness). On the other side, the effective collection length can be tuned by varying
the space among VACNTs without significantly
affecting the absorption.
The study (Figure 20 (b)) suggested that the
power conversion efficiency of OPVs with the
proposed interdigitated bulk heterojunctions
can exceed 12% when a small band gap polymer
donor, PCPDTBT, is used. However, such structure requires VACNTs to be well controlled over
spacing and length and hence requires a highly
accurate growth method for VACNTs.
Recent studies have attempted to further
improve these devices efficiency with success
recorded in a few attempts. Some of these attempts include Kymakis et al. (2012) study where
SWNTs films with dichloroethane were evaluated
as the HTL in poly(3-hexylthiophene) (P3HT) and
1-(3-methoxy-carbonyl)-propyl-1-phenyl-(6,6)
C61 (PCBM) PV devices. Insertion of a 12.2 nm
thick SWNTs layer led to power conversion ef-
Figure 20. (a) An inverted organic PV cell with interdigitated bulk heterojunctions (BHJs) based
on PCPDTBT:PCBM ([6,6]-phenyl C61-butyric acidmethylester) implemented by polythiophene
(PT:polythiophene)-coated VACNTs. (b) Comparison of power conversion efficiency of PCPDTBT:PCBM
devices in three scenarios with respect to device thickness: black-dotted line for planar devices under current condition; magenta-dashed line for planar devices with hole mobility matches P3HT:PCBM devices;
blue-solid line for devices with interdigitated BHJs under mobility matched condition (Li & Liu, 2011)
294

ficiencies as high as 3.04%, compared to 1.16%

and 2.84%, respectively, for devices without and
with the traditional PEDOT: PSS as the hole
transfer layer. Stylianakis et al. (2012) investigated the effect of incorporating SWNTs in both
the active and HTL of bulk heterojunction OPV
devices recording an outstanding increase in the
conversion efficiency from 2.67% (pristine device)
to 3.74%, i.e. by 40%. This gain was attributed
to a more efficient excitons dissociation due to
SWNTs presence in the photoactive layer and an
overall enhanced hole transport and collection
through the SWNTs percolation paths, which
are extended in both the active layer and the hole
transfer layer. A compilation of important studies
which have succeeded in improving OPV by the
incorporation of CNTs is presented in Figure 21.
For more details on the use of CNT in OPV, the
reader can refer to the references (Cataldo, Salice,
Menna, & Pignataro, 2012; Bounioux, Katz, &
YerushalmiRozen, 2012).
DISCUSSION AND
RECOMMENDATIONS
Proper incorporation of CNTs in PV devices has
been shown to be capable of increasing the performance of these devices. Encouraging efficiency
of CNT incorporated solar cells is attributed to
their large surface area, good conductivity, and
good catalytic activity. Also, due to their abundance and stability, CNTs can improve crystallinity and ordering of the active layer if processed
properly towards enhancing cell performance
(Seah, Chai, & Mohamed, 2011). However, the
intrinsic physical and morphological heterogeneity
of as-produced CNTs and the sensitivity of the
CNT-based PV system to processing conditions
resulted in a diversity of reported observations and
the occasional debatable findings. In as much as
the isolation and alignment of individual CNTs
has been proven critical for improving conversion
efficiency, the combination of CNTs of different structures, correspondingly, different band
gaps, presents an avenue to obtain a continuous
Figure 21. Performance trend of CNT incorporated OPVs
295

response over a spectral range. This suggests that

a somewhat optimized configuration of CNT
incorporated in PV devices might exist indicating a possible expansive nature of the knowledge
base in this field.
In the 3rd generation cells, guaranteeing reasonable cost is equally as important as obtaining high
performance, hence it is essential to produce high
quality CNTs, and then synthesize eventual solar
cells in ways that are reproducible, scalable, and
controllable. Making structures at the nanometer
scale can be labor-intensive, and laboratories have
made these CNT incorporated solar cells only in
small, bench-scale batches. The commercialization of CNT incorporated PV devices is highly
dependent on the commercialization of CNTs
which have been limited by the lack of reliable,
large-volume production capacity, their high cost,
and little selectivity in controlling the properties
of the product (Sinnott & Andrews, 2001). The
parameters for growing high quality CNTs are
even more complicated to control, which makes
this process challenging. Numerous methods for
synthesizing these CNTs have been explored
(Seah, Chai, & Mohamed, 2011; Jorio, G. Dresselhaus, & Dresselhaus, 2008), however every
method has its own shortcomings. None of the
available techniques totally fulfills the criteria of
being cost effective, fast, and mass scale.
The success of CNT in this field is reliant on
two factors: (1) increased knowledge of the CNT
material and; (2) the ability to synthesize these
cells commercially. Questions that have to be answered include: what CNT configurations produce
the best solar cells? In which components of the
various solar cells are its application advantageous? What type of environment is optimal for
the bulk synthesis of the different types of CNT
incorporated solar cells? Paradoxically, as knowledge is usually garnered based on experience, the
advent of improved knowledge on bulk production
practices is somewhat dependent on continuous
industrial-scale production of these devices and
vice versa. To perplex the situation further, obtain-
296
ing bulk quantities of CNTs at competitive prices

is also dependent on the available market and vice
versa. The most logical route out of this dilemma
is for scientist and researchers alike to site the
indications of this device prosperity and use this
as a prerogative to improve the knowledge base
in this field. Once these devices prove to satisfy
the criteria of the 3rd generation cells, the market
would definitely respond.
CONCLUSION AND SUMMARY

This review presents how CNT outstanding
physical and electrical configurations have been
extensively exploited in the PV field, over the
past two decades. Soon after CNTs discovery,
the photosensitivity of the Si-CNT heterojunction
came to light, inciting several studies which contributed to this field knowledge base. PV devices
based on CNT heterojunctions have now come a
long way, achieving power conversion efficiencies greater than 10%. Notable in this field is the
junction potential as IR detectors, which opens up
an area of research on CNT possible applicability
in multi-junction solar cells, making use of almost
the entire energy range of sunlight. In DSSC, the
high cost of the Pt counter electrode necessitated
the exploration of CNT as a replacement. Obtaining efficiencies comparable to Pt electrode DSSCs
suggested the promise of CNT in this field. This
potential was reiterated by the achievement of
efficiencies even higher than the control cells,
upon the inclusion of CNTs in the cell photoactive layer. The use of CNTs in the TCO layers of
OPVs has just been recently achieved as such, it
is expected that more researchers would explore
this field in the near future. Pioneering studies
on the use of CNTs in OPVs demonstrated an
improvement in OPV conversion with the inclusion of low weight fractions of CNTs (specifically
about 1% w/w CNT produces max efficiency
(Kymakis & Amaratunga, 2002; Kymakis et al.,
2007)). Since then improved cell performances

have been recorded and this trend is expected

to continue. Some other studies on the use of
CNT in OPV include space applications (Landi
et al., 2005), organic-inorganic hybrid solar cells
(Somani, Somani, & Umeno, 2008) and aqueous
solution processing (Khatri & Soga, 2011). As
studies have now demonstrated carbon materials
replacing the majority of the components of PV
cells, it is only a matter of time before solar cells
made entirely of carbon materials are fully demonstrated. As a matter of fact, a first of this kind
has been recently reported (Ramuz et al., 2012)
however, with associated challenges.
The success of CNTs in bridging the gap
between low cost and high efficiency solar cells
is highly dependent on further understanding of
the structure fundamental physics, the synthesis
of CNTs and the commercial fabrication of CNT
incorporated solar cells. In order to commercialize
CNTs, the knowledge base of this material has to
be improved and continuous ton-scale production
techniques of these nanotubes have to be enabled.
Current progress in the physics and fabrication of
CNTs indicates that these are achievable in the
near future. The research on the synthesis and applications of CNTs in solar cells is ongoing, and
there are still many challenges to be addressed.
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310
Characterization: The study and analysis

of a material or a device in order to determine
its characteristics and properties. These can be
physical, chemical, electrical, optical, magnetic,
mechanical, catalytic, thermal, etc.
CNT: Abbreviation commonly used for Carbon
Nano-Tube.

Functional Properties: The properties that

some materials can have and that make them useful
for specific applications such as electrical, optical,
magnetic, thermal, mechanical, etc.
Growth: It is often referred to the process of
depositing or growing a layer on a given material
used as a substrate.
Junction: The physical contact of a semiconductor material with another material that
may be a semiconductor or a metal. The typical
example is the p-n junction used as the basis for
many devices.
Photovoltaics: The process of converting light

directly into electricity using the photovoltaic
effect.
Solar Cell: A device based on a typical semiconductor p-n junction and that converts photons
directly into electricity. Solar cell can be made
using a variety of semiconductor materials.
Thin Films: Materials with a thickness in
the nanometer or micrometer range, grown or
deposited on a substrate using a given physical or
chemical method. They are used as active layers
in devices or as coatings.
311
312
Chapter 13
Overview on Hydrogen
Absorbing Materials:
Structure, Microstructure,
and Physical Properties
G. Walker
University of Nottingham, UK
Mohamed Bououdina
Z. X. Guo
University College London, UK
D. Fruchart
CNRS de Grenoble, France
ABSTRACT
Hydrogen is a promising and clean fuel for transportation and domestic applications, but is difficult to
store. Many systems have been investigated in order to improve the maximum hydrogen storage capacity
(reversibility), high kinetics, moderate equilibrium pressure and/or decomposition temperature, and better cyclability. In this chapter, a review of studies related to stability of Zr-based Laves phase system as
well as in-situ neutron diffraction investigation, the kinetics of TiFe, surface treatment of LaNi5 system,
mechanically alloyed Mg-based hydrides, and graphite nanofibers are reported.
1. INTRODUCTION
In the search for alternative fuels, hydrogen is
the ideal candidate as a clean energy carrier for
both transportation and stationary applications.
The storage of hydrogen in the form of metallic
hydrides is the safest method and presents several

advantages, e.g.: i) relatively large hydrogen storage capacity compared with the gaseous, liquid
and even the solid form (see Table 1); and ii) good
reversibility of hydrogenation/dehydrogenation
with many metallic hydrides.
DOI: 10.4018/978-1-4666-5824-0.ch013

Overview on Hydrogen Absorbing Materials
Table 1. Density of hydrogen in selected compounds

Compound
method of storage is far less hazardous than the

other forms of storage.
Number of H atoms / cm3 (x 1022)
Liquid Hydrogen (20 K)
4.2
Solid Hydrogen (4.2 K)
5.3
TiH2
9.2
For optimum hydrogen storage, metal hydrides

should meet the following criteria: high storage
capacity, low dissociation temperature, moderate
dissociation pressure, low heat of formation in order to minimise the energy necessary for hydrogen
release (and also less heat to dissipate during the
exothermic hydride formation); low cost, light
weight (in particular for transport applications such
as electric vehicles), and high stability against O2
and moisture for long cycle life.
The major challenges in the development of
new hydrogen storage materials, with particular
reference to batteries and fuel cells, are improved
energy storage density, kinetics, cycle life, using
readily available elements at a reasonable cost.
Many studies have been devoted to the increase
of the storage capacity by alloying modifications,
whereas kinetics was improved via both alloying and processing. Different types of materials
have been investigated for the purpose, including
LaNi5 and TiFe compounds, Zr- and Ti-based
Laves phases, Mg2Ni and Mg based materials,
and composites. Recently, carbon nanostructures
(nanotubes, nanofibers) and complex light metals
hydrides (such as sodium alanates) have also attracted attention as promising materials for hydrogen storage. Table 2 reports some characteristics
of some selected hydrides. This report outlines
the pros and cons and promises of these groups
of materials, with an aim of providing a balanced
view of this rapidly developing technology.
The hydride formation is endothermic and the
reverse reaction exothermic. Hence, hydrogen can
be released by simple heating of the hydride. This
2. THERMODYNAMICS OF
HYDROGEN ABSORPTION/
DESORPTION
2.1 Desirable Properties of Hydrides
For optimum hydrogen storage, metal hydrides
should meet the following criteria: high storage
capacity, low dissociation temperature, moderate
dissociation pressure, low heat of formation in order to minimise the energy necessary for hydrogen
release (and also less heat to dissipate during the
exothermic hydride formation); low cost, light
weight (in particular for transport applications such
as electric vehicles), and high stability against O2
and moisture for long cycle life.
2.2 Pressure-CompositionTemperature (PCT) diagrams

Pressure-Composition-Temperature (PCT) diagrams are often used for the evaluation of hydrogen
storage behaviour of metal hydrides. A typical
PCT isotherm is shown in Figure 1, where, the
absorption-desorption reactions depends very
much on temperature:
M+
s
H MH s
2 2
(1)
where M is the metal, MH is the hydride and

the subscript s corresponds to the maximum
hydrogen content in the hydride.
The above reaction can be controlled by the
hydrogen equilibrium pressure as a function of
the quantity of hydrogen absorbed.
Figure 1, represents the solid solution (MHx,
x<<s), the full hydride (MHs), PA the equilib-
313

Table 2. Characteristics of selected hydrides
Material
Equilibrium
conditions
P/T (atm/C)
Heat of
formation
kJ/mole
Activation
conditions
Kinetics
Price
Zr
ZrH2
2.14
P=1 / T=881
-217
average, needs
high purity H2
good at high
temperatures
high
Ti
TiH2
4.01
P=1 / T=643
-164
average, heat up
to 400-600C
average
low
VH2
3.78
P=1 / T=20
-40.12
very difficult
good at high
temperatures
high
YH2
YH3
2.20
3.26
/
/
-72.0
-69.0
/
/
/
/
very
high
Mg
MgH2
7.60
P=1 / T=295
-75.24
350C, 30 atm
30 hours
very slow
low
FeTi
FeTiH2
1.89
P=1 / T=0
-24.66
400C, 10 atm
10-20 hours
quite fast
quite
low
LaNi5
LaNi5H6
1.37
P=1 / T=10
-31.8
25C, 10 atm
1 hour
fast
high
ZrCr2
ZrCr2H3.4
1.71
P=1 / T=166
-45.2
heat to 500C
under vacuum
quite fast
average
TiCr1.8
TiCr1.8H3.5
2.4
P=1 / T=-91
-20.2
difficult
cheap
Mg2Ni
Mg2NiH4
3.59
P=1 / T=253
-64.37
difficult
slow
average
Mg2Cu
MgH2+Mg2Cu
1.44
P=1 / T=290
-66.0
difficult
slow
average
ZrNi
ZrNiH3
1.96
P=1 / T=292
-76.85
easy
fast
high
NaAlH4
3NaAlH4
Na3AlH6 + 2Al
+ 3H2
Na3AlH6
3NaH + Al +
3/2H2
NaH
Na + 1/2H2
3.7
T=185 C
1.85
T=230 C
1.85
total: 7.4
T=260 C
very slow
low
8.4 *
P=0.75 /
T=-191
very
high
SWNT
Hydrides
Theoretical
capacity
(wt.%)
depend on purity
(see Table 3)
*: Measured value.
rium absorption pressure and PD the equilibrium

desorption pressure.
2.3 Enthalpy (Heat) of Formation

It is necessary that the amount of hydrogen must
be readily released under the conditions of dissociation. Hence, the amount of heat must be
available to supply the enthalpy of dissociation.
The heat of formation (enthalpy change) of the
314
MHs hydrides can be calculated from the Vant

Hoff equation:
Ln( PH ) =
2
2.H f
s.R.T
+C
(2)
where PH is the equilibrium plateau pressure at

2
a given temperature, H f is the heat of formation,

T is the temperature, R is the gas constant and C
a constant of differentiation.

Figure 1. Absorption-Desorption PCT curves
Hence, experimentally, the heat of formation

of the hydride can be determined from the slope
of the following equation:
1
Ln( PH ) = f
2
T
(3)
G f (T ) = H f (T ) T .S f (T ) As the free
energy of hydride formation at a given temperature
can be written as:
G f (T ) = H f (T ) T .S f (T )
and
(4)
s
R.T .Ln( PH ) (5)
2
2
is free energy, S f (T ) and is the
G f (T ) = R.T .Ln( K p ) =
where G f (T )
entropy.
We can establish the following relationship:
( )=
Ln PH
LnPH =
2
2.H f
s.R.T
2.H f
s.R.T
2.S f
s.R
2.S f
s.R
(6)
Here, the values of enthalpy and entropy

changes of hydride formation can be determined
experimentally. Table 2 reports the heat of formation of some selected intermetallic hydrides.
The heat of formation H, which represents
the amount of heat absorbed or liberated during
hydrogen (H) uptake by a metal (M) or an alloy,
has been measured for many M-H systems as can
seen from Table 2. The knowledge of H is
therefore of great importance for practical applications of M-H systems concerning the energy
storage since the dissociation pressure PH is
2
directly related to H by the VantHoff relation

(see Equation 6). The sign of H is related to the
amount of the dissolved hydrogen: metal hydrides
with (-H) dissolve large quantities of hydrogen
while systems with (+H) dissolve very small
quantities of hydrogen.
The stability of the hydrides can be discussed
from their heat of formation. So far, the heat of
formation of stoichiometric binary and ternary
hydrides can be estimated through two models:

atomic cell model based on semi-empirical

calculations, which is known by Midemas
model (Miedema, 1973; Miedema et
al., 1975; Boom et al., 1976; Miedema
et al., 1976; Bouten & Miedema, 1979;
315

Miedema & van der Woude, 1980; Bouten

& Miedema, 1980; Miedema et al., 1980),
and
band structure based calculations developed by Griessen et al. (Griessen &
Huisman, 1983; Griessen & Driessen,
1984).
Midemas Model
Midemas model can be described by the following equation:
H = P. f (c).g(c). e *
Q
n ( ws )
P
(7)
where, * represents the difference in the

electronegativity of the two elements, n(ws)1/ 3
represents the difference in the electronic density
of the two elements, f(c) and g(c) are functions
of the concentration, and P, Q and R are constants
depending on the type the two metals.
The first term representing a negative contribution results from the equality of the chemical
potential at the boundary of the two similar cells
of the two elements, whereas the second term
representing a positive contribution is a factor
favouring the formation of the alloy and it is related to the discontinuity in the electron density
n(ws) at the boundary of the Wigner-Seitz cells.
The model is based on binary systems and can be
easily extended to ternary systems:
H ( Ax B y H 2 m ) = H ( Ax H m ) + H ( B y H m ) H ( Ax B y )
(8)
Electronic Band Structure Model

The heat of formation H (kJ/mol H) of metal
hydrides was found empirically to vary linearly to
a characteristic energy E (eV) of the electronic
band structure of the host metal:
316
= E + = ( E F Es ) +
(9)
where, EF is the Fermi energy, Es the center of the

host metal electronic band with a strong s character
at the interstitial sites occupied by hydrogen, and
and are constants (=29.62 kJ/eV mol.H and
= -135 kJ/mol.H). This model can be generally
used for binary hydrides and extend to ternary
hydrides by introducing some modifications to
the equation (9).
Midemas model has been used to discuss the
phase stability of the system ZrCr2-xMx, both alloys
and their corresponding hydrides (Bououdina et
al., 1997). It is found that M=V, Mo favour the
formation of the cubic C15-type structure, while
M=Mn,Fe,Co,Ni,Cu favour the formation of the
hexagonal C14-type structure (see Figure 2). The
results are in good agreement with the experimental data (Bououdina et al., 1997).
2.4 Hydrogen Storage Capacity

This is usually presented in terms of the number of
hydrogen atoms absorbed by the metal or the alloy
per a unit formula (H atm/f.u.), or the number of
stored hydrogen atoms per unit volume (H atm./
cm3) or amount of hydrogen per unit weight (wt.%
H). It represents the hydrogen storage density,
g/cm3, one of the most important criteria in the
choice of hydrides. Hydrogen storage capacity
depends on many factors, such as:
1. the number of available Interstitial Sites
(I.S.) in the crystal structure,
2. size of the interstice which depend on the
size of the elements forming it,
3. the distance between two I.S.s, two neighbours sites cannot host simultaneously
hydrogen atoms if the distance between the
two sites is less than 2.1 (Switendick, 1978),
and

Figure 2. Heat of formation change in the system ZrCr2-xMx
4. the attraction of the I.S., which depends on

the hydrogen affinity of the atoms forming
the I.S.
For a ternary Laves phase system, ZrCr2-xMx

where M is another transition metal, hydrogen
capacity can be estimated from the equation:
Table 2 reports the theoretical hydrogen storage

capacity of some selected intermetallic hydrides.
A simple model has been proposed to estimate
the hydrogen capacity. The investigation of Ti-Fe,
Ti-Cr-Mn and Ti-V-Mn related hydrides showed
that the hydrogen absorption capacity depend on
the valence electrons, in particular on the concentration of d electrons (Bernauer & Halene,
1987). For alloys with a cubic or hexagonal type
structure, the hydrogen capacity can be expressed
by the equation:
nZr + (2 x ) nCr + x nM
H
= 5

M
3
H
= 5 DEC
M
(10)
With
DEC =
(d electrons)
number of metallic atoms
(11)
It has been noted that transition metal alloys

absorb hydrogen until the 3d band is half full.
(12)
where nZr, nCr and nM represent the number of d

electron of Zr, Cr and the metal M respectively.
Hence, the effect of the type of the transition
element and its amount can be pointed out. From
Figure 3, it is clearly noted that:

Fe, Co, Ni and Cu elements tend to decrease the capacity,

Mn and Mo do not seem to show any effect
on the capacity, and
Only V leads to increase to hydrogen capacity of the parent ZrCr2 intermetallic
compound.
2.5 Hysteresis Phenomenon

Hysteresis phenomenon is observed by the difference in the absorption and desorption pressures
in an isothermal cycle. It represents a loss in the
317

Figure 3. Evolution of hydrogen capacity H/M versus the substituted element M and its amount x
thermodynamic efficiency during the use of the

hydrides. It should be noted that a certain amount
of the hysteresis is due to the non-reversible elastic
effects. The absorption is usually accompanied
by an important lattice expansion, around 20%
for AB2 Laves phases. The lattice deformation
after H-absorption requires a certain quantity of
energy, which during H-desorption is not completely recovered.
The width of hysteresis in M-H systems depends on various parameters: temperature (Ludin
& Lynch, 1978; Suda, 1982), chemical composition (Ivey & Northwood, 1986), heat treatments
and the number of absorption/desorption cycles
(Flanagan & Biehl, 1981), and the particle size

of the alloy (Reilly et al., 1983).
In the investigation of the pseudo-binary Laves
phase ZrCr2-xFex system, (Qian & Northwood,
1989), it has been identified that the width of the
hysteresis loop depends on the Fe concentration
as can be observed in Figure 4, where
R=
P
1
RT ) .ln a
(
Pd
2
with Pa and Pd are the absorption and desorption

plateau pressures. It can be noted that the increase
Figure 4. Effect of the chemical composition on the hysteresis of the ZrCr2-xFex -H system (Qian &
Northwood, 1989)
318

of Fe content increases the hysteresis loop while

an increase of temperature reduces it.
2.6 Plateau Slope

The plateau pressure in the PCT diagram shows
the range of co-existence of the metallic phase and
its hydride. The plateau slope, d(LnPa)/d([H/M])
for absorption, varies from compound to compound and is influenced by chemical segregation
occurring during the solidification process of the
alloy. It has been noted that a reduction in the
plateau slope can be obtained by heat treatment
of the alloy before grinding and activation process
(Sandrock, 1978). It is also important to note that
sloping plateaus are more likely to be observed
in M-H systems showing a relatively slow kinetics. It is originally due to defects in the lattice or
disorder in atomic arrangements, which creates
slightly different potentials for crystallographically identical interstitial sites.
2.7 Hydrogenation/Dehydrogenation
Processes and Kinetics
The exposure of metal or alloy to H2 under appropriate conditions leads to the formation of
hydrides. Generally speaking, the hydrogenation
process can be simply considered as shown in
Figure 5, e.g. for LaNi5.
Moreover, the hydrogenation process can be
also considered in more details, which involve
mainly 7 steps and can be schematically represented as follows:
H2 (gas)

H (surface)
H*2
H (sites)
(H) surface

(H) ads
(H) volume

(H) hydride
1. mass transport
2
2. chemisorption of molecular H
2
3. dissociation of H 2
4. diffusion of H 2 from the sites to the surface of the metal
5. transformation from chemisorbed state into adsorbed statte

6. diffusion through hydride phase
7. phase transformation
The dehydrogenation can be regarded as the

reverse process and hence involves the same number of steps in an opposite direction. Each step
plays an important role in controlling the kinetics.
Hence it is necessary to understand and model
each mechanism in order to be able to improve
the kinetics. The hydriding/dehydriding kinetics
can be improved through various ways, such as:
2.7.1. Chemical Alloying

The substitution of a small amount of an element of
a stoichiometric compound by another appropriate
element has been reported to enhance the hydrogenation/dehydrogenation (charging/discharging
during electrochemical measurements) kinetics.
Many pseudo-binary systems have been studied
and show good results, such as in the ZrCr2-xMx
Laves phase system, where single phase shows a
low kinetics, M=V-Co (Bououdina et al., 1996).
In this case, the substituted element does not form
any secondary phase; it only affects the thermodynamic properties of the main compound and the
surface properties. The formation of oxides on the
surface of the alloy during processing or storage
has been reported to affect both the activation
process and the kinetics. The substituted element
improves the oxidation resistance.
Figure 5.
319

2.7.2. Precipitation of Secondary Phase

The substitution/addition of certain elements in a
binary compound may provoke the formation of
secondary phases, which enhances the kinetics.
The grain-boundaries play the role of pathways for
hydrogen diffusion. In the study of Zr1-yTiyCr2-xNix
(Bououdina et al., 1998), it has been found that
the replacement of some amounts of Zr by Ti and
Cr by Ni enhances the kinetics by the formation
of multi-phase systems. The type and the amount
of the secondary phase depend on the type and
the amount of the substituted element. Moreover,
the addition of another element has been also
successful to the precipitation of a secondary
phase, such as the addition of La/Ce elements to
a Zr-Cr-Ni Laves phase alloy, which leads to the
formation of LaNi/CeNi phases (Sun et al., 1996;
Percheron-Gugan et al., 1997), showing a better
solid-gas and electrochemical kinetics.
2.7.3. Composite Materials

The combination of a hydrogen-storage metal/
compound with another of complementary properties results in most cases in improved and balanced
properties in these composites. For instance, the
addition of LaNi5 to Zr-Ti-Cr-Ni single Laves
phase of very slow kinetics has shown a large
enhancement of the kinetics (Bououdina et al.,
1999). The addition of LaNi5 (Sun et al., 2000)
to Mg also reveals improved kinetics of hydrogen
absorption-desorption compared to pure Mg. The
grain boundaries between the major phase and
the added phase play a major role of pathways for
hydrogen diffusion.
2.7.4. Processing
It is known that both chemical alloying and microstructure have great effects on physical properties of a metal/compound. The microstructure
can be modified by processing route that allow
the formation of very fine grain sizes (melt spin-
320
ning) or nano-particles (mechanical alloying

MA). It has been reported that synthesis of some
hydrogen storage materials via MA leads to a
great improvement of their kinetics, such as the
formation of nanocrystalline Mg2Ni (Zaluski et
al., 1995). Moreover, the addition of a catalytic
element during MA process leads to a much improved kinetics and prevent the oxidation after MA
of the material during handling, such as Pd with
Mg2Ni, LaNi5 and FeTi (Zaluski et al., 1995), or
Ni with TiFe (Bououdina et al., 1999).
MA under controlled and reactive atmosphere
is another way of improving hydrogenation process. MA results in powder decripitation, leading to the formation of fine particles even in the
nanometer scale with fresh surfaces and hence
accelerates the adsorption and then the diffusion
of H2. MA of Mg under H2 atmosphere (Aoki et
al., 1994) shows a rapid hydrogenation with faster
kinetics. However, the exposure to air after MA was
found to reduce readily their kinetics, attributed
mainly to the rapid formation of an oxide film on
the surface of nanocrystalline particles.
2.7.5. Surface Treatments

Most of MH systems suffer from oxidation during
processing or storage. Another way of improving
the kinetics of M-H systems is the improvement of
metal surface oxidation resistance or the reduction
of the formed oxidation during thermodynamic/
electrochemical measurements. Liu et al. have
found a way of improving the kinetics via surface
treatment: fluorination (Liu et al., 1997). It consists
on the removal of an oxide layer from the surface
and forms a fluoride layer, which drastically improves the activation characteristics.
2.7.6. Coating
One of the major problems of using metal hydrides
in NiMH batteries is their oxidation behaviour
within the alkaline solution, which results in
slow kinetics, reduced discharge capacity and

short cycle life. Recently, surface modifications

of LaNi5-based hydrides, by means of deposition of a small amount of Pt group metals on the
surface of the electrode, enabled rapid charging/
discharging and a longer cycle life (Pratt et al.,
1999). The coating treatment improves the stability
of the alloy in air and involves an enhancement
of H2 sorption rates within the alloy.
a. Reaction Controlled by Diffusion
Evaluation of Kinetics
where 2x represent the thickness of the reacted

layer.
For a reaction controlled by bi-dimensional
diffusion within a cylinder of radius r:
The most common method of evaluating the

kinetics during hydrogenation/dehydrogenation
properties of a material is to measure the variation of hydrogen concentration absorbed/desorbed
versus time (Gerard & Ono, 1992). Many factors
have been identified to influence the absorption/desorption rates, including: i) the quantity
of the sample, ii) the sample shape (container),
iii) porosity which can be related to the particle
size, iv) thermal conductivity of the sample, v)
the thermal contact between the sample and the
holder, vi) particle size distribution of the sample,
vii) particle shape, viii) H2-pressure during the
measurement and viiii) gas purity.
M-H reactions can be considered as solid-gas
reactions, which can be expressed by the general
relationship:
F(C) = k. t or F() = K. (t/t0.5)
(13)
where C is the H2 concentration, =C/C0 represents

the reacted fraction of the material normalised by
the final concentration C0, and t is the time which
is normalised by t0.5, the time at half concentration
(Sharp et al., 1966).
The function F() depend on the mechanism
that controls the reaction of the material with H2,
the size and the shape of the particles. Hence, the
shape of the normalised curves help to determine
the rate controlling mechanisms of a M-H system
reaction:
For a mono-dimensional diffusion process with

a constant diffusion coefficient, the reaction can
be simply described by a parabolic law:
t
k
D1 ( ) = 2 = t = 0.25
t0.5
2 x
(14)
t
k
D2 ( ) = (1 ) ln (1 ) + = 2 t = 0.1534
r
t0.5
(15)
And for a reaction controlled by diffusion with a

spherical symmetry:
2
t
1
k
D3 ( ) = 1 (1 ) 3 = 2 t = 0.0426
r
t0.5
(16)
b. Reaction Controlled by Diffusion through

Grain Boundaries
The reaction is simply controlled by the movement of an interface with a constant viscosity, .
For a cylinder:
t
1

D4 ( ) = 1 (1 ) 2 = t = 0.2929
r
t0.5
(17)
and for a sphere:

t
1

D5 ( ) = 1 (1 ) 3 = t = 0.2063
r
t0.5
(18)
321

c. Reaction Controlled by the Chemical

Reaction Order
The mechanism can be modelled by:
d
= k (1 )n
dt
(19)
where n represents the order of the reaction. Only

the reaction orders 1, 1/3 and 2/3 are believed to
be physically meaningful (Mitz, 1991).
The most conventional approaches regarding
the kinetic models are based on the assumption
that one of the microscopic mechanisms or steps
involved in the reaction M-H is considered much
slower and hence being the rate-determining step
of the overall process (Mitz, 1991).
3. RECENT ADVANCES IN METALHYDROGEN STORAGE MATERIALS

Since the discovery by Graham of the reversible
hydrogen absorption capability of Pd in 1886
(Lewis, 1982), many fundamental and technological studies have been undertaken in MetalHydrogen (MH) systems. Table 2 reports some
selected hydrides and their properties.
3.1 Metal, Alkali Metal, Rare Earth

and Alkali Rare Earth Hydrides
Metal hydrides can be divided mainly into 5
groups (more details are reported in reference
(Libowitz, 1995).
1. Ti, Zr and Hf: they form dihydrides with a
tetragonal structure. A cubic phase exists at
room temperature for a wide range of hydrogen compositions, TiH1.0 to TiH2.0, ZrH1.0 to
ZrH1.61, HfH1.0 to HfH1.7. These hydrides are
known to be stable to very high temperatures.
Hydrogen can be released around 650C for
TiH2 and 880C for ZrH2.
322
2. V, Nb, and Ta: these metals form a relatively

stable monohydride MH1.0. Both Nb and
V also form much less stable dihydrides;
NbH2.0, with Pp=1 atm at T=31 C and VH2.0
with Pp=1 atm at T=13 C.
3. Alkali metals: Li, Na, K, Rb and Cs form
monohydrides with a cubic NaCl-type
structure.
4. Rare earths: rare-earth metals form dihydrides (REH2 with R = La, Ce, Pr, Nd, Sm,
Gd, Tb, Dy, Ho, Er, Tm, Lu, Sc and Y) with
cubic fluorite type structure and trihydrides
(REH3 with R = Sm, Gd, Tb, Dy, Ho, Er, Tm,
Lu, and Y) with an hexagonal structure. EuH3
and YbH3 crystallise with an orthorhombic
structure and YbH3 crystallise with a cubic
structure.
5. Alkali rare earths: Ca, Sr and Ba form dihydrides with an orthorhombic structure.
3.2 AB2 Laves Phases

AB2 Laves phases have attracted great attention
as potential hydrogen absorbing materials. AB2
exists in three types of crystal structure: Cubic
C15 (MgZn2, such as, ZrV2, low temperature
TiCr2 and high temperature ZrCr2); Hexagonal
C14 (MgCu2, such as, ZrCr2 low temperature,
TiCr2 high temperature and ZrMn2) and double
Hexagonal C36 (MgNi2). The structural stability of
the Laves phases depends on the geometric factor
(ratio of the atomic radii of the two elements), the
electronic factor related to the electronegativity,
and the valence of the elements (Laves & White,
1936). Laves phases show relatively high capacities (ZrV2H5.3, ZrMn2H3.6, ZrCr2H3.4,), faster
kinetics, longer life and a relatively low cost in
comparison to the LaNi5 related systems. However,
their hydrides are too stable at room temperature.
Multi-component Laves phase systems:
Zr1-xTx(Mn,Cr)2-yMy

where T=Ti,Y,Hf,Sc,Nb and M= V,Mo,Mn,

Cr,Fe,Co,Ni,Cu,Al,Si,Ge. have been studied
extensively as H-storage materials, where both
thermodynamic and electrochemical properties
depend on the nature of the substituted element
and its amount.
Neutron diffraction study of the hexagonal
Laves phase ZrCr2-xMx system and related hydrides (M=Ni,Mo and 1.0 x 0.0), showed a
relative preferential metallic site occupancy for 2a
site by both Ni (Bououdina et al., 1997) and Mo
(Bououdina et al., 2000). Moreover, it is found
that although the decrease of the unit cell volume
with increasing Ni content, the hole size of the
A2B2 interstices (ab-initio calculations based on
a geometrical model) indicate an increase of the
radius when increasing Ni content (Bououdina
et al., 1997).
The investigation of the multi-component
Zr1-xTxCr2-yMy system (Bououdina et al., 1998)
by the Rietveld analysis indicated: (1) the system crystallises within the hexagonal C14-type
structure for yNi<1.0 then transforms into cubic
C15-type with the formation of an additional Zr-Ni
phases, (2) single phase compositions were found
to absorb large amount of hydrogen ( 1.8wt.%)
but possesses very poor kinetics, (3) multiphased
systems have a moderate hydrogen capacity (
1.4wt.%) and exhibits faster kinetics. A linear
correlation between the heat of formation of the
hydrides estimated from the band structure model
and the unit cell volume of the alloys was found:
decrease of the hydride stability with increasing
unit cell volume.
The effect of the nature of the transition metal
and its amount on the stability of the Laves phase
ZrCr2-xMxH3 hydrides system (0.0 x 0.8 and
M=V,Mo,Mn,Fe,Co,Ni,Cu) through the calculation of the heat of formation, has been carried out
using the atomic cell model based on semi-empirical calculations, Miedemas model (Midema,
1976; Bouten et al., 1980; Miedema et al., 1980).
It is found that hydrides with M=V,Mo are more
stable than ZrCr2, while with M=Mn,Fe,Cu,Co,Ni

form less stable hydrides (Bououdina et al., 1997).
In-situ neutron diffraction investigation of
the hydrogenation/dehydrogenation processes of
a Laves phase-rich multi-component ZrCr0.7Ni1.3
system were carried out in order to clarify to effect
of the second phase on the hydrogen absorption/
desorption mechanisms (Bououdina et al., 2000;
Bououdina et al., 2001a; Bououdina et al., 2001b).
The as-cast alloy crystallises in the C15-type Laves
phase, in equilibrium with 36% of Zr7Ni10 phase
and 5% of elemental Cr. The hydrogenation/dehydrogenation was found to be very fast, attributed
to the presence of Zr7Ni10 as a secondary phase.
During absorption, Zr7Ni10 phase the transforms
into an amorphous phase (all diffraction peaks
disappear, see Figure 6: 3D absorption), which
lead to a slopping plateau pressure as observed in
PCT diagram. The lattice parameters of the C15
phase due to the increase of the H2 content. The
non-reversible H2 amount was attributed to the
amorphous Zr7Ni10 phase, which does not desorbs
all absorbed H2. During annealing under vacuum,
the Zr7Ni10 phase begins to recrystallise at 101C
(Figure 7: 3D recrystallisation).
3.3 TiFe Intermetallic Compound

TiFe is a well-known hydrogen storage compound
with a total hydrogen capacity of around 1.9
wt.% and its constituent elements are inexpensive. However, the activation process of TiFe is
troublesome due to the formation of Ti-oxides
layer. Both high pressure and high temperature
are required to achieve a reproducible absorption/
desorption of the maximum amount of hydrogen
in the compound (Reilly & Wiswall, 1974). The
application of mechanical alloying under different
atmospheres with the use of catalytic elements,
e.g. Pd, enhanced dramatically the activation
process and the hydriding/dehydriding kinetics
of TiFe (Zaluski et al., 1996). Ball milling under
pure argon atmosphere (20-30 hours) of TiFe with
323

Figure 6. 3D diffraction pattern evolution during absorption cycle at 50C of as-cast ZrCr0.7Ni1.3 sample
(Bououdina et al., 2000)
Figure 7. 3D diffraction pattern evolution during recrystallisation process of Zr7Ni10 phase (Bououdina
et al., 2000)
324

small amount of Ni can readily absorb H2 without

activation (Bououdine et al., 1999). The drastic
improvement of the kinetics is due to the formation
of fine powder of TiFe covered by nanocrystalline
Ni particles, which act as catalytic centres for the
decomposition of H2 molecules.
The PCT diagram at 40 C reveals the presence
of two plateau pressures with the formation of
three types of hydrides: solid solution FeTiH0.1,
phase FeTiH1.0 and phase FeTiH2.0. However,
nanocrystalline FeTi obtained by mechanical alloying shows the presence of a single plateau and
the width is reduced. No phase transformation
from into is observed (Tessier, 1995).
In several studies, Fe has been replaced in part
by other transition metals of similar atomic sizes,
e.g. Ni (Nan & Zhangda, 1987), Mn (Chung & Lee,
1990), and by other elements, e.g. Zr (Lanyin et
al., 1988), Pd (Nagai et al., 1988) and Mischmetal
(Yamashita et al., 1997). These substitutions have
resulted in changes of thermodynamic properties
of the pseudo-binary systems due to the catalytic
effect of the 3d metals (Ni,Mn,Pd), the presence
of the elements that form stable hydrides (Zr, Ms,
Pd), and an increase of the oxidation resistance
of the alloy (Zr,Ni). The major effects are: i) improved activation process; ii) faster kinetics; iii) an
increase (or a decrease) in the equilibrium plateau
pressure; iv) low hysteresis; and v) improved cycle
life with vi) a relative reduction of the hydrogen
capacity which is strongly dependant on the nature
of the substituted element and its amount.
The application of mechanical alloying under
different atmospheres with the use of catalytic elements, e.g. Pd and Ni, enhanced dramatically the
activation process and the hydriding/dehydriding
kinetics of TiFe (Zaluski et al., 1996; Bououdina
et al., 1994).
3.4 LaNi5 System and

Related Compounds
LaNi5 is the most studied compound as a hydrogen
storage material. Several investigations have been
devoted to the crystal structure, thermodynamic

and electrochemical properties. So far, the multicomponent system:
La1-xRExNi5-xMx
With M=Mn,Cr,Fe,Co,Cu,Al,Sn,Ge,Si and
RE=Mischmetal,Ce,Nd. has been extensively
studied (. Both the thermodynamic and electrochemical properties were found to be strongly
dependent on the nature of the substituted element and its content. The parent compound LaNi5
absorbs about 1.0 H/LaNi5 (1.5 wt.%) and is easy
to activate (5 bars at T=100C after a few cycles,
to achieve the maximum hydrogen capacity). The
PCT diagram shows a flat plateau, low hysteresis, but unfortunately the hydrogen capacity is
degraded after a few cycles. In the LaNi5 related
intermetallic compounds, the thermodynamic
properties vary strongly with the composition.
The investigation of La1-xCexNi5 (0.3 x
0.0) system (Corre et al., 1998) shows that with
increasing Ce content: (1) an important decrease
of the cell volume, (2) the hydrogenation kinetics
were found to be lower when, (3) both plateau
pressure and hysteresis increase. After Co surface
treatment, the retention time of H2 under normal
conditions was extended. Increasing Ce content
in CO-treated hydrides leads to a decrease in the
retention time: 820ks for complete dehydrogenation of CO-treated LaNi5 hydride compared to 110
ks for CO-treated La0.9Ce0.1Ni5 hydride.
LaNi5 is the most studied compound as a
hydrogen storage material. Several investigations have been devoted to the crystal structure,
thermodynamic and electrochemical properties.
Both metallic sites have been substituted by other
elements: Ni by 3d metals, such as Mn, Cr, Fe, Co,
Cu, Al, Sn, Ge and Si (Wiswall, 1978; PercheronGuegan, 1995; Luo et al.,Witham et al., 1997,
1995; Srivastava & Srivastava, 1998; PercheronGuegan & Resiter; 1988; Van Mall et al., 1974),
and La by Mischmetal and other rare earth metals,
such as Ce and Nd (Corre et al., 1998). Both the
325

thermodynamic and electrochemical properties

were found to be strongly dependent on the nature
of the substituted element and its content.
The parent compound LaNi5 absorbs about 1.0
H/LaNi5 (1.5 wt.%) and is easy to activate (5 bars
at T=100C after a few cycles, to achieve the maximum hydrogen capacity). The PCT diagram shows
a flat plateau, low hysterisis, and unfortunately the
hydrogen capacity is degraded after a few cycles.
In the LaNi5 related intermetallic compounds, the
thermodynamic properties vary strongly with the
composition. A large improvement in the cycle
life has been obtained by the substitution of some
Ni by Sn (Van Mall et al., 1974).
LaNi5 based alloys are the only materials that
have already been used as negative electrode in
the NiMH rechargeable batteries. However, the
increase in demand of rechargeable batteries with
specific properties (higher capacity, lower price,
longer life, faster recharge/discharge, etc) for some
specific electric equipment (laptop computers,
mobile phones, etc) shows that the LaNi5 related
system should be replaced by new types of hydrogen absorbing materials. The most recent research
programme related to LaNi5-related systems, are
oriented for electric vehicle batteries.
3.5 Mg-Based Hydrides

Both MgH2 and Mg2NiH4 (7.6 wt.% and 3.8 wt.%
respectively) show a very hard activation process
and a high decomposition temperature. Recently
the use of mechanical alloying combined with
the use of a catalytic element (such as Pd) shows
a drastic improvement of the activation and both
hydrogenation/dehydrogenation processes occur
with rapid kinetics (Zaluski et al., 1995a,1995b).
The final product consists of nanocrystalline MgNi with homogeneously distributed nanometer2
sized Pd particles. However, despite the recent
positive results, there still exists an important
obstacle for their use, especially in batteries or
fuel cells: the high decomposition temperature
of the hydrides. Some studies show that by the
326
substitution of one or both metallic sites by another

type of elements, the thermodynamic properties
are strongly modified: a decrease of the hydride
decomposition temperature, an improvement of
the activation process, and enhanced hydriding/
dehydriding kinetics (Tsushio et al., 1996; Yuan
et al., 1999).
Mg 8 at.% M (TM=Ni, Cu, Al, and Nb)
system has been mechanically alloyed to tailor
the hydrogen storage properties of Mg (Guo et
al., 2001). After milling, XRD analysis reveals
much enhanced dissolution of Al, Nb, Ni then
Cu into Mg, respectively. New phases have been
formed, such as Mg2Ni, Mg2Cu, Mg12Al17 and
(Nb,Mg) bcc solid solution. The observed volume
contraction (Figure 8) due to the formation of the
(Mg,M) solid solution should lower the dissociation temperature. Moreover, the formation of such
composites materials is expected to improve the
kinetics. Electronic structure calculations reveal
that Al provides the highest stabilizing effect on
Mg, followed by Ni, Cu and Nb. These results
are in line with the XRD analysis. The stabilizing
effect is directly associated with volume contraction of the crystal, which in turn may reduce the
decomposition temperature of the hydride.
Mechanically alloying of MgH2 with 8 at.% of
M (M=Al,Ti,Fe,Ni,Cu,Nb) has been carried out
in order to tailor the thermodynamic properties of
MgH2 (Shang et al., 2004). The results show the
formation of new phases (TiH2, Mg2NiH4, MgCu2,
and bcc-(Nb,Mg)Hx) with remaining of elemental
Al, Fe, Ni, or Cu (Figure 9). The high pressure
-MgH2 phase has been formed. SEM analysis of
mixtures milled for 20 hours shows the formation
of very fine particles in nanometer-sacle. The effective particle size refinement is attributed to the
relatively hard and brittle hydride, which assists
the breaking of particles in the powder mixture.
Dehydrogenation at 300C clearly shows the beneficial effect of the alloying on both kinetics and
level of H2 desorption, which decreases from Ni,
Al, Fe, Nb, Ti, to Cu (Figure 10). The electronic
structure calculations based on first-principal

Figure 8. Variation of the unit cell volume with alloying element: Comparison between theory and
experiment [76]
simulations, accurately predicted the effect of

the selected elements on the heat of the formation of the mixtures. The destabilising effect on
MgH2 reduced from Ni, Fe, Al, Nb to Ti, which
is in agreement with experimental results. The
discrepancy between theoretical calculation and
experiment for Cu is still unclear and needs further
investigation. Moreover, more detailed investigation of (Mg+Nb) and (MgH2+Nb) mixtures has
been undertaken (Shang et al., 2003). A bcc type
structure has been formed for both mixtures. The
bcc phase was attributed to (Nb,Mg) solid solution
for (Mg+Nb) mixture, whereas for (MgH2+Nb)
mixture the bcc phase cannot be identified unambiguously as (Nb,Mg) solid solution (as-received
MgH2 powder contain 5% of pure Mg), or NbHx
(x<1.0) or (Nb,Mg)Hx since the lattice parameter
are found to be similar to that of the bcc-(Nb,Mg)
solid solution formed in (Mg+Nb) mixture.
3.6 Amorphous Alloys

Some amorphous alloys have shown their capabilities to absorb/desorb hydrogen reversibly.
However, there are two parameters that make a
difference compared to intermetallic hydrides:

i) the PCT curves do not show the presence of a
plateau and ii) the occupation of interstitial sites
by H2 is quite different to that of the M-H solid
solution.
Zr-Ni related phases have shown their ability to transform into amorphous phases via melt
spinning or MA (Al-Hajry, 2000), and to absorb
large amount of hydrogen, such as Zr37Ni63 (ZrNi2),
Zr50Ni50 (ZrNi) and Zr67Ni33 (Zr2Ni) compositions
(Aoki et al., 1984). ZrNi mechanically ground
under various H2 pressures (Fuji et al., 1995)
reveals the formation of ZrNiH1 and/or ZrNiH3
and then the appearance of an amorphous phase.
At the end, depending on the H2 partial pressure,
a composite material may exist containing both
crystalline hydrides (ZrNiH3 and/or ZrH2) and
amorphous (-Zr1-NiHx) phase.
MA has been successfully used to synthesise
amorphous Mg-Ni alloys. These have good properties able to absorb/desorb electrochemically
a large amount of H2 at room temperature that
makes them very promising materials for NiMH
batteries. But later, a rapid degradation of the
discharge capacity has been observed (Lei et al.,
327

Figure 9. X-ray diffraction pattern evolution of

mechanically alloyed (MgH2+M) mixtures milled
for 20 hours (Shang et al., 2004)
Figure 10. TG curves of mechanically alloyed

(MgH2+M) mixtures milled for 20 hours (Shang
et al., 2004)
the form of a hydride. The amorphisation process

occurs during milling under hydrogen.
3.7 Hydrogen Storage

in Quasicrystals
1994), attributed mainly to the formation of Mg
and Ni oxides. The cycle life was found to be
improved by a partial substitution of Ni by Co,
Si or Al with a reduction of their initial discharge
capacity (Sun et al., 1995).
Moreover, Hydrogenation Induced Amorphisation (HIA) of intermetallic compounds has been
reported in other systems, such as RNi2 Laves
phases where R is a rare earth element (Aoki et
al., 1987). Upon hydrogen absorption, the Bragg
peaks of the crystalline phase become wider with
weaker intensities. In this case, hydrogen is used in
328
Titinium/zirconium-3d transition metal icosahedral quasicrystals (i-phase class) are the most
ordered and stable materials thermodynamically
(Stroud et al., 1996; Kelton et al. 1997a). They
show great promise for hydrogen storage applications due to their large hydrogen capacity compared with normal crystalline materials. Among
the family, Ti45Zr38Ni17 i-phase has a capacity of
2.5 wt.%, which is greater than that of LaNi5 and
TiFe based alloys (Kelton et al. 1997b). Once
started, full hydrogenation takes only 30 minutes.
However, hydrogen loading from the gas phase
was preceded by a long induction time, varying

from several hours to several days, due to the

formation of oxide layer preventing the hydrogen
diffusion. Plasma etching of the surfaces in argon
followed by deposition of a thin Pd layer (15 to
30 nm) largely reduces the induction time. Such
treated quasicrystals absorb hydrogen readily.
As-cast sample of Ti45Zr38Ni17 forms the crystalline C14 phase (high temperature phase) and
does not load a significant amount of hydrogen,
even at elevated temperatures. Both crystalline
C14 phase and quasicrytalline i-phase Pd-coated
samples load an important hydrogen amount, H/M
near to 1.7, even at room temperature. The noncoated crystalline phase tends to form a strongly
bounded hydride, preventing hydrogen release at
reasonable temperatures.
High Temperature X-ray Diffraction (HTXRD)
(Stroud et al., 1996) demonstrates the thermodynamic stability of Ti-Zr-Ni quasicrystalline phase
during dehydrogemation. A reversible transformation between the quasicrystal and a crystalline
hydride phases was observed. This was the first
evidence for a stable Ti-based quasicrystal and
for reversible hydrogen storage in a quasicrystalline phase. This work demonstrated the hydrogen
desorption from a (Ti-Zr-Ni)-H quasicrystal, with

a desorption onset temperature less than 350oC.
3.8 Graphite Nanofibers

as Potential H2
Graphitic Nanofibers (GNFs) belong to carbon
nanostructures based on that for graphite. The basic
microstructure consists of stacked graphite layers,
which can be arranged parallel / perpendicular
to the fiber axis (Chambers et al., 1998), or herringbone (Rodriguez, 1993) structure, often with
an amorphous component. The angle between the
graphitic planes and the fiber axis which determine
the type of structure is determined by the shape
of the catalyst particle, as reported by Boellard
et al. (Boellard et al., 1985). The herringbone
structure seems to be favoured when the catalyst is
an alloy (Rodriguez, 1993). The as-prepared GNF
morphology and microstructure depend on catalyst
composition, catalyst support, gas mixture, and
reaction temperature. In addition, GNFs can be
produced with different diameters, ranging from 10
to 200 nm. Baker (Baker, 1989) reported that the
size of catalyst particle is a key factor to determine
the growth of GNF, the fibers growth has an inverse
Figure 11. XRD patterns of as-prepared GNFs at different temperatures (Bououdina et al., 2005a)
329

square root dependence on the catalyst particle

size, which means a high growth rate is obtained
when using smaller catalyst particles. Recently,
H2 adsorption exhibited by GNFs, have attracted
attention as potential candidate as a Hydrogen
Storage Materials (HSM) [88]. There is some H2
storage capacities reported for GNFs from 1-2
wt% up to 10 wt% (Kumar and Srivastava, 2000;
Poirier, 2001; Browning et al., 2002; Youn et al.,
2002), but there is a lack of reproducibility in
these measurements. Theoretically, H2 is adsorbed
on the surface and then incorporated between
graphitic sheets of GNFs (Chambers et al., 1998).
The space between the sheets which is 3.35
acts like a slit-shaped pore hence enabling GNFs
to physisorb large amounts of H2, whose kinetic
diameter is only 2.89 (Chambers et al., 1998).
GNFs were successfully synthesised by thermal CVD method using unsupported NiO powder
as catalyst and H2/C2H4 mixture gas. XRD (Figure
11), XPS and TEM (Figure 12) analyses confirmed
the formation of GNFs. Both H2/C2H4 ratio and
temperature show an effect on GNFs growth efficiency, size distribution and length of fibers, and
surface properties (Bououdina et al., 2005A). A
high growth yield was obtained when using high
C2H4 percentage, about 60 g gcatalyst-1 h-1. A herringbone structure was formed at temperatures
400C (Figs. 13d and 13e), while regular platelet
structures were obtained at temperatures 500C
(Figure 12). Relatively high temperatures (700C)
allow the formation of more crystalline structure,
more uniform platelets along the growth axis. It
is important also to note that Ni3C form at low
temperatures 400C (Fig. 12), while Ni forms
at high temperatures 500C. It is possible that
Ni3C phase favours the formation of herringbone
structure while Ni favours platelet structure. The
surface area of as-prepared GNFs increased with
lowering preparation temperature, about 3 times
higher from 700 to 500C, from 170 to 50 m2.g-1,
respectively. The structure and microstructure
modifications here obtained should bring great
330
Figure 12. TEM analysis of as-prepared GNFs at

different temperatures, T=700C (a), (b) and (c);
(d) and (e) T=400C (Bououdina et al., 2005a)
benefits, hence correlating the catalytic phases

(Ni3C or Ni metal) on H2 uptake.
Reflux treatment at 120C using nitric acid with
different molarity has been applied on selected

Table 3. H2-uptake measurements of GNF sample prepared at 500C after various treatments (Unpublished results)
As-prepared
CO2-treated
CO2/H2-treated
MaxSorb
SA (m g )
170
173
214
3000
H2-uptake (wt.%)
0.00
0.45
0.62
0.57
-1
GNFs samples in order to remove the catalyst

particles, the amorphous carbon formed on the
edges of the fibers, as well residual oxygenated
species. After treatment, no hydrogen uptake has
been noticed (Bououdina et al., 2005b).
Further treatments have been applied in order
to improve the hydrogenation of GNF samples,
including selective oxidation using CO2 gas at
600C followed by reduction under hydrogen
flow at 400C (Bououdina et al., 2005b). Hydrogen uptake measurements have been carried out.
Table 3 shows the effect of various treatments
on the surface area modifications as well as the
hydrogen uptake.
3.9 Sodium Alanate Related Hydrides

Alkali metal hydrides AH (A=Li, Na, K, Rb and
Cs) form monohydrides and are considered as
salt-like compounds where hydrogen plays the
role of anion. Although H2 capacity is high, as
in the case of Li and Na respectively, 12.6 and
4.2 wt.%, these are known to be relatively stable
(Alefeld and Vlkl, 1978), their dissociation
pressures reach 1 bar at LiH/894C, NaH/421C,
KH/428C, RbH/364C and CsH/389C.
Moreover, one of the Li alloys, LiAl was found
to react with H2 to form LiH accompanied by
lowering the decomposition temperature, about
580C at 1 bar:
LiAl + H2 LiH + Al
Light metal hydrides, in particular AlH3 was
thouroughly studied and thought to be used as
rocket fuel due to its high H-capacity, more than

10 wt.% and decomposes on heating around 100C.
However, the indirect syntheses were too costly,
and the compound cannot be formed directelty
from the elements even at high H2 pressures,
P=270 bar at 196C or P=570 bar at room temperature (Alefeld and Vlkl, 1978). Al hydride
can be stabilised by a combination with other
hydrides, known as alanates (based on complex
anion AlH
4 ) by using chemical solvents, such
as LiAlH4 and NaAlH4:
4 LiH + AlCl3 LiAlH4 + 3 LiCl
Complex hydrides, based on light metals such
as Li, Na and Al have been studied due to their high
hydrogen capacity. Later, more sodium aluminium
hydrides (and other alkali metal aluminium) have
been reported to be synthesised directly from
Na (or NaH) and Al (or AlH) under very high
H2 pressure and in various solvents (Ashby &
Kobetz, 1966):
Na + Al + 2H2 NaAlH4 (T < 270-280C and
P > 170 bar)
Na + Al + 3H2 Na3AlH6 (toluene/165C/AlEt3
and P = 350 bar)
NaAlH4 + 2NaH Na3AlH6 (heptane/160C and
P = 140 bar)
However, above reactions are not reversible.
The dehydrogenation process or the decomposition of NaAlH4 and Na3AlH6 hydrides occurs via
the following reactions:
331

2-steps reaction: NaAlH4 1/3 Na3AlH6 + 2/3

Al + H2 NaH + Al + 3/2 H2
1-steps reaction: Na3AlH4 3NaH + Al + 3/2 H2
AlH3 and LiAlH4 belong to the unstable metal
hydride group. These decompose readily at temperatures around 100-160C with a relatively
good kinetics. This type of hydrides shows a high
pressure in equilibrium with the gas phase, which
makes difficult their preparation from gaseous
phase. A chemical reaction is required to form
the compounds (Finholt et al., 1947).
Moreover, ABH4 alkali metal hydrides (A=Sr,
Ba, Eu and B= Mg, Li) with perovskite structure
have been synthesised (Messer, 1970; Gingl et
al., 1994). More recently, NaH-MgH2 system
was investigated (Ronnebro et al., 2000). Different molar ratios of NaH/MgH2 hydrides powders
were mixed together, pressed to a tablet which
was then put in a standard Alsint reaction tube
further enclosed in a stainless steel reaction tube.
The sample holder was heated in a tube furnace,
part of the hydrogenation system connected to
H2 bottle. The mixtures were heated up to 380C
under 70 bar hydrogen pressure for one week. A
new phase NaMgH3 has been successfully synthesised and further characterised by X-ray and
Neutron diffraction.
Complex Alanate Related Hydrides (CARH),
based on the AlH3-complex, e.g. LiAl2H7, NaAlH4,
Mg(AlH4)2, Be(AlH4)2, Zr(AlH4)2, and Ca(AlH4)2,
are very attractive H-storage materials, they offer very high H-capacities (5.6 to 12 wt.%) and
desorb H2 easily at temperatures between 100
and 180C. However, they cannot normally be
re-hydrogenated at hydrogen pressures lower than
100 atm, due to surface passivation. Recently,
Bogdanovic et al. (Bogdanovic & Schwindeman,
1997) have developed a method of doping SARH
with Ti-based catalysts and showed for the first
time that hydrogenation cycling is feasible in
CARH, but the reactions still require many hours
and high H2 pressures to complete. Several studies
332
have subsequently focussed on even more effective

catalysts, e.g. Ti- or Zr- related liquid alkoxides
(Zidan et al., 1999) and on kinetic improvement,
e.g. by complementary mechanical grinding and
chemical modification, but the modified sodium
alanates only exhibit a reversible H2 storage capability up to 2.5 to 3.0 wt.% (around 80 to 140C),
which is only 50% of the theoretical capacity, due
to oxygen contamination from the liquid catalysts.
Practical hydrogen storage materials require
that the alloys should exhibit one fundamental
property: reversibility of hydrogen absorptiondesorption under practical conditions. Recently,
Bogdanovic and co-workers (Bogdanovic &
Schwindeman, 1997) developed a method of
doping sodium alanates with Ti-based catalysts
and showed for the first time that hydrogenation
cycling was feasible in complex sodium alanates,
although the reactions still require many hours and
a high hydrogen pressure to complete. Since then,
several studies have been focussed on even more
effective catalysts Bogdanovic and Schwindeman,
1997) and other methods of improving the kinetics of hydriding/dehydriding reactions of sodium
alanates (Zaluski et al., 1999; Zaluska et al., 1999).
In a more recent investigation of NaAlH4 and
Na3AlH6 compounds, it has been shown that the reaction kinetics can be improved by complementary
mechanical grinding and chemical modification
of the alloy Zaluski et al., 1999). The modified
sodium alanate compounds exhibit reversible
hydrogen storage capabilities at relatively low
temperatures between 80C and 140C, around
2.5 to 3.0 wt.%. Complex alkali-metal hydrides
can then be produced by a mechano-chemical process via ball milling of different commercialised
reagents, e.g. Zaluski et al., 1999):
2NaH + NaAlH4 Na3AlH6
NaH + LiH + LiAlH4 NaLi2AlH6
NaBH4 + NaAlH4 Na2BaAlH6
LiH + NaH + NaAlH4 Na2LiAlH6

3.10 Rare Earth Metals and Related

Compounds Thin Films with
Switchable Optical Properties
The fact that those RE hydrides are known to fall
apart into powder when x approaches 3 has limited
the investigation of their electrical and optical
properties. Huiberts and co-workers (Huiberts et
al., 1996) have shown that the preparation of thin
films coated with a thin layer of Pd improved their
structural stability. The authors discovered that
Y-, La and RE-hydrides films exhibit a remarkable optical properties near their metal-insulator
transition: the dihydrides are metallic and shiny
while the trihydrides are semiconductive and
transprent (Figure 13). The shiny/transparent
transition is reversible and can be obtained by
changing the hydrogen pressure (Griessen et
al., 1997). Reversible hydrogen loading, and
consequently, reversible optical switching of
Pd-coated Y electrodes have been accomplished
by electrochemical means (Notten et al., 1996).

The reported phenomenon is not limited only to
RE-hydrides, it may be extend to other related
compounds. Further investigations of RE and
their related alloys are of significance both from
a fundamental and a technological point of view.
More recently, a new class of switchable mirror based on transition metals, Ni-Mg thin films,
have been discovered (Richardson et al., 2001). A
rapid reversible conversion from a highly reflecting metallic state to a transparent semiconducting
state is due to the formation of stable hydrides,
MgH2 and Mg2NiH4.
3.11 Zeolites
Hydrogen is stored in the intermetallic compounds
in the interstitial sites (mostly tetrahedral). As an
alternative, hydrogen can be stored by encapsulating in microporous media. Although reversible
occlusion of gases in Zeolites is a well-known
Figure 13. 500 nm thick Y film covered with 20 nm Pd. The film and the transparent chess board pattern
are illuminated from the back (to monitor the frequency) and from the front (to see the mirror image of
the white horse). All are placed within a 20 cm diameter of glass under 105 Pa of H2 pressure (Griessen
et al., 1997).
333

phenomenon, little attention has previously been

paid to their use as a medium for hydrogen storage (Fraenkel & Shabtai, 1977; Weitkamp et al.,
1992, 1995). The guest molecules are forced, under
elevated temperatures and pressures, into cavities
of the molecular sieve host. Upon cooling to room
temperature or below, hydrogen is trapped inside
the cavities. It can be released again by raising
the temperature.
The results reported in Ref. (Weitkamp et al.,
1995) show that zeolites could reversibly occlude
hydrogen. The storage capacity depends strongly
on the framework structure as well the composition. Unfortunately, the maximum storage capacity
obtained so far (VH2,N/mZ=9.2 cm3/g) is very low,
compared with the present metal hydride systems
(V H2,N/mZ150 to 190 cm3/g (Weitkamp et al.,
1995) . However, in order to improve the hydrogen
storage capacity, modern techniques of zeolites
synthesis and modification should be applied.
4. PRINCIPLES OF KEY
H-STORAGE PROPERTIES
As mentioned before, a desirable hydrogen storage material should possess: 1) a high capacity,
2) sufficient hydriding/dehydriding kinetics, 3)
a low dissociation temperature under a moderate
dissociation pressure, and 4) low cost. Hydrogen
storage capacity depends on: i) the number and
size of available Interstitial Sites (IS), ii) the distance between two ISs, which should be larger
than 2.1 for two neighbouring sites to host
simultaneously hydrogen atoms, and iii) the attraction of the IS, associated with the hydrogen
affinity of the atoms. Kinetics may be improved
by processing and chemical alloying. Mechanical
Alloying (MA) is known to produce: i) a high
density of defects (dislocations) which provide
pathways for hydrogen diffusion, and ii) clean
and fresh surfaces that accelerate hydrogen adsorption and diffusion. Composite materials offer another way of enhancing the kinetics where
334
phase boundaries can provide suitable pathways

for hydrogen diffusion. The addition of catalytic
elements, e.g. Ni or Pd, can improve the kinetics
by destabilising possible surface oxides (Notten
et al., 1991). A low dissociation temperature of
a hydride is beneficial to practical applications.
Minimising the activation energy for absorption/
desorption can reduce temperature of dissociation, which depends on material chemistry and
structure. It has been empirically found that for
LaNi5 and ZrMn2 based systems, a decrease in
lattice volume (parameter) leads to an increase
of the plateau pressure and hence a decrease of
the dissociation temperature (Vant Hoff relation,
see later). Hence, by replacing the main elements
with other elements of a smaller atomic size, it is
possible to decrease the dissociation temperature
to appropriate values for applications. Another
way of lowering the dissociation temperature of
hydrides is to synthesise composite materials that
facilitate hydrogen release from the main phase
via phase boundaries. Low cost is essential in the
development of new materials for technical applications, in particular for large-scale production
such as hydrides for fuel cells. Hence expensive
elements, forms, or processing routes should be
avoided (another reason that C nano-tubes are
not chosen here). Continued development of new
materials for hydrogen storage for NiMH type batteries of fuel cells needs the optimisation of these
parameters, with large reversible storage capacity
at the conditions required by each application as
a first target, followed by improved absorption/
desorption kinetics and low cost.
5. CONCLUSION
The development of a new material hydride for fuel
cells applications need to have a reversible storage
capacity of 6.5 wt.%, with improved thermodynamic properties (decomposes at temperatures
below 100C as required by DOE target and faster
kinetics) and long cycle life, is still not achieved

yet. At this stage, only Mg-based system, complex

light metal hydrides and carbon nanostructures
are the main materials which can provide such
relatively high capacity. Recently, many efforts
have been devoted to those materials in order to
decrease their decomposition temperature, achieve
a reversibility of the H2-uptake, and enhance the
kinetics and cycle life. Although the results show
some positive results, such as the synthesis of new
light metal hydrides, improved kinetics, and lower
decomposition temperatures, more research work
is needed to bring significant improvement, in particular, lowering the decomposition temperatures
and making the H2-capacity reversible.
Aoki, K., Yamamoto, T., & Matsumoto, T. (1987).

Hydrogen induced amorphization in RNi2 laves
phases. Scripta Metallurgica, 21(1), 2731.
doi:10.1016/0036-9748(87)90401-7
ACKNOWLEDGMENT
Boellaard, E., Debokx, P. K., Kock, A., & Geus, J.

W. (1985). The formation of filamentous carbon on
iron and nickel catalysts: III: Morphology. Journal
of Catalysis, 96, 481490. doi:10.1016/00219517(85)90316-1
Dr. Bououdina would like to take this opportunity to thank CNRS de Grenoble (France), STA
(Japan), and EPSRC (UK) for the research funds
in supporting his work.
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341


Carbon Nanostructures: All types of carbon
based materials that possess a microstructure at
the nanoscale, such as nanotubes, nanofibers,
graphene, etc.
Hydrogen Storage Capacity: The amount of
H2 absorbed/adsorbed by a material under specific
conditions (temperature and pressure).
Hydrogenation and Dehydrogenation: When
a material absorbs (uptake) OR desorbs (release)
a certain amount of H2 under specific temperature
and pressure.
Intermetallics: Alloys of at least 2 elements
that combine to form a material with a defined
crystal structure, such as ZrCr2, LaNi5, TiFe, etc.
342
Kintetics: Behaviour of a material during

hydrogenation and dehydrogenation.
Light-Complex Hydrides: Ionic hydrides
containing usually alakali metals such as NaBH4,
LiAlH4, etc.
Mg-Compounds: Compounds that contains
Mg element such as Mg1-xMx, Mg1-xMxH2, Mg2Ni,
etc.
Thermodynamics: The interaction of a material with hydrogen (H2) at specific temperature,
where H2 uptake (released) depends on H2 pressure.
It is usually expressed by Vant Hoff equation.
Thin Films: Layer of materials deposited onto
substrate, classified as 2 dimension materials.
343
Chapter 14
Conductive Probe Microscopy

Investigation of Electrical
and Charge Transport in
Advanced Carbon Nanotubes
and Nanofibers-Polymer
Nanocomposites
Tewfik Souier
ABSTRACT
In this chapter, the main scanning probe microscopy-based methods to measure the transport properties in advanced polymer-Carbon Nanotubes (CNT) nanocomposites are presented. The two major approaches to investigate the electrical and charge transport (i.e., Electrostatic Force Microscopy [EFM]
and Current-Sensing Atomic Force Microscopy [CS-AFM]) are illustrated, starting from their basic
principles. First, the authors show how the EFM-related techniques can be used to provide, at high spatial
resolution, a three-dimensional representation CNT networks underneath the surface. This allows the
studying of the role of nanoscopic features such as CNTs, CNT-CNT direct contact, and polymer-CNT
junctions in determining the overall composite properties. Complementary, CS-AFM can bring insight
into the transport mechanism by imaging the spatial distribution of currents percolation paths within
the nanocomposite. Finally, the authors show how the CS-AFM can be used to quantify the surface/
bulk percolation probability and the nanoscopic electrical conductivity, which allows one to predict the
macroscopic percolation model.
DOI: 10.4018/978-1-4666-5824-0.ch014

Conductive Probe Microscopy Investigation of Electrical and Charge Transport
1. INTRODUCTION
Since their identification, (Oberlin et al., 1976;
Iijima, 1991) carbon nanotubes (CNTs) have
captured the imagination of society as much as
engineers and scientists. At small scales, and for
pristine CNTs, CNT properties are unrivaled by
any other material, especially when the properties
are normalized to density, for example, specific
stiffness, modulus over density (E/).CNTs are
envisioned as a constituent in numerous applications, particularly as reinforcement in advanced
structural and functional composites, owing to
their numerous and attractive multifunctional
properties. The unique CNTs properties includes
their high aspect ratio length/diameter (1000),
high strength-to-weight ratio, and extraordinary
mechanical properties: their axial elastic modulus
and tensile strength were theoretically predicted
to be as high as 12 TPa and 200 GPa(Lu, 1997;
Wong et al., 1997), respectively. Furthermore,
CNTs have superior thermal and electrical properties: thermally stable up to 2800C in a vacuum
or inert atmosphere, thermal conductivity about
twice as high as diamond (Kim et al., 2001), and
electric-current-carrying capacity 1000 times
higher than copper wires (Collins et al., 2000).
Polymers can be easily processed and fabricated
into intricately shaped components without damaging CNTs during processing using conventional
methods, and hence the manufacturing cost can be
certainly reduced. Therefore, CNT based polymer
nanocomposites (CNT/polymer nanocomposites)
stimulate great interests and have been extensively
investigated. Several recent reviews summarizing
different aspects of the composite investigations
display a broad spectrum of properties useful for
production of electrodes for batteries and fuel
cells, sensors for chemical vapour, electromagnetic
radiation shielding materials, electrical heaters,
as well as pressure, deformation and temperature
sensors and photovoltaic cells (Thostenson et al.,
2001; Popov, 2004; Breuer & Sundararaj, 2004;
Ramirez, 2005; Moniruzzaman & Winey, 2006;
344
Baibarac & Gomez-Romero, 2006; Rajesh et

al., 2009; Spitalsky et al., 2010). Specials interest is represented by electrical properties of the
composites because of the variety of potential
applications.
A lot of the research work aimed at understanding the properties and associated mechanisms
of these materials has focused largely on bulk
properties. An important conclusion of these
works is that because of the complexity of the
system during the formation of aggregates (from
a uniform dispersion of nano-fillers to formation
of the mesostructure), the analysis of the overall
electric and dielectric response has often been
done on a phenomenological basis. It is now clear
that the dispersion of the individual tubes inside
the polymeric matrix is of a major concern, and
the processing conditions must carefully realized
to avoid the tendency of CNTs to agglomerates.
Furthermore, understanding the interaction of
nanoparticles and polymer matrices, structural and
transport property characteristics at the nano- and
micrometer range is crucial to exploring their
full potential in various applications. While it is
critical to characterize the composite structure/
properties at the sub-micron or nanoscale, only
a few techniques are suitable for this purpose.
Although electron microscopy techniques such
as scanning electron microscopy (SEM) and
transmission electron microscopy (TEM) have
high spatial resolution, high energy electrons
can damage polymer films and induces undesired
structural changes to CNTs (Banhart, 1999; Li &
Banhart, 2004; Yuzvinsky et al., 2005). Scanning
probe microscopy (SPM), however, has proven
itself to be a valuable tool for nanocomposite
characterization and often used to quantify the
bulk/surface properties.
This chapter consists of a review of recent
experimental studies on carbon nanotubes (CNT)
polymer nanocomposites using electrical techniques derived from atomic force microscopy
(AFM). It falls in the conjunction of two recently
developed research fields: (1) on the one hand,

the field of carbon nanotubes-filled composites

and the strong interest in the field of aerospace,
nanoelectronics, organic solar cells and batteries,
and (2) on the other hand, the invention of the
scanning tunneling microscope (Binnig et al.,
1982) followed by the AFM (Binnig et al., 1986),
allowing electrostatic or electronic measurements
on insulators at the nanometer scale, either by direct measurement of electrostatic forces and local
surface potentials, or by the measurement of local
electrical conductance/conductivity. The aim of
this chapter is to review the experimental studies
carried out in the intersection of these fruitful domains. The growth techniques of carbon nanotubes
and the fabrication process of polymer/carbon
nanotubes nano-composites are not presented in
this chapter. However, some book chapters and
papers dealing with the subject are given (Wardle
et al., 2008; Choudhary & Gupta., 2011).
This chapter starts with a general introduction about the electrical transport in CNT-filled
composites with much focus on the description
of different techniques used for measurements of
the macroscopic electrical properties (Sect. 2). We
introduce than the electrostatic force microscopy
(EFM) and its related techniques that are used
for 3D-imaging of CNTs networks in polymer
nanocomposites films (Sect. 3). We show how
this technique allows quantifying of the dielectric
properties of the composite and studying dispersion/connectivity of embedded CNTs which shed
light on the role of nanotubes in the photo-active
layer in organic solar cells. In Sect. 4, we introduce
the current-sensing force microscopy (CS-AFM)
that allows studying the electrical percolation of
CNT-network and distinguishing between bulk
and sub-surface conduction and its consequences
in the overall electrical transport. In sect. 5, we
address the case of un-aligned and aligned CNTfilled composites, and especially the study of the
nanoscale effects on the percolation law. Finally,
we present the analytical model to quantify the
electrical conductivity of individual CNTs, and
studying the role of nanoscopic features such as
CNT-CNT direct contact junctions, inter-tube

polymer layers and polymer- CNT junctions in
determining overall nanocomposite properties.
2. ELECTRICAL PROPERTIES OF
CNTPOLYMER NANOCOMPOSITES
When a metallic phase is randomly dispersed
in an insulating matrix, the resulting composite
typically has a bulk electrical conductivity well
described by percolation theory (Stauffer & Aharony, 1992) and reads:
( p ) = 0 ( p pc ) p > pc
t
(1)
where p is the volume fraction of conducting

phase, pc is the percolation threshold (i.e. critical
filler concentration at which a conversion from
nonconductive to conductive state occurs), and t
is the critical exponent. As the mass fraction increases beyond the percolation threshold the
conductivity increases sharply as conductive paths
begin to form. Therefore, it seems promising to
prepare composite materials with small conductive
filler content, which preserves mechanical properties of a polymer along with high electrical
conductivity. Random filler distribution typically
shows the value of percolation threshold pc
within 1030% for dispersed metals and5-15%
for carbon black and carbon fibers (Foulger, 1999;
Mamunya et al., 2002a). Considerably lower
value of percolation threshold c compared to
usual filled polymers can be obtained by using
high aspect ratio filler that forms ordered network
in polymer matrix (Chan et al., 1997; Bouchet et
al., 2000; Mamunya et al., 2002b, Simien et al.,
2008). Combination of these two factors, by using
the highly conductive carbon nanotubes or nanofibers, can lead to conductive polymer nanocomposites at extremely low content of conductive
phase. All the CNT/polymer nanocomposites
exhibit a typical percolation behavior and intro-
345

duction of CNTs to polymers can increase the

conductivity by several orders of magnitude or
even higher than ten orders of magnitude. However, very different percolation thresholds have
been obtained by different research groups (see
Table 1). Low percolation threshold pc
=0.02250.04wt% was found by mixing CNTs
with an epoxy (Sandler et al.,1999), while by
dispersing SWCNT in P3OT the threshold pc
increases up to 11 wt% (Kymakis et al.,2002).
These differences can be attributed to many factors. The electrical properties of CNTs used by
different research groups are generally significantly different depending on their purity, morphology, aspect ratio, etc. In addition, the interaction between matrix and CNTs influences the
quality and quantity of electrical contacts between
the CNTs. As reported by (Shaffer et al., 1999),
it seems that the P3OT is easier to form an adsorbed
layer on the surface of CNTs than epoxy resin,
which reduces the quality and quantity of electrical contacts (tunneling junction at point contacts
of interconnecting tubes), thus the percolation
threshold of CNT/P3OT composite cannot be
reached at a relatively lower CNT loading. Nevertheless, compared with carbon black (CB) and
carbon microfibers (CF) based composites, CNT/
polymer nanocomposites still have much lower
electrical percolation threshold due to their high
electrical conductivity, high aspect ratio and small
diameter. Therefore, in many fields, CNTs are
expected to substitute CB and CF as conductive
fillers. In addition to the interaction between CNT
and the polymer, the percolation threshold can be
reduced significantly by ordering the conductive
filer in the polymer matrix. By featuring aligned
SWCNTs and mixing them with epoxy matrix,
(Sandler et al., 2003) presented a composite with
the lowest threshold of pc =0.0025 wt%, thus
more than ten times lower in comparison to unaligned CNT-epoxy composites.
These experimental works reveal the importance of imaging the morphological nanofeatures
346
(CNT percolation network, CNT-CNT contacts

and CNT-polymer-CNT contacts) and studying
their effects on the overall electrical behavior
of the nanocomposite. The electrical SPM techniques (EFM and CS-AFM) satisfy these two
requirements since they allow simultaneous characterization of the morphology and the electrical
properties with sub-micron and even nanometer
spatial resolution. The second parameter in the
percolation law, the critical exponent t, is also
strongly affected by the properties of CNTs, the
nature of the polymer and the manufacturing
process. While the percolation theory predicts the
value of t2 for 3D composite (which reflect the
dimensionality of the conductive phase), it has
been experimentally observed that the value of t
deviates from the predicted one. For example, the
investigation of MWCNT/UHMWPE composites
has revealed a low value of percolation threshold
(pc=0.072%) and critical parameter t1.15 (Gao
et al., 2008). In contrast, in PVC/MWCNT and
PI/CNF composites the critical exponents were
found to be t3.3 and t3 respectively (Mamunya,
2011; Arlen et al., 2008). The explanations of this
deviation include low conductance bonds between
conductive tubes, polymer-assisted-tunneling conductance between interconnecting tubes, and nonstatistical ordered distribution of CNT networks.
However, since the value of t is extracted from
electrical macroscopic tools (described later), the
above hypothesis lack the experimental validation
that requires nanoscale measurements. We point
out that the percolation theory predicts other
exponents, , , associated with geometric properties of the conducting network: is associated
with the percolation probability, is associated
with the correlation length (the linear dimension
of the largest metallic cluster not contributing to
electrical transport); is associated with the number of finite clusters in the system (Nan, 1993).
These parameters where poorly studied in filed
on the electrical nanocomposites due to the lack
of the appropriate techniques. We will show in
Sect. 5 how the CS-AFM was applied for the first

time to measure experimental the above critical

exponents and to provide more in-depth insight
into the cause of the non-universal behavior of t.
Besides the effect of the aforementioned nanostructural features, the measurements of the electrical conductivity of CNT-polymer composites
is not without challenges. Figure 1 summarizes
reports from the literature on the measured bulk
conductivities of epoxy-based composite at different CNT volume fraction. The data used here
corresponds to CNT-epoxy composites but similar
behavior is observed using other polymer systems.
The bulk conductivity values of unaligned (or
randomly oriented) CNTs-epoxy campsites ranges
from 10-5 to 1 S/m, and varies with the CNT
fraction as predicted by the percolation theory.
Incorporating vertically aligned CNTs into polymer matrices increases both the packing density
and the electrical conductivity up to 40% and
105 S/m, respectively (Hinds et al., 2004; Souier
et al., 2013). While these experimental works
show the enhancement of the electrical transport
by increasing the CNTs content and improving
their alignment, they also reveal the wide variation of the conductivity values of the composite
measured by different groups. Apart from the
effect of CNTs purity and dispersion, we note that
these electrical measurements were performed by
using different methods and different conducting
electrodes. By using two probe techniques and
silver paint contacts, a conductivity of 1.3104S/m
was measured in 10% CNT-epoxy composite
(Cheng et al., 2010). While, Cebeci measured
a conductivity of 50 S/m was measured on 20%
CNT-epoxy composite by using copper contact in
the two probes configuration (Cebeci et al., 2009).
Recently, as reported in (Florent, 2012), the material of the electrode affected strongly the value of
the conductivity of 10% CNT-epoxy composite
in the two probe configuration set up: a value of
2700 S/m as measured by using evaporated gold
films as contacts, while a value of 240 S/m was
measured by contacting the same composite with
silver paint. The discrepancy between different
experimental data shows the importance of the

surface preparation and the electrical contact
with CNTs to measure the bulk conductivity.
Furthermore, measurements conducted at this
length scale (millimeter or greater in dimension)
can obscure physical in homogeneities in the
composite material related to differences in CNT
volume fraction throughout the composite, spatial
distribution of CNT properties arising from synthesis processes, or the presence of defects such
as voids or polymer segregation. Thus, advanced
techniques, with higher spatial resolution, are
necessary in order to more thoroughly evaluate
composite electrical properties.
3. EFM STUDY OF CNT

DISTRIBUTION IN POLYMER
NANOCOMPOSITES FILMS
Conductive atomic force microscopy techniques,
that use a conductive probe, allow the simultaneous mapping and correlation between the surface
topography and the electrical properties. Unlike
the current-sensing techniques (see Section 4), the
Electrostatic force microscopy (EFM) measures
the long-range electrostatic interaction between a
sample and conductive probe when voltage is applied between them. The EFM related techniques
can be divided into two main techniques DC-EFM
and AC-EFM where Vdc or Vac bias is applied between the tip and the sample, respectively. Due to
the long-range nature of the electrostatic forces,
these techniques have been employed for imaging CNT network in insulating matrix including
polymer nanocomposites.
DC-EFM Imaging of Embedded CNT

Polymer Nanocomposites Films
Measurements are generally carried out in a twostep procedure in which each EFM scan line is
interleaved between topography scan lines (see
Figure 2). This enables to probe only the electro-
347

Figure 1. Review of the reported electrical conductivities of CNT-epoxy composites; conductivity plotted
versus volume fraction of CNTs.
static force during the second pass. In practice, the

cantilever is mechanically excited at its resonance
frequencyf0. We note k and Q the cantilever spring
constant and quality factor, respectively. Under
applied dc-voltage Vdc, the resultant electrostatic
force, assuming no charge inside the tip-sample
capacitor, can be expressed as:
F (z) =
1 C
2
(Vdc Vs )
2 z
(2)
C(z) stands for the tip-sample capacitance, and

Vs the surface potential accounting, for example,
for the tip-surface work function difference and
surface states. The capacitive force F(z) felt by
the cantilever oscillating at mean distance z0from
the surface (few tens of nm) can be written in a
first-order approximation as:
F ( z ) = F ( z 0 ) + F / z ( z 0 ) . ( z z 0 ) .
348
Figure 2. Left: Schematics of the topography

measurement (here in tapping mode). Right:
EFM measurement, in which the cantilever is
lifted at a distance z above the substrate plane.
The cantilever is mechanically excited close to
its resonance frequency f0, and the EFM signal
consists in the cantilever eigen frequency shift
f (or in the cantilever phase shift , see text)
In this expression, F / z ( z 0 ) is the force

gradient acting on the tip (expressed in N m-1).
In frequency modulation (FM) (or amplitude
modulation (AM)), the electrostatic forces lead
to frequency shift f (or phase shift ) that is
related to the gradient of the force by:

1 F / z ( z0 )
f
=
=

2
f 0 2Q
k
(3)
The main physical property imaged in this

method EFM is the conductive nature of nanotubes
with respect to their insulating environment, giving rise to highly contrasted EFM images, with
the possibility to even reveal carbon nanotubes
not visible in topography images. The mapping of
individual nanotubes buried in thin poly-(methyl
methacrylate) (PMMA) films has been reported
by (Jespersen &Nygard, 2007), in a way that
illustrates the capacitive detection performed
by EFM. Figure 3a shows a schematic of the
composite sample made of SWCNTs dispersed in
PMMA and spin-coated as 60 nm-thin film on a
SiO2-covered doped silicon substrate. In addition,
it shows the principle of EFM detection, using the
cantilever phase shift to track electrostatic force
gradients. The topography image of the sample is
shown in Figure 3b. As nanotubes are buried into
the PMMA film, they cannot be revealed from

this image. This contrasts with the EFM image
(see Figure 3c) acquired simultaneously with topography, where single or agglomerated carbon
nanotubes can be revealed and imaged as dark
lines in the EFM image. The EFM signal stems
from the much higher conductance of SWCNT
compared with the PMMA matrix, leading to a
significant increase of the tip-sample capacitance
because of the presence of the carbon nanotube in
this capacitance, and, thus, to a cantilever negative phase shift.
In the previous example, EFM was used for
subsurface imaging of CNTs dispersed in CNT/
PMMA thin films and the concentration of CNTs
was below the percolation threshold. The mapping of a network of SWCNTs buried in thick
polyimide films (thickness between 25 and 65 m)
has been reported by (Zhao et al., 2010). Figure
4 shows the EFM phase shift of the composite
with different loading of SWCNTs. Similarly
Figure 3. (a) Schematic illustration of the polymer/SWCNT sample and EFM operation. (b) Topography
image of the 60 nm-thick film of PMMA/SWCNT composite. Because of the polymer, the tubes cannot
be observed. (c) Corresponding EFM image (tip-substrate distance h = 35 nm, tip biased at +7V), in
which individual SWCNTs are clearly seen as dark lines (negative phase shifts). Adapted from (Jespersen
& Nygard, 2007)
349

Figure 4. EFM subsurface imaging of SWCNTpolyimide (Hipco) composites with SWCNT mass fraction
of (a) 0.05%, (b) 0.2%, (c) 0.5%, (d) 2% and (e) 10%. Left column: height, scale 50 nm. Middle column:
AFM phase, scale 40. Right column: EFM phase, scale 40. EFM bias voltage and lift height are 3
V and 20 nm, respectively. Adapted from (Zhao et al., 2010).
to the previous example; the nanotubes are not

detected in topography images which indicate
that CNTs are not present on the top surface but
embedded in the polymer matrix. However, as
the SWCNTs loading increases from 0.05% to
10%, more curved line features with darker phase
contrast that correspond to the CNTs, are revealed
in the EFM images.
In order to explain the contrast EFM phase
shift images, we point out first that the surface
potential Vs is a characteristic of the top-surface
where no CNTs were observed. Accordingly,
the phase shift in the EFM image corresponds
to the local dielectric constant of the composite
and more exactly to the second derivative of the
tip-sample capacitance. This is described in the
following equation:
350
Q F Q 2C
2
=
V Vs )
2 ( dc
k z 2k z
(4)
Assuming a simple plan-capacitor model, the

second derivative of the tip-polymer capacitance
can be written as fellow:
2C ( z )
1
1 + cos

= 8 0 ln

3
2
z
{z 0 + t / }
1 cos
(5)
2
where 0 is the permittivity constant (8.854 1012

C2 N1 m2), is the AFM tip cone half-angle, h
is the distance between tip apex and top surface
of the composite (dielectric), t is the thickness of
composite and is its permittivity. In the free-CNT
region of the composite, the Equation (5) can be
applied directly by to fit the experimental phase
shift by substituting the permittivity with the
nominal value of the permittivity of the polymer.
In dark regions of the phase images, the local
capacitance depends further on the permittivity
of the CNT filler as well as to the distance be-

tween the tip and the filler. Because the dielectric

constant of SWCNTs is much higher than that
of the polyimide and PMMA, it is reasonable to
obtain negative EFM contrast when SWCNTs are
dispersed in the polyimide matrix.
According to the above explanations, the EFM
subsurface imaging of CNT filler composite works
when the dielectric constant of the matrix (polymer) is low to avoid strong electric field shielding
effect. It is also worth to emphasis that the EFM
signal depends strongly on the surface properties
and humidity level. It has been shown by Zhao et
al. that low RH is preferred to maximize the EFM
signal for subsurface imaging. Indeed, at high RH,
a thick water layer form on the surface and acts as
electric field shield since the dielectric constant
of water is high (80). We point out also that the
variation of the surface potential due to the top
surface features add difficulties to the interpretation of the EFM contrast. In fact, the surface
potential signal (surface) and the capacitance
signal (dielectric) cannot be distinguished in the
DC-EFM method.
AC-EFM Imaging of Embedded CNT:

Polymer Nanocomposites Films
Unlike the DC-EFM, the AC-EFM method is
based on the measurements of the electrostatic
force and not to the force gradient. In this technique, the cantilever is electrostatically actuated
by applying an additional AC-bias to the tip at
frequency f elec far from the resonance frequency
f 0 ( f elec f 0 ). With elec = 2 f elec , the tips a m p l e vo l t a ge c a n b e w r i t t e n a s :
Vtip = Vdc + Vac cos (elect ) . By substituting Vdc
with Vtip in the equation (2), the resultant electrostatic
force
now
reads:
F ( z ) = 1 / 2C / z (Vdc + Vac cos (elect ) Vs )
and hence exhibits one static component and two

oscillating components at 1 elec and 2 elec :
1 C
Vac2
2
F
=
V
V
+
(
)
dc
s
0
2 z
2
C
(Vdc Vs ) Vac cos (elect )
F 1 =
1 C 2
=
F
Vac cos ( 2elec t )
2
(6)
We note that probing the second harmonic,

unlike the DC-EFM method, the cantilever oscillations depends only on the capacitance term.
Under the quasistatic approximation (
elec 2 f 0 ), the amplitude of oscillation A2
is very low compared to the resonance amplitude
and to the tip-sample distance z. Thus, the gradient of the tip-sample capacitance can be directly
measured by recording the amplitude A2 as fellow:
C 4 F 2 4kA 2
=

z
Vac2
Vac2
(7)
An interesting way to implement the AC-EFM

technique includes an additional feedback loop,
so as to nullify the cantilever oscillation amplitude
at 1 elec by adjusting the dc component of the
electrostatic modulation voltage. From (6) this
condition is obtained provided Vdc = Vs , that is,
when dc bias on the tip exactly matches the local
surface potentials Vs . This method is called
1 / 2 KFM (Kelvin force microscopy) since
it allows the simultaneous measurements of the
local surface potentials and the local capacitances.This technique has been employed, in
single-pass configuration (Figure 5a), to study
the electronic/dielectric properties of 2535 m
thick PI-SWCNT nanocomposites (Cadena et al.,
2013). The measurements of surface topography
and electrostatic forces are performed in the noncontact mode.
351

Figure 5. Top: (a) Schematic of the setup for single-pass EFM and single-pass KPFM in the Agilent
5500 AFM. The block enclosed in the square with dotted lines is an added part in the KPFM technique,
used to apply a controlled DC voltage to obtain the surface potential of the sample. Bottom: Sub-surface
images of the PISWNT film with 1 wt% of nanotubes. (First row) (b) Topography, (c) surface potential
and (d) C / z map obtained from single-pass KPFM/AC-EFM applying Vac as in EFM. The scan size
of the images is 10 m by 10 m at a resolution of 512 by 512 pixels. (Second row) (e) Topography, (f)
surfacepotential, and (g) C / z after surface cleaning. Adapted from (Cadena et al., 2013)
Figure 5 b-g shows the topography and electrostatic scans of PI-SWNT film with 1 wt % of
SWCNTs. The surface potential and the capacitance gradient are mapped separately from the 1
elec and 2 elec signals respectively. Figure 5b
clearly shows that the CNTs cannot be identified
in the surface topography maps, indicating that
they are buried beneath the surface. However,
352
SWNTs are clearly revealed in the other output

channels, namely, surface potential maps (Figure
5c) and C / z (Figure 5d). It is quite surprising
to reveal the SWCNTs in the surface potential
maps since this quantity is a surface property.
However, it is important to point out that the
surface potential measurements depend on many
factors such as surface preparation, contamination,

trapped charges and surface states. It was experimentally observed how the contrast in the
surface potential map is sensitive to the surface
preparation and treatment. While, the surface
potential map shows a clear contrast between the
CNTs and the polymer matrix, after cleaning with
isopropanol, the nanotubes were no longer distinguishable (see Figure 5f). On the contrary, C / z
images always reveal the nanotubes located below
the surface independently on the surface treatments
(see Figure 5g).
In this section, we presented non-invasive
electrical techniques, based on dynamic AFM,
for sub-surface imaging SWCNT networks formed
in polymer matrix. These methods are characterized by relatively minimum sample prepared when
compared with other microscopy methods such
as scanning and transmission electron microscopes
(SEM and TEM) and offer non-destructive and
high resolution capabilities under ambient conditions. From the above examples, it is suggested
that EFM technique opens up abroad range of
options to characterize nanocomposites, using the
sub-surface compositional images to extract information about CNT connectivity, dispersion,
and the local surface potential. We conclude that
C / z is the most robust channel for visualization and characterization of CNTs buried in
polymer matrix. Moreover, it allows a quantification of the local capacitances and thus the local
effective dielectric constant of the composite in
presence of CNTs.
4. CS-AFM INVESTIGATION OF BULK

AND SURFACE PERCOLATION
In this section, we first intend to remind the
principle of operation of the second family of
conductive force microscopy techniques namely
current-sensing atomic force microscopy CSAFM. We shall illustrate by experimental data,
i.e., current maps and I-V curves, the capability of
the techniques for qualitative and semi-quantitative
structural and electrical description of aligned

and dispersed CNT-polymer composites and
membrane. The connectivity and percolation of
CNT networks by CS-AFM will be discussed and
compared to EFM and SEM/TEM microscopy
techniques.
Principles and Implementation

of CS-AFM
Current-sensing atomic force microscopy (CSAFM) is a variant of scanning tunneling microscopy STM (Binning, 1982) that measure the
surface/bulk electrical resistance by touching
the substrate with a biased conductive probe. Unlike the STM, CS-AFM can be used on resistive
samples such as polymer, oxides and biological
membrane. Moreover, by using a conductive probe
with a sharp tip, it measures the current flowing
through the sample, while simultaneously probing the surface topography under force feedback
control. With this method, dc current, ac current
and current fluctuations can be measured at the
nanoscale, thus offering the extraordinary possibility of measuring the spatially resolved properties
of electrical transport, such as nanoscale electrical
resistance, impedance and noise. Furthermore, by
obtaining a simultaneous map of surface topography, the correlation between electrical properties
and morphological structure of material surfaces
and devices can be investigated. In this chapter,
we focus on the use of CS-AFM imaging under a
dc-bias. The use of anac-bias or the measurements
of current fluctuations give rise to other techniques
namely scanning capacitance microscopy (SCM)
electrical noise microscopy (ENI) that are out of
the scope of this chapter. A detailed review of
these two techniques can be found in (Fumagalli
et al., 2008).
It should be noted that CS-AFM also goes
by several other names including: conductive
AFM (C-AFM), conducting probe AFM (CPAFM), scanning spreading resistance microscopy
(SSRM), scanning resistance microscopy (SRM),
353

nano spreading resistance profiling (nano-SRP),

and tunneling AFM (TUNA). Unfortunately, the
lack of consensus can be a source of confusion
and a barrier for finding literature in the field.
Throughout this review, we will refer to the technique by the name CS-AFM.
Over the last decade a whole range of CS-AFM
techniques have been developed to specifically
measure dc currents (Murrel et al., 1993, GmezNavarro et al., 2004). In CS-AFM a stationary (dc)
voltage bias is applied between the AFM probe
and the sample and the corresponding dc electric
current flowing through the sample is acquired,
from which the conductance of the sample can
be mapped locally. In addition, by sweeping the
dc voltage between predefined values, one can
measure the dependence of conductivity on the
applied bias at specific locations of the sample.
In some cases, a low-frequency voltage is applied instead of a dc voltage and the differential
conductance (dI/dV) is measured. The CS-AFM
measurements set up is shown schematically in
Figure 6. Current detection is normally performed
using a transimpedance amplifier, which is available in most commercial atomic force microscopes
with different gain values. A logarithmic ampli-
fier (Houze et al., 1996, Sato et al., 2001) and a

semiconductor parameter analyzer (Blasco et al.
2005) have also been used in order to measure the
current in an extended dynamic range.
Conductive Probes for CS-AFM

Although CS-AFM is conceptually simple, it can
be tricky to apply in practice. There are several
reasons for this. Unlike the EFM and KFM, the
CS-AFM procedure, operating in contact-mode,
might induce irreversible damages to the tip conductive coating and/or to the sample. The optimal
choice of the cantilever and the tip material for
imaging and I-V acquisition is important to get
reliable and reproducible data. The choice of the
conductive probe influences many factors such
as the nature of the electrical contact (ohmic,
schottky, or junction), the value of the contact
resistance, and the amount of the applied force that
should be applied to ensure a stable mechanical
and electrical contact. Additionally, the measured
current largely depends on the contact area between the tip and the sample, which is related to
the shape and the size of the tip apex. The use
of conductive probe with high wear resistance is
Figure 6. Schematic of the experimental setup used in DC current-sensing AFM measurements
354

Table 1. C-AFM tip characteristics

Tip Material
Stability During Imaging
Electrical Contact
Doped silicon
Stable
Poor readily forms oxide in air
Metal coating
Tip wear easily on hard surfaces
Excellent
Doped diamond coating
Stable
Good
highly recommended, since the size of their tip

apex is often preserved when adequate forces are
applied. The choice of conducting tip material is
also important. Several types of materials have
been used to date, including doped silicon, metal
coatings, doped-diamond coatings, and carbon
nanotubes. Studies have also been performed with
chemically modified tips. A summary of the tip
characteristics is provided in Table 1.
Doped silicon tips, although they are reasonably conductive, do not work well for C-AFM
because they readily oxidize in air. This results in
an additional tunneling barrier and a large contact
resistance. Metal coatings, primarily gold and
platinum, are the most frequently used tip materials for C-AFM measurements. This is mainly
because they are chemically well defined and easy
to prepare. The coating is usually deposited by
evaporating a 5 nm adhesion layer of chromium
or titanium and then a 2040 nm film of the desired metal onto a silicon cantilever. Cantilevers
with metal-coated tips are also commercially
available. Metal-coated tips generally form good,
low-resistance contacts (hundreds of Ohms on a
metallic substrate). However, these types of tips
wear easily during contact mode imaging on hard
substrates, rendering the tips insulating. Platinumiridium is sometimes chosen over gold or other
metals because of its relatively high durability. It
should be noted that contact mode and C-AFM
imaging of certain soft, yet robust surfaces such
as polymers is possible with metal-coated tips.
Boron-doped diamond coatings exhibit a good
electrical conductivity and are highly resistant
to wear, making it possible to reliably alternate
between imaging and electrical measurement.
However, the contact resistance associated with

these tips (about 100k on a metallic substrate)
is higher than that for metallic tips. This does not
pose a problem for resistive samples, but can be
an issue for highly conducting samples such as
carbon nanotubes (CNTs), where the samples
electrical characteristics maybe hidden by the large
contact resistance. Conducting diamond-coated
tips are commercially available. Still, despite
the advantages related to these tips, they are not
widely used owing to their high costs.
CS-AFM Imaging of CNTPolymer Nanocomposites

Unaligned and Dispersed CNT Network
The bulk electrical properties of carbon nanotubes (CNT)-polymer nanocomposites are well
described by the percolation theory and the bulk
conductivity depends on the volume fraction of
CNT-fillers. However, almost all processing approaches for polymer nanocomposites result in
a different distribution of CNTs near the sample
surface relative to that within the bulk. These
structural heterogeneities arise from numerous
factors, such as topological packing constraints of
rods near a boundary, settling of filler particles,
hydrodynamic flows, and drying induced stresses.
Details of the surface structure have substantial
impact on the formation of electrical contacts, and
thus measurement of macroscopic characteristics.
As it was shown earlier, the initial CNT
distribution underneath the processing-induced
polymer-rich skin layer can be quantified with
EFM-based techniques. Complementary, CS-
355

AFM can be employed to investigate the effects

the surface insulating layer on the interfacial conductivity and thus on the bulk electrical properties
of the composite. The mapping of conductive
MCNTs and CNFs buried in thin polyamide sample
(thickness between 100 and 200 m) has been
reported by Trionfi (Trionfi et al, 2008), in a way
that illustrates the conductive detection performed
by CS-AFM. The topography image of the native
surface of 3.5 vol % sample is shown in Figure7a.
Noticeable is the complete lack of any visible CNF,
i.e. as the nanofiber are buried into the polymer
nanomembrane, they cannot be revealed from this
image. Similarly, scanning electron microscopy
(SEM) image, reported in Figure 7c, reveals that
a polymer-rich skin layer has formed on the native surface of the composite. Cross sectional
SEM images reveal that the polymer skin layer
is typically about 50 nm, but its thickness differs
from sample to sample and could vary across the
surface. Although the presence of polymer-rich
layer, the CS-AFM image acquired simultaneously
with topography, reveals few carbon nanofibers
as white spots in dark insulating matrix (see Figure 7b). This result indicates the existence of a
percolation network of CNFs near the surface of
the composite. After statistical treatments of 24
2020 m2 scans for each of the 3.5 vol% samples,
the conductive area was found to be 0.2020.114
m2, which represents about 0.05% of the top total
area. This is much lower than the nominal 3.5%
of CNFs bulk density. The local current-voltage
(I-V) characteristics reveal non-ohmic behavior
attributed to high tunneling resistance between
the tip and the polymer-coated CNFs.
In order to take full advantage of the high
electrical conductivity of the carbon fillers, the
electrical contact should be improved by revealing
the CNFs. The oxygen plasma, generated at an
rf power of 250 W, etches both side of the nanocomposites during 50s and removes 60 nm of
the polymer top layer. The resultant surface after
plasma etching (see Figure 7f) is representative of
the cross section (bulk) morphology of the mate-
356
rial. As evident, CNFs are readily present on the

surface. Figures 7d and 7e show representative
topography and current maps of the 3.5 vol%
samples after the oxygen plasma treatment, as
reported by Trionfi (Trionfi et al, 2008). Despites
the poor contrast due to surface roughness, some
CNFs could be resolved in the topography images
(see Figure 7d). However, due to the large difference in the electrical conductivity of CNFs (here
7000 S/cm) and the insulating polyamide (
10-14 S/cm), the current maps present high contrast revealing all the protruding and conducting
CNFs (see Figure 7e). Furthermore, almost all the
recorded point-current-voltage (I-V) curves reveal
ohmic behavior characteristics of a continuous
percolation path and tip-CNT metallic contact.
This confirms the effectiveness of plasma etching
to remove the polymer skin layer and improve the
electrical contact between the AFM tip and the
sample. After statistical treatments of 24 2020
m2 scans, the conductive area was found to be
21.9 3.77 m2, thus about 5% of the top total
area. This is much even higher than the nominal
3.5% of CNFs bulk density. However, on 0.35% vol
samples, the areal density of conductive regions,
after plasma etching is much smaller, (< 0.029%).
The comparison between the areal density of superficial conductive spots and the volume fraction
of CNFs or CNTs will be discussed later. However,
we can state that unlike the EFM techniques, the
CS-AFM probes only the CNFs (or CNTs) that are
part of a conductive percolation network within
isotropic nanocomposites.
Finally, other works on MWCNTs-epoxy
nanocomposites present similar results by means
of CS-AFM (Njuguna et al., 2010; Njuguna, 2012).
After plasma etching, CNTs are revealed in both
topography and current images for filler contents
of 2-3%. The thickness of the nanocomposites
was about 150-170 m. The authors report also
a significant improvement (up to 76%) of the
macroscopic electrical conductivity. This shows
the importance of surface conductivity due to the
skin-polymer layer on the macroscopic electrical

Figure 7. 2020 m2 [(a) and (c)] CS-AFM topography and [(b) and (d)] current maps of 3.5 vol%
material [(a) and (b)] before and [(c) and (d)] after the oxygen plasma treatment. A 20 mV bias was
used for current imaging. SEM scans of (e) an untreated 3.5 vol% sample and (f) the same material
after oxygen plasma etching, revealing CNFs. Scans are made with a 5 kV beam accelerating voltage
and working distance of 6 mm. Bright areas are caused by charging in polymer-rich regions. Adapted
from (Trionfi et al., 2008).
properties of the composite. However, unlike in

Trionfi work where predominantly ohmic curves
were obtained, the local I-V curves recorded by
CS-AFM exhibit a non-ohmic behavior after a deep
plasma etching of 300s. The authors suggested that
air plasma etching, even for prolonged duration
was not effective to remove the insulating layer.
On the contrary, as reported by Souier (Souier et
al., in press), plasma reactive-ion-etching (RIE)
successfully removes the insulating skin layer in
thick MWCNTs-epoxy and MWCNTs-HDPE
nanocomposites (thickness 500 m). Accordingly, the authors attributed the non-ohmic I-V
curves, after etching, to tunneling junction at
point contact of interconnecting CNTs rather than

tip-sample junction.
We would like to underline here some
capital difference between EFM and CS-AFM
capabilities. Although the two techniques been
non-destructive and provide complementary
information, each technique has advantages and
limitations. The EFM, based on the long-range
electrostatic forces detection, can probe the
buried CNTs that are underneath the surface by
several hundred nanometers. However, the EFM
detection of CNTs in dielectric layer works only
for relatively thin nanocomposites; to the best
knowledge of the authors, the technique was used
357

in nanocomposites with maximum thickness of

65 m. The CS-AFM, fortunately, can be used
for nanocomposite with any thickness. In the
literature, composite with thickness approaching
the millimeter have been characterized by CSAFM. One of the drawbacks of the technique is
the necessity of surface treatments such as plasma
etching in order to provide more reliable data.
This is because the CS-AFM can probe only the
protruding CNTs from composite top surface.
We need to mention, however, that the current
(resistance) values obtained by this method are
not only characteristics of the surface but also of
the bulk conduction over the composite thickness,
as it will be detailed in the section 5.
Vertically Aligned CNT Network

In this section we explore the use of CS-AFM for
structural/electrical characterization of anisotropic
polymer nanocomposites made of CNFs or CNTs.
In particular we describe the use of CS-AFM
for imaging CNTs that are part of conductive
network and the measurements of CNTs volume
fraction. Moreover, the high resolution imaging
capabilities of CS-AFM is compared to those of
SEM and TEM. Finally, we discuss the existence
of skin-polymer layer and its consequence on
electrical contact in the particular case of Aligned
CNT composites.
Figure 8a shows typical top-view SEM of the
as-polished composite surface, as reported by
(Souieret al., 2012a). The composite used here
is made of epoxy matrix and vertically aligned
MWCNTs grown by CCVD. A TEM analysis
on dispersed tubes confirmed that all the tubes
are MWCNTs with a mean external and internal
diameter of 50 and 7 nm respectively. The CNTs
are protruding from the polymer, their ends appear
open and some of them are not fully circular; the
missing parts are probably removed during the
mechanical polishing procedure. The diameters
of individual CNTs observed by means of SEM
confirm the observation previously carried out by
358
means of TEM. A statistical analysis on several

SEM images reveal a density of CNTs of 4.3
1013 CNT /m2 1.5 1013 CNT m2 and their average surface fraction is about 10%. Comparatively,
Figure 8b shows the typical current image recorded
at low contact force of 6 nN. The image reveals
high resistance regions (black) that correspond
to the polymer matrix and high conducting ones
(white) corresponding to the CNTs. the diameter of
conductive spots (CNTs) lies between 15 nm and
150 nm in good agreements with TEM analysis.
Statistical treatments of several current images
gives a CNT density of 4.8 1013/m2 which
correspond to filling fraction of 10% a result that
matches perfectly the SEM analysis. The topology
and current profile of single nanotube, obtained
from high resolution CS-AFM images, is compared in Figure 8c and reveals a good contrast
at the edge of nanotube as compared to surface
topography. The current profile exhibit an M
shape at the center of which a flat region with
constant and very low current is observed 10-100
pA; this corresponds to the CNT core 7 nm. In
additions to this, maximum current is localized
on the edge of CNT corresponding to the external
walls, whereas minimum current is localized near
to the central core. These results are in agreement
with majority of experiments, which reveals that,
current flows only on external walls and there
is not any significant charge transfer across the
walls, but, no determination of conductive walls
number was provided (Frank et al., 1998, Bourlon
et al., 2004, Gupta et al., 2005). By using high
resolution CS-AFM imaging the conduction of
internal and external walls of MWCNTs could
be investigated experimentally and the number
of conductive walls can be measured. The CSAFM is found to be a tool that can replace both
TEM and SEM for fast, non-destructive and in
situ structural characterization of aligned CNTpolymer nanocomposites.
After a simple thinning process (cutting or
polishing) the aligned nanotubes protrude from
the composite surface. In addition to that, the

Figure 8. SEM scan (a) of 10 vol % vertically aligned carbon epoxy composite, and the CS-AFM current map of the same material after mechanical polishing, revealing protruding MWCNTs ends. Scans
are made with a 5 kV beam accelerating voltage and working distance of 10 mm. Adapted from (Souier
et al., 2012a). (c) Comparison of height and current profile over single aligned MWCNT embedded in
polymer matrix; the CNT exhibiting 100 nm external (De) and 7 nm internal (Di) diameter
surface fraction of conductive regions measured

by CS-AFM matches well the CNT volume fraction of the composite. Accordingly, unlike the
case of unaligned CNTs, no skin-insulating or
polymer rich layer exists. However, one cannot
exclude that some CNT-ends are covered by
polymer molecules creating tunneling junction
and affecting thus the quality of electrical contacts during electrical measurements. Souier et al.
(2012b) investigated this effect by using Reactive
Ion Etching (RIE) on polished surface of aligned
CNT-epoxy composites. Figures 9a-c show the
SEM images of as-polished and etched region
of the same composite surface. As a first result
of the etching process, the mean CNTs density
increases slightly from 4.3 1013/m2 to 4.5 1013/m2
and 5.1 1013/m2 after etching time of 2 min and 5
min respectively. Moreover, the protruding length
of CNTs increases which allows a better electrical
contacts for conductivity measurements. From the
CS-AFM current images, recorded on etched and
non-etched areas, the profile of the corresponding
resistances (R=V/I) is shown in Figure 9d. The
resistance values of conductive spots (CNTs),
on as-polished surface, exhibit a log-normal distribution centered at about 50 k. The authors
mentioned also the existences of highly resistive

spots 0.1-1G which corresponds to tunneling
junction between polymer-covered CNTs and the
AFM tip. After RIE treatments the resistance
profiles are shifted lower values which confirm
the improvements of the electrical contacts with
protruding CNTs. Moreover, after 5min etching,
the high resistance spots no longer exists which
prove the effective etching process of the polymercovered CNTs-ends.
5. OUTLOOK OF QUANTITATIVE
CS-AFM ANALYSIS
Despite the few attempt to quantify nanomaterial properties, CS-AFM have been used since
two decades for mainly qualitative description of
the electrical transport at the nanoscale. In this
section we present two recent works that shield
the light on the possibility of quantification of
transport properties atyb the nanoscale by means
of CS-AFM imaging and I-V spectroscopy. The
first example concern the determination of some
percolation parameters in unaligned CNT polymer
nanocomposites, while the second one present
359

Figure 9. SEM scan of 10 vol % vertically aligned carbon epoxy composite (a) as polished, and after
plasma RIE etching during (b) 2 min and (c) 5 min, (d) the histogram of resistances extracted from CSAFM image of the as polished surface and after RIE etching
the first attempt, in the field, to estimated the

electrical conductivity of aligned CNT-polymer
nanocomposites.
Percolation Probability
Quantification by CS-AFM
The geometric critical exponent, , associated with
the percolation probability(p), (the probability a
metallic filler belongs to the conducting network)
can be experimentally measured (Trionfi et al.,
2009). The method relies on the CS-AFM imaging
and oxygen plasma etching technique that controllably removes processing induced heterogeneities
to reveal representative cross-sections of the bulk
CNT network. Since CS-AFM has nanometer
resolution, it can directly map the current paths
in a two-phase nanocomposite. High resolution
360
C-AFM scans show a clear correlation between

CNF-like topography features and areas of high
conductivity (see Figures 10a and 10b). On the
polymer matrix (dark area) the measured current
corresponds to the instrumental noise. Hence, it
is clear that the current paths are confined to the
conducting network of nanotubes. It should be
pointed out that in order to measure a nonzero
current, the protruding CNTs at the surface, i.e.,
the one that makes contact with the tip, must be
connected to the conducting network in the bulk
of the nanocomposite so that current can flow
through the entire thickness of the sample. Hence,
not every nantubes feature observed in topography
scans is associated with a conducting area in the
corresponding current map. Arrows in Figures
10c and 10d indicate a CNT that is not part of
the conducting network. The investigation of the

conductive and non-conductive CNTs allows the

determination of the percolation probability (p)
and the correlation length of the CNT network.
Accordingly, two of unconventional exponents
andof the percolation law can be determined.
To obtain (p), for example, the authors employed
the principle of Delesse which states that the areal density of conductive phase (here CNTs) in
a random, isotropic nanocomposites is equal to
the volume density (this is true is the measured
area is representative of the bulk). If the total
volume fraction of CNTs p is known, then the
ratio between the conducting areal density ac and
p represents the fraction of the CNTs that is part
of the conducting network, i.e. (p). By analogy
with the percolation law of the bulk conductivity,
the percolation probability reads:
( p ) = ac / p ( p pc )
(8)
The conducting areal density ac can be obtained by statistical treatments of CS-AFM current images of the composite surface. In order
to get reliable data, the surface of the PI-CNT
nanocomposites has to be etched following the
procedure described in (Trionfi et al., 2008). The

exponent can be obtained by measuring (p)
on CNT polymer nanocomposites with different
CNT filling fraction p, and fitting the data with
the equation (8). Figures 11a-d show CS-AFM
current scans of composite with four different
filling fractions 3.5%, 1.4%, 0.7%, and 0.35%.
It is clear that the conductive area and thus the
conducting areal density increase with the CNT
concentration. Figure 11e shows the calculated
(p) for six CNT volume fractions. Using equation (8) to fit the data, the following values were
obtained for 1 and pc 0.2%. The value of the
exponent t was measured by using macroscopic
two probe techniques and was found to be t
1. The authors point out that these values are
higher than the ones predicted by the 3D lattice
percolation model (t 2 and 0.4). This implies that the electrical behavior of the PI-CNT
nanocomposite cannot be predicted by universal
percolation law. In particular, the results show that
the underlying structure of the CNT-network is
more complex than a simple random network; and
thus are crucial in understanding the robustness
of the overall network to external perturbations
or failures at CNT-CNT junctions. Moreover, the
Figure 10. 22 m2 [(a) and (c)] C-AFM topography and [(b) and (d)] current maps of the oxygen
plasma treated 3.5 vol% material using a 20 mV bias. (a) and (b) show a clear correlation between
the long topographic features resembling a nanofiber or bundle and the highly conducting areas in the
current maps. However, not every nanofiber feature is conducting, as indicated by the arrows in (c) and
(d). Adapted from (Trionfi et al., 2008).
361

Figure 11. Example CAFM scans of (a) 0.035, (b) 0.014, (c) 0.007, and (d) 0.0035 vol fraction CNF
composites. In order to keep the current scale the same for all scans, the current magnitude of each
pixel has been increased by a factor of 2, 10, and 20 for (b), (c), and (d), respectively. (e) The percolation probability as a function of CNF volume fraction for the CNFpolymer nanocomposite; the inset
shows the bulk conductivity of the composite as a function of CNF volume fraction. The red line in both
curves is a best fit to the data. Adapted from (Trionfi et al., 2009).
values of the critical exponents t and are closer

to the ones predicts by Berthe lattice (or Cayley
tree) model (Straley, 1977).
It is important to point out that the conclusions above could not have been made without
measuring both geometric and transport exponents and t. This it is crucial to investigate the
geometric parameters that describe the conducting CNT-network by using conductive scanning
probe microscopy techniques. The results also
shows how is critical to revise the percolation
model for nanocomposites where CNTs plays a
role of the nanofiller. Furthermore, it would be
very interesting to apply the same approaches to
investigate the transport properties of other CNTpolymer nanocomposites, and to extend the study
on polymer nanocomposites with other conductive
fillers such as graphene, carbon fiber, and carbon
black and metal nanoparticles.
362
Electrical Conductivity
Measurements by
Quantitative CS-AFM
An important concept to keep in mind when
performing CS-AFM measurements is the idea
of extrinsic and intrinsic properties. Extrinsic
properties depend on the amount of material being
measured while intrinsic properties do not. When
measuring a samples properties, one normally
tries to convert an extrinsic measurement to an
intrinsic one so that it is independent of the quantity of material under consideration. For example,
when measuring the resistance of a sample, one
is normally interested in the resistivity. This measured quantity is converted by accounting for the
cross-sectional area and length of the sample. The
cross-section area to be considered is generally
the area of the nano-contact between the AFM tip

and the sample (or nano-object, here CNTs) that

depends strongly on the curvature of the end of the
tip. Unfortunately, it is well known that the apex
shape and size constantly change when scanning
in contact mode due to plastic deformation and
tip wear. This requires characterization of the tip
radius in a non-destructive and efficient way and
establishes a route to quantify AFM data.
The first method allowing in situ determination
of the tip radius was described in (Sergio et al.,
2012), requires calibration of the tip radius by
monitoring the dynamics of the cantilever in
ambient conditions. The method relies on key trait
of dynamic AFM, namely, bi-stable behavior of
the cantilever dynamic that occurs in ambient
conditions and under amplitude modulation (AM)
feedback control (Gleyzes et al., 1991). In particular, bi-stability involves stochastic transitions
between the attractive and the repulsive regimes
for a set of cantilever-sample parameters (Garcia
& Paulo, 2000). For very small amplitude of
oscillation, the tip-sample forces are attractive
(non-contact mode). As the cantilever free amplitudes is increased, there is a range of amplitudes
for which attractive-repulsive transitions might
be observed in amplitude-phase-distance (APD)
curves or while scanning. This range of critical
free amplitudes is typically termed Ac. Finally,
when the free amplitude is sufficiently increased
above Ac, no bi-stability is observed any longer
and the attractive to repulsive transitions occurs
smoothly and deterministically via a single amplitude branch. The key concept is that the value
of free amplitude Ac for which transitions are
observed, strongly depends on the curvature of
the tip. In practice, the smaller the value of free
amplitude required to observe a transition, the
sharper the tip. This general behavior is remarkably independent of the properties of the sample
and cantilever characteristics and shows the strong
dependency of the transitions on the tip radius.
In particular, a power law was established, based
on numerical simulation (Zitzlet et al., 2002), for
the dependency of Ac on tip radius R, i.e.

Ac R 0.55 . The experimental power law was
established by Sergio et al., by using several AFM
tips on different materials; the exponent coefficient, however, was found to lies between
0.840.92 (see Figure 12). This technique lends
itself very well to dynamic AFM with relatively
stiff levers (k = 1 to 50N/m) and intermediate
quality factors (50 - 500) where the theory behind
force transitions is well established. Accordingly,
it can be applied on commercially available conductive AFM tips.
The second method was reported by (Olsson
et al., 1998) on metallic and highly doped semiconductor, and was adapted recently (Fumagalli
et al. 2007) in case of dielectric substrate. The
method relies on the reconstruction of the tipsample capacitance (or capacitance gradient) from
the APD curves recorded in DC or AC EFM mode
(see, section 3). The tip radius can be deduced by
fitting the capacitance-distance curves by a realistic model for the electrostatic interaction between
the tip and the sample. Several analytical models
as well as finite elements modeling approaches
have been used to simulate the tip-sample capacitance. We show here the example proposed
by (Fumagalli et al. 2007) where two expressions
of the capacitance have been used in case of
metal (gold film) and dielectric (SiO2 film with
r ~ 4 ) to simulate the experimental capacitance
profile (see, Figure 13). The AFM topography
images are used to measure the thickness of silicon oxide SiO2 films used for the fitting. The
simulation fit well the experimental data allowing
the in situ determination of the tip radius.
dielectric
R (1 sin 0 )
Capex ( z, r , h ) = 2 0 R ln 1 +
z + h / r
C metal z = 2 R ln 1 + R (1 sin 0 )
0
apex ( )
(9)
363

Figure 12. Experimental (dashed grey, continuous black and dotted black markers) and predicted, by
R n the law (continuous, dashed and dotted blue lines), values of Ac as a function of tip radius R for a
variety of samples. Each marker shows the data obtained with a different cantilever
In the following, we describe the method

proposed by (Souier et al., 2012b) to quantify
the intrinsic local electrical conductivity of MWCNTs and deduced the aligned MWCNT-epoxy
composite conductivity, from the CS-AFM data.
After recording the current images, the tip is positioned on top of MWCNT by using a specific
procedure. It consists on reducing gradually, during the scan, the size of the current image while
keeping at the center the MWCNts of interest. At
the ends of the last scan (image size of 1 nm) the
tip is exactly positioned at the top of the MWCNT,
364
and the corresponding I-V curve is recorded.

Only the linear I-V curves are considered which
suggest Ohmic contact between the tip and the
CNT, the non-Ohmic I-V curves are related either
to formation of schottky/junction barrier or to
polymer-coated CNT-end. The extracted values
of the CS-AFM resistance are in the range of
100 k in good agreements with the log-normal
distribution of resistance recorded in the same
sample (see Figure 9).
The quantification of intrinsic material properties by CS-AFM, as in the macroscopic two

Figure 13. (a) AFM image and (b) profile of the SiO2 squares on gold surface with 11 m2 area. (c)
Measured Capexvs tip-sample distance taken on a 23-nm-thick SiO2 layer (triangles) and on the gold
surface (circles). The lines are the theoretical fitting to Equation (9). Adapted from (Fumagalli et al. 2007).
probes technique counterpart, requires further the

determination of the tip-sample contact resistance.
Figure 16a shows a schematic of the equivalent
electric circuit of tip-CNT system. The CS-AFM
resistance, estimated from imaging or point I-V
curves, is the equivalent resistance of the circuit
and has several contributions, namely, the resistance of the tip, the tip-sample contact, the resistance of the nanostructure (CNTs), and the backcontact resistance. While the contact resistance
(100) and the back contact resistance ( 10)
can be neglected, the contact resistance of the
constriction between the tip and the sample has
to be taken into account and has generally the

same order of magnitude as the recorded CS-AFM
resistance. Experimental and/or numerical approaches are required to distinguish between the
resistance at the nano-contact and the intrinsic
resistance of the nanostructure. Several models
have been used, in literature, to estimate the contact resistance in CS-AFM mode of operation. In
case of an ohmic contact, different expressions
have been used depending on the electron mean
free path of tip-sample system and on the size of
the nano-contact 2a . At high contact force regime
(N), the spreading resistance Rsp dominates
365

the contact resistance that can be approximated

to Maxwell resistance Rsp = / 2a , where is
the electrical resistivity. In the extreme situation
of very low force ( 10pN) a contact area reduced
to a few atoms, electron transport is ballistic, and
the conductivity is described by the Landauer
Buttiker formula (Buttiker et al., 1985; Hansen et
al., 2004),
2e
Gc =
h
2 Nc
T
i =1
RCS AFM =
(10)
where N c is the number of conductance channels

through the contact and Ti is the transmission
coefficient of the i-th channel. The number of
conductance channels is proportional to the ratio
of contact area to Fermi wavelength F . Transmission coefficients are close to unity when no
scattering sites are involved at the constriction.
Quantized conductance can be observed for small
contacts when only a few channels are involved.
At intermediate force regimes (nN), the contact
radius a is large compared to the Fermi wavelength
F , the resistance converges to the Sharvin equation (Nikoli& Allen, 1999):
Rsharvin =
h F2

2e 2 2 a 2
(11)
The Sharvin resistance can be expressed in

fully classical terms by substituting F with and
using the electron mean free path :
Rsharvin =
4

3 a 2
(12)
For tip-CNT system, the Sharvin formula is

dominant for small contacts (1 nm), whereas it
becomes negligible compared to the Maxwell
formula only for large contacts (100 nm). Since
the contact size of the constriction between the
366
AFM tip and CNT is about 4 nm, sharvin formulas was used to calculate the contact resistance
(Souier et al., 2012b). When the tip is positioned
on top of protruding CNT, the CS-AFM resistance
can be written as RCS AFM = RCS AFM + Rsharvin
and by introducing the electrical resistivity of
CNT it fellows:
L 4
+

A 3 a 2
(13)
where L and A are the length and the cross-section

of the CNT. The contact radius a is evaluated
using Derjagin, Muller, Toporov DMT model
(Johnson, 1985).
1/ 3
aDMT
3r ( P + Pad )
= tip

4E*
(14)
In Equation (2), P is the applied load between

the tip and the sample. E* is the effective Youngs
modulus and Pad is the adhesion force, quantity
that are calculated from the simulation of experimental force-distance curves using DMT model.
rtip is the AFM tip radius that is calculated using
the dynamic AFM method described above. Using
the above equations, it appears that the Sharvin
conductance (1/Rsh) is directly proportional to
P2/3 (1/Rsh=P2/3/). Accordingly, the CS-AFM
resistance reads:
RCS AFM =
L
+ P 2 / 3
A
(15)
By calculating the contact resistance at each

applied load P (using the Equation (1)), the intrinsic CNT resistance can be deduced from the
measured RCS-AFM resistance. The mean value of
the intrinsic CNT resistance RCNT is found to be
approximately 140 k for all the applied loads.
The CNTs average internal and external diameters

were measured to be 7 nm and 48 nm, respectively.

Hence, the estimated resistivity of the CNTs
CNT will have a value of about 10-6.m. Finally,
taking into account the CNTs filling fraction in
the composite, the average cross-plane electrical
conductivity of the composite is estimated to be 105
S/m after removal of the contact effect. In additions
to the nanoscale measurements, the macroscopic
electrical conductivity has been calculated using
macroscopic two probes and four probe techniques.
In the two probe technique, gold electrodes have
been evaporated on the two sides of the composite,
while in the fours probe technique silver paint is
used as contacting electrodes. The macroscopic 2
wires conductivity is found to be 200 S/m, while
the four wires conductivity is 1.07 105 S/m 8.5
104 S/m, thereby confirming, in spite of the large
dispersion of the results, the CS-AFM obtained
values and the significant effect of the electrical
contacts in the two probe measurements. The
wrong estimation of the conductivity with two
probe setup is attributed to many factors including the quality of the electrical contact between
the CNT and the gold electrode as well as the
skin-polymer layer covering a certain fraction of
protruding CNTs.
6. OVERALL SUMMARY
AND PERSPECTIVES
This chapter has been devoted to review the
potential of electrical AFM derived techniques
for the nanometer scale characterization of carbon nanotubes and carbon nanofibers polymer
nanocomposites. Two electrical AFM related
techniques and their applications in CNT polymer
nanocoposites filed have been discussed, namely
electrostatic force microscopy EFM and currentsensing atomic force microscopy CS-AFM.
It has been shown thatthe spatial distribution
of CNTs network within the polymer films can be
imaged, using EFM, and the dielectric properties of
the nanocomposites could be derived by modeling
the tip-sample system as a series of capacitors.

This technique presents a net advantage over the
electron microscopy techniques which not only
require a tedious sample preparation but suffer
from poor contrast due to charging effect within
the polymer matrix. However, the EFM techniques
still suffer relative poor lateral resolution compared to standard atomic force microscopy mainly
due to the stray capacitive effects. The future
directions in the AFM community to enhance
the EFM lateral resolution includes the use of
high aspect ratio metalized AFM tips or carbon
nanotubes terminated AFM tips that minimize
the stray capacitance and enhance the surface
tip-apex electrostatic interactions. Other research
directions include the one-pass EFM techniques
that allow probing the electrostatic force at very
short tip-sample distance thus improving the lateral resolution. The drawbacks of the EFM based
techniques are also discussed and mainly its applicability only for thinner composites (thickness
lower than 60 nm), i.e. the technique can note be
used for thick-composite. In addition to that the
technique still suffers from poor lateral resolution,
in comparison to standard AFM, due to parasitic
capacitances from the base of the cantilever and
the tip-cone. The use of high aspect ratio metallic tips or carbon nanotube ended AFM tips may
improve further the spatial resolution of the EFM
technique.
In the second part of the chapter, it has been
demonstrated that CS-AFM is invaluable so as to
investigate the effects of material processing and
nanoscopic defectson the overall electrical properties of the nanocomposites. Special emphasis was
paid on the effects of the skin-polymer layer and
the effectiveness of the etching process to enhance
the interfacial and consequently bulk electrical
transport. Unlike the EFM based techniques, this
method allows probing the electrical properties of
both ultra-thin and thick composites. In addition,
by an adequate choice of the conductive AFM tips
and experimental conditions (mainly the applied
force), high resolution can be achieved. However,
367

the main drawbacks are the difficulty to reproduce

and quantify the CS-AFM data. This requires
working in control environment (using inert gas,
low humidity, or under vacuum). Nowadays,
quantifying nanosclae electrical transport properties is possible with CS-AFM and this includes
electrical conductivity, percolation threshold, tunneling junctions, percolation probability. C-AFM
based techniques are the only tools that allow
measurements of geometrical critical exponents;
this is crucial to revise the existing percolation
models to explain the transport within the complex
composites involving CNTs and more generally
carbon nanostructures. Suchstudies, together with
the ongoing and future developments of electronic
characterizationtools using nanoscale force measurements should bring a valuable insight forsuch
fields of research combining nanoscience and
nanotechnology.
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Carbon Nanotube: Macro-molecule of carbon analogous to a sheet of graphite rolled into a
cylinder. There are single-walled (one atomistic
layer of graphene) and multi-walled carbone
nanotubes. Their diameter ranges from fractions
of nanometer to few tens of nanometers. They
have a significantly higher aspect ratio than any
materials reaching 132,000,000:1.
373

Composites: Materials made from two or more

constituent with significantly different physical or
chemical properties, that when combined, produce
a material with characteristics different from the
individual components.
Electrical Conductivity: A property of a material that quantifies the ease with which charges
flow inside the material along an applied electric
field or voltage gradient.
Electrostatic: A branch of physics that deals
with phenomena and properties of stationary or
slow-moving electric charges.
374
Polymer: A large molecule or macromolecule

composed of many repeated subunits known as
monomer.
Tunneling: The penetration of an electron
through a potential energy barrier by virtue of
the electrons wave-like behavior.
Work Function: The minimum energy required to remove an electron from inside a metal
to vacuum.
APPENDIX: ABBREVIATIONS
AFM: Atomic Force Microscopy.
CAFM: Conductive Atomic Force Microscopy.
CNF: Carbon Nanofiber.
CNT: Carbon Nanotube.
CS-AFM: Current-Sensing Atomic Force Microscopy.
EFM: Electrostatic Force Microscopy.
KPFM: Kelvin Probe Force Microscopy.
MWCNT: Mutli-Walled Carbon Nanotube.
PI: Polyimide.
PMMA: Poly-(Methyl Methacrylate).
PVA: Polyvinyl alcohol.
SEM: Scanning Electron Probe Microscopy.
SWCNT: Single-Walled Carbon Nanotube.
TEM: Transmission Electron Microscopy.
UHMWPE: Ultra-high-molecular-weight.
375
376
Chapter 15
Nanostructured Materials
for the Realization of
Electrochemical Energy Storage
and Conversion Devices:
Status and Prospects
Imran Shakir
Sungkyunkwan University, Korea & King Saud
University, Saudi Arabia
Zahid Ali
Sungkyunkwan University, Korea
Usman Ali Rana
King Saud University, Saudi Arabia
Ayman Nafady
Mansoor Sarfraz
InasMuen Al-Nashef
Rafaqat Hussain
Universiti Teknologi Malaysia, Malaysia
DaeJoon Kang
Sungkyunkwan University, Korea
ABSTRACT
One of the greatest challenges for the modern world is the ever-increasing demand of energy, which
may soon outstrip the amount of natural resources that can be obtained using currently known energy
conversion and energy storage technologies such as solar cells, fuel cells, lithium ion batteries, and
supercapacitors. It appears that the maximum output efficiencies of these devices have already reached
the intrinsic limits of almost all electrocatalyst materials. Hence, it is a high time to think about new material architectures by controlling size, shape, and geometry, as well as composition that can potentially
make a significant improvement in the performance of these electrochemical devices. Among several
known electrocatalyst materials are nanomaterials and their composites due to their unique electrical,
mechanical, physical, chemical, and structural characteristics. These materials have opened a whole
new territory of possibilities in designing high performance energy storage and conversion devices. In
DOI: 10.4018/978-1-4666-5824-0.ch015

Nanostructured Materials for the Realization of Electrochemical Energy Storage
this chapter, the authors review the recent progress in energy storage and conversion devices that utilize
various nanomaterials and their composite materials and identify future directions in which the field is
likely to develop.
1. INTRODUCTION
A rapidly growing global population, diminishing
natural resources, emission of greenhouse gases
that contribute to global warming and sufficient
energy supply to meet the growing energy demand are some of the most important challenges
mankind is currently facing and the intensity of
these issues is expected to become uncontrollable
in the next few decades (Frhlich, 1968; Dell &
Rand, 2001).An estimate suggests that the current
global energy demand of 15 TW for a population
of ~ 7 billion people will double to 30 TW for a
population of 9 billion in 2050. The current level
of CO2 in the atmosphere is around ~ 394 ppm
and approximately 2 ppm of CO2 is added each
year to this value. These CO2 emissions cause
global warming and according to the International
Panel on Climate Change (IPCC), a CO2 level
~ 450 ppm will cause a temperature rise of ~ 2
C. A 2 C rise in temperature will have severe
environmental impacts. Hence, sufficient supply
of energy with low environmental impact is one
of the biggest challenges facing mankind in the
21st century. One possible solution which has great
potential to fulfill our growing energy demand is
to transform the energy from one form to another
and storage of a particular form of energy by using
the state-of-the-art technology is indispensable
for sustainable future (Woodcock et al., Hasnain,
1998; Walker & Dracoulis, 1999; Sun et al., 2006;
Kaygusuz, 2007; Sar & Karaipekli, 2007; Vera
& Langlois, 2007; Rae & Bradley, 2012). There
has always been an incredible source of unlimited,
free and clean power right above our heads i.e the
Sun but for most of us, it was still out of reach
until now. In order to exploit such an abundant but
intermittent resource to extract energy in future
there is a great need to develop highly efficient
energy conversion and storage devices (Licht,

2001; Aric et al., 2005; Lewis, 2007; Guo et al.,
2008; Liu et al., 2008; Cavaliere et al., 2011; Dai
et al., 2012; Jose et al., 2012; Sahoo et al., 2012).
Currently a vast variety of devices exist that can be
used for energy conversion and storage purposes.
Some of them are supercapacitors, lithium ion
batteries, photoelectrochemical water splitting,
fuel and solar cells, which are the most promising candidates for the generation and storage of
energy from renewable resources. Unfortunately,
we have a limited choice of materials available
which are capable of converting or storing energy.
Moreover, bulk materials have already reached
their inherent limits in performance, which makes
the situation much more challenging for future
development (Tarascon & Armand, 2001; Liu
et al., 2005a, 2005b; Gwon et al., 2011; Nyholm
et al., 2011; Zhao et al., 2011a). During the last
decade, various approaches such as the downsizing
of materials, development of composite structures
and the exploitation of vertical arrays of nanowires or nanotubes for improving the surface area,
reactivity, conductivity and stability of materials
have been investigated to maximize the performance of materials. Among these approaches
downsizing materials to nanoscale has attracted
the greatest interest due to the unusual mechanical,
electrical and optical properties of nanomaterials.
It has been found that the performance of electrochemical energy conversion and storage devices
is dramatically enhanced by using nanomaterials.
In this chapter, we will attempt to review recent
progress concerning the development of energy
storage devices such as lithium ion batteries and
energy conversion devices such as dye sensitized
solar cells, photoelectrochemical cells for solar
hydrogen production and fuel cells.
377

2. ELECTROCHEMICAL ENERGY
CONVERSION DEVICES
2.1. Fuel Cells
In view of the increasing concerns about global
warming and the expected future depletion of oil
resources, the idea of a Hydrogen Economy
is emerging as one of the most efficient and
cleanest ways to overcome the worlds growing
energy demands (Zegers, 2006). With this aim,
researchers have focused on two primary areas:
the production and storage of hydrogen, and the
efficient use of hydrogen in clean and zero emission technologies such as fuel cells (Crabtree et al.,
2004; Zegers, 2006). Although, there are several
different types of fuel cells available (Weaver,
2002), the fuel cell that uses hydrogen is commonly known as a polymer electrolyte membrane
fuel cell (PEMFC). A fuel cell is an electrochemical device that resembles a combustion engine,
which requires some form of fuel to run, but like
a battery it directly converts chemical energy into
electrical energy. Since, in case of PEMFCs, the
by-product is only water and therefore these devices can be considered to generate energy with
zero emissions(Hirschchenhofer, 1998; Barbir,
2005). In addition to the environmental advantages, high efficiency and their adaptability to
use renewable sources of fuel are unique features
of PEMFCs (Hirschchenhofer, 1998; Crabtree,
2004).Figure1shows the schematic operational
view of a PEMFC, where the anode, cathode
and electrolyte make up the Membrane Electrode
Assembly (MEA). At the heart of the fuel cell
is an ion conducting polymer electrolyte membrane, which is sandwiched between two porous
electrically conductive and catalytically active
electrodes. As the mobile ion in the PEMFC is a
proton, the name proton conducting electrolyte
membrane is often used in place of a polymer
electrolyte membrane. During fuel cell operation,
the reactant gases hydrogen (H2) and oxygen (O2)
are first fed to the cathode and anode sides of the
378
PEMFC respectively, resulting in the hydrogen

oxidation reaction (HOR) at anode to produce
protons (H+). The electrons formed during this
process are passed through the external circuit
to go to the cathode side.
A polymer electrolyte selectively transfers
these protons from the anode to the cathode side,
where the chemical reaction between these protons
and reactant (O2 gas) [reduction reaction (ORR)]
produces useful energy in addition to the water as
the only by-product. The individual electrochemical reactions occurring at the cathode and anode
are shown in scheme 1;
Scheme 1
At anode 2 H 2 4 H + + 4e (HOR)
At Cathode O2 + 4 H + + 4e 2 H 2O (ORR)
Overall cell reaction 2 H 2 + O2 2 H 2O
Though fuel cells have a great importance in
the sustainable and green future for the coming
generations, there are some technical barriers and
limitations that restrict the commercialization of
this technology for the mass market production.
Especially the cost factor is still one of the
major roadblocks for the realization of this technology (Epping Martin et al., 2010; Houchins et
al., 2012). Another important type of fuel cell that
has a great importance in the future of fuel cell
technology is direct methanol fuel cell (DMFC).
The main advantage of DMFC is related to the
reasonable stability of methanol that makes it
easy to transport this type of fuel compared to
the hydrogen fuel in PEMFC system (Sharma &
Pollet, 2012). However, the efficiency of DMFC
system is comparatively low and technical barriers such as methanol permeability, processing
cost and life cycle of DMFC systems and several
other technical limitations are some of the main
obstacles in the commercialization of DMFC
technology (Ahmed & Dincer, 2011; Zhao et al.,
2011c; Sharma & Pollet, 2012).

Figure 1. A schematic operation view of a Polymer electrolyte membrane fuel cell (Rana et al., 2012)
2.1.1 Nanostructured Catalyst

Materials for Fuel Cells
If we look at the typical components of PEMFC
system, the electrocatalysts forming cathode and
anode contain significant quantities of Platinum
(Pt), which is the major cause of its high cost
(Bruijn, 2005; Zegers, 2006; Debe, 2012). Apart
from cost factor, the fuel cell efficiency largely
depends on the catalytic activity of the cathode
during oxygen reduction reaction (ORR), and Pt
is not the best candidate as it suffers from deactivation at operational temperatures < 100 C
due to the adsorption of carbon monoxide (CO)
present in the feed gas (Urban et al., 2001; Ham
et al., 2008). Hence, one target area of research in
PEMFC technology is the development of efficient
non platinum electrocatalysts, which do not suffer
from activation losses at low temperatures(Olson
et al., 2008; Atanasoski & Dodelet, 2009; Winther-
Jensen & MacFarlane, 2011; Karim & Kamarudin, 2013). On the other hand, the other possible
routes to bring down the cost of PEMFC system
is to reduce the Pt loading in the catalyst layers
of both cathode and anode without compromising on the overall efficiency of the cell (Su et al.,
2010a, 2010b). More recently, the revolutionary
developments in the area of nanoscience such as
developing nanostructured materials (nanorods,
nanowires, nanotubes, nanoparticles, nanostructured alloys and non-noble metal nanostructured
catalysts), either as catalysts or catalyst supports
has made significant progress and it is anticipated
that the future commercialized PEMFC system
will be based on these nanostructured catalyst
materials(Kim et al., 2010b; Qiao & Li, 2011;
Rabis et al., 2012; Cheng & Jiang, 2013; Ha &
Han, 2013). The reason behind the huge interest
in the nanostructured materials is their relatively
large active surface area and higher catalytic
379

activities that will eventually reduce the loading of noble metal catalysts and therefore will
help in the cost reduction of the fuel cell device
(Travitsky et al., 2006; Kim et al., 2010b; Wang
et al., 2011). Figure 2 shows the various types
of nanostructured materials used or explored for
PEMFC application.
As discussed earlier, Pt is the first and highly
active electrocatalyst material for PEMFC application. Hence, a lot of research efforts are still
underway to reduce the Pt loading, while simultaneously improving its chemical stability and
efficiency to overcome the catalyst related issues
in PEMFC application(Debe, 2012; Gumeci et al.,
2013; Ha & Han, 2013). Interestingly, nanomaterials based catalysts such as Pt nanoparticles have
displayed higher catalytic activity and therefore
have significantly reduced the amount of Pt loading for PEMFC system. Since, size, shape and the
uniformity of dispersion are very important factors in view of mass activity of Pt nanoparticles,
the best electrochemical stability is shown by the
nanoparticles having size around 3 nm (Garbarino
et al., 2010). Further improvements in mass acFigure 2. The schematic illustration of the various
types of nanostructured materials that exhibit
potential characteristics as electrocatalysts materials or catalysts supporting nanomaterials for
PEMFC application
380
tivity has been observed in the case of nanosized

alloy catalysts with core-shell structures, which
have displayed remarkable reduction in Pt loading
with a concomitant increase in catalytic performance (Zhao et al., 2011c). The developments in
core-shell nanostructured catalyst materials with
varying composition of core particles (such as Ni,
Co, Au, Pd and V) and optimized shape of Pt shell
have made significant improvements in achieving
high catalytic activities during ORR (Chuan-Jian
et al., 2010). However, these core-shell materials
suffer from poor chemical stability in acidic media.
Significant improvement in chemical stability is
observed when using Pd/FePt nanomaterial that
contain FePt shell and Pd core(Mazumder et al.,
2010). This nanostructured material has displayed
12 times higher current densities than commercial
Pt catalysts and remained stable even after 10000
potential cycles. In the case of Pt3M (M = Co, V,
Ti, Ni and Fe) type nanostructured materials, it has
been found that for the ORR reaction in fuel cell,
the low index surfaces display significantly higher
catalytic activity (Stamenkovic et al., 2007). In
contrast to other type of nanostructured materials,
the core-shell structured nanoparticles are widely
investigated for fuel cell application, as it is fairly
easy to control their size, shape and composition
and optimize them accordingly. Beside their superior performance, the real time application of
these nanoparticles in a fuel cell configuration is
still need to be investigated. Metallic nanomaterials such as nanorods (Lu et al.), nanowires (Ho et
al., 2012), are another type of electrocatalysts that
show superior electrochemical activities compared
to the low aspect ratio nanostructured materials
due to their large surface areas. Especially for the
DMFC application, bimetallic nanowires such as
PtRu and PtRh having 1:1 atomic ratio (diameter <
60 mm and lengths ~ few hundreds of micrometer)
display higher catalytic mass activity for electrooxidation of methanol compared to the ones with
varying atomic ratios(Kim et al., 2008). However,
similar to the core-shell nanoparticles, the metallic
nanowires are also not been tested in the real time

fuel cell application and several technical issues,

especially the effect of solid surface support for
nanowire catalyst growth need to be investigated
from practical consideration of device application.
The recent progress in the developments of
three dimensional (3D) nanostructured materials
compared to the 1D or 2D nanomaterials have
made a significant improvement to achieve high
catalytic performance of electrocatalyst materials
due to their comparatively higher active surface
area, improved stability during electrochemical reactions (resistance towards leaching) and
enhanced contact conductivity with substrate
materials that help to reduce the over potential
required for facile ORR reaction in fuel cells
(Hussain et al., 2011; Tiwari et al., 2012). Some
of these 3D nanostructures are obtained by direct
growth of single crystal Pt nanowires onto the
surface of carbon black nanosphere (Sun et al.,
2008), or Pt nanowire growth on W and Pt gauze
(Lee et al., 2008). Single crystal Pt nano-branches
grown on porous structured Pd nanocrystals
(Pt-Pd bimettalic nanodendrites) display much
higher catalytic performance compared to the
commercial platinized carbon (Pt/C) or even the
Pt black electrocatalysts during methanol oxidation reaction in DMFC system (Lim et al., 2009).
High catalytic activities in these materials are
ascribed to the high electrocatalytic surface area
and uniform dispersion of nano-branches on the
porous substrate materials. In a relatively different
approach, instead of synthesizing electrocatalyst
materials separately and later used in fabricating
membrane electrode assembly (MEA) for fuel cell,
Pt nanowires are directly electrodeposited on the
Nafion membrane (Liang & Zhao, 2007). This
system has showensuperior performance compared to the conventional E-TEK electrode and
the major reasons behind this high performance
are high electrocatalytic surface area and reduced
methanol cross over (Liang & Zhao, 2007). Again,
no real time fuel cell testing has been performed
on these 3D electrocatalysts so far, while the fuel
cell technology readiness is seeking more con-
crete real time demonstration of these potential

electrocatalyst materials.
The conventional electrodes (both the cathode
and anode) used in PEMFC or DMFC are usually
made up of platinized carbon cloth, that serves
the purpose of both electrocatalyst as well as the
gas diffusion electrode. Typically, to make these
electrodes, the platinum particles are dispersed on
the carbon based supporting substrates, where an
electrical contact is formed between the Pt loading and the substrate underneath. So far, we have
discussed the effect of nanostructured catalyst
materials on the electrocatalytic performance of
the overall electrode system. It is important to note
that the substrate supporting material can also be
tuned to further enhance the efficiency of electrocatalysts for efficient fuel cells performance.
In this context, the carbon nanotubes (CNT) are
found to be the most efficient and promising supporting materials to make electrocatalysts for fuel
cell application (Kim et al., 2011a). The carbon
nanotubes (CNTs) not only display high chemical
stability and good electrical conductivity; they also
provide high active surface area for the deposition
of metal catalyst nanoparticles that eventually
form a highly active electrocatalyst material for
fuel cell system (Liu et al., 2002).
In a recent study, 1D Pt covered multiwall
carbon nanotubes (MWCNTs) showed enhanced ORR mass activity (0.48 A/mgPt at 0.9
ViR-correctedvs RHE) compared to the other known
1D nanostructured catalysts (Kim et al., 2011a).
The enhanced intrinsic ORR activity of these 1D
Pt covered MWCNTs was attributed to the weak
chemical adsorption energy of OHadsspecies
adsorbed on the surface of Pt covered MWCNTs).
Functionalization of CNTs by surface oxidation
using HNO3 or K2Cr2O7/H2SO4 and subsequent
sensitization of CNTs surface using SnCl2/HCl
aqueous solution is known to further enhance the
rate of Pt deposition (Liu et al., 2002). This study
has shown superior electrocatalytic performance
of these Pt/CNT electrodes (using functionalized
381

CNT) in a single stack fuel cell configuration

compared to the conventional Pt/C.
As we can see that the high cost and scarcity
of noble metal catalysts are the major roadblocks
in the commercialization of PEMFC or DMFC
technology. Not only that the noble metal Pt also
suffers from carbon monoxide (CO) poising (CO
is commonly present in the fuel) that significantly
reduces its catalytic performance. Hence, all these
issues with the Pt have opened a new territory of
research for the development of alternate low cost
non-noble metal catalyst materials for fuel cell
application. Graphitic carbon nitrides (g-C3N4)
are recently reported as potential noble metal
free catalyst materials for various electrochemical
device applications (Zheng et al., 2012). Though,
the initial investigations of ORR activity on the
as-prepared pure g-C3N4 were not very promising
(Lyth et al., 2009), blending g-C3N4 with the high
surface area catalyst supporting materials such as
carbon black (CB) (Lyth et al., 2011) or mesoporous carbon (CMK-3) (Zheng et al., 2011)has
exhibited significant improvement in the catalytic
performance and stability of the newly developed
g-C3N4/CB and g-C3N4 @CMK-3 catalyst materials during fuel cell experiments. More recently, the
discovery of vertically aligned nitrogen-containing
carbon nanotubes (VA-NCNTs) have made a
significant breakthrough in the development of
Pt free electrocatalyst materials and scientists
have now started forecasting the realization of
the commercially large scale applications of fuel
cell (Gong et al., 2009). These VA-NCNTs display long term durability, higher electrocatalytic
activity, and greater resistance to the fuel cross
over compared to the Pt for ORR in alkaline fuel
cell configuration. A huge research has now been
directed towards the development and use of
these nitrogen containing nanotubes as potential
electrocatalyst materials for fuel cell application
(Halford, 2009).
382
2.2. Photoelectrochemical
Water Splitting
The past few decades have witnessed an exciting
revolution in the field of water splitting/hydrogen
production, together with the design/development
of a wide range of nanostructured photocatalysts
(Fujishima & Honda, 1972; Linsebigler et al.,
1995; Zou et al., 2001; Altomare et al., 2013;
Iwase et al., 2013; Sim et al., 2013; Wang et al.,
2013d). This revolution has been stimulated by the
urgent need for clean and renewable fuels to fulfill
our growing energy demand and human desire to
mimic the photosynthesis in green plants, where
leaves harvest the energy of sunlight to oxidize
water (Barber, 2006; Meyer et al., 2007; Renger,
2007; Renger & Renger, 2008). Because of its
high energy density, hydrogen as a fuel offers a
long-term solution for the raised concerns about
future depletion of oil resources.
Figure 3 shows that there are two possible
routes to carry out the water electrolysis for
hydrogen production viz electrochemical water
splitting using electricity or by utilizing the
energy of sunlight; hydrogen can be produced
via the photoelectrolysis of water. However, we
should bear in mind that catalytic water splitting
to produce H2 and O2(Equation (1)), in principle,
is accompanied by a large positive change in the
Gibbs free energy(G = 238 kJ mol1).
2H2O 2H2 + O2
(1)
The half-reactions are described as follows:

2H2O O2 + 4H+ + 4e
(2)
4H+ + 4e 2H2
(3)
The multi-electron nature of water oxidation

(Equation (2)) poses significant mechanistic
challenges and makes it thermodynamically demanding reaction since E0 = 1.23 V vs. standard
hydrogen Electrode (NHE) at pH 0. Mechanisti-

Figure 3. Representation of electrochemical and photoelectrochemical cells for water splitting
cally, this reaction is very complex as it involves

the removal of four protons and four electrons from
two water molecules, together with the formation
of an oxygenoxygen bond, following protoncoupled-electron transfer (PCET) mechanism
(Jurss et al., 2010).
Figure 4shows the principle of water splitting
using a semiconductor photocatalyst. When light
with energy larger than the band gap is incident
on the catalyst, electrons in the valence band are
excited into the conduction band, leaving holes
in the valence band. The photogenerated electrons and holes cause redox reactions similar to
electrolysis. Water molecules are reduced by the
electrons to form H2 and oxidized by the holes
to form O2; giving rise to overall water splitting.
These reactions require the bottom of the conduction band to be more negative than the reduction
potential of H+ to H2 (0 V vs. NHE at pH 0), and
the top of the valence band to be more positive
than the oxidation potential of H2O to O2 (1.23 V
vs. NHE) (Maeda and Domen, 2007).
Thermodynamically, the minimum photon
energy required to drive the reaction should be
1.23 eV, which corresponds to a wavelength
of ca. 1000 nm, in the near-infrared region. In
this context, it seems possible to utilize the entire

spectral range of visible light (400 < < 800 nm).
Practically speaking, to overcome the activation
barrier in the charge transfer process between the
photocatalyst and water molecules, thereby driving
the overall water-splitting reaction at a reasonable
rate, it is necessary to apply photon energy greater
than the band gap of the photocatalyst. Additionally, the back reaction in which water is formed
by recombination of H2 and O2, must be strictly
inhibited, and the photocatalysts themselves must
be stable in the reaction.
As illustrated in Figure 5, the steps of water
splitting on nanostructured semiconductor photocatalyst can be summarized as follows: (i) the
photocatalyst absorbs photon energy greater than
the band-gap energy of the material and generates
photoexcited electronhole pairs in the bulk, (2)
separation and migration of the electron-hole pair
to the surface without recombination, and (3) adsorbed species on the catalyst surface are reduced
and oxidized by the photogenerated electrons and
holes to produce H2 and O2, respectively (Krol
& Grtzel, 2012). Indeed, the first two steps are
strongly influenced by the structural and electronic
properties of the photocatalyst. In general, high
383

Figure 4. Basic principle of overall water splitting

using catalyst (Kitano & Hara, 2010)
photocatalytic activity can be accomplished via

decreasing the particle size of a photocatalyst,
as a result of shortening the diffusion length of
photogenerated electronhole pairs (Hisatomi et
al., 2012).The third step is induced by the presence
of a solid cocatalyst, typically a noble metal (e.g.,
Pt, Rh) (Walter et al., 2010) or transition-metal
oxide (e.g., NiOx, RuO2) (Inoue, 2009),which is
loaded onto the photocatalyst surface as a dispersion of nanoparticles (typically <50 nm in size) to
generate active sites and minimize the activation
energy for gas evolution. In most cases, cocatalysts
are loaded for the activation of H2 evolution, since
most photocatalysts are unable to promote hydrogen on the surface. Thus, it is crucial to carefully
design both the bulk and surface properties of the
material so that high activity for photocatalytic
reaction can be achieved.
The PEC water splitting can be regarded as
artificial photosynthesis, where a semiconducting material absorbs the photons from sunlight
and splits water into hydrogen and oxygen (Teets
& Nocera, 2011). A single photoelectrode PEC
device consists of either a photocathode (where
hydrogen evolution takes place), or a photoanode
(where oxygen evolution takes place), electrically
connected to the counter electrode (usually noble
384
Figure 5. Processes involved in photocatalytic

overall water splitting on a semiconductor particle
(Maeda, 2011)
metal electrode) for the counter reaction to take

place. In these types of PEC devices, one of the
electrodes is photoactive and hence only one halfcell reaction can be driven by solar energy. To
maximize the use of the available solar spectrum,
a tandem cell configuration is proposed. A tandem
cell consists of stacked layers of photoelectrodes
(photocathode and photoanode), which are commonly separated by a transparent ion exchange
membrane. The top layer (usually a photoanode)
absorbs high-energy photons and carries out the
half-cell reaction (water oxidation), while the
protons formed from the water oxidation pass
through the transparent membrane to the bottom
layer of photocathode, where hydrogen evolution
takes place due to proton reduction. The products
of water splitting process in these PEC devices
are H2 and O2, which are the feedstock of clean
energy technologies such as Fuel Cells.
Hydrogen production via photoelectrolysis of
water is still an immature technology and requires
significant efforts especially in the development
of high efficiency and durable semiconducting
materials. Literature suggests that the instability of photocatalytic semiconducting materials
under aqueous conditions is the major limiting
factor behind the commercialization and sustain-

ability of PEC devices used for water splitting/

hydrogen production (Chen et al., 2010; Maeda
& Domen, 2010; Walter et al., 2010). Even thestate-of-the-art, monolithic photovoltaic (PV)
based water electrolysis systems have a lifetime
of only few hours in aqueous media. Some of the
most abundant and cost effective photocatalytic
semiconducting materials such as silicon also
suffer from aqueous instability issues (Matsumura
& Roy Morrison, 1983).Improvement in the durability of photocatalysts in the aqueous medium
is one the major challenges facing the scientific
community in order to realize these PEC devices
for practical applications.
The first practical demonstration of a single
photoelectrode PEC device can be seen in the
work of Fujishima and Honda (Fujishima &
Honda, 1972). In their work, the surface of a TiO2
semiconductor (photoanode) was irradiated by
UV light, which resulted in water oxidation, while
the hydrogen evolution reaction occurred at the
Pt black counter electrode (cathode). The n-type
ru tile form of TiO2 has a band gap of 3.1eV and
hence cannot utilize a major portion of the solar
spectrum. Therefore, a number of new semiconducting materials have been explored in the past
decade or so (Chen et al., 2010). To benefit from
a larger part of the spectrum, a semiconductor
with optimal band gap ~ 1.8 2.4 eV is required.
However, the band gap is not the only parameter,
which controls the efficiency of a semiconductor
for the water splitting process.
The heart of a PEC water splitting device is
a semiconducting material. The hydrogen production efficiency and sustainability of a PEC
device is highly dependent on this semiconducting
photocatalyst material. An ideal semiconducting
photoelectrode must demonstrate several essential
characteristics such as efficient light harvesting,
charge transport and charge separation for catalytic
activity and long term durability in aqueous media
(Ohta, 1988). In a more technical description, a
semiconductor is required to have a band gap
between 1.8 2.4 eV, aqueous stability in varying
pH conditions, band edges that must straddle the

H2O redox potentials and a slow rate of charge
recombination compared to the hydrogen evolution/water oxidation kinetics at the catalyst surface
(Krol & Grtzel, 2012).
Taking into account these characteristics,
a wide range of metal oxide semiconducting
materials have been developed for the direct
photocatalysis of water splitting. Most of them
work under UV conditions. A recent review on the
semiconductor-based photocatalytic hydrogen
generation byXiaobo Chen et al. (2010) have
briefly categorized the UV active metal oxide
semiconductors into four groups, on the basis
of their electronic configuration; (1) d0 metal
(Ti+4, Zr+4, Nb+5, Ta+5, W+6, and Mo+6) oxide
photocatalysts, (2) d10 metal (In, Ga, Ge, Sn, and
Sb) oxide photo-catalysts, (3) f0 metal (Ce) oxide
photocatalysts, and (4) a small group of nonoxide photocatalysts (Chen et al., 2010). Some
of the most common non-oxide semiconductors
are ZnS, CdS, InP, GaN and GaAs (Walter et al.,
2010). These transition metal oxide and non-oxide
semiconducting materials are comparatively cheap
and display better stability against photocorrosion
in aqueous solution. Moreover, the band edges of
these semiconducting materials can be matched to
straddle water redox reaction by change in pH of
the aqueous media. Though these transition metal
containing semiconducting materials require UV
irradiation to act as photocathode or photoanode,
these photocatalysts can be made visible light
responsive by various methods. Some of these
approaches are (1) doping with metal or nonmetal
ions for band gap narrowing, (2) incorporating
dye sensitizers to harvest visible light, (3) developing solid solutions by incorporating a wide
band gap and a narrow band gap semiconductor
to adjust the band gap and position, and (4) band
gap engineering to develop single phase visible
light responsive photocatalysts (Chen et al., 2010,;
Maeda & Domen, 2010; Walter et al., 2010).
Much progress has been made in the development
of these transition metal oxides and non-oxide
385

catalysts for the photocatalysis of water splitting

in the past few years. However, some of the main
challenges, which still need to be addressed, are
poor charge transport properties and only moderate
light absorption characteristics. Moreover, while
band gap engineering or solid solution formation
can help to reduce the band gap of the semiconducting material, in the absence of a sacrificial
agent recombination of electron-hole pairs occurs.
So far, the maximum quantum efficiency of ca.
5.9% has been achieved for a complete water splitting cell based on the photocatalysts Rh2yCryO3/
GaNZnO in the range of 420-440 nm (Maeda
et al., 2008). However, the target quantum yield
to split water into H2 and O2 is ~ 30% at 600 nm,
which corresponds to the quantum efficiency of
~ 5% (Abe, 2010). Therefore, for practical applications, significant further developments in
optimizing these metal oxide semiconducting
materials are required to benefit from the visible
light of the solar spectrum.
2.2.1. Nanostructured Materials

for Water Splitting
Nanostructured materials have emerged recently as
efficient components of PEC cells and photocatalysts. Owing to their small size, photogenerated
carriers in nanocrystals are always created near
the surface at which water splitting occurs. For
instance, bulk single-crystal -Fe2O3 (hematite)
has a very low activity as a photocatalyst as its paramagnetic properties tend to shorten the lifetime and
diffusion length (220 nm) of its photogenerated
carriers (Cesar et al., 2006) and consequently, they
recombine within the material before they reach
the electrolyte interface. Whereas, nanocrystalline
-Fe2O3, has been found to photocatalyze water
oxidation more efficiently as a result of the small
dimensions of the crystallites (1020 nm) which
allow the photogenerated carriers to easily diffuse
to the electrolyte interface and react with water.
Importantly, optimizing the nanostructure of the
film can cause absorption of all photons with
386
energies above the band gap. In PEC cells, such

nanoscale effects have led to 5090% increase in
the efficiency (Duret & Grtzel, 2005; Cesar et
al., 2006; Zhong et al., 2009). Possibly, the same
principle can be applied to other metal oxides
with short carrier diffusion lengths.
For many other semiconductors, quantum size
effects can be utilized to increase performance
for solar water splitting. Thus, by changing the
size and shape of semiconductor nanocrystals,
the band energies can be modified, and redox
potentials of electrons and holes can be tuned.
In this regard, Frame et al. have shown, for the
first time, that nano-CdSe (Eg = 2.7 eV) becomes
highly active in photocatalytic H2 evolution from
water containing sulfite/sulfide as a sacrificial
electron donor, whereas bulk CdSe (Eg = 1.7 eV)
is not (Andrew Frame et al., 2008; DAmico et al.,
2010). This activation is due to a raised conduction band edge (0.55 V vs. NHE, pH = 7) that is
caused by quantum size confinement. As a result,
electrons in nano-CdSe are approximately 0.45 V
more reducing than those in bulk CdSe (0.10 V
vs NHE, pH = 7).
2.3. Dye-Sensitized Solar Cells

The basic concept of photovoltaic (PV) device is
based on the charge separation at any interface of
two materials with different conduction mechanism (Grtzel, 2003; Mitzi et al., 2008). Although
silicon based solid state junction devices have
dominated the PV field so far but the evolution of
the third generation PV devices like dye sensitized
solar cells (DSSC) have proclaimed some better
features like compatibility with flexible substrates
and cost-effective fabrication(Pichot et al., 2000;
Ito et al., 2006; Kuang et al., 2008). In a DSSC,
optical absorption and the charge separation processes are accomplished by the association of a
light-absorbing sensitizer with a wide band gap
semiconductor nanoparticulate based film (Grtzel, 2003; Moon et al., 2010). Upon illumination
with the white light source, molecular excitation

of the dye takes place followed by the injection

of excited electrons to the conduction band of the
wide band gap semiconductor which is then used
to transport these electrons to a charge collector
while oxidized dye molecules are reduced by the
electrons in electrolyte which is regenerated by
the electrons injected from the counter electrode
as shown in Figure 6.
Phenomenal progress realized in the area of
nanotechnology has opened up vast opportunities
to optimize the performance of DSSCs. Higher
internal surface area for dye absorption and the
porosity of the nanostructured photo-electrode
films have proven extremely beneficial for the
improvement of cell conversion efficiency.
Nanostructures have shown great potential in the
utilization of optical effects. Different nanostructures can be utilized in different ways to achieve
the maximum cell efficiency through efficient
light harvesting. For example growing tapered
nanowires or -Si nanocone array on the cell film,
that act as antireflection layer help in reducing the
reflection of light or using metal nanoparticles that
scatter light by generating surface plasmon reso-
nance or adopting dielectric spheres having size

comparable to visible light wavelength (Nishioka
et al., 2009). The major types of nanostructured
materials that are being used by the researchers
are briefly discussed below:
2.3.1. Nanomaterials for DyeSensitized Solar Cells

Amongst all nanostructured materials, nanoparticles are most widely studied for DSSC because
they are easy to fabricate and provide the high
specific surface area when used in photo electrode
film. However, large number of grain boundaries
exist in the film that augment the loss of photogenerated electrons by their recombination with
the redox species in electrolyte (Diamant et al.,
2004). Initially the group IV and III-V semiconductors were employed as working electrodes due to
their narrow band gap so that they could absorb
visible light effectively(Eisenberg & Silverman,
1961; Memming, 1980). But they were found to
be corrosive under light irradiation(Alonso V. et
al., 1981). This marked the emergence of oxide
Figure 6. Operating principle of a dye sensitized solar cells (Zhang & Cao, 2011)
387

semiconductors like TiO2, ZnO and SnO etc. with

wide band gap to be used as working electrodes
(Rajeshwar et al., 1978; Ambade et al., 2011;
Gonalves et al., 2011; Kim et al., 2011b; Koonnasoot et al., 2011; Park et al., 2011; Xiao et al.,
2011; Zhang & Cao, 2011). However, their poor
response to the light in visible region manifested
the advent of DSCs in which these wide band gap
oxides were coated with a suitable dye for their
extension of absorption of visible region of the
light spectrum. Generally the efficiency of a DSSC
is largely dictated by the light absorption range
of the dyes as well as the efficiency of the charge
injection to the photoanode and charge transport
by photoanode. Dyes generally have a narrow light
absorption range (Rani et al., 2010) and therefore
the photoanode also has to play an additional role
as an efficient light scatterer. Although TiO2 is
considered as the best material for the photoanode
in DSCs, it suffers from low electron mobility as
well as a high recombination rate at the interface
between the electrode and electrolyte when exploited for solar cell devices (Krger et al., 2003;
Snaith & Ducati, 2010). Furthermore, increasing
the surface area to maximize the dye loading also
results in an inferior light scattering response
due to the reduction in the size of the particles
(Le Viet et al., 2010). In spite of the productive

developments in the 70s and 80s, efficiencies of
the DSCs hovered below 3%: reason being low
film surface area and consequently less absorption of dye. In 1991, an impressive breakthrough
of DSSCs was reported by Grtzelet al. pointing
out that TiO2 nanoparticles sensitized with a
trimeric ruthenium complex could demonstrate
7.1-7.9% overall conversion efficiency (ORegan
& Gratzel, 1991).
The superiority of nanoparticle thin film in
terms of porosity (50-60%) and large surface area
2000 times the flat film) was demonstrated (Park
et al., 2000) and up till now due to the properties
of nanoparticles like efficient dye attachment,
faster charge transfer and electron transport, they
are essential materials for the most efficient DSCs
manufacturedso far.
The core shell nanostructured materials
normally comprise of a core usually made up of
nano-particles or nano-tubes/nano-wires and a
coated layer around the core called as shell. They
were developed upon the consideration that the
core-shell structures may reduce the interfacial
charge recombination by building an energy barrier
between the electrolyte/semiconductor interfaces.
However, the height of the energy barrier should be
Figure 7. Energy level structure of a core-shell structure in DSCs: (a) the edge of conduction band of
the shell material is higher than the excited state of dye molecule, and (b) the edge of conduction band
of the shell material is located between the excited state and the conduction band edge of the core material (Zhang & Cao, 2011)
388

such that it should not affect the electron transfer

from dye molecules to core oxide. To establish
this, the conduction band potential of shell must
be between the conduction band potential of core
material and excitation potential of dye as shown
in Figure 7.
Diamant et al. (Diamant et al., 2003; Diamant
et al., 2004)coated nanoporous film with different
oxides such as Al2O3, SnO2, ZrO2, SrTiO3, and
ZnO (Chen et al., 2001). They showed that the on
a comparison with bare TiO2 nanoparticles made
photoelectrodes, made up of TiO2 nanoparticles
and Nb2O5 shell exhibited 37% increase in solar
cell conversion efficiency.
This result was attributed to the formation of
energy barrier between the more negative shell
material conduction band than that of core material conduction band. This energy barrier led to an
increase in open circuit voltage and the observed
photocurrent. For Al2O3, SrTiO3 and ZnO, it was
suggested that their oxide coatings produce a
surface dipole layer that might have shifted the
conduction band towards TiO2 core, resulting in an
increase in the open circuit voltage. These oxides
showed the increase in open voltage because their
isoelectric point is greater than that of SiO2 (~55.5) and the dipole layer is produced towards the
TiO2. As a result these oxides showed an overall
efficiency of 15% unlike SnO2 that showed an
overall decrease in open circuit voltage and short
circuit current because its isoelectric point was less
than that of TiO2 and this produced the dipolar
layer against the TiO2 core. However, in experiments, sometime decrease in photocurrents is also
observed. Therefore the overall efficiency of the
core-shell nanostructure depends upon the values
of increase in open circuit voltage and decrease in
short circuit currents. For example ZrO2 showed
an overall decrease in conversion efficiency by
~11% though its isoelectric point is greater than
that of TiO2. In another study the high basicity
received by the TiO2 surface due to the high isoelectric point (~ 9.2 Al2O3) helped in better dye
absorption(Kay & Grtzel, 2002; Palomares et al.,
2002). Therefore, the exact effect and mechanism

of shell material is still debatable.
Though 1D nanostructures possess excellent
charge transfer properties, but there are some
limitations in using these nanostructures alone.
For example inadequate surface area, fewer dye
molecules attachment, poor light harvesting are
some of the major challenges. To overcome these
constraints, researchers have used mixtures of
1D nanostructures and nanoparticles so that the
resulting nanostructure possess the efficient charge
transport like 1D nanostructures and larger surface
area as of nanoparticles (Gao et al., 2009; Desai et
al., 2013). As the size of the nanoparticle increases
the intensity of the light scattered in the forward
direction increases. Scientists have incorporated
either 1D nanostructures(Fujihara et al., 2007;
Chuangchote et al., 2008; Yang and Leung, 2011;
Zhu et al., 2011) or large TiO2 particles (Ito et
al., 2007; Koo et al., 2008) as separate scattered
layers on TiO2 nanoparticle electrodes to get improved light harvesting for higher performance
of DSCs. 1D nanostructures can be blended with
the TiO2nanoparticle film (Tan & Wu, 2006) or
randomly embedded and distributed in TiO2nanocrystalline matrix to achieve better light harvesting
and efficient charge carrier support (Joshi et al.,
2010). The use of TiO2 nanoparticles inside the
vertically aligned 1D nanostructures can increase
the surface area and the dye supplementation (Liu
et al., 2009; Lee et al., 2011; Pan et al., 2011).
Also incorporation of ZnO nanoparticles in ZnO
nanowires has increased the efficiency of DSCs
from 0.5-0.8% to 2.2-3.2% (Ku & Wu, 2007a, b).
Xuan et al have recently shown that when TiO2
nanoparticles are infiltered in TiO2 nanotubes,
the dye loading doubles and there isan increase
of 152% in solar cell conversion efficiency when
compared with bare TiO2 (Pan et al., 2011).
However, optimization of the properties of these
materials and the reduction of surface defects
still need to be studied in detail to increase the
efficiency of DSCs in the future.
389

3. ELECTROCHEMICAL ENERGY
STORAGE DEVICES
3.1. Lithium Ion Batteries
Rechargeable lithium-ion batteries (LIBs) have
gained tremendous interest in science and technology and have become the key components of portable and smart electronics, hybrid electric vehicles
telecommunication, transportation and renewableenergy sectors due to their high energy density
and longer lifespan than comparable technologies.
There are three primary functional components
of a lithium ion battery i) negative electrode, ii)
positive electrode, and iii) the electrolyte. These
three parts participate in electrochemical reactions
and during discharging process lithium ions are
extracted from the negative electrode and inserted
into positive electrode while during charging, the
reverse reaction occurs as shown schematically in
Figure 8. In a conventional lithium ion battery,
metal oxides such as LiCoO2 are generally used
as positive electrodes and graphitic carbon as
negative electrode.
Figure 8. Working principle of a lithium ion battery
390
Equations 4 and 5 show the chemistry of a

lithium ion battery during charging discharging
processes:
The half reaction at positive electrode is:
LiCoO2 Li1nCoO2 + nLi + + ne
(4)
The half-reaction at negative electrode is:
nLi + + ne + C Li yC
(5)
The energy output of lithium ion based cell is

equal to the voltage times the charge.
Although such batteries are successfully used
commercially but the performance of these devices
is limited due to the low electronic conductivity, low Li+ transfer efficiency, rate capability,
volume expansion/contraction during repeated
cycling processes and loss of active materials due
to the corrosion by electrolytes or/and collapse
of the stable structure. Great efforts have been
put in exploring advanced active materials with
improved performance in terms of high energy/
power density, good mechanical/thermal stability,
environmental friendliness, and low cost for ap-

plications in consumer electronics especially for

clean energy storage and use in hybrid electric
vehicles. To accomplish these goals, researchers
have proposed various feasible strategies, including optimizing the crystalline lattice of active
materials by doping cations or anions, reducing
particles to a suitable scale to offer enhanced electron/Li+ ion conductivity and reactivity, combining
active materials and other active/inactive materials
together for complementary strengthening (Wakihara, 2001; Zhang, 2006; Li et al., 2007; Xu et al.,
2008; Yoo et al., 2008; Etacheri et al., 2011; Ji et
al., 2011). However, these techniques have some
limitations, as reducing particles to nanoscale
sizes results in agglomeration of particles with an
overall reduced surface area, whereas the benefits
of composite structures are limited to the surface
or interface only. Therefore, the issue at hand is
how to design efficient electrode materials for the
next-generation high-performance lithium ion batteries with higher capacity and longer cycle life.
The rate capabilities and longer life of batteries
can be improved by structuring the electrodes appropriately. The characteristic time for lithium ions
to diffuse through an electrode material varies as
the square of the characteristic diffusion length. To
decrease the diffusion time, one can either increase
the diffusion coefficient (by synthesizing better Li
+ conductors) or decreasing the diffusion length
(by using electrode components with nanometer
dimensions). The latter approach avoids changes
in the battery chemistry, has a larger impact on the
diffusion time because of the square relationship,
and has therefore attracted the attention of many
researchers (Tarascon & Armand, 2001; Aric
et al., 2005; Liu et al., 2005a; Deng et al., 2009).
3.2. Nanostructured Materials as a

Cathode for Lithium Ion Batteries
Nanostructured materials have attracted increasing interest as promising candidates for
cathode electrodes due to their better conducting pathways, faster charge transport and good
strain relaxation(Brutti et al., 2012; Devaraju &

Honma, 2012; Sadeghi et al., 2012a; Aghazadeh
& Hosseinifard, 2013; Cao et al., 2013; Han et
al., 2013; Lee et al., 2013). The most extensively
studied nano-cathode materials include layered
LiMO2, olivine-typeLiMPO4, and spinel-type
LiM2O4, where M is one or more transition metal
elements. Among them, LiCoO2(Kim et al., 2010a;
Tang et al., 2010; Tsujikawa et al., 2010; Quan
et al., 2011; Kim et al., 2012; Pu & Yu, 2012;
Chen-Wiegart et al., 2013; Hutzenlaub et al.,
2013; Maugeri et al., 2013)and LiNiO2(Yamaki
et al., 2006; Yoshimura, 2006; Sathiyamoorthi
et al., 2007; Balandeh & Asgari, 2010; Mohan et
al., 2012; Mohan & Paruthimal Kalaignan, 2012)
transition metal oxides with layered structure,
LiMn2O4(Zhang et al., 2011; Ma et al., 2012; Hu
et al., 2013; Jiang et al., 2013a, 2013b; Khedr et
al., 2013; Suzuki et al., 2013; Tang et al., 2013a;
Wang et al., 2013a, 2013c; Xiao et al., 2013a;
Zhan et al., 2013)with three-dimensional spinel
structure, and LiFePO4(Chang et al., 2013; Feng et
al., 2013; Kim and Shin, 2013; Liu et al., 2013b;
Nguyen et al., 2013; Shu et al., 2013; Wei et al.,
2013; Zhao et al., 2013a)with olivine structure
(Figure 9) are the most successful materials because of their chemical and structural stability,
high lithium ion capacity and favorable electrical
properties, such as high conductivity of lithium
ions and electrons.
LiCoO2 as cathode is the most used transition
metal oxide in commercial LIBs. It is operated
with upper cutoff voltage of 4.2 V versus Li and
provides experimental specific capacitance of
140 mAh/g. The nanostructures of LiCoO2 are
being synthesized by using various routes such as
hydrothermal, co-precipitation, flux and sol-gel.
The nanostructures of LiCoO2 with excellent electrochemical performance even at high discharge
rate of 50C achieved specific capacitance of 100
mAh/g at 50C (Bazito & Torresi, 2006; Xia et
al., 2012b). Although nanostructures of LiCoO2
show excellent rate capability, but they usually
suffer from stability and capacity fading due to
391

Figure 9. Crystal structures of various cathode materials for lithium ion batteries(Manthiram et al., 2008)
agglomeration and increase in contact resistance.

Recently, these issues have been addressed by
coting LiCoO2 with protective layer of various
materials such as aluminum phosphates (AlPO4)
and magnesium oxide (MgO) (Bazito & Torresi,
2006; Xia et al., 2012b). The surface modification of LiCoO2 with these oxide materials shows
stable capacitance even after 40 cycles as shown
in the Figure 10.
Spinel lithium manganese oxide (LiMn2O4)
with a strong edge-shared [Mn2]O4 octahedral
framework has gained attention as an alternative
to LiCoO2(Chen et al., 2013a; Guo et al., 2013;
Khedr et al., 2013; Qiu et al., 2013; Tang et al.,
2013a, 2013b; Zhan et al., 2013). As compared
to LiCoO2, spinel LiMn2O4 exhibits higher rate
performance due to the 3-D lithium pathway in the
spinel framework, low cost, high abundance, low
toxicity and better safety. LiMn2O4 with theoreti-
392
cal capacitance of 148 mAh/g is also 4 V versus

Li/Li+ cathode material like LiCoO2 and shows
experimental reversible capacity of 100125
mAh/g, when cycled between 3.0 and 4.3 V (Xia
et al., 2012b). The nanostructures of LiMn2O4 have
been synthesized by using various methods such
as sol-gel, coprecipitation, sputtering, solution
phase, spray pyrolysis, hydrothermal and combustion, one-pot resorcinolformaldehyde route (Tian
& Yuan, 2009; Karthick et al., 2010; Sadeghi et
al., 2012b; Xia et al., 2012b). The electrochemical properties of LiMn2O4 strongly depend upon
synthesis route as shown in the Figure 11. It can
be seen from the figure 11that nano structures of
LiMn2O4 have better crystallinity and show better performance as compared to low crystalline
material. However, these nanostructures suffer
from capacity fading during the cycling due to
jahnTeller distortion, dissolution of Mn into the

Figure 10. (a) Plot of the retention capacity and Co dissolution in the bare and AlPO4coated LiCoO2
cathodes(Cho, 2003), (b) Cycling stability curves of pristine LiCoO2 () and 1 mol% MgO-coated LiCoO2
(). Potential range: 3.3-4.7 V(Zhao et al., 2004)
electrolyt, formation of two cubic phases in the 4

V regions, loss of crystallinity and development
of micro-strain.
Recently, the researchers have solved these
problem by constructing the nanocomposites
of LiMn2O4 with carbon nanotubes (CNT)
and grapheme nanosheets (GNS)] with high
electrical conductivity, chemical stability and
mechanical robustness. The LiMn2O4/CNT (or
GNS) nanocomposites exhibit very large discharge
capacities that are close to the theoretical capacity
ofLiMn2O4(148 mA h/g) which suggest that the
incorporation of CNT or GNS in LiMn2O4 can
partially solve the problem of particle aggregation and improve the electrical conductivity of the
electrode, thereby improving the rate capability
as shown in Figure 12.
Lithium iron phosphate (LiFePO4) with
olivine structure is considered as an important
candidate for an alternative to positive electrode
of LiCoO2 for a lithium ion battery due to its
environmental friendliness nature, low cost,
high theoretical capacity (170 mAh/g) and high
thermal stability(Chang et al., 2013; Du et al.,
2013; Gao et al., 2013; Liu et al., 2013a, 2013b;
MahootcheianAsl et al., 2013; Nguyen et al., 2013;
Wei et al., 2013; Zhao et al., 2013a). Especially,
LiFePO4 is considered as one of the most potential candidates as a cathode for electric vehicles
and stationary storage applications due to strong
overcharge tolerance as compared with other metal
oxides currently used in commercial lithium-ion
batteries. Various synthetic approaches such as
hydrothermal/solvothermal synthesis, sol-gel
approach, low-temperature precipitation, Electrospinning, hard-template synthesis(Saji et al.,
2011) have been used for its synthesis. Although,
by synthesizing LiFePO4 at nanoscale can improve its electrochemical performances because
nanostructures have shorter the diffusion length
for electrons and lithium ions and increased
effective reaction areas. But, the low capacity
of pristine LiFePO4 is due to the relatively low
electronic conductivity (ca. 10-9-10-10 S cm-1) and
ionic conductivity, slow 1D lithium ion diffusion
within the structure, which limits the amount of
Li+ ions that can be extracted and hence restricts
the further commercial development of this material for high-rate battery applications (Shuqing
& Kejie, 2011). In order to solve these problems
various approaches such as carbon coating, supervalent cation doping, composites with CNTs and
conducting polymers have been adopted. Among
these approaches, LiFePO4/CNT/C composite
393

Figure 11. (a) Comparison of rate performance between nano-LiMn2O4 prepared by resorcinolformaldehyde route and thesolgel prepared LiMn2O4. (b) The discharge voltage profiles of nano-LiMn2O4
at different discharge rates (Shaju & Bruce, 2008; Xia et al., 2012a)
shows better electrochemical performance (Toprakci et al., 2012), good cycling performance and
enhanced electrode reaction kinetics and reduced
polarization due to high surface-to-volume ratio
and better ionic and electronic conductivity as
shown in the Figure 13.
394
3.3. Nanostructured Materials as an

Anode for Lithium Ion Batteries
The materials which can be used as anode for
lithium ion batteries are classified based on three
mechanisms (1) Intercalationdeintercalation (2)
Elements (A) or metals (M) that can form alloys
with Li metal (3) redox or conversion reaction
with Li as shown in the Figure 14 (Reddy et al.,
2013).

Figure 12. (a) First cycle charge/discharge curves of LiMn2O4/10 wt% CNT, LiMn2O4/10 wt% CNT, and
LiMn2O4/10 wt% CNT in the voltage range between 3.3 and 4.4 V at 0.2 C rates, (b) Charge/discharge
curves of the LiMn2O4/GNS nanocomposites electrode at various C-rates between 3.5 and 5 V vs. Li/
Li+ and cycle performance of the LiMn2O4/GNS nanocomposites electrode at different C-rates(Zhao et
al., 2011b; Xia et al., 2012a)
Figure 13. (a) Cycling performance, (b) initial voltage vs. capacity curves, and (c) rate capabilities of
pristine LiFePO4 powder, LiFePO4/C composite nanofibers, and LiFePO4/CNT/C composite nanofibers.
Chargedischarge rate used in a and b was 0.05 C (Toprakci et al., 2012)
395

Figure 14. Classification of oxide anode materials based on the reversible Li insertion and extraction
process: Intercalationdeintercalation, alloying dealloying, and conversion (redox) reaction. In favorable cases, the latter two processes can act synergistically to give rise to large and stable capacities.
Selected examples are given. Schematic diagram of the process is shown. The voltages shown are vs Li
metal (Reddy et al., 2013)
Various materials such as graphite, transition

metal oxides and lithium alloys are being used
and studied as an anode material for lithium ion
batteries (Cai et al., 2013, 2013b; Gnanamuthu et
al., 2013; Huang et al., 2013; Ji et al., 2013; Wang
et al., 2013b; Xiao et al., 2013b; Yeon et al., 2013;
Zhang et al., 2013a, 2013b; Zhao et al., 2013b).
Graphite with its theoretical capacitance of 372
mA h g_1 is commercially used as an anode and
possesses several advantages such as low cost,
excellent cyclic stability and small pulverization
396
due to its high mechanical and chemical stability. On the other hand metal oxides based anodes
possess very high capacity, widespread availability, good stability, and environmental benignity.
Compared with the graphite, metal oxides, lithium
alloys such as Li2Si5 possess very high theoretical
capacitance of 4200 mAh/g (Wang et al., 2013e;
Yong & Fan, 2013), But these alloys usually suffer
from pulverization and exhibit poor cycle stability
due to large volumetric changes induced by the
repeated cycles.

4. CONCLUSION AND
FUTURE WORK
During the past three decades, significant progress
has been made in the design and development of
nanostructured materials which have significantly
improved the performance of energy storage and
conversion devices as compared to bulk materials.
Nanostructured materials exhibit large surface
area, enhanced kinetics and activity which lead
to development of high performance energy storage and conversion devices. Currently we are at a
stage where at one hand there is a vast variety of
newly emerging applications for energy conversion and storage device such as powering EVs/
HEVs and portable electronics and on the other
hand existing materials used for energy conversion
and storage purpose have already acquired their
inherent limits. There is no omnipotent energy
conversion and storage material, therefore the
wise approach is to design and synthesize energy
conversion and storage materials according to
specific application requirements. In order to
further improve the efficiency of energy storage
and conversion devices, balancing the trade-offs
between different material properties could be
achieved by tuning shape, size, geometry and
composition. It is highly desirable that designing
of nano structures is further optimized to meet the
energy needs of future.
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Fuel Cell: An electrochemical device that resembles a combustion engine, which requires some
form of fuel to run, but like a battery it directly
converts chemical energy into electrical energy.
Nanomaterials: Materials that have the size
dimension in the range of 1-100 nm.
Solar Cell: A semiconductor device that converts that converts the energy of light directly into
electricity through the process of photovoltaic.
Supercapacitor: An electrochemical device
which store hundreds of times more electrical
charge quantity as compared to conventional
capacitor.
413
414
Chapter 16
Nucleic Acids-Based
Nanotechnology:
Engineering Principals and Applications

Robert Penchovsky
Sofia University St. Kliment Ohridski, Bulgaria
ABSTRACT
Nanobiotechnology is emerging as a valuable field that integrates research from science and technology
to create novel nanodevices and nanostructures with various applications in modern nanotechnology.
Applications of nanobiotechnology are employed in biomedical and pharmaceutical research, biosensoring,
nanofluidics, self-assembly of nanostructures, nanopharmaceutics, molecular computing, and others. It
has been proven that nucleic acids are a very suitable medium for self-assembly of diverse nanostructures
and catalytic nanodevices for various applications. In this chapter, the authors discuss various applications of nucleic-based nanotechnology. The areas discussed here include building nanostructures using
DNA oligonucleodite, self-assembly of integrated RNA-based nanodevices for molecular computing and
diagnostics, antibacterial drug discovery, exogenous control of gene expression, and gene silencing.
INTRODUCTION
Nanotechnology aims to engineer a variety of
functional systems at a scale of a few nanometers
(Harris et al.). This novel technology presents,
in its original meaning, a various methods for
building systems from the bottom up at molecular and even atomic level. It is believed that the
theoretical envision of nanotechnology was made
by Richard Feynman, a Nobel Prize laureate in
physics, in his famous lecture entitled There is
a plenty of room at the bottom in 1959. In his
lecture Feynman stated that the laws of physics do

not speak against the possibility of creating things
atom by atom. The implementation of the idea of
molecular manufacturing brings new classes of
problems and unfamiliar research areas that are at
the core of the emerging field of nanotechnology.
Nowadays, nanotechnology is emerging as a
crossing point among the natural and engineering sciences. It is an area of exciting discoveries
that includes many different scientific and technological fields. In fact, many natural sciences,
including chemistry and biology along with many
DOI: 10.4018/978-1-4666-5824-0.ch016

Nucleic Acids-Based Nanotechnology
types of chemical and biological engineering at a

molecular and sub-molecular level are involved
in nanobiotechnology.
Many scientists believe that function at the
nanoscale is an essential element of nanotechnology. As nanotechnology developed, its definition
is leading more to the design and engineering of
functional systems at the molecular level rather
than the design of nanostructures. Nanotechnology
is a rapidly improving field that involves several
major developments. In general, it includes a
creation of passive and active nanostructures,
made of many interacting components, and finally
leading to integrated nanodevices (Penchovsky,
2012). The passive nanostructures are engineered
to perform one particular task, whereas the active
structures are designed to execute several different
functions. Active nanostructures can be molecular
sensors, actuators, drug delivery devices, and others (Penchovsky & Stoilova, 2013). For instance,
molecular sensors can detect the presence or the
absence of specific molecules and pass predefined
molecular signals to other sensors. Such molecular
sensors can be used as report systems for many
different biosensoring applications including drug
discovery through high-throughput screening
arrays(Penchovsky, 2013). Moreover, molecular
sensors can be engineered to work as Boolean
logic gates. As a result, they can perform logical
operations and solve computational problems.
Molecular logic gates can be designed to work
together by passing signals between them in various circuits in vitro(Penchovsky & Breaker, 2005)
as well as in vivo.
In fact, nanobiotechnology is one of the fastest
growing fields of nano research based on engineering nanosystems using various biomolecules. It
refers to the intersection of nanotechnology and
biology. This chapter discusses the main applications of designer nanostructures and nanodevices
based on DNA (Seeman, 2004) and RNA (Famulok
& Ackermann, 2010; Guo, 2010) molecules. In
fact, one of the first nanostructures were made
of nucleic acids using the expertise accumulated
in recombinant DNA technology and molecular

biology over the last three decades. Nucleic acids
have been proven to be suitable nanoscale materials. They are relatively easy to synthesize, amplify,
detect, and modify. They can be used both in vitro
and in vivo. Therefore, nucleic acids engineering
plays a very important role in modern nanobiotechnology. Nucleic acid-based nanotechnology
involves the engineering of various nanostructures
based on DNA or RNA molecules.
The progress achieved by the next generation
sequencing (NGS) technologies(Mardis, 2008) in
recent years led to the discovery of novel targets for
drug development and diagnostics. The interplay
among RNA engineering, RNA biology, NGS
technologies, and medical genomics creates new
possibilities for drug development and molecular diagnostics. In this review, I present current
and future RNA-based approaches to medical
genomics as the focus set on drug development
(Penchovsky & Stoilova, 2013), molecular diagnostics (Penchovsky, 2012b) and forthcoming
RNA-based therapeutic strategies (Penchovsky,
2012a; Penchovsky & Kostova, 2013).
As RNA-based biotechnology developed, its
definition is leading more to the design of functional systems that can detect and react to molecular
signals from the environment (Penchovsky, 2013).
RNA technology is a rapidly improving field that
involves several major discovers and technology
developments. The discoveries include ribozymes
and riboswitches (Brantl, 2004), microRNAs and
RNAi (Hsu et al., 2006). The technology development in general, includes a creation of passive and
active nanostructures, made of many interacting
components or integrated nanodevices. The passive nanostructures are engineered to perform one
particular task, whereas the active structures are
designed to execute several different functions.
Active nanostructures can be molecular sensors,
actuators, drug delivery devices, and others. For
instance, molecular sensors can detect the presence or the absence of specific molecules and pass
predefined molecular signals to other sensors. Such
415

molecular sensors can be used as report systems

in many different applications, including drug discovery through high-throughput screening arrays.
Moreover, molecular sensors can be engineered
to work as Boolean logic gates (Penchovsky &
Breaker, 2005). As a result, they can perform logical operations and solve computational problems
(Penchovsky, 2012a). Molecular logic gates can
be designed to work together by passing signals
among them in various circuits in vitro as well as
in vivo (Win & Smolke, 2008).
In fact, RNA-based biotechnology is one of the
fastest growing fields of research based on engineering nanosystems. It is an intersection between
nanotechnology and biology. This paper discusses
the main applications of designer nanostructures
and nanodevices based on RNA molecules. In fact,
one of the first nanostructures was made of DNA
using the expertise accumulated in recombinant
technology and molecular biology over the last
three decades. Nucleic acids have been proven to
be suitable nanoscale materials. They are relatively
easy to synthesize, amplify, detect, and modify.
DNA is mainly used for various in vitro applications in nanotechnology. In contrast RNA can be
used both in vitro and in vivo. Therefore, RNA
engineering plays a very important role in modern
nanobiotechnology.
The main advantages of making structures and
devices with nucleic acids are the possibilities of
applying many established engineering methods
in conjunction with various tools of molecular
biology and nucleic acid chemistry. In fact, it is
easy to chemically synthesize DNA oligonucleotides and to obtain synthetic RNAs by in vitro
transcription using double-stranded (ds) DNA
templates. Moreover, RNA are easy to amplify,
detect, store, and modified. There are powerful
software programs that enable researchers to design automatically specific RNA molecules with
desired properties.
There are three distinct methods for designing RNA-based biosensors. They include in vitro
416
selection (Breaker, 1999), rational design (Tang &

Breaker, 1997), and computational methods (Penchovsky & Breaker, 2005). RNA sensors have many
different applications in nanobiotechnology. Such
applications include molecular computing (Penchovsky & Ackermann, 2003; Penchovsky, 2012),
reporter systems for high-throughput screening
assays for antibacterial drug discovery(Blount,
Puskarz, Penchovsky, & Breaker, 2006; Penchovsky, 2013), synthetic gene control elements for
exogenous regulation(Penchovsky, 2012a). We
discuss these applications in the next sections of
this paper.
PASSIVE NANOSTRUCTURES
BASED ON DNA USING
SELF-ASSEMBLY
DNA nanotechnology is based on the design and
production of artificial nucleic acid structures for
various technological applications. In this case,
DNA is used as an engineering material that does
not carry genetic information, but serves as a blueprint for self-assembly of various nanostructures.
DNA programmable self-assembly employs base
pairing rules of nucleic acids. It is possible to
design DNA oligonucleotides that form complex
nanoscale structures with desired features. Many
of these passive structures in DNA nanotechnology
use topologically branched oligonucleotides containing junctions (Figure 1). Note that biological
DNA exists as an unbranched double helix. One
of the simplest branched structures is a four-arm
junction that consists of four individual DNA
strands, portions of which are complementary in
a specific pattern (Figure 1a). Unlike in natural
Holliday junctions, each arm in the artificial
immobile four-arm junction has a different base
sequence. This fixes the junction point at a certain
position in contrast to the Holliday junctions that
are movable.

Figure 1. DNA self-assembly
(A) Four strands hybridize into a DNA four-arm junction. (B) A double-crossover DNA complex that consists of five DNA
single strands that form two double-helical domains. There are two crossover points where the strands cross from one domain
into the other.
Moreover, multiple junctions can be combined

in the same complex, forming a double-crossover
(DX) motif (Figure 1b), which contains two parallel double helical domains with individual strands
crossing between the domains at two crossover
points. Each crossover point is a four-arm junction, but is constrained to a single orientation.
This provides stability that makes the DX motif
suitable as a structural building block for larger
DNA nanostrucutes.
The research field of DNA nanotechnology has
first proposed and investigated by Nadrian Seeman (Seeman, 2004; Winfree, 2000; Winfree, Liu,
Wenzler, & Seeman, 1998). His research yielded
the first two and three dimensional nanostructures
made of DNA. Erik Winfree was first to propose
the application of DNA self-assembly to molecular
computation(Fujibayashi, Hariadi, Park, Winfree,
& Murata, 2008; Maune et al., 2010; Rothemund,
Papadakis, & Winfree, 2004; Winfree, 2000;
Winfree et al., 1998). Later on DNA and RNA
oligomers were employed for self assembly of
many complex nanostructures and nanodevices
that proved the feasibility of nucleic acid based
nanotechnology (Famulok & Ackermann, 2010;
Guo, 2010; Maune et al., 2010).
ENGINEERING ACTIVE
NANOSTRUCTURES BASED ON
ALLOSTERIC RIBOZYMES
The initial methods applied for engineering
functional nucleic acids were based on various
in vitro selection procedures. As a result, the
first RNA aptamers were obtained. The word
aptamer comes from the Latin aptus - fit,
and Greek meros part. They have the ability
to bind various ligands with high specificity by
forming complex three-dimensional structures.
The first nucleic acids based aptamers were
obtained by an in vitro selection method called
systematic evolution of ligands by exponential
enrichment (SELEX) (Klug & Famulok, 1994).
In fact, the aptamers are still produced by various
in vitro selection procedures.
These findings suggested that nucleic acids,
and particularly RNA, could be very capable
molecular sensors. This makes some researchers
to speculate that RNA molecules may directly
sense the presence of different metabolites in the
cell without involvement of any proteins. In fact,
the bid to find such natural RNA aptamers led to
the discovery up to now of 17 different classes
of RNA sensors termed riboswitches and this
417

number is still growing(Kazanov, Vitreschak,

& Gelfand, 2007). These newly discovered
gene control elements are usually found in the
5 untranslated region (UTR) of messenger (m)
RNAs (Figure 2a). They enable mRNAs to adjust their expression in the presence of specific
metabolites(Mandal & Breaker, 2004).
Genome-wide searches revealed that riboswitches are present mainly in bacteria. In addition, a few riboswitch classes are also found
to control gene expression in some eukaryote
species by alternative splicing. The genome-wide
search of bacterial riboswitches has important
applications to medical genomics. This research
results in the discovery of many riboswitch
classes in over 40 different human pathogenic
bacteria(Penchovsky & Stoilova, 2013). This
opens brand new avenues for targeting new RNAs
in antibacterial drug development (Blount &
Breaker, 2006). The world-wide demand for new
antibiotics is increasing due to the emerging of
many resistant to the common antibiotics stains
of human pathogenic bacteria. Targeting bacterial riboswitches may result in the discovery of
novel classes of antibiotics that have few resistant
strains or any for the time being because there are
not yet developed antibiotics specific targeting
bacterial riboswitches.
The riboswitches consist of a ligand-binding
(natural aptamer) domain and an expression
platform. There are various riboswitch-dependent
expression mechanisms, including transcription
termination, prevention of translation, mRNA destabilization, and others(Penchovsky & Stoilova,
2013). Riboswitches are classified in different
classes according to their aptamer domains,
which have conserved secondary and tertiary
structures. Note that one type of riboswitch can
have different expression platforms. For instance,
the FMN riboswitch regulates gene expression
either by transcription termination or by prevention of translation (Winkler, Cohen-Chalamish,
& Breaker, 2002). In both cases, however, the
aptamer domain of the FMN riboswitch has the
418
some conserved structure that forms highly specific pocket for FMN. As a result of FMN binding,
the flavin riboswitch alters its structure, which
leads to transcription termination or prevention
of translation.
The development of high-throughput screening (Okada et al.) assays based on bacterial
riboswitches is an essential part in this process.
It is important to create HTS compatible RNA
sensors in which the ligand-binding part of a
riboswitch is fused to a reporter domain. Such
HTS compatible reporter systems can be obtained
by fusing the aptamer domain of a riboswitch
(Figure 2a) with a ribozyme. Ribozymes are
conserved RNA molecules, which possess a
catalytic function(Wang, Qiu, & Drlica, 1996).
For our aim, we can employ the minimal version
of the hammerhead ribozyme (Figure 2b, c). It is
called in this way because its specific secondary
structure formed by three stems that looks like a
hammerhead (Scott, 1997). It cleaves itself at the
position indicated by the arrowhead (Figure 2b,
c). The minimal version of the hammerhead ribozyme (Figure 2b) is a short RNA molecule that
requires a high concentration of Mg2+ (10mM)
to exhibit its catalytic function. In contrast, the
extended version of the hammerhead ribozyme
(Figure 2c) works at physiologically-relevant
concentration of Mg2+ (1mM) due to its canonical
and non-canonical interactions between the loop
in stem II and the bulge loop in stem I (Osborne,
Schaak, & Derose, 2005). Therefore, the minimal
version of the hammerhead ribozyme is used in
vitro while the extended form is employed in vivo.
The minimal version of the hammerhead
ribozyme can be fused in stem II with a riboswitch aptamer to obtain different allosteric
sensors (Figure 2d). For this goal, we have used
computational methods based on modeling secondary structures or tertiary interactions in the
presence and in the absence of the ligand. These
approaches are very accurate and time efficient
allowing many different riboswitch classes to be
adjusted for HTS assays based on fluorescence

Figure 2. Engineering allosteric ribozymes as reporter systems in HTS arrays for drug discovery
(A) Supposed secondary structure of the aptamer domain of the flavin riboswitch in the absence and presence of FMN. (B)
The sequence and the secondary structure of the minimal version of the hammerhead ribozyme. The arrowhead indicates the
cleavage site. (C) The sequence and the secondary structure of the minimal version of the extended hammerhead ribozyme
from the human parasite Schistosoma mansoni, which exhibit high-speed of cleavage due to its canonical and non-canonical
interactions between the nucleotides of stem II and these of the bulge loop of stem I. (D) Allosteric ribozymes can be employed
as biosensors which recognize small molecules and cleave external RNA by fusing an aptamer domain (in blue) with a minimal
version of the hammerhead ribozyme. As a detection system can be used a florescence resonance energy transfer (FRET) method.
In this method the external RNA, cleaved by the ribozyme, is attached to a quencher (Q) in its 5 end and to a reporter (R) in
its 3 end. If the effector is not present, the allosteric ribozyme is inactive, and the RNA substrate will not be cleaved. (E) If the
effector molecule is present, it binds to the allosteric domain, so that stem II is formed and the ribozyme will be activated. The
activated ribozyme cleaves the external RNA, which leads to separation of the R from the Q. (F) In this case, we will detect
positive florescence signal. High-throughput machines can be used to perform this array on microtiter plates.
419

detection. We employ a fluorescence resonance

energy transfer (FRET) method for detection
of ribozyme cleavage (Blount et al., 2006) under multiple turnover conditions. In the FRET
method, two fluorescent dyes are employed. One
is attached to the 5 end while the other is on the
3 end. One dye serves as a reporter (Figure 2e,
R) that emits a fluorescence signal upon excitation while the other one is a quencher (Figure
2e), which absorbs the emitted signal. However,
if the FRET-labeled RNA molecule is cleaved
the R and Q are not anymore in close proximity
and the quencher cannot absorb the emitted by
the reporter fluorescence signal.
To make use of such detection system, we have
engineered allosteric hammerhead ribozyme that
cleave external FRET-labeled RNA molecules by
opening stems I and III of the ribozyme (Figure
2d, e). When an effector molecule is not present
stem II is not formed and, therefore, the ribozyme
is inactive (Figure 2d). In contrary, when a molecule specifically binds to the aptamer domain
stem II of the ribozyme is formed (Fig, 1e). This
activates the ribozyme, which cleaves its substrate
RNA (Fig, 1e, in red). This ribozyme serves as a
Boolean logic gate with YES function. As a result,
the quencher and reporter are unconnected and
the fluorescence emitted by the reporter can be
detected (Figure 2f). This approach can be fully
automated in a HTS format testing hundreds of
thousands chemical compound for specific binding to the aptamer domain of any riboswitch. This
can be used as a first step in riboswitch-based
antibacterial drug discovery. The application of
microfluidic technology may further advance
this process (Penchovsky & Stoilova, 2013;
Penchovsky, 2013).
RNA-BASED NANOCIRCUITS
The hammerhead ribozyme can be used to create allosteric molecular sensors with various
Boolean logic function, including NOT, YES,
420
OR, and AND (Penchovsky & Breaker, 2005).

In addition, the ribozyme can be designed to
sense not only small molecules but also specific
oligonucleotide DNA and RNA molecules.
Moreover, the ribozymes can be programmed to
pass signals from one to other within a molecular circuit. Such molecular circuits can be used
for various applications, including molecular
computing and diagnostics in vitro, and for
building synthetic signaling pathways in vivo.
For instance, such a circuit was demonstrated
by two oligonucleotide-sensing ribozymes
termed YES-1 and YES-2 (Figure 3). Both
ribozymes were designed by a computational
procedure(Penchovsky & Breaker, 2005) that
is a subject for a pending patent application.
The computational procedure for designing
oligonucleotide-sensing allosteric ribozymes is
superior to in vitro selection methods both in
terms of time efficiency and design accuracy.
In the absence of effector oligonucleotides
both YES ribozymes are designed to be in
inactive state since stem IV is formed instead
of stem II (Figure 3a). In the presence of oligonucleotide effector-1, the YES-1 ribozyme
is activated since stem II is formed instead of
stem IV when a specific oligonucleotide effector
binds the oligonucleotide binding site (OBS)
of the ribozyme (Figure 3b). As a result, the
YES-1 ribozyme cleaves itself and released a
RNA oligonucleotide that serves as an effector for the YES-2 ribozyme. This results in the
activation of YES-2 ribozyme, which cleaves
itself (Figure 3c).
Note that the effector-1 that triggers the
circuit can be a DNA as well as RNA molecule. The ribozymes are very specific. They
can distinguish perfectly well two mismatches
over the length of 22 nt. In addition, several
oligonucleotide-sensing allosteric ribozymes
can be designed to work sin parallel. This makes
them suitable molecular sensors for various
molecular diagnostic applications.

Figure 3. Molecular computing circuits
(A) The secondary structures of two allosteric ribozymes with YES logic function are depicted. In the absence of an effector
molecule, both ribozymes are inactive. (B) When effector 1 is present, it binds to the oligonucleotide binding site (OBS1) of the
first ribozyme that activates it. As a result, the YES-1 ribozyme undergoes self-cleavage. (C) The 3 cleavage fragment (effector
2), released after the self-cleavage of YES-1, targets the second ribozyme. As a result, YES-2 is also activated.
421

INTEGRATED RNA BASED

NANODEVICES WITH A COMPLEX
LOGIC FUNCTION AS A TOOL FOR
MOLECULAR DIAGNOSTICS
Integrated nanodevices made of nucleic acids can
combine the function of several molecular logic
gates in a single functional molecule or in an
assembly of molecules. Therefore, such devices
can work as integrated circuits at a nanoscale
level. There are some conceptual, designing, and
engineering obstacles that need to be overcome
before routine production of integrated devices
with nucleic acids, including RNA. For the time
being, there are a few nucleic acids based devices
that integrate the functionality of several logic
gates and can be used for diagnostic purposes.
However, even now, there are examples that provide experimental validation on the feasibility of
engineering such nanodevices.
An example for a RNA-based device that can
sense the length of its target RNA molecules was
recently described(Penchovsky, 2012b). This
nanodevice has the complexity of an integrated
circuit and can serve as three input AND Boolean
logic gate (Figure 4). Such gate has a true output
signal only in the presence of all three inputs. Our
ribozyme-based three-input logic gate is capable
of sensing the length of its target RNA molecules.
It has two OBSs that can sense two domains of
a target RNA molecule. They are embedded into
stem II of the minimal version of the hammerhead
ribozyme. This ribozyme is designed to cleave
an external RNA molecule that has two effector
domains and a substrate domain that are complementary to the OBSs of stem II and the substrate
binding site (SBS) of the ribozyme that forms stem
I and III. In fact, if the spacer between the effector
domains and the SBS of the ribozyme is too short
the forms stems I and III will not be formed and
the target RNA will not be cleaved. In contrast,
if the spacer of the target RNA molecule is long
enough stems I and III will be properly formed.
As a result the target RNA will be cleaved.
422
There are many genetic diseases that are associated with triplet repeat expansion in mRNAs
(Tan, Xu, & Jin, 2012) such as the Huntingtons
disorder. In all these disorders, the mutant mRNA
molecules are longer than the normal ones. The
triplet repeats tend to form stable hairpin structures that makes the length detection of such
triplet repeat expansions very difficult (Figure
4a). To overcome this problem, we can open the
hairpin structure by heating it in the presence of
antisense oligonucleotide. As a result, the hairpin
will form a double-strained structure. In this case
if the target mRNA is long enough stems I and
III will be formed (Figure 4b). Therefore, the
target RNA will be cleaved. This approach can
be used for diagnostic purposes by seeking and
destroying specific RNA molecules with a certain
length that are indicative for certain triple repeat
expansion disease.
ALLOSTERIC RIBOZYMES AS
DESIGNER CIS-ACTING GENE
CONTROL ELEMENTS
There are many disorders that are associated with
abnormal expression of certain RNA molecules
in the cell. We could oligonucleotide-sensing
ribozymes that can detect such abnormal expression of important RNAs in the cell and to react by
altering expression of exogenous proteins that can
overcome the disorder. In this way, we can achieve
two main functions for prevention and curing various diseases. In the first place, we can monitor the
emerging of the disease indicative RNAs in real
time. In the second place, we can take immediate actions upon detection of such RNAs. This is
a future therapeutic strategy based on allosteric
ribozymes that work as cis gene control elements
in the cell. (see Figure 5)
We can embed high-speed oligonucleotidesensing ribozymes at the 3 end of synthetic
mRNAs expression in the cell by viral vectors
(Figure 6). If the designer ribozyme is a NOT

Figure 4. Integrated RNA based nanodevice that sense the length of target RNAs
(A) The secondary structure of a three input logic gate with AND logic function is depicted. If the target RNA molecule is too
short the stems I and III are not formed and the ribozyme is inactive. (B) When the target molecule is long enough all three
stems of the ribozyme are formed the substrate RNA is cleaved.
gate, it will cleave itself in the absence of disease indicative RNA in the cell. As a result, the
synthetic mRNA will be decayed and will be not
translated into a protein (Figure 6a). In contrast,
in the presence of disease indicative RNA the
ribozyme will be deactivated. The synthetic
mRNA will be translated and therefore, the desired
protein will be expression, which will prevent the
diseases development. For instance, if there are

cancer related RNAs in the cell we could induce
the expression of exogenous p53 that could kill
the cancer cell (Penchovsky, 2012a).
We may also sense health indicative RNAs in
the cell and expressed a certain protein only in the
absence of such RNAs. To achieve this we need
to employ an allosteric ribozyme with YES logic
423

Figure 5. Ribozyme-mediated regulation of gene expression in eukaryotes
The gene expression in eukaryotes can be regulated through destabilization of mRNAs controlled by allosteric ribozymes. We
can insert a designer ribozyme in the 3 UTR of mRNA that encodes a desired protein. If the ribozyme is activated, it undergoes
self-cleavage that leads to mRNA decay. (A) An allosteric ribozyme with NOT logical function can be inserted in the 3 UTR.
In the absence of effector, it cleaves itself, which destabilizes the mRNA. When a specific ligand is present, the ribozyme is
inactivated. The mRNA remains stable and is translated into protein. (B) When a ribozyme with YES logical function is inserted
in the 3-UTR, it will be inactive in the absence of effector, and the gene expression of our protein will be activated. If the effector is present, it will activate the ribozyme. As a result, the mRNA will be decayed and there will be not protein synthesis.
function as depicted in Figure 6b. Note that all

high-speed allosteric ribozymes are based on the
extended version of the hammerhead ribozyme
(Figure 2c). In this case, the OBS is introduced in
stem III to preserve the interactions between stems
I and II that are responsible the in vivo function
of the ribozyme.
424
GENE SILENCING TECHNIQUES

VIA TRANS-ACTING RIBOZYMES
In modern pharmaceutical research, all tools,
which are manufactured at a nanoscale level are
termed nanopharmaceutics. There are two basic
types of nanopharmaceutics. One type of them

Figure 6. Ribozyme-based gene silencing techniques
(A) Without an effector RNA the YES gate is designed to fold into an inactive structure where a stem IV is formed instead of
stem III. (B) The YES switch binds the effector RNA and folds into an active state in which stem III is formed. (C) As a result
the ribozyme undergoes self-cleavage and shRNA is produced. (D) Dicer converts shRNA into dsRNA with sticky ends. (E)
In the presence of RISC complex the dsRNA is single-stranded and used for gene repression either by microRNA function via
translational suppression prevention of RNA translation by RNA decay. When there is a mismatch(s) with the target mRNA
the microRNA function is often executed. However, mRNA decay is observed not only with perfectly matching dsRNA but also
in the presence of some mismatches. (F) High-speed ribozyme can be designed to directly cleave a specific RNA in the cell.
425

are those where therapeutic molecules themselves

act as drugs. The other type includes nanocarriers
that are used for drug delivering. In this case, the
drugs are directly coupled to the nanocarriers.
There are various methods for drug attachment
to nanocarriers such as functionalizing, loading,
and encapsulating. As nanocarriers can be used
polymer particles, nanobeads, nanotubes, and
quantum dots. Nanodrugs (Khanbabaie & Jahanshahi, 2012) can be produced in various forms
such as nanosuspension, nanoemulsion, nanogels,
and nanospheres.
It is believed that the nanopharmaceutical research may be very beneficial for improving drug
stability and delivery. Nanopharmaceutics offers
some important advantages such as improved
bioavailability, specific molecular targeting, and
controlled release. In addition, nanopharmaceutics
can be engineered to pass intracellular compartments and the blood to brain barrier and to protect
fragile drugs. They have many different ways of
administration including ocular, pulmonary, oral,
topical, parenteral, nasal, and intravenous.
In some cases, the usage of nanopharmaceutics results in reducing toxicity. However, some
nanocarriers have been found to be toxic in certain
ways of administration. This has to be well studied to avoid adverse effects when applying novel
nanopharmaceutics. Nanocarriers are particulate
systems with various sizes between1 and 1000 nm.
They have been successfully used in the treatment
of various diseases.Many types of nanocarriers
have been introduced up to now. They include
polymer micelle, dendrimers, liposomes, and
quantum dots.
RNA molecules can be delivered in the cell
by various types of liposomes. In addition, they
can be expressed in the cell by different types of
viral vectors. In fact, nucleic acids show immense
potential to treat cancer, acquired immune deficiency syndrome, neurological diseases and other
incurable human diseases. Intracellular delivery
of nucleic acids is facilitated by nanovectors, both
viral and non-viral. A major advantage of non-
426
viral vectors over viral vectors is safety. Therefore,

RNA molecules can be delivered in many different
ways in the cell.
The advancements of these methods will
further empower the application of various
ribozyme-based gene silencing techniques as
novel therapeutics. We can employ high-speed
allosteric ribozymes with YES logic function
(Figure 6a) for conditional expression of short
hairpin (sh) RNAs only in the presence of some
specific RNAs such as viral RNAs (Figure 6b,
c). The shRNAs expressed in the cell will be cut
by the dicer (Figure 6d) and will enter a RNA
interference (RNAi) pathway (Fjose & Drivenes,
2006; Hammond, 2006). They can work as microRNAs preventing the translation of specific
mRNAs related to certain disease development
or can decay some target mRNAs in conjunction
to the RISC complex (Figure 6e). Note that these
processes tolerate some mismatches and, therefore,
can affect several different mRNAs simultaneity.
In fact, one shRNA sequence usually targets many
mRNAs in the cell and therefore it silences many
different genes. Thats why, in most cases, we
cannot afford to constantly expressed shRNAs.
Instead we need to express shRNAs only under
certain conditions and for limited time. Such
future approach could deal with this problem. In
addition, we can design a high-speed ribozyme to
cleave some specific RNA in the cell (Figure 6f).
However, this approach will be not as efficient as
shRNAs because it will have limited turnovers. All
these ribozyme-based gene silencing techniques
may have potent applications to medical genomics by targeting specific genes in vivo. The future
development of RNA delivery systems in the cell
will play a key role in successful applications of
these methods.
CONCLUSION
RNA based research has proven to be a productive field of modern science and technology that

has many important applications to discovery of

novel molecular targets for drug development and
diagnostics, creating reporter systems in HTS arrays, allosteric biosensors, integrated nanodevices,
designer gene control elements, drug delivery,
and others. Moreover, the discovery of new
mechanisms for control of gene expression such
as microRNAs, RNAi, and riboswitches gives us
not only better understanding for the complexity of
the RNA function within the cell but also provides
us with bigger opportunities for applying novel
RNA-based engineering strategies both in vitro and
in vivo. The advancement of RNA biology and engineering, on one hand, and the progress achieved
in the medical genomics by the HTS machines,
on another hand, offer new exciting opportunities
for developing of novel therapeutic strategies for
tackling various forms of cancer, viral infection
diseases, deployment of novel antibiotics, and
others. In addition, RNA engineering promises to
create original gene therapies by reprogramming
the cell fate. All this would be possible if the medical genomics discovers RNAs that are important
targets and/or markers in a disease development
process. Our abilities to identity such RNAs by
NGS technologies will improve over time due to
advancement of sequencing technology.
pivotal role in developing various strategies for

disease-dependent reprograming of cell fate in the
near future together with our ability to specifically
inhibit the expression of targeting mRNAs in the
cell. In addition, targeting bacterial riboswitches
may lead to the development of novel classes of
antibiotics with less resistance pathogenic bacterial strains.
FUTURE PROSPECTIVE
Brantl, S. (2004). Bacterial gene regulation: From

transcription attenuation to riboswitches and ribozymes. Trends in Microbiology, 12(11), 473475.
doi:10.1016/j.tim.2004.09.008 PMID:15488385
The application of novel safe and efficient viral

expression vectors will be critical for reaching
clinical trials of these methods in the future. The
development of more effective nanoparticle methods for cell delivery of siRNAs will increase our
abilities to develop various RNAi based therapeutic approaches. There will be some years to come
before the RNA-based technology matured and
become a widely spread in medicine. The proper
interaction between the RNA engineering and
medical genomics can significantly speed up this
process. The progress achieved in the computational design of allosteric ribozymes may play a
ACKNOWLEDGMENT
Robert Penchovskys research is supported by a
grant number DDVU02/5/2010 awarded by the
Bulgarian National Science Fund (NSF).
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Allosteric Ribozymes: They are usually engineered ribonucleic acid (Harris et al.) molecules.
They can possess various Boolean logic functions,
including NOT, YES, OR, AND, and others. They
can sense different molecular signals (effectors),
including small molecules, RNA and DNA oligonucleotides, polypeptides, and others. The allosteric domain(s), which bind the effector(s), is
distant from the catalytic center of the ribozyme.
Apoptosis: Various inducible biochemical
pathways that lead to a programed cell death. This
process plays an important role in prevention of
cancer development.
430
Bacterial Riboswitches: RNA molecules,

usually residing at the 5untranlated region
(UTR) of mRNAs that control gene expression
by directly binding metabolites. They consist of
ligand-binding aptamer domain and an expression platform.
Computational Design of Allosteric Ribozymes: Fully computerized approaches for
obtaining allosteric ribozyme sequences with
predefined properties.
Exogenous Control of Gene Expression:
An engineering approach for a regulation of
synthetic genes.
Gene Therapy: A set of methods for curing
different diseases by employing viral vectors.
Ribozymes: Functional RNA molecules that
catalyze specific biochemical reactions. They are
widely spread in all kingdoms of life.
RNA Aptamers: These have complex tertiary
structures that form pockets for selectively binding
a specific ligand. The first aptamers are synthetic
RNA molecules obtained by in vitro selection.
Later, naturally occurring RNA aptamers are
discovered in the gene control elements termed
riboswitches (see above).
431
Chapter 17
Theoretical Assessment of the

Mechanical, Electronic, and
Vibrational Properties of the
Paramagnetic Insulating Cerium
Dioxide and Investigation
of Intrinsic Defects
Mohammed Benali Kanoun
King Abdullah University of Science and Technology (KAUST), Saudi Arabia
Souraya Goumri-Said
ABSTRACT
First-principles calculations are performed by taking into account the strong correlation effects on ceria.
To obtain an accurate description including f electrons, the authors optimized the Coulomb U parameter
for use in Local-Density Approximation (LDA) and Generalized Gradient Approximation (GGA) calculation. A good agreement with experimental data is obtained within the GGA+U (Wu-Cohen scheme).
Elastic stiffness constants are found in correct agreement with the available experimental results. Born
effective charge, dielectric permittivity, and the phonon-dispersion curves are computed using density
functional perturbation theory. The origin of magnetism in undoped ceria with intrinsic defects is investigated. The authors show that both of Ce and O vacancies induce local moments and ferromagnetism
without doping ceria by magnetic impurities in this chapter.
DOI: 10.4018/978-1-4666-5824-0.ch017

Theoretical Assessment of the Mechanical, Electronic, and Vibrational Properties
INTRODUCTION
Cerium dioxide or ceria has gained a large interest for technological and industrial applications.
For instance, it is widely applied in automobile
exhaust catalysts as an oxygen storage material,
due to its ability to take and release oxygen under
oxidizing and reducing conditions. Properties
of ceria-based materials, such as electrical conductivity and diffusivity, have been reviewed for
its use as an electrolyte in solid oxide fuel cells
(Dresselhaus, 2001, Skorodumova, 2001). CeO2
is one of the most studied of the fluorite oxides
(Wang, 2003) because of their particular physical
properties. Mainly, the lattice mismatch to Si and
high dielectric constant, make ceria a potential
material for use in microelectronic applications,
high-quality epitaxy on Si and buffer layers of
high-temperature superconductors (Luo,1991).
Because of its wide technological usage, several
studies have already been conducted for CeO2
compound. The hydrostatic pressure dependence
of structural properties of CeO2 were investigated
by high-pressure Raman (Kourouklis, 1988) and
x-ray diffraction (Duclos 1988, Gerward,1993)
studies and it has been found that bulk CeO2 has a
phase transition from fluorite-type to -PbCl2-type
structure at about 31 GPa pressure. For nanocrystalline CeO2 the transition occurs at significantly
lower pressures 26.5 or 22.3 GPa (Wang, 2001).
Indeed, the experimental elastic constants were
derived from the sound velocity for each acoustic
phonon mode estimated from the frequency shift
of Brillouin scattering lines (Nakajima,1994).
On the theoretical side, many calculations have
been reported by various methods such as periodic
Hartree-Fock (Gennard,1999), self-interactioncorrected local-spin-density approximation (Gerward,2005), local-density approximation (LDA),
and generalized gradient approximation within
density functional theory (DFT) (Skorodumova,
2001, Koelling, 1983 - Da Silva, 2007). More
generally, it is well known that LDA and GGA
432
functional usually lead to qualitatively wrong

results when they are applied to lanthanide oxide
materials containing localized electrons (Perdew,
1981). The main reason for this shortcoming is
the self-interaction error (the electrostatic interaction of an electron with itself) that is contained in
these approximate functionals and their associated
potentials. Corrections to these approximations,
LDA+U and GGA+U methods (Anisimov,1997)
are usually applied to CeO2 (Grel, 2006- Sevik,
2009) where Hartree-Fock type interactions were
parameterized with Coulomb U and exchange J
terms.
Recently, the room temperature ferromagnetism has been observed in undoped ceria-based
nanostructures as films (Fernandes, 2009)
nanoparticles (Sundaresan, 2006) and nanocubes
(Ge, 2008). The origin of this magnetism is still
under debate (Han, 2009), but recent experimental
works and band structure calculations have suggested that ferromagnetism observed in ceria and
several other undoped oxides, e.g., HfO2 (Han,
2009), ZnO (Wang, 2008), MgO (Hu, 2008),
SnO2 (Rahman, 2008), and CuO2 (Chen, 2009)
is due to the existence of intrinsic point defects.
Most of these works explore the magnetism with
a minimum concentration of defects; i.e., in the
diluted defects limit. More recently, an experimental work have suggested that the observed ferromagnetism in nanostructured CeO2 is intrinsic,
and that magnetic moment is mostly associated
with the point defects (Ce and O vacancies) in the
structure (Fernandes, 2010).
In this chapter, we address the structural,
mechanical, and electronic properties by means
of ab-initio method. In particular, we focus on
ground-state properties, elastic stiffness constants and electronic structure with the inclusion
of on-site Coulomb interaction. The application
of GGA+U and its implementation leads us to
describe correctly the relativistic effect on 4f electrons and to derive correctly the prediction of the
material properties. We also extend our work to

investigate the intrinsic defects in undoped CeO2

in order to reproduce the ferromagnetic behavior.
Our results show that the oxygen or cerium vacancies lead to a ferromagnetic state.
METHODOLOGY AND
COMPUTATION
The theoretical calculations were carried out
using the full-potential (linearized) augmented
plane waves plus local orbitals (FP-(L)APW+lo)
method based on the density functional theory
as implemented in WIEN2K package (Blaha,
2001). The electronic exchange and correlation
functions have been treated by utilizing the LDA
and GGA with the Wu-Cohen scheme (Wu, 2006)
together with their on-site Coulomb interaction
added versions, (LDA+U) and (GGA+U). To
improve the description of cerium 4f electrons,
we used the LDA/GGA+U (U is the Hubbard
term) which corresponds to the LDA/GGA+U
methods described in Ref. (Liechtenstein, 1995)
with the GGA correlation potential instead of
LDA. The muffin-tin radii (RMT) are considered
to be equal to 1.9 and 2.2 a.u. (bohr units) for Ce
and O atoms, respectively. The self-consistent
procedure has been carried out with the energy
cutoff constant RMT Kmax = 9 and the Brillouin
zone integrations were performed with the special
k-points method over 121212 Monkhorst-Pack
mesh (Monkhorst, 1976). The convergence has
been followed with respect to the energy and the
density. In order to determine the Ueff = U - J (setting J = 0), available experimental data such as
lattice constant, bulk modulus, and band gap have
been compared with the calculated values. Hence,
Ueff is treated as an empirical fitting parameter.
Furthermore, we have conjointly used the
CASTEP package (Clark, 2005) which is a
plane-waves pseudopotential DFT code, within
a variational approach to density functional perturbation theory (DFPT) (Clark, 2005, Gonze,
1997) and using the plane-wave pseudopotential.
Norm-conserving pseudopotentials (Vanderbilt,

1990) and a plane-wave expansion of the wave
functions are employed. As the former method,
we used the Gradient conjugate approximation
(GGA) Wu-Cohen (Wu, 2006) scheme form to
describe the exchange and correlation potential.
The convergence criteria for structure optimization
and energy calculation were set to ultrafine quality
with a kinetic energy cutoff of 650 eV. The Brillouin zone integration was sampled using a 444
special k-point grid according to the MonkhorstPack scheme (Monkhorst, 1976) except for the
calculations of phonons dispersion and phonon
densities of states where a denser 10 10 10
k-point grid was required to reach convergence.
The self-consistent convergence accuracy was set
at 5.0 x 10-6 eV/atom. The convergence criterion
for the maximal force between atoms was 0.01
eV/ and the maximum displacement was 5.0 x
10-4. The dynamic matrix and dielectric tensors
were computed within a variational approach to
density functional perturbation theory (Gonze,
1997). Phonon-dispersion relations have been determined by using ab initio force-constant method
as described by Parlinski et al. (Parlinski, 1998),
in order to correct LO-TO splitting. Born effective charges have been calculated with the finite
difference method as implemented in CASTEP
code (Clark, 2005, Gonze, 1997).
PROPERTIES OF THE PURE CERIA

The crystal structure of CeO2 is equivalent to that
of CaF2, whose space group is Fm-3m as shown
Figure 1 a and b. First, to determine the Ueff parameter for this rare earth oxide lattice parameter,
the bulk modulus, and band gap (Egap = O 2p - Ce
4f and Egap = O 2p - Ce 5d) values are calculated
by LDA+U and GGA+U, and then these results
are compared with the experimental data as shown
in Figure 2. The equilibrium lattice parameter,
the bulk modulus, and its pressure derivative for
CeO2 are gathered in Table 1, in order to perform
433

Figure 1. (a) Crystal structure of CeO2, (b) Brillouin Zone for the primitive cell of CeO2
comparison with experimental (Gerward, 1993,

Wang, 2001, Gerward, 2005, Villars, 1991) and
theoretical values (Skorodumova, 2001, Fabris,
2005- Da Silva, 2007, Grel, 2006, Shi, 2010,
Sevik, 2009). The equilibrium lattice constant
(a) and the bulk modulus (B) were estimated by
fitting the Murnaghan-Birch equation of states
(Murnaghan 1944, Birch, 1978) to the resulting
energy-volume data. The lattice parameter is underestimated by 0.62% at the purely LDA level
(Ueff = 0 eV) compared to experiment. Thus,
introducing Ueff > 0 shows that a is always larger
than experimental value but increases as function
of Ueff for GGA+U(see Figure 2a). In the case of
LDA+U, the lattice parameter is smaller than the
experimental. In the case of GGA+U, the calculation at Ueff = 0 eV gives that a is overestimated
by 0.13% compared to experimental data and
for a Ueff value between 4 and 5 eV the lattice
parameter matches the experimental value. As
indicated in Figure 2b, the bulk modulus value
is also steadily increasing with increasing Ueff
but this observable is even less affected by the
latter parameter. However, our a and B values
calculated by the GGA+U approach with Ueff
values 5 eV compare well with the experimental
data. In addition to consistent reproduction of
a and B with the chosen values of Ueff for CeO2
434
compound, the calculated values for band gaps

are reasonably good, given the well-known fact
that DFT underestimate band gaps of insulators
(see Fig. 2c). Furthermore, our systematic study
of these three parameters shows that the GGA+U
(with Wu and Cohen scheme) approach works
better than LDA+U and also PBE+U.
The elastic constants Cij were calculated within
the total-energy method, where the unit cell is
subjected to a number of finite-size strains along
several strain directions. The obtained elastic
stiffness constants C11, C12, and C44 are gathered
in Table 2, were found by imposing different
deformations (see Ref. (de la Roza, 2009)) to
the equilibrium lattice of the cubic unit cell and
by determining the dependence of the resulting
energy changes on the deformation. Furthermore,
the mechanically stable phases or macroscopic
stability is dependent on the positive definiteness of stiffness matrix (Born, 1982). For a
stable cubic structure, the independent elastic
constants should satisfy the well-known BornHuang criterion (Born, 1982), given by: C44 > 0,
C11 > | C12| and C11+2 C12 > 0. We have to notice
that the CeO2 is mechanically stable because all
elastic constants are positive and satisfy the Born
mechanical stability restrictions. We compare the
elastic constants in the GGA+U (Ueff = 5 eV) with

Figure 2. Lattice constant (a), bulk modulus (b) and band gap (c) as a function of the Hubbard Ueff
those of GGA (Ueff = 0). However, the C11, C12 and

C44 of GGA+U at Ueff = 5 eV agree much better
with the experimental data (Wang,2001), than U
= 0 cases. Note also that our results are in close
agreement with the available theoretical works
(Grel, 2006, Sevik, 2009). The bulk modulus
BVRH, shear modulus G, Youngs modulus Y, and
Poissons ratio are obtained by Voight-Reuss-Hill
(Hill, 1952) formalism (following the procedure
detailed in ref. (Kanoun-Bouayed, 2011)) and are
also summarized in Table II. So, the bulk modulus
obtained at U = 0 results show a slightly better
agreement with the experimental value 204 GPa
(Villars, 1991) than finite U cases. Moreover, our

computed Poissons ratio at Ueff = 5 eV is slightly
smaller than U = 0. In fact, Poissons ratio can
formally take values between -1 and 0.5, which
correspond, respectively, to the lower bound where
the material does not change its shape and to the
upper bound when the volume remains unchanged.
It has been proved that = 0.25 is the lower limit
for central-force solids and 0.5 is the upper limit,
which corresponds to infinite elastic anisotropy
(Ledbetter, 1983). The calculated Poissons ratio
values are larger than 0.25, which means that CeO2
is affected by central contributions.
435

Table 1. Equilibrium lattice parameter

a
FP-(L)APW+lo GGA (U = 0)
5.417
193.7
4.20
This work
FP-(L)APW+lo GGA+U, 5 eV
5.426
207.5
4.60
This work
FP-(L)APW+lo LDA (U = 0)
5.376
204.2
4.80
This work
FP-(L)APW+lo LDA+U, 5 eV
5.384
221.3
4.90
This work
SIC-LSD
5.384
176.9
Gerward, 2005
FPLMTO
5.48
187.7
Skorodumova, 2001
PW-PP
5.48
178.0
Fabris, 2005
PAW GGA+U
5.48
187.0
Loschen, 2007
PAW GGA+U
5.38
202.4
Loschen, 2007
PAW GGA
5.45
194
Yang, 2004
PAW PBE0
5.39
PAW PBE
5.47
172
4.417
Da Silva, 2007
L/APW+LO PBE
5.47
170
4.4
Da Silva, 2007
PAW GGA+U
5.40
217
Ge, 2008
HGH PP
5.40
211.11
Grel, 2006
PAW LDA+U
5.366
210.1
Sevik, 2009
Experiment
5.410
204 - 236
Gerward, 1993; Wang,

2001; Gerward, 2005;
Parlinski, 1998
Da Silva, 2007
a, (), bulk modulus, B, (GPa), and its pressure derivative, B, (dimensionless) of CeO2 compared to other theoretical and experimental
data. (FP LMTO, full potential linear muffin tin orbital; PW-PP, plane-wave pseudopotential method; PAW, projector-augmented wave
method; SIC, self-interaction corrected; LSDA; HGH, Hartwigsen-Goedecker-Hutter; TB LMTO, Tight binding linear muffin tin orbital).
The calculated total and partial density of states

(DOS) curves at the predicted equilibrium lattice
constants for CeO2 are shown in Figure 3 within
the framework of GGA approach with and without
Ueff, where the vertical line is the Fermi level (EF).

A common trend can be proposed from total DOS
graphs that the influence of Ueff on the electronic
structure is basically restricted to the unoccupied
Table 2. Calculated elastic constants

C11
C12
C44
BH
205
91.5
238.8
0.306
Our work
182.4
80.2
209.7
0.308
Our work
GGA-
371.8
121.5
74
WC+U
345
101.2
60.2
GGA-WC
390
130
82
PAW Sevik, 2009
LDA+U
375
123
72
PAW Sevik, 2009
LDA
386
124
73
HGH PP Grel, 2006
LDA
354.79
139.27
51.19
PAW Shi, 2010
LDA+U
403
105
60
Wang, 2001
Expt.
Cij (GPa), Bulk moduli BVRH (GPa), shear moduli G (GPa), Youngs modulus Y (GPa), Poissons ratio and anisotropy factor for CeO2
436

Figure 3. Total and partial density of states at GGA+U (with U = 0 and 5 eV) for CeO2. Since the spinup and spin-down channels are identical, only the spin-up channel is shown. The vertical solid line
denotes the Fermi level
f state and this does not drastically change the

electronic distribution especially occupied states.
Hence, the gap between the valence O (2p) and
conduction Ce (5d) bands is 5.5 eV, however
this calculated value is slightly smaller than the
measured one at 6 eV (Wuilloud, 1984; Kanoun,
2012) and agrees with a previous theoretical
study (5 - 5.5) eV ((Skorodumova,2001; Loschen,
2007, Andersson, 2007). Moreover the distance
between the valence band and the Ce 4f states is
2.5 eV, to be compared with 3 eV in experiments
(Wuilloud, 1984). So, the width of the O 2p is
4.38 eV, which agrees with experimental data and
theoretical calculation. Another consequence of
higher values of Ueff is a slightly reduced width
value of the Ce 4f peak and increases the intensity
of this peak, which reflects stronger localization.
The charge density contour for a cut in the
(110) plane of CeO2 is displayed in Figure 4. It
clearly seen that CeO2 is characterized by a nearly
spherical charge-density distribution around the
Ce and O atoms and a low charge density in the
interstitial region. It can be also seen that the ionic

bonding is the determinant of the chemical bonding
in CeO2, even though the covalency is strong in
the sense of orbital participation in forming the
valence state. According to our density of states
analysis and results obtained by Nakamatsu et al.
(Nakamatsu, 1995), we have attributed to CeO2 a
covalent character due to the strong hybridization
between O 2p and Ce 4f and 5d states and ionic
character to O p and Ce 5s and 5p states. Moreover,
the components of Ce 5s, 5p make a repulsive
interaction with O 2p because of overlap of the
essentially filled states. Concerning the bonding in
CeO2, this repulsion cancels the covalent bonding
between Ce 4f, 5d and O 2p.
DIELECTRIC PROPERTIES
The electronic dielectric permittivity tensor, ,
is related to a second derivative of the electronic
energy with respect to an electric field and can
437

Figure 4. Charge density distribution (electrons/ 3) in (110) plane of CeO2
be computed using a linear response technique

(Gonze, 1997). In our calculations, no scissor
correction has been included in the calculation.
Because of the symmetry properties of the CeO2
crystal structure, this tensor is diagonal with
only one component (). This component is found
equal to 6.78, which suggest that CeO2 is a positive uniaxial cubic crystal with a quite isotropic
electronic response to a homogeneous electric
field. Then, this value is in overall agreement to
the theoretical and experimental data reported in
(Grel, 2006) and references therein. The static
dielectric tensor (0) is calculated by adding the
lattice vibration contribution to the electronic
dielectric tensor. The component of (0) is found
equal to 37.02 which is in good agreement to the
experimental value (0)=23 (Marabelli, 1987)
and the recent theoretical work (Grel, 2006). This
can prove also the excellent dielectric properties
along all the directions and may provide an optical
methodology for gate dielectric films on silicon
substrate as application.
438
LATTICE DYNAMIC AND

THERMODYNAMIC PROPERTIES
Dynamical properties were obtained by the use
of linear response method, within DFPT (Wang,
2008, Hu, 2008). In fact DFPT is not only one of the
most robust methods for the calculation of dynamic
properties but also a method that naturally enables
the calculation of the second-order derivatives of
the total energy with respect to atomic position,
and thus the properties of phonon modes to be
evaluated directly. The long-range behavior of the
Coulomb interaction gives rise to macroscopic
electric fields for longitudinal (LO) and transverse
(TO) optical phonons, and the coupling between
the phonon modes and the electric field leads to the
LO-TO splitting at the point (Segall, 2002). The
Born effective tensor is a very important quantity,
which determines the well-known phenomenon of
LO-TO splitting (Santha, 2004) LO-TO splitting
affects only infrared active modes near the point,
raising the frequencies of LO modes above those
of TO modes. Figure 5 shows dispersion curves

Figure 5. Calculated phonon dispersion through high symmetry points of Brillouin and Total Phonon
density of states of CeO2
and partial densities of states of the phonons for

CeO2 as obtained from the frozen technique along
the XKXWL directions (see the BZ).
We have to mention here, that we are displaying
only the phonon calculations with lattice parameter obtained from GGA+U. In fact, it was shown
that +U approach has marginal effect on phonon
dispersions (Grel, 2006).
Zone-centered phonon modes can be classified according to the irreducible representations
of the Oh point group. The group theory predicts
the following symmetries of the modes: 3A1g+3
A1u+3A2g+3A2u+6Eu+6Eg+9T2u+9T2g+9T1u+9T
. A factor group analysis gives the decomposi1g
tion of the zone center modes as 2T2u+T1g. The
threefold-degenerate T1g mode is only Raman
active while one of the T2u modes is only infrared
active; the other threefold-degenerate T2u mode is
the acoustical mode. The degeneracy of the optical
T2u is partially lifted by the inclusion of polarization effects, which leads to LO-TO splitting (see
the phonon dispersion curve at point). In order
to have a clear picture of the vibrational patterns;
we have illustrated the atom displacements for
the modes at various frequencies, as shown in
the Supporting Information. The low-frequency

region (<200 cm-1) contains one IR mode at 185
cm-1, and from the analysis of vibrational patterns,
we find that the Ce atoms along the diagonal axes
move in parallel in the same direction, while they
move against each other at 376 with three different
intensities of 325, 325.10 and 324.99 A4 in the
Raman modes. Overall, the general agreement
between our results and the experimental data are
excellent. Born effective charges of Ce and O for
CeO2 are found to be and with GGA-WC, which
is in good agreement compared to the calculated
effective charges of CeO2 (Grel, 2006; Segall,
2002, Santha, 2004).
Employing quasi-harmonic approximation
(Maradudin, 1971) we evaluate the thermodynamic properties under finite temperatures. In fact,
the heat capacity at a constant volume Cv can be
calculated directly from the phonon DOS under
the harmonic approximation (Kanoun-Bouayed,
2011, Ledbetter, 1983) . We display in Figure 6,
our calculations of Cv and the temperature dependence of the Debye temperature D for CeO2. From
the red dashed curve (plot a), we can see that the
heat capacity increases rapidly below 400 K and
439

Figure 6. Constant volume heat capacity (Cv) and temperature dependence of Debye temperature (D)
for CeO2
reaches a maximum of 11.52 J/ (molK) at about

600 K. By fitting the theoretical Cv with the Debye model, we derive the temperature-dependent
Debye temperature D (T), as it is shown in blue
dash-doted curve. We evaluate this temperature
around 3000 K, which is an important parameter
for the measurement of CeO2 crystal physical
properties.
VACANCY-INDUCED
MAGNETISM IN CeO2
The origin of the magnetism in undoped CeO2 is
studied by generating a single Ce or O vacancy.
In fact, we model defect properties using 222
supercell with 47 sites, derived from the ideal
fluorite structure, where one Ce or O atom is
removed which leads to Ce or O concentration
of 6.25%. Figure 7 compares the spin-resolved
DOS calculated with GGA+U approach for one
440
Ce vacancy as well as for one O vacancy. These

results show that the presence of a Ce vacancy (VCe)
turns CeO2 into a ferromagnetic with the Fermi
level intersecting the minority O 2p state. Note
that the magnetic moment is found about 4.1 B
per Ce vacancy which would be mostly associated
with O 2p states. The O vacancy (VO) produces
also a ferromagnetic where the Fermi level cuts
the majority Ce f states, which are mainly on two
Ce atoms that are the nearest neighbors to the O
vacancy. It can be also find that the magnetic moment is found about 2 B per O vacancy.
The total energies of the ferromagnetic (FM)
and paramagnetic (PM) orderings were examined.
The energy differences between FM and PM orderings E = E(FM) - E(PM) were 36.2, and
14.7 meV/cell for a single Ce and O vacancy,
respectively, indicating that the FM state was
more stable than the PM state. Those theoretical
results are supported by an experimental report
(Fernandes, 2009, Wen, 2007), where the Ce

Figure 7. Total and partial density of states at GGA+U for one Ce vacancy and for one O vacancy in CeO2
or O vacancy induced ferromagnetism was observed in CeO2. Furthermore, it should be noted

that stoichiometric CeO2 showed an evidently
enhanced stability of ferromagnetism as the Ce
or O deficiency increases. Figure 8 a shows the
isosurface plot of the spin density of CeO2 with
one Ce vacancy. It can be seen that the iso-surface
plot of the spin density gives a clear scheme about
the strongly localized spin polarization near the
O atoms surrounding VCe. This localized spin

polarization reflects the local magnetic moments
in the system. We have also presented in Figure 8
b isosurface plot of the spin density of CeO2 with
one O vacancy. It is evident that the spin density
of VO exhibits a planar isosceles triangle shape,
showing the spin polarization strongly localized
on the three-neighbor Ce atoms and the vacancy
site. The remaining few magnetic moments are
Figure 8. Iso-surface spin-density plot for (a) VCe and (b) VO in CeO2
441

localized on O and Ce atoms far away. Generally,

one oxygen vacancy as a donor can leave two
electrons in the system.
SUMMARY
We have investigated the structural, elastic, electronic, properties of CeO2 within the DFT framework. To achieve our goal, first we realized a set
of simulations to predict Ueff Coulomb parameter
used in LDA+U and GGA+U calculations. The
GGA+U method gives better agreement compared
to LDA+U method, and the most convenient results are obtained for Ueff =5.0 eV. Consequently,
elastic properties and related polycrystalline
properties are predicted with reasonable accuracy.
Our study covers all of the linear couplings among
applied static homogeneous electric field, strain,
and periodic atomic displacements, including the
Born effective charge, dynamic matrix at the zone
center and optical dielectric tensor. We have found
a good agreement between the calculated and the
recently reported theoretical and experimental
dielectric constant using the norm-conserving
pseudopotentials. Interestingly, we demonstrated
that depending on the type of the introduced vacancies, spin-polarized O 2p states are induced near
the Fermi level, generating a magnetic moment
of 4.1 B per Ce vacancy and 2 B per O vacancy
respectively which provide a strong half-metallic
character to Ceria.
ACKNOWLEDGMENT
Calculations using Wien2k and Castep codes
were carried out with help of Research Computing team of King Abdullah University of Science
and Technology (KAUST).
442
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Dielectric Properties: These are concerned
by the storage and dissipation of electric and
magnetic energy in materials.
GGA+U: An efficient method used to overcome the difficulties of classical DFT method
mainly for highly correlated systems and transition metals.
Oxides: A chemical compound that contains
at least one oxygen atom and one other element.
Vacancy Defects: Lattice sites which would
be occupied in a perfect crystal, but are vacant.
447
Chapter 18
Implementation of
Nanoparticles in
Cancer Therapy
Ece Bayir
Ege University, Turkey
Eyup Bilgi
Aylin Sendemir Urkmez
ABSTRACT
Cancer is a wide group of diseases and generally characterized by uncontrolled proliferation of cells
whose metabolic activities are disrupted. Conventionally, chemotherapy, radiotherapy, and surgery are
used in the treatment of cancer. However, in theory, even a single cancer cell may trigger recurrence.
Therefore, these treatments cannot provide high survival rate for deadly types. Identification of alternative methods in treatment of cancers is inevitable because of adverse effects of conventional methods. In
the last few decades, nanotechnology developed by scientists working in different disciplinesphysics,
chemistry, and biologyoffers great opportunities. It is providing elimination of both circulating tumor
cells and solid cancer cells by targeting cancer cells. In this chapter, inadequate parts of conventional
treatment methods, nanoparticle types used in new treatment methods of cancer, and targeting methods
of nanoparticles are summarized; furthermore, recommendations of future are provided.
1. CANCER BIOLOGY
Cancer, although one of the worlds most widely
studied medical conditions, remains as the leading
cause of death after the heart failure, accounted
for 7.6 million deaths (around 13% of all deaths)
DOI: 10.4018/978-1-4666-5824-0.ch018
in 2008. According to comprehensive, 184 country survey of WHOs International Agency for
Research on Cancer (IARC), about 70% of all
cancer deaths occur in low- and middle-income
countries. Worldwide cancer mortalities are envisioned to continue to rise to over 13.1 million
in 2030 (http://globocan.iarc.fr/).

Implementation of Nanoparticles in Cancer Therapy
Normal eukaryotic cells tend to increase

their number by mitosis and meiosis, and the
cell division process is triggered by activation
of the metabolic pathways when the cell size
and the environmental conditions are favorable.
The metabolic pathways that are necessary
for cell division include the specific signaling
pathways, the transmitting signal molecules,
enzymes and proteins (Cooper & Hausmann,
2013). After completion of division process, the
cell enters into a new cycle again and the cycle
is repeated approximately 50 times before the
cell goes to apoptosis. Apoptosis is the death
of a cell programmed by specific genes. The
reason for the limited number of cell divisions
is telomeres, regions of repetitive nucleotide
sequences at each end of a chromatid, which
protect the ends of the chromosomes from
deterioration or from fusion with neighboring
chromosomes. Telomeres shorten with each
cell division and eventually the cell cannot be
divided further, progresses into senescence or
dies (Counter et al., 1992).
Some cells, due to hereditary and environmental factors, continue to grow and proliferate even in the presence of cell growth and
division inhibitory factors. Thereby, cells start
division without special signals. Cell growth is
disrupted, cells begin to divide too quickly and
telomere shortening stops due to telomerase
activity (Yoshida et al., 1997).When unnatural
telomerase activity is observed, cell structure
changes, adhesion property increases, abnormal
signal transduction occurs, tumor suppressor
genes are silenced and growth factors and their
receptors are generated irregularly. These are
typical characteristics of cancer cells. Therefore,
the researchers specify that cancer originates
in fast-growing and immortal cells. Abnormal
cells affect the cells around them and they also
lead to deterioration of their functions. The other
most important feature of these cells is that
they may maintain their lives regardless of the
448
specific microenvironment. Thereby, they can

easily spread to the surrounding tissues, blood
and entire body (metastasis). These abnormal
cells generate new blood vessels around them
by secreting vascularization factors, and they
can make the metastasis process more quickly
and efficiently (Sooriakumaran & Kaba, 2005)
(Figure 1).
Formation of such a cell abnormality is
caused by mutations due to environmental factors and/or heredity. X-rays, UV light, tobacco
products, diet and obesity, environmental pollutants and viruses are considered the most
common environmental carcinogens.
Although many methods have been developed in the treatment of cancer, the WHO figures
suggest that a highly effective treatment technique is yet to be found. Surgery, radiotherapy,
chemotherapy, immunotherapy and hormone
therapy, which are the most commonly used
conventional methods have specific advantages
and disadvantages. The chosen treatment type
depends on the location, the progress status and
the type of cancer. The limitations of status quo
treatments are commonly due to nonspecific
bio-distribution and insufficient targeting of the
therapeutic agents, poor oral bio-availability,
low therapeutic indices, dose-limiting toxicity
to healthy tissues, and almost invariably emerging drug resistance and subsequent challenge
of providing remissive therapy. Multimodal
therapy methods are under investigation, and
researchers are looking into developing alternative therapies. Oncology is one of the
disciplines that will potentially benefit the
most from nanotechnology. The nanoparticle
based targeted delivery vehicles can effectively
overcome the major challenges in successful
clinical translation, including specificity, proper
dosage, overcoming various biological barriers
and demonstrating better therapeutic efficacy
than that of the current clinical standards.

Figure 1. Emerging hallmarks of cancer for therapeutic targeting (Adapted from Hanahan & Weinberg,
2011)
Conventional Approaches
for Cancer Therapy
Surgery
Surgery is the oldest treatment method used to treat
cancer (Wu et al., 2006). Initially patients who
have an operation had died because of excessive
blood loss, difficulties of anesthesia and respiratory insufficiency. Thanks to the advances in the
drugs and medical sector, the number of deaths
caused by operation is significantly reduced and
the therapeutic outcomes are increased.
Surgery is the preferred treatment method for

initial stages of solid cancer tumors and benign
(non-metastatic)tumors. The efficacy of treatment
is inversely proportional to the ability of tumor
metastasis. Despite the surgery eradicates solid
tumors, it generates low success rate on non-solid
and spreading tumors (Rani et al., 2012).
Primarily the tissue specimen is removed by
surgical cutting and examined by microscopic
analysis. The tumor tissue can be removed by
surgery if the structure of the tumor is suitable
to be removed. Regional lymphatic nodes are excised during the operation to prevent metastasis.
To eradicate the metastatic cells, the surgery is
449

supplemented by another treatment modality. One

of the most important disadvantages of surgery is
that the surrounding tissues can also be damaged
besides the tumor tissue during the operation. The
entirety of cancer cells must be cleaned during
the operation, because even a very small number
of remained cancer cells may lead to recurrence
of the tumor. To achieve this, some parts of the
healthy tissues around the tumor are also removed
during the surgery. Substantial tissue loss can
lead to physiological and psychological issues for
patients. In addition, locations in the body where
operation is very dangerous is an extra limitation
for the surgery (Haskell & Berek, 2001).
Radiotherapy
Radiotherapy is a treatment method used to destroy
the cancer cells that cannot be removed by surgery
from tumor tissue (Love et al., 1999; Haskell &
Berek, 2001). In some cases, it can also be used
to reduce tumor size. In radiation therapy, X-rays,
gamma rays and electrons are used. Radiation
therapy is used at certain time intervals to provide
a period for recovery of the normal cells that are
damaged beside the cancer cells during the treatment. Generally, normal cells are less sensitive
than tumor cells to radiation. Nevertheless, the
dose and location of radiation given to the patient
must be arranged very accurately in order to
minimize the damage to normal cells (Love et al.,
1999). The sensitivity of tumor cells to radiation
is also different. Therefore, the effectiveness of
radiation therapy is directly proportional to the
sensitivity of the tumor to radiation.
Radiation therapy can be used for therapeutic
purposes; it can also be used in palliative therapy.
Palliative care is also called comfort care or
supportive care given to a patient who has a
serious or life-threatening disease, such as cancer,
and it can be given at the time of diagnosis and
throughout the course of illness. There are two
kinds of radiation therapy according to the mode
450
of administration. Beams are generated outside

the patient and are targeted at the tumor site in
External Beam Radiation method (Murray &
Robinson, 2011). In The Internal Radiation
method, the radioactive materials are placed directly into the tumor tissue. The most important
parameters for treatment planning and dose calculations are energy loss of radiation, range and
scatter of radiation, dose and isodose of radiation
(Chopra, 2011).
Radiation therapy kills the cancer cells by
damaging their DNA. This treatment damages
cells DNA either directly or by forming free
radicals. Damaged cells which are not repaired
stop dividing or die. Radiotherapy has serious
side effects related to radiation dose, volume of
the tissue and administration rate. Radiobiological
effects critically depend on the pattern of ionization at the level of the biomolecule. The most
common side effects are fatigue, nausea, vomiting,
inflammation and edema of the irradiated organ
in the early days, and possibly chronic blood supply disorders, neutropenia (sudden drop in white
blood cell count), and anorexia (Soussain et al,
2009; Shafiq et al., 2009).
Chemotherapy
Chemotherapy is the use of chemical agents to kill
or suppress the growing cancer cells. In contrast
to surgery and radiotherapy, chemotherapy is not
local and affects the entire body. The main target is
rapidly dividing cells in chemotherapy since most
cancer cells are characterized by the ability of rapid
division. Intestinal epithelial cells, bone marrow
cells, mucosal and hair follicle cells and stem cells
are rapidly dividing cells in the body and these
cells are damaged as well by chemotherapy (Rani
et al., 2012). On the other hand, all of the cancer
cells are not capable of dividing rapidly. Types of
tumors with doubling rate more than 70 days to
less than 30 days exist. Due to this non-specificity,
selective and/or targeted agents are necessary

to expand the effectiveness of chemotherapy.

The main target of traditional chemotherapy is
prevention of replication and transcription by
targeting DNA and thus inhibition of cell growth
and division by suppression of protein synthesis.
In addition, nowadays, specific protein synthesis
pathways, mitotic vehicles, specific antigens and
protein kinase inhibitors are studied to target with
drugs that may be effective in different cell division phases, and impair the formation of mitotic
spindles (Miglarese & Carlson, 2006).
The biggest problem in chemotherapy is toxicity. The toxic effects are often observed because
the chemotherapeutic agents have high toxicity
and elevated doses are used for the treatment of
many cancer types. It is possible to classify these
effects under two headings as long and short term
toxicity. The short-term toxicity usually emerges
quickly and occurs in tissues that have rapid division capability. Vomiting, nausea and dizziness
are the main side effects of short-term toxicity
(Poli-Bigelli et al., 2003). Long-term toxicity
usually leads to carcinogenesis, teratogenesis
(defect births) and infertility. In addition to these
problems, cancer cells can develop resistance to
chemotherapy drugs and this constrains effectiveness of chemotherapy. Drug resistance may
occur because of over expression of multidrug
resistance genes, membrane uptake reduction
and the increasing of tolerance to cytoplasmic
detoxification, DNA repair and DNA damage.
This situation makes it necessary to have new active substances in cancer treatment continuously
(Tiwari et al, 2011; Yap etal. 2009).
All these treatments can be used single or in
combination. However the point to be considered
is that the damage to the healthy cells may be increased with combined and/or repeated therapies
since they are not specifically targeted. In recent
years, new methods of treatments are applied in
order to reduce exposure rates to normal cells. The
most prominent of these methods are immunotherapy and hormone therapy (De Schryver et al.,
1992; Fong et al., 2001; Burch et al., 2004). The

patients own immune system fights cancer and
reduces treatment-related side effects in immunotherapy. The hormones that help the development
of tumor may be stopped, or the activities of the
hormones that can fight cancer cells, make cancer
cells grow more slowly are increased.
2. NANOPARTICLES IN
CANCER THERAPY
Nanotechnology is a research area with the
potential to be used in a wide variety of fields
from biomedical technologies to textiles and
from food packaging to informatics. Nanoparticles (NPs) have been available in all areas of
human life for a long history, although the word
nanoparticle has begun to be used widely with
developing nanotechnology in late 20th century.
People are exposed to nanoparticles in the air,
food and beverages constantly (Buzea et al.,
2007). Nanoparticles offer unique physical and
biological properties particularly in the medical
field to overcome cellular barriers and improve
the delivery of various bioactive molecules and
drugs as well as to enhance molecular imaging,
to facilitate early tumor detection, to implement
monitoring of therapeutic response and to minimize side effects. There are different mechanisms
for the internalization of nanoparticles by cells
influenced by nanoparticles physicochemical
properties (Hillaireau&Couvreur, 2009; Susa et
al., 2009). However the biggest obstacle against
the development of nanoparticle drug delivery
systems is the ambiguity in nano-toxicology issues. Although there are comprehensive studies
on nano-toxicology, a definitive concensus has
not been revealed yet. Many studies have shown
possible negative effects of nano-materials on
mammalian cells. However, the number of works
to prevail these adverse effects has been limited.
NPs need to be analyzed more critically and their
451

Table 1. Selected nanoparticle-based therapeutics approved by FDA or in clinical trials in cancer

treatment
Nanoparticle type
Biological NPs
Liposome NPs
Active
pharmaceutical
ingredient
Situation
References
Product name
Company
CALAA-01
Calando
Pharmaceuticals
siRNA
Phase 1b
(Yu et al., 2012)
SGT53-01
SynerGene
Therapeutics
p53 gene
Phase 1b
(Yu et al., 2012)
ALN-VSP
Alnylam
Pharmaceuticals
siRNA
Phase 1
(Vaishnaw et al., 2010)
ABI-009
(Abraxis
Biosciences)/
Celgene
Rapamycin (mTOR
inhibitor)
Phase 1
(Schtz et al., 2013)
ABI-010
(Abraxis
Biosciences)/
Celgene
17-AAG
Phase 1
ABI-011
(Abraxis
Biosciences)/
Celgene
Thiocolchicine
dimer
Phase 1
ASG-22ME
Seattle Genetics
Anti-Nectin-4
Phase 1
ASG-5ME
Seattle Genetics
Human monoclonal
antibody directed to
SLC44A4
Phase 1
SPI-77
Sequus
Pharmaceutical
Cisplatin
Phase 2
(Swami et al., 2012)
Doxil/Caelyx
Schering-Plough
Doxorubicin
Approved
(Haley & Frenkel, 2008)
DaunoXome
Galen US Inc.
Daunorubicin
Approved
(Bawa, 2008)
Myocet
Enzon
Pharmaceuticals
Doxorubicin
Approved
INGN-401
Introgen
Therapeutics
FUS1
Phase 1
(Bawa, 2008)
MBP-426
Mebiopharm
Oxaliplatin
Phase 2/3
(Yu et al., 2012)
MCC-465
Mitsubishi Pharma
Corporation
Doxorubicin
Phase 2
(Yu et al., 2012)
Lipoplatin
Regulon
Cisplatin
Phase 3
(Stathopoulos & Boulikas,

2011)
Thermodox
Celsion
Doxorubicin
Phase 3
(Wood et al., 2012)
2B3-101
to-BBB technology
Doxorubicin
Phase 3
Aroplatin
Aronex
Pharmaceuticals
NDDP, Oxaliplatin
analog
Phase 2
(Zamboni, 2008)
CPX-351
Celator
Pharmaceuticals
Cytarabine and
daunorubicin
Phase 2
(Venkatraman et al., 2010)
LE-DT
Insys Therapeutics
Inc. (NeoPharm)
Docetaxel
Phase 2
LEP-ETU
Insys Therapeutics
Inc. (NeoPharm)
Taxol (paclitaxel)
Phase 2
(Zamboni, 2008)
continued on following page
452

Table 1. Continued
Nanoparticle type
Liposome NPs
Product name
Company
Active
pharmaceutical
ingredient
LE-SN-38
Insys Therapeutics
Inc. (NeoPharm)
Sarcodoxome
Situation
References
7-ethyl-10-hydroxy
camptothecin
Phase 2
(Heidel & Davis, 2011)
GP Pharma
Doxorubicin
Phase 2
S-CKD602
Alza Corporation/J
&J
CKD602
Phase 2
(Zamboni, 2008)
SLIT cisplatin
Insmed
Cisplatin
Phase 2
(Wittgen et al., 2007)
Tocosol paclitaxel
Eagle
Pharmaceuticals
Taxol (paclitaxel)
Phase 2
(Constantinides et al., 2008)
EmPAC
Cornerstone
Pharmaceuticals
Taxol (paclitaxel)
Preclinical
(Bremerich et al., 2007)
Liploxa
LiPlasome Pharma
Oxaliplatin
Preclinical
(Jensen et al., 2004)
LE-rafAON
Insys Therapeutics
Inc. (NeoPharm)
c-Raf antisense
oligodeoxy
nucleotides
Phase 1
(Dritschilo et al., 2006)
LiPlaCis
LiPlasome Pharma
Cisplatin
Phase 1
(de Jonge et al., 2010)
NL CPT-11
Irinotecan = CPT11
Phase 1
TKM-PLK1
Tekmira
Pharmaceuticals
siRNA directed
against PLK1
Phase 1
Depocyt
Pacira Pharms/
Sigma-Tau
Pharmaceuticals
Cytarabine
Approved
(Glantz et al., 1999)
Mepact
IDM Pharma
Mifamurtide
Approved
(P. Anderson et al., 2010)
Marqibo
Inex/ Enzon/ Thalon

therapeutics
Vincristine sulfate
Approved
(Rodriguez et al., 2009)
Alocrest
Thalon therapeutics
Vinorelbine
Phase 1
(Zamboni, 2008)
Adventrx
Docetaxel
Phase 1
(Curran & McCormack,

2008)
ANX-530
Adventrx
Vinorelbine
Phase 1
(Zamboni, 2008)
ATI-1123
Azaya Therapeutics,
Inc.
Docetaxel
Phase 1
(Zamboni, 2008)
Atu027
Silence therapeutics
siRNA targeting
PKN3
Phase 1
(Aleku et al., 2008)
Brakiva
Thalon therapeutics
Topotecan HCl
Phase 1
(Zamboni, 2008)
CNF1010
Conforma
Therapeutics
Corporation
17-AAG
Phase 1
IHL-305
Yakult Honsha Co.,

Ltd
Irinotecan
Phase 1
BIND-014
BIND Biosciences
Docetaxel
Phase 1
(Yu et al., 2012)
Prolindac (AP5346)
Access
Pharmaceuticals
Oxaliplatin
Phase 2
(Sood et al., 2006)
Opaxio (Xyotax)
Cell Therapeutics
Taxol (paclitaxel)
Phase 3/4
(Alexis et al., 2010)
ANX-514
Polymeric NPs
453

Table 1. Continued
Nanoparticle type
Polymeric NPs
Inorganic NPs
Active
pharmaceutical
ingredient
Situation
References
Product name
Company
NC-6004
NanoCarrier
Corporation
Cisplatin
Phase 1
(Uchino et al., 2005)
NK-105
Nippon Kayaku
Corporation
Taxol (paclitaxel)
Phase 2
(Hamaguchi et al., 2007)
NK911
Eagle Lifestyle
Nutrition
Doxorubicin
Phase 1
(Matsumura et al., 2004)
Docetaxel-PNP
Samyang Co.
Docetaxel
Phase 1
DOX-OXD
Doxorubicin
Phase 1
(Danhauser-Riedl et al., 1993)
Livatag
BioAlliance Pharma
S.A.
Doxorubicin
Phase 3
NKTR-102
Nektar
Irinotecan
Phase 3
(Vicent et al., 2009)
Taxoprexin
Luitpold
Pharmaceuticals
Taxol (paclitaxel)
Phase 3
(Zamboni, 2008)
AP5280
Access
Pharmaceutical
Carboplatine platine
Phase 2
(Rademaker-Lakhai et al.,
2004)
CRLX101
Cerulean Pharma
Inc./Calando
Camptothecin
Phase 2
(Svenson et al., 2011)
CT-2106
Cell Therapeutics
Camptothecin
Phase 2
DE-310
Daiichi Sankyo
Co. Ltd
DX-8951f, exatecan
mesylate
Phase 2
(Shiose et al., 2007)
FCE28068
Pfizer
Doxorubicin
Phase 2
(Seymour et al., 2009)
FCE28069
Pfizer
Doxorubicingalactosamine
Phase 2
(Seymour et al., 2009)
Pegamotecan
Enzon
Pharmaceuticals
Camptothecin
Phase 2
(Scott et al., 2009)
MAG-CPT
Pharmacia &
Upjohn Inc.
Camptothecin
Phase 1
NKTR-105
Nektar
Docetaxel
Phase 1
PNU166945
Pharmacia &
Upjohn
Taxol (paclitaxel)
Phase 1
(Meerum Terwogt et al.,

2001)
XMT-1001
Mersana
therapeutics
Camptothecin
analog
Phase 1
(Walsh et al., 2012)
XMT-1107
Mersana
therapeutics
Fumagillin analog
Phase 1
Aurimmune (CYT6091)
CytImmune
Sciences
Gold TNF-
Phase 2
(Bawa, 2008)
AuroLase
Nanospectra
Biosciences
Gold nanoshell
Phase 1
(Bawa, 2008)
AuriTol
CytImmune
Sciences
Gold Paclitaxel +
recombinant TNF-a
Preclinical
AntiEpCAM
Triton biosystems
SPION + antibody
Preclinical
(Morrow Jr et al., 2007)
454

Table 1. Continued
Nanoparticle type
Product name
Company
Active
pharmaceutical
ingredient
Protein NPs
Abraxane
Abraxis Bioscience
Taxol (paclitaxel)
Approved
Oncaspar
Enzon
Pharmaceuticals
Pegaspargase
Approved
(Davis, 2008)
ABI-008
Abraxis Biosciences
Docetaxel
Phase 2
Taxol
Bristol Myers
Squibb
Paclitaxel
Approved
Micelles
Polymerprotein
conjugates
Antibody-drug
conjugates
Situation
References
Taxotere
Sanofi-Aventis
Docetaxel
Approved
Genexol-PM
Samyang Co.
Paclitaxel
Approved
(A. Z. Wang et al., 2012)
Docetaxel-PM
Samyang Co
Docetaxel
Phase 1
(Simon, 2006)
Paxceed
Angiotech
Paclitaxel
Phase 2
(J. A. Zhang et al., 2004)
SP1049C
Supratek Pharma
Doxorubicin
Phase 2
(Valle et al., 2011)
SP1060C-O
Supratek Pharma
Topotecan
Preclinical
(Kabanov & Alakhov, 2002)
Nanoxel
Fresenius Kabi
Oncology Ltd/
Dabur Pharma
Taxol (paclitaxel)
Phase 1
NC 4016
NanoCarrier
Oxaliplatin
Phase 1
ADI-PEG 20
Polaris Group
- Phoenix
Pharmacologics
Arginine deaminase
Approved
(Shen & Shen, 2006)
CDP 791
UCB S.A.
Anti-VEGFR2 Fab
fragment
Phase 2
(Pasut & Veronese, 2009)
Trastuzumab
emtansine
Genentech
Mertansine (DM1)
Phase 3
(Mathew & Perez, 2011)
Human mAb to
GPnMB- auristatin
conjugate
Phase 2
Glembatumumab
vedotin
SGN-CD19A
Celldex
Therapeutics
Seattle Genetics
effects on organisms must be investigated by welldesigned in vitro and in vivo studies to eliminate
this problem.
In this section, general information about NPs
that are used in drug delivery and targeting in cancer therapy will be presented with their advantages
and disadvantages. Selected nanoparticle-based
therapeutics approved by federal agencies or still
in clinical trials in cancer treatment are tabulated
at the end (Table 1).
Antibody antiCD19
(Naumovski & Junutula,

2010)
Preclinical
Polymeric Nanoparticles
Polymeric NPs are obtained by using natural or
synthetic polymers in the core/corona part (Alexis
et al., 2008). Polymeric NPs are often used for
controlled drug delivery systems. Drugs which are
used for therapeutic purposes can be encapsulated
in the polymer, or loaded on either the surface or
the core (MuFei Tang et al., 2010). NPs can be produced from biodegradable or non-biodegradable
polymers depending on the purpose. Biodegrad-
455

able polymer NPs may be removed from the body

through the normal metabolic pathways by eroding
into its constituent oligomers. Their degradation
and drug release rates or kinetics can be adjusted
by changing the physicochemical properties of the
polymer and thus they can be used for different
delivery systems (Alexis et al., 2010).
Polymeric nanoparticles may cause tissue
damage depending on the toxicity and dosage of
the polymer by accumulating in certain parts of
the body. However, polymeric NPs are the most
preferred NPs in drug delivery/targeting systems
and cancer treatment due to their higher biocompatibility, lower immunogenicity and toxicity,
biodegradability, easy preparation methods and
surface functionality (Nahar et al., 2006). Drug
delivery systems can be adjusted as controlled,
delayed or triggered release from these particles.
Some polymer based nanosystems such as Oncaspar (pegaspargase) that is L-asparaginase
modified by covalently conjugating units of mono
methoxy polyethylene glycol (PEG) to treat acute
lymphoblastic leukemia, Opaxio (paclitaxel
poliglumex) that links paclitaxel active ingredient to a biodegradable polyglutamate polymer for
lung cancer and ovarian cancer treatment and also
Livatag, NKTR-102, Taxoprexinare approved by
FDA and available in the market or on phase 3-4
trials as shown in Table 1.
The surface of the polymer particles can be
functionalized with various methods. Hydrophilic
polymers such as polyethylene glycol (PEG), dextran and chitosan are most widely used polymeric
NPsdue to their stable surface and their high
availability of functional groups to be conjugated,
grafted or absorbed to other surfaces and bioactive molecules. Thereby, circulatory half-life of
the bioactive molecules is increased and hepatic
uptake is reduced (Alexis et al., 2010). Not only
drugs which have low molecular weight but also
therapeutic agents such as nucleic acids, genes,
proteins and peptides can be carried with polymeric NPs. Functional groups on the particle and
the surface charge have a great importance for
456
avoiding the phagocytic system cells (Yang et al.,

2009). Positively charged particles are taken into
the phagocytic cells more than the neutral and
negatively charged particles (Alexis et al., 2008).
Properties which directly affect the treatment
such as circulation half-life and release rate can
be arranged as requested by adjusting functional
groups on the particle and surface charge (Karmali
& Simberg, 2011; Fadeel, 2012; Zaki et al., 2011).
Liposomal Nanoparticles
Liposomes are artificial spherical vesicles that
allow encapsulation of drugs in liquid phase
owing to their lipid bilayer structure with sizes
varying between 50 nm 5 m (Malam et al.,
2009). Hydrophilic drugs are transported in the
center of liposome whereas hydrophobic drugs
are transported within the lipid bilayer (Sharma
& Sharma, 1997) (Figure 2). It was put forward
that liposomes could be used in drug delivery
systems in the early 1970s (Gregoriadis, 1995).
Despite more than 40 years have passed after the
discovery of liposomes, liposome based systems
still has not been exploited adequately today.
Liposomes are classified as conventional liposomes (CL), pH-sensitive liposomes, cationic
liposomes, long-circulating liposomes (LCL)
and immune-liposomes according to their structures (Sharma & Sharma, 1997). Liposomes
help to increase pharmacokinetics, efficiency
and bioavailability, and decrease the toxicity of
the drug or bioactive agent in the body because
these particles can be adopted to target-driven
treatments by functionalizing (Drulis-Kawa &
Dorotkiewicz-Jach, 2010). However, their use is
limited because liposome NPs are not very stable,
and do not always remain in desired site for long
periods of time to show the therapeutic effect, although local deposition of the drugs is higher when
encapsulated with liposomes since liposomes
can be internalised quickly by macrophages and
other cells in the body (Hatefi & Amsden, 2002).
The drug delivery systems based on liposomes

Figure 2. Liposomes can be used in dual drug delivery. Hydrophilic drugs are transported in the center
of liposome whereas hydrophobic drugs are transported within the lipid bilayer
are among the most studied nanoparticles such

as Myocet, DaunoXome, DepoCyt, liposomal
doxorubicin/Caelyx, Mifamurtide (Mepact),
Marqibo (vinCRIStine sulfate liposome) have
been approved by FDA among other liposomal
medicines in pre-clinical or clinical trials as summarized in Table 1.
The basis for properties of liposomes is their
lipid bilayer structure which forms hydrophilic
space inside. Therefore, the instability disadvantage can be eliminated with appropriate modification of this membranes internal and external
structure (Felnerova et al., 2004). Liposomes
should be produced with prudently selected
methods to be able to load proper amounts of the
drugs and adjust the drug release rate (Koudelka
& Turanek, 2012).
Dendrimer Nanoparticles
Dendrimers with hollow internal structure are treelike nanostructures which have been discovered
in the 1980s (Tomalia et. al, 1986 (Dang et al.,
2012). Due to their three-dimensional structure
which is smooth and highly branched, and easy
functionalization of their surface, dendrimers are

commonly used in medicine, in host-guest chemistry and as catalysts (Luo & Sun, 2007). Dendritic
structure can be examined in four sub-classes, (i)
randomly hyper-branched polymers around the
inner core structure (ii) dendrigraft polymers,
(iii) dendrons and (iv) dendrimers. More than a
hundred different dendrimers and more than a
thousand different surface chemistries are known
(Oliveira et al., 2010).
Owing to properties such as high degree
of molecular uniformity, monodispersity and
multifunctional surface, dendrimers are distinguished from other linear and branched polymers
(Devarakonda et al., 2005). One of the most
widely used dendrimers is poly(amidoamine)
(PAMAM) dendrimer. PAMAM dendrimers
possess important properties such as biocompatibility, non-immunogenicity, water solubility
and manipulability of their functional groups for
binding to variety of guest molecules (Strydom et
al., 2013, Ouyang et al., 2010), and can be used
for controlling the release rate and increasing
dissolution of the drugs with low water solubility (DEmanuele & Attwood, 2005). In addition
457

to PAMAM; poly(propylene imine) (PPI), polylysine (PLy), arborols (ARB), poly(benzyl ether)
(PBzE), polyphenylene (PHEN), thiophosphorylphenoxymethyl (methylhydrazono) (PMMH) are
also widely used (Caminade et al., 2005).
It has been shown that dendrimers can be used
for theranostic applications as well as drug delivery systems due to their compatibility with many
nanostructures such as genetic and/or bioactive
materials, fluorescent molecules etc. Despite all
the potential, the accumulation, redistribution and
the adverse effects to other tissues have not been
fully revealed (Oliveira et al., 2010), and there is
eminent need for large scale in vivo studies.
larger than 800 kDa) tend to accumulate in tumor

tissue much more than they do in normal tissues
(Maeda et. al., 2009). On the other hand, some
studies show that albumin has a tumor targeting
ability by using special pathways to overcome
the endothelial barrier in biological environment
(Alexis et al., 2010).
Protein-based NPs produced by protein engineering can minimize the toxicity of solvent-based
systems. Hydrophilic drugs may be directly toxic
when they are given into the body because of
their solubility in the water. Protein-based NPs
allow loading hydrophilic drugs into hydrophobic
formulations (Hawkins et al., 2008).
Protein Nanoparticles
Polymersome Nanoparticles
Proteins can be used as drugs themselves as well

as carriers for drug delivery systems since they
are biodegradable, non-antigenic and can reduce
unwanted side-effects. Another distinctive advantage of protein NPs is their functional diversity
(Vzquez & Villaverde, 2010).Desired proteins
can be produced easily by using classical biotechnological methods or recombinant technologies
by macro/microorganisms. Although studies on
protein nanoparticles have accelerated relatively
recently, there are some nano-systems such as
Abraxane, Oncaspar and ABI-008 that are FDA
approved or are ongoing phase trials as shown in
Table 1. Their biocompatibility is high because
these protein NPs are synthesized using biological
building blocks like amino acids and peptides, and
toxic chemicals are not used in provision.
Protein-based drug-loaded NPs produced by
albumin have received FDA approval and have
been used in clinical applications for some time
(Pazdur, 2012; Elzoghby et al., 2012). Enhanced
permeability and retention (EPR) effect has an important role for accumulation of albumin in tumor
site. The EPR effect, a universal phenomenon in
solid tumors, is the property by which certain sizes
of molecules (typically liposomes, nanoparticles,
and macromolecular drugs above 40 kDa, even
Polymersomes are self-assembled vesicles and

synthetic amphiphilic block copolymers, like
natural phospholipids and liposomes (Discher,
1999; Sachsenhofer et al., 2007). Although they
have similar structure to natural membranes,
properties of polymersomes are quite different
than the liposomes. To exemplify, their weight,
mechanical and thermal stability is higher than
those of biological lipids (Sachsenhofer et al.,
2007). In addition, polymersomes possess lower
permeability compared to liposomes; and the
chemical composition, structure and sizes of
polymersomes can be changed by adjustment
of the block copolymers (Amstad et al., 2012).
The size and shape of the polymerosomes
directly affect their pharmacokinetics and biodistribution properties. Under 10 nm, they can
be quickly cleared in capillary beds and lymph
nodes, while those above 200 nm are rapidly
removed from circulation via splenic filtration
(Ho & Shoichet, 2013). In addition to removal
from the body, polymerosomes shape and
size also affecttheir degradation and release
behavior, transportation in the body, targeting
ability, uptake by immune cells or the targeted
cells, thus biocompatibility (Champion et al.,
2007;M. Anderson et al., 2008).
458

Owing to their amphiphilic structure, they

can be loaded with hydrophilic and hydrophobic
molecules at the same time and targeted toward
desired cell types (Surovtseva et al., 2012). The
hydrophilic molecules are captured in the core
and hydrophobic molecules in their thick bilayer
membrane (Amstad et al., 2012). The specific
structure of polymersomes allows theranostic drug
carrier systems that include both water soluble
and insoluble substances such as therapeutic and
imaging agents together (Levine et al., 2008).
Additionally the surface of polymersomes can
be modified by specific biological molecules for
targeting the desired tissue sites (Johnson et al.,
2011).
Inorganic Nanoparticles
Although it is possible to produce organic
nanoparticles such as liposomes, polymersomes
and polymeric nanoparticles to design nanoscale
drug delivery systems, and many of them are in
clinical and preclinical stages, the research on inorganic nanoparticles increase day by day because
of their unique optical, electrical, magnetic, and/
or electrochemical properties (H. C. Huang et
al., 2011). The biological delivery systems (viral
carriers) are the most effective carriers for drug
delivery, but they tend to cause immune response
or mutagenesis so that the success of the cellular
delivery of these systems is low. Liposome and
polymersome based devices may prevent these
problems, but they are often instable and may
show toxicity to the cells. Owing to their low
toxicity and highly controllable release rates, inorganic nanoparticles are alternatives to organic
nanoparticles (Z. P. Xu et al., 2006; Mironava et
al., 2013).
Metallic nanoparticles such as gold, silver, iron,
titanium, platinum etc. have been used for medical
applications like imaging, targeting and treatment
of cancer. Easy control of their shape and size,
as well as their easy surface functionalization are
the main advantages of inorganic nanoparticles
as compared to organic nanoparticles (Son et al.,

2007).Generally super-paramagnetic iron oxide
nanoparticles (SPIONs), due to their magnetic
properties and gold nano-vehicles due to their high
X-ray absorption coefficient have been widely
used as contrast agents. Also SPIONs and gold
nano-vehicles can be used in hyperthermia and
photothermia treatment where these inorganic
particles are heated selectively by application
of an external high frequency magnetic field,
microwave irradiation, radiofrequency pulses or
ultrasound waves leading to thermal destruction
of the tumor when targeted effectively. Metallic
nanoparticles can also be used in drug delivery
systems, but recently other applications are more
popular than drug delivery because loading of the
drugs on inorganic NPs is more difficult and laborious. However certain gold nano-systems such
as Aurimmune (CYT-6091), AuroLase, Auritol
and some SPIONs like AntiEpCAM have been
used for treatment.
Silver NPs have unique thermal, electrical,
optical and antibacterial properties, and they are
investigated for diagnostic and conductive applications such as biosensors, imaging and antibacterial dressings. Although known and used for
quite a long history, there is still active debate on
toxicity and biocompatibility of silver. Titanium
dioxide NPs have interesting dielectric and optical
properties, and they are also tested as drug eluting vehicles and in photodynamic therapy where
these normally non-toxic, light-sensitive particles
are exposed selectively to light, whereupon they
become toxic to targeted malignant and other
diseased cells (Moreno-Vega et al., 2012).
In addition to metallic NPs, quantum dots
(Qdots) and carbon nanotubes are also among the
most studied nano-systems. Solutions of Qdots of
varying size have different color, and the variation
in optical absorption each solution illustrates the
particle size dependence for each sample (L. Wang
et al., 2010; Pathakoti et al., 2013). Qdots can be
used both in in vitro diagnostics and in imaging
systems due to their specific absorption properties.
459

The selection of nanoparticles intended for

medical applications is very imported. In most
cases, toxicity is the more important criteria for
the selection if the particles will be used especially
in vital systems such as central nervous systems
(Suh et al., 2009).To exemplify, although Qdots
possess very specific optical features, they cannot
be used widely in treatment of diseases because
of their Cd/selenide core which are very toxic for
mammalian cells. In addition to particle chemistry,
researchers must also account for other properties of the particles such as geometry, size, dose,
surface area and aspect ratio to select the most
appropriate delivery system for distribution of the
therapeutic agent with minimum adverse effects.
For example, many studies specify that size of
CNTs is one of the most important reasons of
their toxicity. With increased fiber size, clearance
of CNTs by macrophages becomes harder. The
surface properties also affect the uptake of CNTs
to the cells, their interactions with cell surface
molecules and the signaling pathways (X. Zhao
& Liu, 2012).
Other Biological Nanoparticles

Some unicellular microorganisms including
bacteria with different shapes and sizes are also
classified as biological nanoparticles. The different
sizes of microorganisms are useful for encapsulating both hydrophobic and hydrophilic molecules.
Although biological nanoparticles have been
investigated more recently than the other types
of NPs, there are some biological nano-systems
such as CALAA-01, SGT53-01, ALN-VSP,
ABI-009, ASG-22ME on phase 1 trials.Despite
some studies carried on animals verify that these
nanoparticles show no significant toxicity, there
has been a potential for immunological response
because of the containment of the microorganism
specific lipo-polysaccharides. In addition to unicellular microorganisms, bio-based nanoparticles
comprise many agents such as DNAzymes (catalytically active DNA molecules), short interfer-
460
ing RNAs, antisense oligonucleotides, aptamers

(oligonucleic acid or peptide molecules that bind
to a specific target molecule) and ribozymes (an
RNA molecule that is capable of performing specific biochemical reactions). They possess ability
of silencing non-desired genes with appropriate
design (L. Zhang et al., 2012). In order to obtain
an effective medicine for tumors, short synthetic
nucleic acid nanoparticles may be designed for
the targeted therapy of the genes associated with
the disease (Fuessel et al., 2007).
Radiotherapy aims to kill the cancer cells by
ionizing radiation and also by regulating the genes
that provide resistance to radiotherapy (Ghisolfi et
al., 2012). However in many cases, radiotherapy,
as well as chemotherapy cannot achieve the
success for the treatment due to the presence of
cancer stem cells (CSCs) which play a key role in
cancer recurrence and resistance (Clarke & Fuller,
2006). It is possible to prevent the development
and growth of the cancer cells and even CSCs
by using these biological gene silencers. For
the most effective treatment, gene silencing and
radiotherapy can be used simultaneously. In this
case the therapeutic agents can silence the genes
that are responsible for radiation resistance and
stop the proliferation of the cancer stem cells.
Concurrently, radiotherapy may kill the cancer
cells that are present in the tumor sites.
3. NANOPARTICLE
TOXICITY AND SAFETY
Developments in nanotechnology also caused an
increase of concerns about nanotoxicity. Especially
the adverse effects caused by nanoparticles on
healthy cells must be the priority interest. For
this reason, there are many toxicology studies for
each type of nanoparticles. In vitro toxicity assays
used in these studies are different from each other,
and their results may sometimes be controversial.
European Commission supports Joint Research
Center (JRC) Institute for Health and Consumer

Protection for safety assessment of nanomaterials,

particularly for developing methods for detection
of nanomaterials in food and consumer products,
validation of analytical methods for nanomaterials
and developing standardised protocols for toxicity testing (www.jrc.ec.europa.eu). A forty seven
institute consortium FP-7 Project, MARINA,
Managing Risks of Nanomaterials, aims for integrated and intelligent testing, integrated assessment, and modular interconnection of knowledge
and information for validated science-based risk
management methods (http://www.marina-fp7.
eu/). NanoLINEN is another consortium of seven
European laboratories and Indian Institute of
Toxicology Research (CSIR Laboratory) from
India to strengthen the research ties in the area
of Nanomaterial Toxicology. The goal of this
project is to develop robust risk assessment methodologies that will be useful for the community
manufacturing and using nano-products (http://
www.nanolinen.org/).
Some of toxicity tests which can be used for a
variety of different nanoparticles include;

Morphological
changes:
Light
microscopy.
Cell viability and/or cell growth:
Neutral red assay, Trypan blue,
Calceinacetoxymethyl / ethidiumhomodimer, Lactate dehydrogenase, Tetrazolium
salts (MTT, MTS, XTT, WST), Resazurin
or Alamar blue, Propidium iodide, (Choi &
Wang, 2011).
Celldeath: Lactate Dehydrogenase (LDH)
assay.
Apoptosis/necrosis: Acridine orange/
ethidium bromide, Propidium iodide,
Caspase-3 activity, DNA laddering.
Oxidative stress: Levels of reduced
(GSH) andoxidized (GSSG) glutathione,
superoxide dismutase (SOD), glutathione
peroxidase (GPx), catalase (CT), ROS production, Vitamin E, levels of lipid peroxidation, DCF assay.
Visualization of intracellular localization: Transmission electron microscopy.

Cellular
uptake:
radiolabelled
nanoparticles.
Genotoxicity: in vitro micronucleus test,
Allium cepa chromosome damage test.
DNA damage: Comet assay.
Cytotoxicity: Colony forming efficiency
test.
Hemolysis: Hemoglobin estimation.
Nano-vehicles should be fully characterized

and tested in order to pass judgment on toxicity.
Different test methods, surface modifications,
nanoparticle size, shape, dose, surface charge,
targeted cells, organisms, and route of administration may obtain different results on toxicity.
For further details on nanotoxicity issues, Won
HyukSuh et al. 2009 can be referred for a wide
analysis about titanium dioxide (TiO2), iron oxide
(Fe2O3), silicon oxide (SiO2) and cerium oxide
(CeO2) nanoparticles and Xingchen Zhao and Liu
2012 is recommended for the effects of different
carbon nanotubes on different mammalian organisms and cell lines (Suh et al., 2009; L. Zhao et
al., 2011). Although the toxicity caused by characteristic features of different nanoparticles may
be diverse, it is possible to generalize the factors
which influence the toxicity as follows:

Increasing the surface area of nanoparticle

increases the toxicity significantly more
than increasing nanoparticle mass (Stoeger
et al., 2006).
Nanoparticles smaller than 100nm are
more successful in drug delivery but these
particles lead to more side effects related
to respiration compared to larger particles
(Donaldson & Stone, 2003).
Whether nanoparticles are biodegredable
or not does not seem to have a significant
effect on toxicity. It is possible to do the
classification from less toxic toward the
most toxic as: (i) biodegradable and larger
461

462
than 100 nm, (ii) non-biodegradable and

larger than 100 nm, (iii) biodegradable and
less than 100 nm and (iv) non-biodegradable and less than 100 nm nanoparticles
(Keck & Muller, 2013).
The geometry of nanoparticles may play an
important role in nanoparticle toxicity. For
example, although single walled or multi
walled carbon nanotubes and nano-60
fullerenes are both based on carbon, their
toxicity is not the same in vitro(Sanvicens&
Marco, 2008).
Generally high concentration of NPs show
less toxic effects than low concentration of
NPs, because higher concentration of NPs
often cause formation of aggregates (Gurr
et al., 2005).
Surface modifications of inorganic
nanoparticles can also affect their toxicity
(Sanvicens & Marco, 2008).
Even allotropes of the same material can
cause different toxic effects on same organism. For this reason, the chemical structure
and crystallinity are highly effective on the
toxicity (Buzea et al., 2007).
Generally it has been strived to form less
toxic particles by coating the material surface with various biocompatible polymers.
However, in the end it may end up with
higher toxicity when the interactions of
coating materials with other factors are not
known.
High aspect ratio indicates higher toxicity, because macrophages are unable to
phagocytose long fibers (Hoet et al., 2004).
Some long fibers break transversely when
they degrade in the body and they can be
cleared by phagocytosis, but some long fibers such as asbestos break longitudinally
and they cannot be cleared by phagocytosis
(Oberdrster, 2002).
4. MAJOR CANCER TARGETS

FOR NANOPARTICLE SYSTEMS
The recovery rate has not increased significantly on
cancer patients in the last twenty years in spite of all
the advances in tumor biology, cancer biomarkers,
surgical procedures and chemo-radiotherapy. Early
diagnosis, pathological characterization of the
tumors and personalized treatments are substantially candidates to improve recovery rate figures.
Negative side effects on healthy cells, especially
rapidly dividing cells besides the tumor cells,
are the major problem of conventional therapy
methods. Researchers have been investigating
new therapy methods that specifically target only
tumor cells to overcome this problem.
Targeting systems can be examined in four
groups;
1.
2.
3.
4.
Cell marker targeting,

Signaling pathway targeting,
Micro-environment (niche) targeting, and
Angiogenesis associated targeting.
The best target for the treatment of cancer cells

is the molecules which are found in cancer cells
but not found in normal cells. However, in practice,
this approach is not possible sincecancer cells
actually evolve out of normal cells, and therefore,
there are no clear distinctive markers. Some of the
more commonly synthesized molecules in cancer
cells compared to normal cells are considered good
targets for therapy. A greater number of cancer
cells can be damaged with adjusting the dosage
of chemotherapeutics that target these molecules
in comparison with conventional therapies.
Cell Marker Targeting via Antibodies

An antibody (Ab), also known as an immunoglobulin (Ig), is a large Y-shaped protein produced by
B-cells and used by the immune system to identify
and neutralize foreign objects such as bacteria

and viruses. The antibody recognizes a unique

part of the foreign target, called an antigen. The
cell membrane contains many surface and transmembrane molecules such as peptides, proteins,
saccharides, antibodies and glycoproteins. Some
of these molecules are specific for particular
cell types, and can be targeted effectively with
monoclonal antibodies for therapeutic purposes.
Some surface antigens synthesized by cancer cells
are different from normal cells and this circumstance is an important opportunity for targeting
via antibodies. The main scheme of treatment of
cancer by targeting these specific molecules is to
attach the nanoparticles only on the cancer cells
by integrating these surface markers or affinity
molecules to tumor cells, or the molecules that
increase the uptake of the nanoparticles into the
targeted cells (Figure 3).
Specific antibodies are produced by injecting

an antigen into a mammal, such as a mouse, rat,
rabbit, goat, sheep, or horse for large quantities
of antibody. Monoclonal antibodies (mAb) are
monospecific antibodies made by identical immune cells that are all clones of a unique parent
cell, in contrast to polyclonal antibodies which
are made from several different immune cells
(Binyamin et. al., 2006).
Cancer cell signaling pathways are affected
by the use of monoclonal antibodies in various
ways. Antibodies can be used to prevent communication between the signaling molecules
and their receptors. Human tumors express high
levels of growth factors and their receptors, and
many types of malignant cells are stimulated by
these signal molecules. In anti-receptor directed
therapies, antibodies targeted by nanoparticles
Figure 3. The main scheme of treatment of cancer by targeting via antibodies is to attach the nanoparticles only on the cancer cells by integrating the surface markers (or affinity molecules to tumor cells
or the molecules that increase the uptake of the nanoparticles to the targeted cells) that are specific to
the cancer cells on the nanoparticles.
463

are bound to cell surface receptors and block

their interaction with signal molecules (Baselga&
Mendelsohn, 1994; Hicklin et. al., 2001; Capdevila
et. al, 2009). MAbs directed against epidermal
growth factor (EGF), transforming growth factor
(TGF), G-protein, fibroblast growth factor (FGF),
IL-2, andIL-6 receptors are examples of this approach. Antibodies can also be used as a vehicle
for delivering the chemotherapeutic agents to the
tumor sites (Adler &Dimitrov, 2012; Perche et. al.,
2012; Cirstoiu-Hapca, 2010). They can damage the
targeted tumor cells by releasing their chemotherapeutic agents locally. Another promising approach
is to target tumor cells by antibodies that trigger
immune response to destroy the cells by bodys
own defense mechanisms (Miller et al., 2002).
In recent years, targeting studies with surface
markers are engineered to target cancer stem cells
(Hu & Fu, 2012; Wicha, 2009). For a long time
researchers believed that every cancerous cell
has the potential to excessively proliferate and
regenerate a tumor in consequence of internal and
external factors that cause mutations. This model
has been called as stochastic model (Wicha et al.,
2006; C. Tang et al., 2007; Shackleton, 2010; Chen
et al., 2012). Numerous contemporary studies
indicate that the formation of tumor depends on
the differentiation of a relatively rare cell groupstermed as cancer stem cells (CSCs)due intrinsic
and extrinsic inducement (Hanahan& Weinberg,
2011; Clarke & Fuller, 2006; Dean et. al, 2005).
The functional capabilities of CSCs are associated
with normal stem cells such as the high ability for
self-renewal, the capacity to differentiate, active
telomerase expression, activation of anti-apoptotic
pathways, increased membrane transport activity and immense potential to migrate and evolve
(Wicha et al., 2006). Eliminating these cells is
very difficult by conventional methods due to
their immense resistance to chemotherapy and
radiotherapy. Consequently, CSC targeted therapies are escalating fast in literature, and they hold
great promise in cancer treatment.
464
Monoclonal antibodies have some limitations

even though they have effective potential in targeted therapies. The most important limitation is
that, the antibodies can be used primarily to target
surface molecules because they are large proteins
and they cannot pass the cell membrane easily.
Other main limitation is that different cancer
cells possess different markers, and same marker
can be found also on some healthy cells causing
significant toxic side effects. At present, there is
insufficient number of recognized markers and
deficient knowledge on them. Antibodies derived
from animals can sometimes cause immune reactions. Antibody fragments containing only the
variable region of the antibody can also be used
for active targeting for less immunogenicity. They
retain the specificity for the target, while they
result in less foreign body reaction or undesirable
interaction with other cells (Byrne et al., 2008).
Targeting Signaling Pathways

Signaling (or signal transduction) pathways are
the cascade processes existing in the cells to perform specific cellular tasks. For example, a cell
needs signaling molecules and pathways that are
activated by these molecules to grow and divide.
The signal molecules, including growth factors
and inhibitors, must be attached to receiver cells
surface receptors for activation of the signaling
pathway (Cho et al., 2007; Lee et al., 2013). When
the signaling pathway is activated, the information
that comes from receptor reaches into the cell, may
even be delivered to DNA. Activation of the signaling pathways leads to accumulation of proteins
that are inhibiting or activating the cell response.
The amounts of proteins which stop and start cell
division are under control in normal cells. On the
other hand, the amount of the activator molecules
and proteins that promote the cell proliferation
are increased in cancerous tissues. Therefore, the
inhibition of the aforementioned pathways has
a high potential for preventing the uncontrolled

proliferation of cancer cells (Kelleher et al., 2012).

The main purpose of targeting signaling pathways
are blocking a molecule in the pathway to stop
interaction with other molecules and thus blocking
the signal transduction (Leonarduzzi et al., 2010).
For instance, targeting of the Mitogen Activated
Protein Kinase (MAPK) pathway has a potential
for therapy since the dysregulation of this pathway
is observed in many cancer types (Wancket et al.,
2012). The MAPK pathway is controlled by a
complex cascade mechanism through extracellular
signals in normal cells. Disruption of this pathway
leads to increased cell proliferation, angiogenesis,
metastasis and increased cell survival, thus cancer
development (R. Xu et al., 2011). The biggest
problem in the MAPK pathway inhibition is that,
pathway has several signal molecules that activate
this pathway, and other signal molecules can
activate the pathway even if a specific molecule
is inhibited (Lugli et al., 2006). Several studies
have shown that more than one signal protein and/
or pathway must be targeted simultaneously. The
chemical agents are given to the patient orally or
intravenously in conventional methods, where
the agents can be inactivated before showing any
therapeutic effect since they are passing through
different compartments in the body such as the
gastrointestinal tract. On the other hand, drug
doses must be very high to show the desired effect
since the drug is distributed throughout the entire
body, and inhibition without targeting increases
the side effects (Diaz-Moralli et al., 2013). Nanotechnology is used to overcome these problems
as it allows the production of multifunctional
transport systems that can implement multiple
genetic and pharmaceutical agents (Nair et al.,
2010). The surface of the nanoparticles can be
functionalized with molecules that inhibit signal
pathways as well as with chemotherapeutic agents
targeting other schemes. The most effective treatment method will emerge when different targeting
systems are used in a single nanoparticle. There
are several options for pathway selection, including Notch signaling pathway and mitochondrial
signaling pathways to overcome drug resistance,

phosphoinositide 3-kinase (PI3K) pathway and
nuclear factor-Bto induce apoptosis in tumor
cells, transforming growth factor- signalling
pathway to attack promotion of tumor growth,
invasion and colonization of secondary organs,
phosphatidylinositol 3-kinase (PI3K)/Akt pathway
to suppress angiogenesis, etc. Recently, targeting
apoptosis pathways in cancer stem cells is also
under investigation (Signore et. al., 2013; Fulda
&Pervaiz, 2010)
Niche Targeting
The local microenvironment, or niche, of a cancer
cell plays important roles in cancer development
(Hu & Polyak, 2008). Thereby, targeting tumor
microenvironment is another commonly used
method for targeting studies for cancer therapy,
and particularly metastasis prevention (Joyce,
2005). The microenvironment of the cancer has
a direct effect on life and behavior of the cancer
cells. Cancer cells are fed by the niche and the
exchange of necessary molecules can be mediated
through this microenvironment. Extracellular
matrix (ECM), an important part of the cell niche,
contains components such as collagen I-III-IV,
decorin, hyaluronan,versican, fibronectin, laminin
and osteonect in that can contribute to developing
of tumor resistance to chemical agents (Ioachim et
al., 2002; Sung et al., 2005). For example, laminin
and fibronectin was shown to provide resistance
to apoptosis while collagen I-III-IV, versican and
osteonectin increase the proliferation of tumor
cells (Whatcott et al., 2011).
Desmoplasiais defined as the formation and
proliferation of fibroblasts and fibrous connective
tissue, especially in solid tumors. Desmoplasia
causes a significant increase in the synthesis
of ECM proteins (Walker, 2001), preventing
perfusion of chemotherapeutic agents. In order
to overcome the chemo-resistance, targeting of
these ECM proteins has a very high potential.
For example, hyaluronan, which is a component
465

of ECM and provides protection of connectivity

and rigidity of connective tissue, is over-produced
in tumor cells due to desmoplasia. Excessive hyaluronan concentration in ECM causes increased
interstitial fluid pressure and limits entrance of
any substance from outside (Whatcott et al., 2011).
Chemo-resistance may be reduced by targeting
hyaluronan via hyaluronansynthetase inhibitors
or through destruction of these molecules by
enzymes such as hyaluronase.
The slightest alteration -even a single amino
acid replacement- in the components of ECM
generates variations in the physicochemical properties of the tissue and also leads to changes in
the cellular phenotype and cell-matrix relations.
It has been shown in various studies that ECM is
needed to protect the structure and polarity of tissues. ECM components of cancer cells differ from
normal tissues. Abnormal ECM also influences
cancer development indirectly via influencing
stromal cells behavior including fibroblast cells,
immune cells and endothelial cells. These stromal
cells continue synthesis of the abnormal ECM
creating the appropriate microenvironment for
migration of cancer cells and formation of new
vessels(Y. Tang et al., 2005). ECM also has an
important role in reaching of the cancer cells to
surrounding capillaries and lymph nodes. Local
tumors constitute appropriate microenvironment
by imposing necessary changes in the ECM in
order to maintain their survival. Most of the tumor
cells die when they leave their microenvironment,
a type of apoptosis called anoikis. Therefore, it
has been a subject of curiosity how the metastatic
cancer cells can adapt and continue to live in other
parts of the body. Some studies specify that cancer
cells which have receptors for ECM components
exhibited a higher survival rate than those without
these receptors (Lu et al., 2012). Survival rates
of cancer cells can be significantly reduced by
targeting these ECM receptors. To prevent the
development and spreading of cancer, multiple
ECM components can be targeted with appropriate nano-tools.
466
Angiogenesis-Associated Targeting
All living cells in the body need oxygen and nutrients in order to survive. For this reason, all the
living tissues are nourished with capillary blood
vessels. Since the cell division in tumors is faster
than normal physiological conditions, the capillaries become insufficient for the expanded tumor
size. Cancer cells often secrete particular growth
factors tore-model the ECM and form a suitable
microenvironment to trigger the sprouting and
growth of new capillary blood vessels (Chatelain
et al., 2011). This phenomenon is defined as angiogenesis, and it is vital for tumor tissue to grow and
reach its maximum extent (Nishida et al., 2006).
The blood vessel cells (endothelium) only divide
about once every 3 years, and do not form new
capillaries in normal tissues when they are in a
quiescent state. However, they are activated within
the tumor site and they form new capillaries due to
these secreted angiogenic factors within (Liekens
et al., 2001).Once activated, these endothelial cells
begin to divide at an accelerated pace and also
secrete matrix metalloproteinases(MMPs) that
degrade the extracellular matrix (ECM) further
allowing other endothelial cells to migrate towards
the tumor (Petros&DeSimone, 2010).
A lot of molecules that promote endothelial
growth and the formation of new blood vessels are
convenient for targeting angiogenesis for cancer
therapy (Makrilia et al., 2009). In tumor tissues, the
balance between inhibitors and activators that are
present in normal tissues is disturbed; the numbers
of activators are increased and the formation of
new blood vessels is begun by rapid proliferation
of endothelial cells. Rapid vascularization also
helps metastasis, as the cancer cells find more
chance to enter the blood stream. Even when the
tumor is removed or destroyed by means of any
therapy, the cancer has high risk of recurrence
(and/or metastasis) due to these cancer cells that
had already entered the circulatory system. The
prevention of tumor vasculature before the tumor
reaches the critical size is crucial (Bjerkvig et al.,

2009). Developments in nanotechnology and discovery of molecules that are capable of inhibiting
angiogenesis have led to a boost in studies targeting angiogenesis. Some of these studies include
targeting molecules and pathways that cause the
alteration on the extracellular matrix structuring
which provides appropriate environment for the
formation of new vessels. Another approach is
targeting angiogenesis activators or sending angiogenesis inhibitors directly to the tumor site.
The most important criterion to achieve success
is detection of the primary tumor before reaching
critical size for metastasis. Nanotechnology offers
important opportunities for early diagnosis and
treatment of the tumor. There are many proteins
including vascular endothelial growth factor
(VEGF), basic fibroblast growth factor (BFGF)
and platelet-derived growth (PDGF) that promote
angiogenesis (Ishihara et al., 2002; Li et al., 2006).
It has been shown that the installation of the
nanoparticle delivery systems with the inhibitor
antibodies to these growth factors improve both
accumulation of the nanoparticles in the tumor
tissue and toxicity of the anti-cancer drug on
the tumor cells. The treatment of the tumor by
targeting multiple angiogenesis activators along
with other anti-cancer drug will ensure the most
effective cure.
5. TARGETING SCHEMES
The effectiveness of vehicles used in cancer
therapy is measured by their ability to eliminate
tumor cells without harming healthy tissues (Byrne
et al., 2008). Multi-drug resistance, exposure of
the entire body by the treatment and related side
effects, insufficient efficacy levels of the drugs
given orally or via systemic circulation due to
different parameters such as pH of different
body compartments, and the increasing number
of cancer patients force researchers to discover
alternative therapies. Nanotechnology, by enabling
specific targeting to the affected area, offers great
opportunities for the elimination of these problems. For instance, the targeted chemotherapeutic
agents with pH-sensitive nanoparticles may remain
intact until getting into the area of the appropriate
pH. Heat-sensitive nanoparticles enable elimination of unwanted cells by generating local heat
by external forces such as magnetic field when
they reach the desired location (Yu et al., 2012).
Although there is a large amount and variety of
nanodevices under investigation, the number that
received FDA approval and can be used in the
medical field is very small (Alexis et al., 2010).
Nanomaterials produced for cancer treatment
should have several additional properties such as
high selectivity, high penetration ability, multifunctionality, appropriate pharmacokinetic and
pharmacodynamics characteristics, therapeutic
and diagnostic properties, high biocompatibility,
causing low immune response, high physical and
chemical stability (Chopra, 2011; Rani et al.,
2012). Nanotechnological therapeutic devices
that are implementing several of these parameters
will provide glorious change in the development
of new cancer therapeutics (Swami et al., 2012).
There are three basic methods used to target
the nanoparticles to desired tumor sites; passive
targeting, active targeting and triggered targeting.
In order to develop the most efficient system,
these methods used for diagnosis and treatment
of cancer must be analyzed thoroughly, and combinations of the three methods may also be used
for improved success.
Passive Targeting
Owing to their size, NPs can accumulate in many
tumor tissues several times higher than other parts
passively via the enhanced permeability and
retention (EPR) effect (Maeda et al, 2009;Wu et
al., 2006). This accumulation is a non-selective
process that occurs due to leaky, underdeveloped tumor vasculature that allows macromolecules of a certain size range to accumulate in
the tumor(Figure 4).The gap junctions between
467

Figure 4. NPs can accumulate in many tumor tissues at several times higher rates than other parts of
the body passively via the enhanced permeability and retention (EPR) effect due to leaky, underdeveloped tumor vasculature
adjacent endothelial cells in tumor tissues are much

larger than those in normal blood vessels (Kazuo,
2011). The macromolecules can exit the circulation owing to the leaky vasculature, but remain
at the tumor site as a result of impaired lymphatic
drainage properties (Petros & DeSimone, 2010;
Wang & Thanou, 2010; Mousa & Bharali, 2011;
Sailor & Park, 2012).
There is no need for specific biomarkers in
passive targeting (Rani et al., 2012; Danhier et
al., 2010).The structure of the blood vessels supplying normal tissues is very tight and permeable
for particles smaller than 10 nm. In contrast, the
blood vessels that feed the tumor tissues lose their
tight structure and become permeable as their pore
dimensions become 100 nm 1 m (Emerich &
468
Thanos, 2006; Cole et. al., 2011). Using these

features, drug loaded nanoparticles can be sent
to tumor site by the circulatory system and accumulate without needing any cell surface markers;
thereby, sufficient amount of medication can be
sent to the tumor site without giving high doses
of medications to the patients (Kim et al., 2011;
Sailor & Park, 2012; Swami et al., 2012). The most
important points to consider in this method are the
size, surface properties and duration of exposure
in the circulation of the used nanoparticles. The
nanoparticle surface must be hydrophilic to be
protected from macrophages. If otherwise, this
can be achieved by modifying the surface with a
hydrophilic polymer. The polymer most widely
used for this purpose is poly(ethyleneglycol)

(PEG),called stealth polymer (Egusquiaguirre

et al., 2012). However, hydrophobic surfaces are
more suitable for penetrating into the tumor cells
and thus increasing efficiency and efficacy. The
dilemma may be solved by functionalizing the
nanoparticles with a copolymer which has both
hydrophilic and hydrophobic domains (Cho et
al., 2008).
It has been shown that positively charged
nanoparticles are easily taken up by cells, but
they cause immune reactions. Therefore, for
clinical applications, neutral or negatively charged
nanoparticles are preferred (Gratton et al., 2008).
Particles less than 5 nm are rapidly cleared
from the circulation through extravasation or renal
clearance. Nanoparticles that are smaller than
100 nm can be phagocytosed by the reticuloendothelial system cells (mainly by macrophages).
For larger particles sized in the range of up to
few micrometers, accumulation occurs primarily in the liver, the spleen and the bone marrow.
Spherical particles in100200 nm size range have
the highest potential for prolonged circulation
because they are large enough to avoid uptake in
the liver, but small enough to avoid filtration in
the spleen (Kim et al., 2011; Petros & DeSimone,
2010; Huile et al., 2011).
Nanoparticle degradation rate and duration
of exposure in the circulation should be appropriately engineered to increase the effectiveness
of treatment and in order for the concentration of
nanoparticles in the tumor site reach the desired
level.
In addition to leaky vasculature, the acidic
conditions of the tumor microenvironment can
also be exploited to deliver antitumor therapeutics selectively to the tumor tissues by designing
nanodevices to obtain a pH-controlled drug release
(Egusquiaguirre et al., 2012; Danhier et al., 2010;
Manchun et al., 2012; Shen et al., 2012).
Passive targeting has some limitations; it may
not show the same success in each cancer because
of the fact that the EPR effect varies depending
on the tumor site, tumor size and the patient, and
there can even be huge differences in different

areas of a single tumor (Jee et al., 2013). The
duration that the nanoparticles will stay in circulation intact (half-life)should be long enough and
their structures should not degrade or release the
therapeutic agent before reaching the target tumor
site (Oh et al., 2013).
Active Targeting
When low nonspecific binding and internalization of the drug by the cells is highly desirable,
the carrier system must be functionalized by
conjugation of receptors to specific ligands, like
monoclonal antibodies (mAb), short peptides
or RNA aptamers for active targeting (Figure
3).The ligands bind to receptors that are overexpressed on the surface of rapidly dividing cancer
cells. For example, many types of cancer cells
overexpress transferrin and folate receptors due
to the high metabolic demands generated by
rapid proliferation, and this makes conjugation
of transferrin, folic acid or antibodies to these
receptors a successful targeting approach for
engineered nanoparticles (Petros&DeSimone,
2010). If the targeted receptors activate endocytosis pathways and are present in excess on
the surface of tumor cells, the success of the
penetration of nanoparticles and thus the success of chemotherapeutic agents are increased
(Gary-Bobo et al., 2012).
Most obvious target is the surface markers
expressed by the specific cancer cells. There
is tremendous amount of literature trying to
identify specific markers for these cells (Hu
& Fu, 2012; Adler & Dimitrov, 2012). But the
main challenge of active targeting tumors is
that the cancer cells are often very similar in
characteristics to its surrounding healthy tissue,
and finding specific markers is troublesome.
Other popular approaches are to target tumor
vasculature via vascular endothelial growth factor receptor (VEGFR), v3 integrin, vascular
cell adhesion molecule-1 (VCAM-1), and to
469

target cell proliferation via human endothelial

receptors (HER), transferrin (Tf) receptors, and
folate receptors, instead of the tumor cells. As
these molecules have less phenotypic variations
and they are not specific to cancer type, they
are easier targets (Kumar & Li, 2001; Byrne et
al., 2008; Goel et al., 2011).
There are several biological barriers at the
cellular level that an engineered nanoparticle
must overcome. For example, the cell membrane
blocks diffusion of complexes larger than ~1
kDa. The blood-brain barrier (BBB) is one of
the strongest barriers in terms of delivery of
cancer therapeutics. The blood-brain barrier
is a physiologic obstruction to the delivery of
systemic chemotherapy to the brain parenchyma
and central nervous system (CNS), since endothelium in the CNS is distinctly different from
the vasculature found in the periphery. Passive
delivery does not work in CNS malignancies,
because the leaky vasculature is not present in
CNS, and only highly lipophilic molecules can
passively diffuse through BBB to reach CNS.
Therefore, nanodevices cannot be accumulated
specifically to tumor cells in the brain without
the active targeting (Zhan & Lu, 2012; Zhou et
al., 2012; Chen & Mitchell, 2012).
Concentration of surface ligands is another
parameter in active targeting scheme that affects
the ligands targeting efficiency. Higher ligand
densities are used as a method of increasing the
probability of nanoparticle interactions with cell
receptors (Wang &Thanou, 2010).
The immobilization of the ligands to the
nanoparticles is another important parameter
of concern since several ligands have three
dimensional, tertiary structures. If the immobilization is random, it can alter the ligands 3-D
configuration and reduce or completely block
its binding capacity to the target cell. Therefore
ligands need to be selected or engineered to bind
onto the nanoparticles in a site specific manner
in order for their activity to be retained.
470
Triggered Targeting
Certain nanoparticles can be activated by the
external forces for diagnosis and treatment after
given to the patients body owing to their unique
characteristics. This targeting type is named triggered targeting. Magnetic nanoparticles are used
commonly in this targeting scheme and magnetic
field is used as the trigger. Magnetic NPs given
into the body can be positioned to the desired
tumor site by applying external magnetic field
(Pradhan et al., 2010).
This method also includes triggering nanoparticles targeted with active or passive methods for
drug release with stimulus. Potential stimuli can
be electromagnetic or electric fields, pH, solvents,
heat, ultrasound, mechanical stress, irradiation
and chemical or biological agents. Nanodevices
which are sensitive to these stimuli can be reacted
by changing their chemical, electrical, optical, superficial or permeation properties (Schmaljohann,
2006). Drugs can be released from heat-sensitive
nanodevices within specific temperature ranges.
The systems that are designed for higher temperatures than the body temperature are used in this
method. After the accumulation of the nanoparticles in the tumor site, this area is heated locally
until it reaches the necessary temperature and drug
release is provided (May & Li, 2013; Liu et al.,
2010). The biggest disadvantage of this system is
that, the healthy tissue around the tumor can also be
damaged because this region reaches hyperthermia
temperature. Therefore, studies are being directed
to non-thermal treatment methods. One of the
most promising methods is photodynamic therapy,
where light-sensitive nanosystems are exposed to
irradiation after sent to tumor site. Drug delivery
system is activated by irradiation and the drug can
be released in a controlled manner (Derycke& de
Witte, 2004; Keall, 2011).Using ultrasound sensitive nanodevices is another promising approach
(Mo et al., 2012; Paliwal&Mitragotri, 2008).The
biggest advantages of triggered targeting are that
they do not need any invasive operation and they

potentially can overcome the problem of drug

resistance since they release the therapeutic agent
only in the desired region of the body (Rapoport
et al., 2004).
Triggered targeting systems mainly consist
of four steps;
1. Giving nanoparticles into the systemic circulation or locally to particular area,
2. Accumulation in the tumor site (actively or
passively),
3. Activation of the vehicles by external forces,
and
4. Processing to apoptosis of undesired cells
(Chatterjee et al., 2008).
Thermal therapies have been used to treat
cancer for a long time and are based on killing
cancer cells by heating them up to 45C (Martirosyan, 2012). There are basically two types
of thermal treatments; magnetic nanoparticlebased hyperthermia and photothermia. Inorganic
nanoparticles used in these systems can be utilized
for both tumor imaging and treatment. Gold NPs
are good contrast agents due to strongly absorbing and scattering capability in the near-infrared
(NIR) region of the radiation spectrum. Absorption
band can be adjusted by tuning gold nanoshell
thickness, changing shape and size of the NPs.
Recently, carbon nanotubes have been also used
in photothermal therapy due to their naturally
NIR absorption property. Long-wavelength laser
irradiation is applied in the body in photothermal
therapy and NPs (particularly gold NPs) absorb
irradiation and generate heat to kill cancer cells
(X. Huang et al., 2006). The efficiency of the
treatment depends on nanoparticle concentration
and laser power. In order to ensure death of cancer
cells without killing normal cells these two criteria
should be standardized (Lal et al., 2008).
First attempt to hyperthermia had been done
by Gilchrist and his coworkers in 1957 and iron
oxide particles were distributed in lymph nodes
of dogs and after exposure to alternating magnetic
field,5C increase in temperature was observed.

Magnetic nanoparticle-based hyperthermia is
based on the heating of nanoparticles under
exposure to alternating magnetic field by energy
absorbing. However main disadvantage of hyperthermia is that healthy tissues can also be affected
because of the nonselective heating (Hilger et al.,
2005; Cassim et al., 2009; Johannsen et al., 2010;
L. Zhao et al., 2011). Therefore, only cancer cells
must be heated by using selective systems such as
active targeting. The therapy also can be achieved
by not only killing cancer cells but also activating
anti-cancer immunogenicity with hyperthermia
(L. Zhao et al., 2011). Low pH and hypoxic
conditions are more effective for hyperthermia.
Hyperthermia has fewer side effects than
chemotherapy and radiotherapy. Hyperthermia
increases perfusion and oxygenation, therefore the
chemotherapeutic agents are taken into the tumor
cells easier and formation of free radicals may be
enhanced (Cassim et al., 2009). For this reason,
hyperthermia gives better results in therapy if it
is used in conjunction with chemotherapy and/
or radiotherapy (Martirosyan, 2012). Magnetic
properties of the particles, magnetic field strength,
frequency of oscillation, and cooling capacity of
the blood flow in the tumor site have effect on
the extent of temperature rise (Monica Tang et
al., 2009). However, heating rate and time should
be controlled to avoid damaging of healthy cells.
6. NANOPARTICLE-MEDIATED
GENE THERAPY
The main objective in cancer gene therapy is the
development of efficient, non-toxic gene carriers
that can encapsulate and deliver foreign genetic
materials into cancerous cells. This genetic material can inhibit the expression of a specific defective gene or express a normal gene. The classical
media for gene delivery is viral vectors, but these
have great disadvantages in terms of their safety,
immunogenicity, and limited capacity of carry-
471

ing transgenic materials. Nanotechnology has

enabled the development of new, non-viral vectors for gene therapy like cationic polymers such
as poly(ethylenimine) (PEI) and poly (L-lysine)
(PLL), cationic peptides and cationic liposomes.
Yet, these non-viral vectors are less efficient than
viral vectors, but they have great promise for
improvement (El-Aneed, 2004).
There are four major problems to be solved for
success of cancer gene therapy (Scanlon, 2004):
1. Identification of key target genes critical for
disease pathology and progression;
2. Identification of the appropriate therapeutic
gene to inhibit disease progression;
3. Optimal trans-gene expression for suppressing the target gene;
4. Delivery of therapeutic product to the target
tissue at an efficient dose.
Small interfering RNAs (siRNAs) are new
tools for gene therapy. They silence the expression of specific target genes by mediating RNA
interference (RNAi) in mammalian cells. They
have demonstrated great potential in cancer
therapeutic applications caused by abnormal gene
over-expression or mutation (Wang et al., 2010).
Chemical modifications as well as nanoparticle
conjugation of siRNAs, aptamers, ribozymes,
antisense (AS) oligonucleotides (ONs), and microRNAs (miRNAs) are shown to improve the
pharmacokinetic and pharmacodynamic properties, reduce immunogenicity, increase target affinity and specificity, decrease susceptibility to
nuclease degradation (Singh et al., 2010; Zheng
et al., 2012; Lam et al., 2013; El-Aneed, 2004).
As in previous schemes, tumor vasculature is
another viable target for gene therapy simply on
the basis of anatomical accessibility. Particularly,
combination of transductional and transcriptional
targeting should allow a higher selectivity against
tumor vasculature. Antiangiogenic molecules
such as angiostatin and endostatin regulating
proliferation of normal endothelium are suitable
472
as therapeutic mediators. Several cytotoxic gene

products like ricin and diphtheria toxin can also
be targeted and may be used to destroy tumor
vascular endothelium directly (Bazan-Peregrino
et al., 2007).
7. FUTURE PERSPECTIVES
Nanotechnology is beginning to allow scientists,
engineers, and physicians to work at the cellular
and molecular levels to produce major advances
in life sciences and healthcare. Nanotechnology
holds the promise of novel and more effective
treatments for serious human health issues. Utilisation of nanoparticles in diagnosis and treatment
is becoming widespread, and these particles are
en route to become indispensable in the medical
arena. The diagnosis and the treatment of diseases
can be combined by nanoparticles (theranostics).
This combinatorial approach provides point of
care cure without needing repeated treatment
steps such as biopsy which damage the patient
physiologically and psychologically. Although
many nanodevices and production strategies have
been produced to date, the challenge still remains in
creatively integrating the different functionalities
into single full-featured tools.
Another challenge is that, there are no reliable
control mechanisms or standards of nanoparticles biocompatibility. The results may differ
from method to method or even from laboratory
to laboratory. To achieve the implementation
of nanoparticles in clinical or preclinical level
studies, international agencies must accelerate
focused work on the development of in vitro and
in vivo validation assays as well as standards for
production of nanodevices that possess desired
properties.
At present, the main cell types that are targeted
in the tumor vasculature are endothelial cells
and stem cells. However, tumor vasculature also
includes pericytes and smooth muscle cells that

could be important targets for nanoparticle based

drug therapies.
Like normal stem cells residing in a stem cell
niche that maintains them in a stem-like state,
CSCs also require a special microenvironment
to control their self-renewal and undifferentiated
state. The CSC niche is likely to be the one of
the most compelling targets in the nanoparticle
based treatment of cancer.
Advanced delivery strategies are critical to fully
harness the power of RNA and the flexibility of
RNA-based therapeutics. The future prospects of
RNA-based drugs and gene delivery will require
biochemical refinements to minimize off target
toxicity and immunogenicity.
Each type of nanoparticles has its own distinguishable advantages and disadvantages.
Utilisation of individual characteristics of different
types of nanoparticles will help improve multifunctional nano-theranostics and development of
personalized medicine. Every person has a unique
metabolism, genetic background and health history, and is affected differently by the internal and
external factors. Therefore, even if each disease has
same or similar symptoms, it progress diversely
in each individual, and diagnosis and treatment
must be performed on the basis of patients own
information. This difference is more prominent
in diseases such as cancer caused by bodys own
cells mutations and differentiation. Thanks to
nanoparticle based personalized approaches it will
be possible to develop patient-specific therapies
in near future. It is anticipated that the patients
own antibodies can be used and concentrations
of drugs and targeting systems may be adjusted
according to the individual needs.
The production of controlled, uniform and
functionalized nanoparticles and systems are
developing very quickly. Comprehensive investigations have been made to overcome existing
problems such as toxicity, non-biodegredibility,
insolubility, non-effective targeting and more
promising results are obtained each day. Future
nano-systems will include the necessary tools
for both diagnosis and treatment, and they will

be activated from outside in order to ensure local
and specific treatment. Thus, using unnecessary
amounts of toxic chemicals will be prevented.
Advanced nano-systems can be engineered to
determine pathogen microorganisms and harmful cells that are in motion and they can be incorporated protective and preventive properties
supplementary to the bodys own immune system.
With an ideal hybrid nano-device, it may be
possible to treat different diseases simultaneously
and effectively without causing any adverse effect on the patient by efficiently controlling the
release rate and concentration of the therapeutic
agents. Improved sensitivity and selectivity will
allow diagnosis of the disease at a very early stage,
or even reveal the disease before it commences.
To attain these goals, research groups must be
multidisciplinary so that engineers, doctors,
fundamental scientists and materials scientists
can collaborate.
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Cancer: A serious disease generally characterized by uncontrolled proliferation of cells whose
metabolic activities are disrupted.
Conventional Therapies: Used to describe
traditional cancer treatment methods used in
clinic today.
Gene Therapy: A technique that uses genetic
modification to treat or prevent disease.
Nanoparticle Drugs: Drugs or drug delivery
systems, which are approved and/or under phase
trials.
Nanoparticle Toxicity: The possible threats
of nanoparticles to the patients.
Nanoparticle: A small particle whose two or
three dimensions are between 1 100 nm.
Targeted Therapy: A relatively new method
for the treatment of diseases by targeting specific
organs, tissues, cells, and even biomolecules.
491
492
Chapter 19
Understanding the Numerical

Resolution of Perturbed
Soliton Propagation in
Single Mode Optical Fiber
Nawel Boumaza
Tlemcen University, Algeria
Tayeb Benouaz
Tlemcen University, Algeria
Souraya Goumri-Said
ABSTRACT
The authors solve the propagation soliton perturbation problem in a nonlinear optical system based on
a single mode optical fiber by introducing Rayleighs dissipation function in the framework of variational approach. The adopted methodology has facilitated the variational approach to be applied on
a dissipative system where the Lagrangian and Hamiltonian are difficult to solve. The authors model
the propagation in a nonlinear medium by using a nonlinear Schrdinger equation (NLSE). This is a
mathematical model used to describe the optical fiber. The chapter is focused on the propagation of
perturbed solitary waves in single mode fiber.
INTRODUCTION
Optical fiber devices communications are now
an essential value to human life progress. The
number of system users canceled and the amount
of information conveyed is increasing (Calvez,
2001). The invention and development of ampli-
fiers / regenerators erbium-doped fiber (Agrawal,

2007), and optical directional couplers has been
the revolution in telecommunications fiber technology (Svalgaard, 1997; Chiang, 1995). This
new all-optical technology, which combines the
principle of issue stimulated in erbium with the
guiding properties of the fiber, allows, without the
DOI: 10.4018/978-1-4666-5824-0.ch019

Understanding the Numerical Resolution of Perturbed Soliton Propagation
conversion steps optical-electronic and electronicoptical increase rates of transmission (Romagnoli,

1992). The fiber can be an optical amplifier, an
optical switch converter wavelength, solitons in
a source, a compressor noise, a filter, an optical
memory..., where the total internal reflection is
the basic phenomenon responsible for guiding of
light. Although most applications of fiber only use
their linear characteristics, nonlinear effects have
been studied since 1982 and can lead to all-optical
switching among other applications (Chu, 1993,
Akhmediev, 1993). The characteristics of soliton
propagation in a nonlinear guided medium have
evoked immense interest when subject to perturbation or to various forms of pulse degradation
evolving through non conservative and conservative perturbing processes.
As with any occupational hazardous phenomena, in telecommunication, the control technology
is targeting the reduction of the noise to acceptable levels by action on the devices parameters.
Such action involves the implementation of any
measure that will reduce noise generated, by reducing the noise transmission through the air or
through the structure of the fiber device. In fact,
the best approach for noise hazard control in the
optical fiber is to eliminate or reduce the hazard at
its source of generation, either by direct action on
the source or by its confinement. In certain cases,
the solution may be found in a combination of the
cited measures which by themselves would not
be enough to avoid the noise effects. To achieve
a part of the required reduction through environmental measures, it is possible to complement
them with protection measures such as adding
protection cladding for only few hours. The characteristics of soliton propagation in a nonlinear
guided medium have evoked immense interest
when subject to perturbation or to various forms
of pulse degradation evolving through non-conservative and conservative perturbing propagation
processes. In real physical systems, two-photon
absorption, gain dispersion, higher order group
velocity dispersion, noise control filtering and
modulation, two-soliton interaction, higher order

nonlinearity, intrapulse Raman scattering (IPRS),
and self-steepening are considered to be the prime
perturbing effects on a propagating optical pulse.
The dissipative effects on the pulse are expected
due to the influence of TPA, GD, and filtering,
whereas in case of other perturbations, the pulse
energy is likely to be conserved mathematically
in [8], the generalized Kantorovitch method has
been introduced in order to solve the extended
nonlinear Schrdinger equation (NLSE) which
describes the nonlinear loss and/or gain. Currently,
the concept of this technique is frequently being
associated with different perturbation problems
(Akhmediev, 1993, Chu, 1995). In all the described
techniques, the prime objective is to evaluate the
differential equations that predict the evolution
dynamics of different pulse parameters under various perturbations. The perturbing effects which
are associated with a nonlinear pulse evolution
have been solved mostly through variation al
formalism. In an attempt, we try to evaluate the
perturbing effects on soliton pulse parameters by
introducing Rayleighs dissipation function (RDF)
with a similarity to a mechanical system where
the frictional dissipative problems are solved by
using RDF (Wang, 2006- Marcuse, 1982). Several
Numerical simulations based on the Split-Step
Fourier (SSF) were used to simulate the evolution
of solitons in single mode optical fiber. Before
presenting the detailed resolution of NLSE, we
recall here some basics on how to calculate the
number of modes in optical fibers.
MODAL ANALYSIS: HOW TO

CALCULATE THE NUMBER OF
MODES IN AN OPTICAL FIBER
The optical fiber is very thin transparent thread
that has the ability to conduct light and is used in
terrestrial broadcasting and oceanic data. Cylindrical, it is composed of a core refractive index
493

Figure 1. Optical fiber
n1 in diameter, surrounded by a cladding of index

n2, all wrapped in a plastic coating (see Figure 1).
The principle guiding light in an optical fiber is
based on a series of total reflections of light rays
at the interface of core-sheath, a condition that
will be respected if n1 is greater than n2.
A multimode planar waveguide is a conventional dielectric waveguide. Thissystem can be
outlined from a three-layer model (see Figure
2), with respective indices n1a, n1b and n1a. Such
a system combines two approaches: modal and
geometrical optics. From geometrical optics point
of view, guidance of the signal in an optical fiber
is a problem of propagation of the light beam in a
three-layer system, already treated in the literature
(Yariv, 1973).
Our system is a symmetrical waveguide,
because the two extreme media have the same
refractive index n1a. We have two interfaces 1-2 and
2-3, where the propagation of radiation depends
on the value of the angle , which is other than
the complementary to the angle of incidence at
each interface. This angle is related to the angle
of incidence via the relationship of
=
and check also
494
Figure 2. Propagation of a light beam in a planar

waveguide with three layers.
cos
n1a
.
n1b
These angles, , must always check the condition of total reflection at the two interfaces,
which means that the light is confined in the
middle layer, (i.e. the core of the waveguide). The
above conditions are necessary for the existence
and propagation of a guided mode in the fiber.

The propagation is governed by an exponential

of the form exp(iy), when the incident wave
propagates in the direction y, and is the propagation constant related to the angle by
= n1b k cos . In order to secure the existence
of a mode in the optical fiber, its effective index
must satisfy the relation:
n1b ni n1a
(1)
with ni = n1b sin i = n1b sini

The minimum value of for a guided propagation, also known as a cut-off conditionmode
is equal to n1ak. However, and can only take
discrete values [15]. Taking into account the reflections that appear on the interfaces of the guide
zone 1, the resonance condition can be expressed
as follows:
2 Dkn1b sin 12 13 = 2N
(2)
where 12, 13 are the phase shifts which occur at

interfaces 1-2(x=-D) and 1-2(x = 0), respectively.
In the TE polarization, where the electric field is
normal to the plane of incidence, the phase shifts
are given by:
12 = 13 = 2tan
1/ 2
2 n12a k 2
2 2

n1b k 2
(3)
We introduce new variables p, q and r as follows:

p 2 = 2 n 2 k 2
1a
q 2 = n 2 k 2 2
1b
2
2
r = n12a k 2 = p 2
(4)
Then injecting these values in Equation (2)

we obtain the values of the Eigen value equation
(Yariv, 1973) as follows:
tan ( Dq N ) =
q ( p + q)
q2 pr
where N=0,1,2,
This eigen-value equation determines the possible number of eigen-modesin the guided fiber.
As we can see, this number depends essentially
on refractive indices and the size of the guide (i.e.
fiber diameter). In order to have the number of
possible eigen-modes in the guide, the previous
equation can be expressed as a function of the
refractive indices of the three layers as follows:
tan Dkc n12b n12a
1/ 2
1/ 2
n 2 n12a
N = 12b

n + n 2
1b
1a
where kc is the wave vector corresponds to the

cutoff condition. We also define a normalized
frequency
=
Dk 2
n n12a
2 1b
1/ 2
The number of modes always takes integer values

and is given by:
1/ 2
2
2
1
1 n1b n1a

M = 2 tan 2

2
n1b + n1a
integer
(5)
THE STUDY OF SOLITON

PROPAGATION IN A MONOMODAL OPTICAL FIBER
In order to understand the nonlinear phenomena
in optical fibers, it is mandatory to consider the
theory of electromagnetic wave propagation in
dispersive nonlinear media. The objective of this
section is to obtain a basic equation that governs
495

propagation of optical pulses in single-mode fibers

(Ramos, 1999, Jensen, 1982).
The description of the propagation of solitons
in an optical fiber is modeled by the following
equation, called nonlinear Schrdinger NLSE:
2
A ( z, t )
2
2 A ( z, t )
+ j
+ A ( z, t ) A ( z, t ) = 0
2
2
z
(6)
It is a nonlinear partial differential equation, for

which it is very difficult to obtain the analytical
solution. Then for the case of anomalous dispersion
( < 0) the following hypothesis are considered:
z: is the distance of propagation and t: time delayed (to take into account the speed of
propagation).
A(z, t): is the complex envelope of the optical field.
2: Chromatic dispersion of order two.
: The nonlinear coefficient of Kerr.
2
A (t ) A (t, z ) is the self-phase modulation term

induced by Kerr effect (Intrachat, 2003).
In a nonlinear transmission system, the ideal
soliton communication becomes restricted due
to several physical mechanisms. Amplified
spontaneous emission (ASE)-induced timing
jitter is one of the dominating factors among
them. In practice, it is necessary to introduce an
amplification mechanism to compensate for loss
for long-distance transmission. However, coherent amplification is always accompanied by the
generation of ASE noise. The generated noise
added with soliton field results in a random shift
of soliton carrier frequency with corresponding
change in its velocity. Such random speed change
produces a shift in the temporal pulse position
leading to GordonHaus timing jitter (Gordon,
1986). In frequency domain control, optical filters
are used to block the ASE noise, where a periodic
amplitude and/or phase modulation is applied in
time domain control, having the period which is
496
same as the bit period, to the soliton pulse train.

During the filtering process, some soliton energy
is always lost (Haus, 1993). Apart from the energy,
other different parameters like amplitude, temporal
position, frequency,
The NLSE equation including the effect of
filters is expressed by the following dynamics:
i
2
u 1 2u
2 u
+
+
u
u
=
i
u
+
i

2 2
2
(7)
We make the following assumptions:

j
2
A( z, t ) 2 2 A( z, t )
+
+ A( z, t ) A( z, t) = 0
2
2
z
(8)
A ( z, t ) 2 A ( z, t )
2
j
+ 2
+ A ( z, t ) A ( z, t ) = 0
2
2 3
z
2
2
22 3
(9)
2
1
1 v ( z, t ) 1 1 v ( z, t )
+
+ 2 3 v ( z, t ) v ( z, t ) = 0
22 3
j
z 2 2
2
(10)
and we set
1 v ( z, t ) 1 1 v ( z, t )
+
2
z 2 2

2
1
+ 2 3 v ( z, t ) v ( z, t ) = 0
2
(11)
A ( z, t ) 2 A ( z, t )
2
= 0
j
2
+
A
z
,
t
A
z
,
t
+
(
)
(
)
z
2
22 3
2
22 3
(12)
v ( z, t )
2 v ( z, t )
1
3
+ 2
2 j
2
z
+ v ( z, t ) v ( z, t ) = 0
(13)

2
1
1 v ( z, t ) 1 1 v ( z, t )
+ 2 3 v ( z, t ) v ( z, t ) = 0
+
22 3
j
2
z 2 2
2
(14)
In frequency domain control, optical filters are

used to block the ASE noise, where as periodic
amplitude and/or phase modulation is applied in
time domain control having the period which is
same as the bit period to the soliton pulse train.
During the filtering process, some soliton energy
is always lost (Haus, 1993). Apart from the energy,
other different parameters like amplitude, temporal
position, frequency, may affect the propagation
of the soliton.
FREQUENCY DOMAIN
FILTER SYSTEM
(16)
(17)
We set also the following considerations:
(20)
(21)
R
L L L
+
= 0

+
r
z ri ri ri

z

z
(22)
(23)
+ v ( z, t ) v ( z, t ) = 0

q 3
Lg = 2
+ + 2
z
z 3
+ j
2 23 v ( z, t )
(24)
2
3
1 2 v ( z, t )
+
j
z
2
2
2
+ v ( z, t ) v ( z, t ) = jv ( z, t )

(18)
2
2 2 A ( z, t ) 2 22 2 A ( z, t )
+
j
2 2 3
z
2
223
2

2
1
+ 2 3 2 A ( z, t ) 2 A ( z, t ) = 0
2
(19)
2
1 v ( z, t ) 1 1 v ( z, t )
+
2
z 2 2

2
1
+ 2 3 v ( z, t ) v ( z, t ) = 0
2
2
2
2 A ( z, t )
A
z
,
t
A ( z, t ) = 0
+
+
(
)
2
2
1 = 2
22 v ( z, t )
We make the following calculations:

A ( z, t )
2
4
j
1
1
AAZ A AZ + A A
2
2
2
v ( z, t )
2
+ 1 3 v ( z, t )
22 j
z 2 2 2
The NLSE equation including the effect of filters

is expressed by the following dynamics:
2
u 1 2u
2u
i
+
+
u
u
=
i
u
+
i

2 2
2
L=
(25)
If we consider parameters of the perturbation

created due to the use of a filter in the optical
fiber, we introduce the new following parameters:
p j =
q

, ,
,
z z z z
1 = 22 4
497

We are aiming to evaluate the perturbation

created due to the use of a filter exploiting the
proposed RDF technique. The NLSE including
the effect of filters may be expressed by the following dynamics:
2

= 21 a 2q2
6
z
2
q = q
a
z
32

= 0
z
1 2
2q
= + 2 a
2
32
z
(26)
(27)
R = j1 AAZ A AZ j1 A
AZ A
AZ
(28)
where, L, and R, are the Lagrangian, Rayleighs
dissipation function (RDF), respectively. Here,
the suffixes represent corresponding derivatives.
The algebraic modification to project the extended
NLSE as a frictional problem suggests the idea to
introduce the RDF analogically in EulerLagrange
(EL) equation in order to solve soliton perturbation problems. The generalized EL equation in
classical form(Wang, 2006- Marcuse, 1982) is
written as follows:
498
where L, R, q j , and q j are the Lagrangian, Ray-
L L L
R
+ = 0
+
z AZ A A
AZ
(30)
The generalized EL equation can be written

in the explicit form as
where A, , and represents complex field

distribution of the soliton, normalized excess gain
coefficient, and curvature of the transmission peak
of the filter per unit length, in the optical fiber
respectively. Having the dynamics of the pulse
envelope, the corresponding Lagrangian and RDF
may be constructed as:
(29)
leighs dissipation function (RDF), th generalized

coordinate, and its time derivative, respectively.
2
4
j
1
1
L=
AAZ A AZ + A A
2
2
2
R
d L L
+
=0
t q j q j q j
R
L L L
+
= 0
+
z ri ri ri
r
i
z

z
(31)
where the index (i) varies between 1 and 2, r1 = A
and r2 = A . The construction of L and R are
performed in such a way that the governing equation (2) may be regenerated by using a generalized
(EL) equation. Now we introduce the following
ansatz (Sen, 1987) which is basically the solution
of unperturbed NLSE:
A ( z, ) = ( z ) sec h ( z ) q ( z )
exp i ( z ) ( z ) q ( z )
)}
(32)
where ( z ) , q ( z ) , ( z ) , and ( z ) represent

amplitude, temporal position, phase, and frequency, respectively, and all are allowed to vary
with propagation distance. The reduced Lagrangian and RDF are now explicit functions of different pulse parameters and their derivatives and
finally get


q 3
Lg = 2
+ + 2
z
z 3
(33)

q
Rg = 41
+
z
z

q 1
41
+ 2 + 2
z 3
z
8
+ 13
3
z
(34)
(35)
)( AA
A AZ
(38)
Inserting the given ansatz (32) and reducing

it accordingly, we get
Using (31), the dynamics of four parameters

may be developed as
When a represents modulation strength per

unit distance. The reduced Lagrangian of this
system will have the same mathematical form as
represented in (36). However, RDF should have
a modified form and may be stated as follows:
q

, ,
,
z z z z
+
2
2
=
1
1
z
3
q
=

z

4
2
= 1
3
z
1 2
= + 2
2
z
A ( z, t )
R = j 1 a 2
If we consider: p j = , q, ,
p j =
2
2
1 A ( z, t )
+ A ( z, t ) A ( z, t )
2

z
2
2
= j1 A ( z, t ) j a A ( z, t )
(37)
The reduced Lagrangian and RDF are now

explicit functions of different pulse parameters
and their derivatives. Next, exploiting the reduced
EL equation, one can construct the four equations of motion corresponding to the four pulse
parameters as follows:
Lg Lg Rg
+
= 0
z p j p j
p j
does not influence the temporal position directly.

It may be noted that the soliton perturbation
theory [5,6] predicts the same set of expressions
in a different way.
Now we concentrate on the problem related to
time domain control. Soliton propagation under
the effect of synchronous amplitude modulators
is normally modeled by

q
Rg = 41
+
z
z

2 q
q 2
2

+2 a
+ + 2q
3 z
z
z
(39)
(36)
The reduced Lagrangian and RDF are now

explicit functions of exploiting the reduced ELS
equation as above we generate a set of four coupled
differential equations revealing the dynamics
of the different pulse parameters influenced by
modulation:
Examining the set of expressions (36), it can be

seen that not only the amplitude but the frequency
is also controlled by the filter. However, the filter
499

2q2
2
=
1
a
z
6
2
q
q
= a 2
3

z

= 0
z
1 2
2q
= + 2 a
2
32
z
(40)
APPLICATION AND DISCUSSION

OF SIMULATION RESULTS
The numerical method Split-Step Fourier (Agrawal, 2001) was employed to simulate the evolution
of solitons in single mode optical fiber. In order
to plot equations of the perturbed system (36) and
(40) we used the Runge-Kutta Method to solve
differential equations numerically, well known by
ODE(45) in MATLAB. We consider a single mode
optical fiber length in pure silica of length L =
11835m and width 140 m, where the parameter
value of group velocity 2 = -10.2 ps2 / km at the
wavelength = 1.55m, = 0.05, = 0.05, with:

1 = 0.1 and 1 = +0.8 .
The evolution of different parameters of perturbed soliton are shown for filter control system
with 1 = 0.1 and 1 = +0.8 . The initial
values of the parameters are taken in the simulation as = 1 , q = 0.5 , = 0.5 , and = 0 .The
value of nonlinear coefficient is used = 2W-1km-1.
The input pulse is given as U (0, t) = N sech (t),
with N = (1) is the pulse nonlinear solitary fundamental.
We display in Figure 3, the temporal position
of the perturbed soliton. We are displaying also
its amplitude in versus the propagation distance
as well as a 3D presentation of this amplitude in
the inserts.
We note from these three figures that the soliton
moves unperturbed in the considered dispersion
medium without being deformed, it suffers no
distortion during propagation. Therefore, the
soliton has the wonderful property of spread in
a dispersive medium without changing its shape
(see Figure 5). Furthermore, it is noted that the
Figure 3. Temporal position of perturbed soliton and its amplitude (in the insert), for different pulse
parameters are shown for filter control system with 1 = 0.1 and 1 = +0.8
500

Figure 4. Frequency and pulse of perturbed soliton versus the propagation distance (m). In the second
insert, the intensity from NLSE package (Agrawal, 2007) for comparison
intensity of the pulse after propagation decreased

but it maintains the same initial shape.
Figures 3 and 4 show that the amplitude increases as a function of the distance spread with
a change in the time position. The phase and frequency are also influenced, while the frequency
gradually decreases as a function of the distance of
propagation, the phase increases with the distance.
It shows that adding of the filters is very beneficial
and greatly reduces the fluctuations of the phase.
The simulation results for another case of
perturbed solution propagation are shown in the
following Figures 6, 7 and 8 respectively. Where
the evolution of different parameters of the perturbed soliton are shown for modulator control
system with 1 = 0.1 and a = 0.05 . The
initial values of the fiber parameters considered
in the simulation are = 1 , q = 0 , = 0.1 , and
= 0.
Figure 5. Three-dimensional evolution of an

unperturbed fundamental soliton in single mode
optical fiber
501

Figure 6. Temporal position of perturbed soliton and its amplitude (in the insert), for different pulse
parameters are shown for filter control system with 1 = 0.1 and 1 = +0.8
Figure 7. Frequency and pulse of perturbed soliton versus the propagation distance (m)
These figures show that the pulse has changed

compared to the first example. The envelope amplitude has decreased but keeps the same initial shape.
Figure 8 represents the evolution of a perturbed
soliton, which exhibits a different shape relative to
the unperturbed soliton. We note from these results
that the perturbed soliton moves in this scattering
medium with a deformation compared to the motion of perturbed disturbed soliton. However, it
502
suffers no distortion during propagation. We may

notice that in the area of the temporal modulation
frequency remains unchanged, but the three other
parameters of soliton (i.e. amplitude, the time
position and phase) are influenced. The increase
in amplitude is controlled, in the presence of the
modulation but the temporal position is explicitly
influenced the field of temporal modulation.

Figure 8. Three-dimensional evolution of a fundamental perturbed soliton in single mode optical

fiber about the solution of (36)
problems. Using the methodology, we obtained

different dynamic equations of associated pulse
parameters which are influenced by perturbations
originated due to filtering,
Finally concluded, nonlinear effects have
been studied throughout the resolution of NLSE
equation for propagation of soliton under perturbation in a single mode fiber. It is important to
notice that the introduced perturbation (noise) is
limiting the performance of solitons in optical
communication, leading the consideration of the
filters as a unique solution. These filters have been
considered in the non-linear equation to see their
impact on the shape, amplitude and speed of the
soliton propagation.
CONCLUSION
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NLSE: It is a nonlinear variation of the
Schrdinger equation. It finds application in area
of light propagation of light in nonlinear optical
fibers and planar waveguides.
Optical Fiber: A flexible and a transparent
fiber made of silica or plastic, slightly thicker than
a human hair. It can function as a waveguide, or
light pipe.
Solitons: It is a self-reinforcing solitary wave
or a pulse that maintains its shape while it travels
at constant speed.
505
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About the Contributors
Mohamed Bououdina is the Director of the Nanotechnology Centre at the University of Bahrain.
He obtained his Ph.D. in Condensed Matter Physics, University Joseph Fourier in 1995. He worked at
various places including University of Nottingham and Queen Mary University of London, National
Institute of Materials and Chemical Research, Japan, Institute Neel, France, etc. He is co-author of
more than 140 papers published in international journals and contributed to some book chapters. He is
associated editor in numerous international journals such as International Journal of Hydrogen Energy,
International Journal of Nanoscience, etc. He supervised and co-supervised MSc and PhD students. He
was awarded numerous research grants and had extensive research projects with industry. He has broad
areas of expertise including Renewable Energy, Advanced Materials, Nanoscience and Nanotechnology,
Nanomaterials for Spintronics, Carbon Nanostructures, Neutron Diffraction, Nanoparticles for Biomedical Applications, Biomaterials, Functional Nanoparticles, Nanostructured Intermetallics, etc.
J. Paulo Davim received his PhD degree in Mechanical Engineering from the University of Porto in
1997 and the Aggregation from the University of Coimbra in 2005. Currently, he is an Aggregate Professor at the Department of Mechanical Engineering of the University of Aveiro. He has more 25 years of
teaching and research experience in manufacturing, materials and mechanical engineering with special
emphasis in machining and tribology. Recently, he has also interest in sustainable manufacturing and
industrial engineering. He is the Editor-in-Chief of six international journals, guest editor of journals,
books editor, book series editor, and scientific advisory for many international journals and conferences.
Presently, he is an editorial board member of 20 international journals and acts as reviewer for than 70
prestigious ISI Web of Science journals. In addition, he has also published in his field of research as
author and co-author more than 40 book chapters and 350 articles in journals and conferences (more
180 articles in ISI Web of Science, h-index 25+).
***
Brahim Assa received the B.Sc. and M. Sc. degrees in electrical engineering in 1998 and 2002,
respectively, and a Ph.D. degree in materials and Energy science from the University of Quebec, Institut
National de la Recherche Scientifique: Centre Energie, Materials and Telecommunications, Canada,
in 2010. His research deals with the controlled synthesis of carbon nanostructures and the investigation of their electrical and optical properties for electronic applications. Actually, he is working with
MPB Technologies Inc. at the department of Smart Materials and Sensors for Space missions. He has
authored more than 50 refereed journal papers and holds one patent, and has participated in more than
60 international conferences. He is a regular referee in more than 20 scientific journals. Dr. Brahim has
numerous international awards, prizes and fellowships including the prestigious NPI award from European
space agency. Part of his work was selected in the best TOP-10 scientific discovery in Quebec (2009).
Usman Ali Rana has received his M.S degree in Chemistry from Punjab University, Pakistan, in
2001. After working on the position of lecturer in chemistry at various government and semi-government
institutions in Pakistan, he later went to Monash University, Australia in 2008 and successfully completed
his PhD in the discipline of Materials Engineering in 2012 under the tutelage of Prof. Maria Forsyth and
Prof. Douglas. R. MacFarlane. His PhD work mainly focused on the development of proton conducting
organic ionic liquid and plastic crystal based electrolytes for H2/O2 Fuel Cell applications. After working
for 6 months as research associate with Prof. MacFarlane, he joined Sustainable Energy Technologies
(SET) center, at King Saud University as an Assistant Professor in October 2012. He authored over
20 research publications. His current research interests concerns the electrolytes and electrocatalysts
developments for the advanced energy storage and conversion applications.
Zahid Ali has received his M.S degree in material engineering from the Pakistan Institute of Engineering and Applied Sciences (PIEAS), and PhD from Sungkyunkwan University, South Korea. Currently,
he is working senior scientist in National Institute of Lasers and Optronics, Islamabad, Pakistan. He has
worked with Samsung, Electronics, Korea for more than three years for the development of functional
nanomaterials for efficient energy storage and devices. In this regard, he has several scientific and technological breakthroughs in this field and published more than 10 international publications.
Salim Barbhuiya is a Lecturer in the Department of Civil Engineering at Curtin University of
Technology, Australia. He completed his Bachelor degree in Civil Engineering from National Institute
of Technology Silchar, India (1999), Masters degree in Structural Engineering from Asian Institute of
Technology, Thailand (2005), and obtained his PhD in Structural Materials from Queens University
Belfast (2009). From 2009 to 2012, Dr Barbhuiya worked as a Post-doctoral Research fellow in three
different UK Universities namely Queens University Belfast, University of the West of Scotland and
Loughborough University. In September 2012, Dr Barbhuiya joined Curtin as a Lecturer and his research at Curtin is on Cement and Concrete Science with a key emphasis on the use of nanotechnology
to characterise and improve their physical and durability properties.
Ece Bayir is an MSc Student in the Department of Biomedical Technologies at the Ege University
in Izmir, Turkey. She completed her undergraduate studies in the Department of Bioengineering at Ege
University. Her research interests are the effects of magnetic nanoparticles on mammalian cells and
their potential usage on cancer treatment, biocompatible polymers, tissue culture and artificial organs,
angiogenesis and the effects of the electromagnetic fields on cancer cells and pathogen microorganisms.
She is a member of Ege Research Group of Animal Cell Culture and Tissue Engineering (EgeREACT).
Mohammed Benali Kanoun was born in Tlemcen, Algeria. He received his PhD degree from University of Tlemcen (Algeria) in collaboration with University of Grenoble (France) in 2004. Then he
worked as assistant Professor for 2 years at Lille 1 and Poitiers universities. He was awarded a research
fellow in Belgium for 2 years where he worked as computational scientist for an industrial project within
606
AGFA research and development department and Namur University. Since 2010, he is working as research fellow at KAUST. His main area of research is DFT applied to material science and modeling
the physical properties of functionalized materials such as spintronic, nanodevices, hydrogen storage
energy, catalysis and nanoparticles, photovoltaic materials. Mohammed Benali is a reviewer editor of
the interdisciplinary section of Frontiers physics journal.
Tayeb Benouaz works as a full professor since 2002 at department of physics at Abu-Bakr Belkaid
University of Tlemcen (Algeria). He was a director of post-graduation program related the electronic
physical modeling in the same university. Director of several researches projects and has several activities
in these fields; include modeling and simulation in the field of renewable energy, automatic, electronic,
microelectronic. Very recently, he took the responsibilities of LMD program on the modelling physical
system and information processing.
Eyup Bilgi completed his undergraduate studies in the Department of Bioengineering at Ege University. He is currently an MSc Student in the Department of Biomedical Technologies at the Ege University in Izmir, Turkey. He is also a member of Ege Research Group of Animal Cell Culture and Tissue
Engineering (EgeREACT). He is interested in the usage of magnetic nanoparticles on animal cells and
their potential usefor cancer treatment, natural biocompatible polymers especially bacterial cellulose,
cell culture, and the effects of the electromagnetic fields on cancer cells and pathogen microorganisms.
Rabah Boukherroub received a PhD in organometallic chemistry from the University Paul Sabatier
in Toulouse, France. He is a research director at the CNRS, Lille, France and a group leader at the Interdisciplinary Research Institute (CNRS & University Lille1). His research interests are in the area of
chemistry, surface chemistry, functional materials, and photophysics of semiconductor nanostructures
with emphasis on biosensors and lab-on-chip applications, and development of new tools for studying
molecular dynamics in vivo. He is a co-author of 280+ research publications and wrote several book
chapters in subjects related to nanotechnology, materials chemistry, and biosensors. He has 8 patents
or patents pending.
Nawel Boumaza, born in Tlemcen in western Algeria she received the Bachelor degree at Abu-Bakr
Belkaid University of Tlemcen (Algeria). Then se undertake postgraduate studies in option of electronic
and physical modeling when she received the master degree in June 2007 at the same University under
the supervision of Prof. Tayeb Benouaz. She obtained her Docorat thesis in the field modeling and simulation of nonlinear systems related to the physical, electronic and electromagnetic problems in optical
fibers. During her thesis, Nawel Boumaza has developed numerical tools using MATLAB to resolve
NLSE on optical fibers for optical communication purposes.
Ayoola Brimmo completed his bachelor degree in mechanical in his home country of Nigeria and
then joined Masdar Institute (UAE) where he completed his MSc. in mechanical engineering in 2013.
He has since then been working as a research engineer in the same institution.
Manash R. Das is, since 2008, a Research Scientist at Materials Science Division, CSIR-North East
Institute of Science and Technology (CSIR-NEIST), Jorhat, India. He is also Assistant Professor in Acad-
607
emy Council of Scientific and Innovative Research (AcSIR), India. He has carried out his PhD research
work at CSIRNEIST, Jorhat and received his PhD degree from Dibrugarh University, Assam, India in
2007 in the field of Surface Chemistry. Between 2007 and 2008, he worked as a postdoctoral fellow with
Dr. Rabah Boukherroub at the Interdisciplinary Research Institute (IRI), France. He has published 33
peer reviewed research articles and 3 book chapters. His research interests include functionalization of
graphene, metal nanoparticlegraphene composite materials and their biological and catalytic activity,
surface chemistry of mineral oxide.
Ashvini Deshmukh received her Bachelor of Science and Master of Science in Chemistry from
Swami Ramanand Teerth Marathwada University, Nanded, Maharashtra, India. She is currently working
as project fellow with Dr. (Mrs.) Manjusha V. Shelke in CSIR-National Chemical Laboratory, Pune, India.
Her research interest is synthesis of nanocomposite electrode materials for energy storage application.
Mahieddine Emziane spent the past 18 years working in the area of semiconductor materials and
devices for solar cell applications. Among the founding faculty, he joined Masdar Institute (UAE) in 2007
from Oxford University (UK), following which he spent one year as a Visiting Scholar at MIT (USA).
Prior to that, Dr. Emziane held appointments at the Universities of Sheffield, Liverpool and Durham in
the UK, and as a Guest Scientist with Siemens in Germany. Dr. Emziane is author or co-author of over
100 peer-reviewed publications and technical reports. He delivered about 140 conference contributions,
invited talks, seminars, lectures, and tutorials. He is associate editor of 2 new international journals and
member of the scientific committees of 15 international conferences. He is a reviewer for 45 international
journals and conferences and he received all his university degrees in Applied Physics and Materials.
Daniel Fruchart is Research Director Emeritus at Institut Nel, Grenoble, France. He is the Founder
and former head of group Intermetallics & Interstitials Energy Conversion (IICE). His interests includes hard and soft magnets, metal hydride and applications, magnetocaloric, thermoelectric and shape
memory, zircaloy, etc. He supervised over 40 PhD students and managed 30 R&D contracts. His expertise
includes synthesis and processes, crystal structure, magnetism, group theory analysis, neutron scattering,
EXAFS and XMCD, etc. He published over 650 papers, 14 patents with H-factor 34, Research Gate >
46. He is the Founder and Research Manager of McPHy Energy SA. He is member of Int. Steering Committees: MH (Int. Symp. Metal Hydrogen), SCTE (Int Conf. Solid Compounds Transition Elements),
IMC (Intermetallic Compounds). He has many awards such as French Division Mineral Chemistry and
Metallurgy (86), Spanish Society Materials (92), Btancourt-Perronet, Development French-Spanish
Research (2), Techniques Innovantes pour Environnement ADEME (4), etc.
Souraya Goumri-Said was born in Toulouse, France. She received her PhD degree from the Bourgogne University in Dijon (France) on 2004. Souraya then spent one year in Val de Marne University
as assistant professor then joined the condensed matter group in physics department of Technical University of Kaisterslautern in Germany. Since then, she was awarded different research fellows in France
and Belgium as postdoctoral and assistant teacher at Maine University (Le Mans). Then she worked as
researcher at Namur University Souraya worked and managed an industrial project within ArcelorMital
research and development department in collaboration with three universities in Wallonie region. Her
main area of research is DFT applied to material science and modeling the physical properties of func-
608
tionalized materials such such as spintronics and materials for storage hydrogen. She also specializes
in modeling optical, photonic devices and nanostructures for photovoltaic applications. Souraya is an
associate editor of the Central European Journal of Physics, within Springer Verlag edition.
Xiao Guo is a Professor of Materials Chemistry at University College London. His research interest
focuses on multiscale syntheses and simulations of materials and nanostructures for applications in clean
energy and healthcare technologies, particularly in carbon capture, chemical / photo-electro-chemical
catalysis, chemical/electrochemical energy storage, biofuel cells, and biointerfaces. Fundamental theories are coupled with ab initio, molecular dynamics, cellular automata and finite element simulations
for materials discovery, while selected materials are synthesised and harnessed by sol-gel, mechanochemical, self-assembly, exfoliation, deposition and co-precipitation methods. He has contributed over
180 high-quality journal publications and over 300 conference papers/presentations in the field. He is
a member of the editorial boards for several international journals. He was awarded the Beilby Medal
2000, jointly by the Society of Chemical Industry, the Royal Society of Chemistry, and the Institute of
the Minerals, Metals, and Materials.
Issifu I. Harruna is a Professor of Chemistry at Clark Atlanta University, Atlanta, USA. He earned a
B.Sc. degree in Biochemistry with specialization in Medicinal Chemistry, M.S. in Industrial Chemistry,
and a Ph.D. in Organic Chemistry (research in Polymer Chemistry). Dr. Harruna has over 50 scientific
publications in technical peer-reviewed journals and several book chapters. He has three United States
patents issued. He is also a fellow of the American Institute of Chemists and a member of the American Chemical Society. His research interest is in the synthesis and characterization of novel polymers,
nanomaterials and antiviral compounds.
Najrul Hussain received his Bachelor of Science in 2010 and Master of Science in 2012 from Gauhati
University, Assam, India. Since October 2012, he has been working as a project fellow in a DST funded
project at Materials Science Division in CSIR-North East Institute of Science and Technology, Jorhat,
India under the supervision of Dr. Manash R. Das. He is co-author of two research publications and one
book chapter. His research interest is in the area of functionalization of graphene and its catalytic and
biological activity.
Rafaqat Hussain is a senior lecturer at the Ibnu Sina Institute for fundamental Science Studies (IIS)
at UTM. He joined UTM in December 2010. Prior to Joining UTM, he was involved in setting-up the
first ever Interdisciplinary Research Centre in Biomaterials in Pakistan. He received his Bachelors of
Science, Maters of Science degree in Chemistry and doctorate in Biochemical Engineering from University College London.
DaeJoon Kang is a Professor of Physics at Sungkyunkwan University, Korea, whose interests include
condensed matter physics and nanoscience. He has published more than 150 SCI peer-reviewed articles
with total citations over 2,500 in the top journals including Nature Nanotechnology, Nano Letters and
Advanced Materials, and several book chapters in solid-state physics and nanotechnology area covering
from nanofabrication to materials synthesis and to device physics. He has served as an editorial board
member for several internationally renowned scientific journals including IOP journal Nanotechnology
609
since 2006. He has given numerous lectures at international conferences including ACS 2006, TNT 2003
and 2011, Nano KOREA 2013, etc.
Chaitanya Krishna Kamaja received his Bachelor of Science from Andhra University, Andhra Pradesh,
India and Master of Science in Chemistry from University of Hyderabad, Andhra Pradesh, India. He is
currently the graduate student with Dr. (Mrs.) Manjusha V. Shelke in CSIR-National Chemical Laboratory, Pune, India. His research focuses on nanostructured materials for energy conversion applications.
Huayang Li is Research Scientist at Clark Atlanta University, Atlanta, USA. His current research
field is organic chemistry and functional nanomaterial of graphene and carbon nanotubes. He accepted
postdoctoral training in Georgia institute of Technology and University of Michigan. Dr.Li received a
Ph.D. in Organic Photochemistry and Organic Synthesis from Institute of Chemistry, Chinese Academy
of Sciences, Beijing China in 2004. Dr. Li has published over 20 research papers, book chapters and
patents in material chemistry and organic chemistry.
Mingguang Li is a Research Scientist at Optimum Therapeutics, LLC. Dr Li has over 10 years
experience in research of nanoparticles for drug delivery. He is the author of 17 scientific publications
including journal articles and book chapters. Dr Li also serves as the expert reviewer for multiple top
scientific journals and international conferences in the field of Nanomedicine and drug delivery. Dr Li
received a Bachelors Degree in Pharmaceutical Sciences from Shandong University, China, and a PhD
Degree in Pharmaceutics from Peking University, China. He then did postgraduate work at Wayne State
University and other institutions.
John Melnyczuk is a Biochemist PhD candidate for Clark Atlanta University in the Center for
Nanomaterial (CFNM). Prior to his research at CAU, he obtained degrees at University of West Georgia, Georgia Institute of Technology, and The University of Alabama in the areas of BS Chemistry, BS
Chemical and Biomoleculer Engineering, and Masters Chemical Engineering, respectively. His broad
areas of expertise include mathematical molecular modeling (under Dr. Ludivice at GIT), Analytical
chemistry (under Dr. Kahn at UWG), and hyperthermia treatment of cancers cells (under Dr. Brazel at
UA). He also initiated 3 pilot plant start-ups. His masters thesis is on the development and characterization of thermally sensitive hydrogels for drug delivery in cancer cells using Iron Oxide Nanoparticles.
John also interned at P&G as a formulation engineer for the global health organization creating over the
counter sustained release drug delivery systems. Currently he is working on the development of novel
and biologically safe routes for metal removal from bloodstreams.
Maha Mohammed Khayyat is a staff member at KACST (King Abdulaziz City for Science and
Technology), Riyadh, KSA. She received her undergraduate and MPhil (2001) from UQU, Makkah,
KSA. Then she received her PhD (2004) from Cavendish laboratory on structural phase transformation
of semiconductors due to micro- and nano-indentations. In 2008 Dr Khayyat worked on solar cells based
on silicon both bulk and nanowires at T.J. Watson Research Center IBM-NY-USA, where she started
making innovative and breakthrough contributions to improve the nanowire technology by replacing
the conventional gold seed by aluminum seed the applying Nanoscale Chemical Templating (NCT)
technique. Dr Khayyat further applied this technology to patterned silicon substrate for potential use in
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silicon CMOS technology. She then started a completely new field of controlled spalling for flexible
solar cells application. Recently, she worked at MIT, mechanical engineering department for a year on
advanced solar cells.
Inas Muen Al Nashef began his academic career at Kuwait University, JUST University, Jordan,
and UAE University before pursuing his PhD at the University of South Carolina, Columbia, USA, in
2000. He joined King Saud University, Riyadh, Saudi Arabia as assistant professor in 2004. In the year
2011, Al Nashef was promoted to associate professor. He is currently co-advising six Ph. D. students at
the University of Malaya and two of them have graduated. Al Nashefs research interests include green
engineering using ionic liquids and deep eutectic solvents and electrochemical engineering. Al Nashef
has more than 50 published articles, six US patents, and one EU patent. In addition, Al Nashef has been
recognized several gold medals and awards for his outstanding research including King Abdullah Award
for Best Inventions 2013.
Ayman Nafady began his academic career at South Valley University, Sohag, Egypt and University
of Vermont, Burlington, USA before pursuing his PhD at University of Vermont, USA/South Valley
University, Egypt (Jointly award), in 2004. He worked as Senior Research Associate School of Chemistry, Monash University, Clayton, Victoria, Australia from 8/2010-4/2012. He have developed training
and introductory courses for conducting solution phase and solid-state electrochemistry, in-situ IR and
UV/Vis spectro-electrochemistry, and utilization of vacuum Atmosphere drybox and Schlenk lines and
have trained both members of Prof. Alan Bonds research group, visiting scientists and postgraduates,
and staff from the University of Melbourne, Curtin University, University of Sydney and RMIT. Ayman
Nafady joined King Saud University, Riyadh, Saudi Arabia as associate professor in 2012.
Soubantika Palchoudhury is a postdoctoral fellow at the University of Alabama, MINT Center.
Prior to her research at UA, she was a postdoctoral researcher at Yale University and University of South
Carolina. She completed her Ph.D. and M.S. in Chemical Engineering from the University of Alabama
on the synthesis and characterization of Pt decorated iron oxide nanoparticles for biomedical applications. She has published over 10 articles in nanoscience journals such as Nano Letters, Langmuir, and
ChemComm. She has authored two book chapters and has reviewed for Langmuir, ES&T, APL, JAP,
Nanoscale, Nanotechnology, and Nanomater. Nanotechnol. Dr. Palchoudhury is an expert in the synthesis
and surface modification of anisotropic nanoparticles, nanoparticle-based environmental remediation
routes, DNA-nanoparticle interactions, hybrid nanoparticles, and nanoparticle characterization techniques
such as transmission electron microscopy.
Robert Penchovsky is an associate professor of genetics, bioinformatics and molecular evolution, and
synthetic biology at Sofia University St. Kliment Ohridski, Bulgaria, where he obtained his Masters
degree in biochemistry and molecular genetics, and Associates degree in applied computer sciences.
He earned his Doctoral degree in genetics from Cologne University, Germany, while researching in the
fields of microfluidics and nanobiotechnology for Fraunhofer Gesellschaftat Schloss Birlinghovenin
Sankt Augustin (near Bonn), Germany. Robert did his postdoctoral study in the fields of computational
biology and RNA synthetic biology at Yale University, New Haven, CT, USA. Robert teaches master
classes of bioinformatics and molecular evolution, genomics, and synthetic biology at the Faculty of
611
Biology. He is a head of the master program of genetics and genomics there. In addition, Robert teaches
a bachelor class in molecular genetics. He has supervised the diploma theses of many master students.
M. Rajaperumal received his Bachelor of Science in chemistry from St. Josephs college, Trichy,
Tamilnadu, India and Master of Science in Chemistry from Indian Institute of Technology, Roorkee,
India. He is currently doing PhD with Dr. (Mrs) Manjusha V. Shelke in CSIR-National Chemical Laboratory, Pune, India. His research topic is developing advance nanostructure electrode material for energy
storage application.
Manish Roy graduated from IIT, Kharagpur. After a short stay with an integrated steel plant as
Junior Manager and his post graduation, he joined Defence Metallurgical Research Laboratory as
scientist. His areas of research interest are materials and surface engineering for tribological application
and nanotribology of self-lubricating films. He is particularly interested in various interactions between
oxidation/corrosion and tribology. Meanwhile, he has visited various European universities and research
laboratories under prestigious programmes of Royal Society (London), Austrian Science Fund (FWF),
and European Commission. Dr. Roy has around 100 papers in various reviewed national and international journals. He is edited a book on Surface Engineering for Enhanced Performance against Wear.
He has been guest editors of several special issues of several international journals. He is also in the
editorial board of several international journals. Dr. Roy has organised several international symposium
in India and abroad.
Mansoor Sarfraz has received his M.S degree in nuclear power engineering from the Pakistan Institute of Engineering and Applied Sciences (PIEAS), and currently working as Lecturer at Sustainable
Energy Technologies (SET) center, at King Saud University. His current research interests mainly focus
on the development of high capacitance, high-energy density energy storage and conversion devices.
Aylin Sendemir Urkmez has received her B.S. degree at Mechanical Engineering, M.S. degree at
Biomedical Engineering from Bogazici University, Turkey, and PhD. Degree at Materials Science and
Engineering from University of Illinois at Urbana-Champaign, USA. She has been working as an assistant
professor at Ege University Faculty of Engineering, Bioengineering Department since January 2009. She
has been conducting research on tissue engineering using biodegradable polymer composites produced
by nanotechnology and investigating cell-surface interactions, particularly using tissue engineering tools
for developing in vitro physiological models. She also has experience on nanotoxicity evaluation with
various polymer coatings.
K. A. Shah is a young scientist, with MSc / M. Phil degrees from University of Kashmir and Ph. D.
from Jamia MIllia Islamia - India in Physics. He has co-author two books titled Nanotechnology: The
Science of Small published by M/S Wiley India and Physics through Modern Experiments published
by M/S Kapoor Sons, India. He published a number of research papers in reputed National and International Journals and International conferences proceedings. He was awarded Jawaharlal Nehru Memorial
fellowship-2005 for Doctoral studies and stood first among the awardees at National level as well as
DSTs (J&K), Young Scientist Fellowship-2010. He is presently handling two major research projects
on synthesis, characterization and device applications of carbon nanotubes, awarded by UGC and DST-
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SERB Govt. of India. He is guiding number of research scholars. His fields of interest include carbon
nanotubes, nanoparticle research, water purification and solid-state electronic devices.
M. A. Shah has doctorate in Condensed Matter Physics from Jamia Millia Islamia - India and graduate from University of Kashmir. He joined National Institute of Technology, Srinagar in 1999 as an
Assistant Professor in Physics. He is the author of three books on Nanotechnology and Nanosciences
published by John Wiley and has more than 50 research publications. He is reviewer and editor of many
scientific journals and has been invited to deliver talks in international conferences and symposia. He
is honoured as a visiting scientist in many prestigious institutions and has worked with the eminent personalities of the world. At National Institute of Technology, Srinagar, before departure to Middle East,
he has established World Bank funded Sophisticated Instrumentation Centre under TEQIP programme
and after returning to home land, he is organising many INSPIRE Programmes launched by the Honble
Prime Minister of India for the genius students of valley.
Imran Shakir is currently employed in the capacity of Assistant Professor at Sustainable Energy
Technologies (SET) center, KSU. Dr. Imran Shakir completed his PhD and postdoc from, Sungkyunkwan
university, South Korea. He has worked with Samsung, Electronics, Korea for more than three years
for the development of functional nanomaterials for efficient energy storage and devices. In this regard,
he has several scientific and technological breakthroughs in this field and published more than 60 international publications. His current research is mainly focus on the development of high capacitance,
high-energy density energy storage devices and also to provide a fundamental understanding of the
microscopic underlying mechanisms in the ionic transport properties and the change in the electronic
structure of state-of-the-art nanostructures.
Ponchami Sharma received her Bachelor of Science in 2005 and Master of Science in 2007 from
Dibrugarh University, Assam, India. She started her research career as CSIR-Diamond Jubilee Research
Intern at Coal Chemistry Division, CSIR- North East Institute of Science & Technology in April 2008.
Since October 2011, she has been pursuing her PhD research at Materials Science Division, CSIR-North
East Institute of Science & Technology under the supervision of Dr. Manash R. Das. She is a co-author
of eight research publications and two book chapters. Her research interest is in the area of surface
chemistry and synthesis of nanomaterials.
Manjusha Shelke obtained her Ph.D. in Chemistry from CSIR-Advanced Materials and Processes
Research Institute, Bhopal, India. She is currently Scientist at CSIR-National Chemical Laboratory,
Pune, India. She worked as a postdoctoral researcher at Institut de electronique de microelectronique et
de nanotechnologie (IEMN), CNRS, Lille, France. Her research interests are in the area of multifunctional materials and their chemistry for advanced applications. The focus of her current research is the
synthesis of nanomaterials-by-design for energy conversion (photoelectrochemical cells) and energy
storage (Li-ion battery, Supercapacitors) applications.
Tewfik Souier obtained his Ph.D. in materials science from Grenoble Institute of Technology in
2006, then continued his research as a research fellow of the Laboratory of Physics and Chemistry of
Surfaces and Interfaces, research unit of the CEA (Alternative Energies and Atomic Energy Commission)
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in France. He worked on characterization and study of surfaces of oxides and nanostructures (including
Carbon nanotubes) by using most modern set of devices: an XPS Kratos as well as (STM/AFM) operating
in air, liquids, and under ultrahigh vacuum. Since 2010, he joined the Masdar Institute of Science and
Technology as research scientist, where he contributed to establishing a new laboratory (LENS) and a
very active research group for the study of physics and chemistry of surfaces at nanoscale. He has been
focusing on the development of new AFM-based methods for the study of electrical and thermal transport at nanoscale. In the past, he has successfully applied these methods to study and explain numerous
fundamental and applied physico-chemical phenomena.
Sabine Szunerits is since 2009 Professor in Chemistry at the University Lille 1, France and was
nominated 2011 as member of the Institut Universitaire de France (IUF). Her current research interests
are in the area of material science with emphasis on the development of novel analytical platforms and
interfaces for the study of affinity binding events and in the modification of nanostructures (diamond
particles, magnetic particles, nanographene) for biomedical applications. She is co-author of more than
170 research publications, wrote several book chapters, and has 6 patents.
Gavin Walker graduated in 1994 with Chemistry BSc (hons) and a PhD from Durham University,
UK. After postdoctoral research at Warwick University, he took up a lectureship position at the University of Nottingham in 1997 where he has established a leading research group in hydrogen storage and
hydrogen systems. In recognition of his research, Gavin was awarded a Carbon Trust / EPSRC Low
Carbon Leadership Award and in addition to over 100 publications in the area, he is also Editor of
the text Solid State Hydrogen Storage Materials Chemistry and Materials. In 2010, Gavin was appointed as the Sir Harry and Lady Djanogly Chair in Sustainable Energy and 2014 became Director of
the University of Nottinghams Energy Technologies Research Institute (ETRI). The ETRI has a 70
million portfolio of research, which spans green coal, energy storage, smart grids, creative energy homes
and renewable energy generation.
Rahana Yoosuf received her B.Sc. (April 1998) and M.Sc. (April 2001), both in Physics, from Mahatma Gandhi University, Kerala, India. She then completed her Ph.D. in Materials Science (September
2008) from Cochin University of Science and Technology, Kerala, India. She joined Masdar Institute
(UAE) in 2010 as a postdoctoral researcher.
Guangchang Zhou is currently a Research Scientist and Research Associate at Clark Atlanta University, Atlanta, USA. He has been Research Assistant Professor in University of Chicago in 2008 2011,
accepted Postdoctoral training from University of New Orleans in 2001 2002, and The University
of Sheffield, Sheffield, and The Polymer Centre, Lancaster University, Lancaster, UK. He has earned
B.Sc. degree in Science in Chemistry, Specialization in Chemical Education. He also obtained PhD in
Organic & Polymer Chemistry from Beijing Institute of Technology in China. Dr. Zhou has published
over 30 peer-reviewed journals and 2 patents. His research interests are in the field of polymer science
and nanomaterials.
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Index
A
Aggregation of Nanoparticles 225
Allosteric Ribozymes 414, 417-430
Apoptosis 29, 430, 448, 461, 465, 466, 471, 478,
481, 487
Atomic Force Microscopy (AFM) 49, 50, 66-70, 85,
87, 109, 118-120, 125, 126, 129, 206, 238, 242,
264, 344, 345, 350-356, 359, 362-368, 375
Atomic Layer Deposition (ALD) 129, 205, 230, 238,
246, 261, 265
Autonomic Systems 6-9, 12, 15, 16, 22-25
B
Bacterial Riboswitches 418, 427, 430
Band Structure 52, 131, 136-139, 143, 144, 180,
316, 323, 337, 432
Biodistribution 149, 151, 159-163, 474, 476
Biomimetic Systems 1, 21, 24, 25
Bipyridine 26-40, 52, 59, 61
Bottom-Up Fabrication 29, 47, 110, 129, 131, 274
Brillouin Zone 131, 134-138, 141-145, 433, 434
C
Cancer 29, 90, 99-102, 106, 161, 171, 215, 219, 423,
426-430, 447-452, 455, 456, 459-491
Carbon Nanofibre 175
Carbon Nanostructures 54, 275, 309, 313, 329, 335,
339, 342, 368
Carbon Nanotubes (CNT) 18-29, 35-45, 53-61, 86,
131-145, 157, 165, 169-175, 180, 194, 224,
247, 260, 268-310, 343-355, 358-361, 364-375,
382, 393, 395, 399-407, 410, 413, 428, 459462, 471, 491
Chemical Vapor Deposition (CVD) 63, 86, 110, 125,
129, 180, 189, 190, 233, 253, 270, 280-282,
292, 330
Composites 1-13, 16-24, 40, 42, 50-53, 56, 164,

165, 169-176, 181, 185, 189-197, 208, 213225, 274, 297-300, 313, 320, 326, 340, 344350, 353, 358, 359, 362, 367-376, 393, 398,
410, 411
Computational Design of Allosteric Ribozymes 427,
430
Computational Model 153, 163
Conventional Therapies 462, 491
Co-Precipitation 89-91, 94, 95, 100, 107, 391
D
Delaminations 12, 25
Density of States 131, 132, 137-145, 246, 303, 436441
Dielectric Properties 246, 251, 261, 345, 351, 367,
437, 438, 443-446
Dispersive Medium 492, 500
DNA Nanotechnology 414-417
Drug Development 415, 418, 427
E
Elasticity 63, 80-82, 88, 169, 372
Electrical Conductivity 40, 171, 190, 213, 239, 240,
244, 246, 270, 280, 308, 343-347, 355, 356,
360-364, 367, 368, 371, 374, 381, 393, 432
Electrostatic 98, 155, 187, 188, 195, 197, 206-208,
213, 218, 283, 343-352, 357, 363, 367-370,
373-375, 432, 490
Energy Density 178-181, 192, 195, 382, 390
Epitaxy 126, 129, 227, 231, 235, 252, 256, 262, 265,
266, 432
Exogenous Control of Gene Expression 414, 430
Ex Situ Method 206, 225
Index
F
Fuel Cell 376-382, 398-403, 407, 410-413
Fullerene 26-29, 35-39, 54-61, 132, 163, 290, 298,
305, 307
Functional Properties 226, 227, 236, 250, 251, 267,
311
G
Gene Therapy 430, 471-474, 478, 482, 486, 491
Graphene 26-29, 35, 37, 47, 48, 52, 55-61, 132-141,
145, 169, 175-209, 212-225, 270, 281, 282,
298, 300, 309, 342, 362, 373, 398-403, 411-413
Graphene Oxide 57, 186, 192, 193, 197, 208, 217225, 400, 412
H
Heat-Up Method 92-96, 100, 107
Hydrogenation and Dehydrogenation 312, 342
Hydrogen Storage Capacity 312, 316, 317, 334, 342
I
In2S3 226-231, 236-240, 246-248, 252-266
In2Se3 226, 227, 231-235, 241-244, 248, 251, 254266
In2Te3 226, 227, 235, 236, 245-248, 251-261, 264,
266
Indium Chalcogenides 267
In Situ Method 225
Intermetallics 312, 339, 342
Iron Oxide Nanoparticle 94, 103-107, 475
K
Kintetics 5, 7, 106, 147-161, 259, 287, 312, 313,
319-326, 332-337, 342, 385, 394, 397, 408, 456
L
Ligand 23, 26, 27, 30, 33, 35, 42, 44, 57, 61, 92, 98,
100, 104, 107, 152, 155-159, 163, 418, 424,
430, 470
Ligand Exchange 92, 98, 100, 104, 107
Light-Complex Hydrides 342
Liquid Source Misted Chemical Vapor Deposition
(LSMCVD) 130
M
Medical Genomics 414, 415, 418, 426, 427
616
Metal Oxide 175, 196, 197, 206-209, 212-216, 219225, 301, 309, 385, 386, 391, 407
Metal Oxide-Graphene Nanocomposites 196-199,
202-207, 212-216, 225
Mg-Compounds 312, 342
Microencapsulation 13, 14, 19, 20, 24, 25
Microstructures 6, 67, 102, 173, 226, 251, 267, 268,
300, 312, 320, 329, 330, 336, 342
Molecular Beam Deposition (MBE) 130, 231, 232,
244-248
N
Nano-Al2O3 164-167
Nanocomposite 53, 64, 67, 79, 82-88, 165, 181, 183,
188, 193-196, 199-202, 205, 208-211, 214-225,
343-346, 358-362, 398, 404, 412, 491
Nanocrystal 101, 105-107, 130, 166, 284
Nanocrystalline 63-67, 72-75, 79-81, 85-88, 228,
231, 232, 238, 257, 266, 301, 320, 325, 326,
341, 386, 389, 402, 403, 432, 443-446
Nano-Fe2O3 164-167, 175
Nanoflowers 90, 97-100, 103, 107
Nanohardness 62-64, 72, 75-80, 83-85, 88
Nanolithography 130
Nanomaterials 26-29, 45, 53, 58, 108, 124, 131, 132,
147, 153-156, 161, 164-166, 169-175, 192,
193, 198, 215, 223, 301, 376, 377, 380, 381,
387, 398, 399, 408, 413, 461, 467, 475, 490
Nanoparticle Drugs 491
Nanoparticles 6, 11, 35, 57, 58, 89-94, 97-107, 111,
146-166, 170-175, 185-188, 192-205, 208-212,
215-225, 279, 283, 286, 290, 299, 308, 309,
344, 362, 379-381, 384, 387-389, 397-410,
413, 427, 432, 445-448, 451, 455-491
Nanoparticle Toxicity 151, 460, 462, 491
Nanoplates 90, 97-100, 103, 107, 202
Nanoscale Chemical Templating 114, 127, 130
Nano-SiO2 164-168, 173-175
Nano-TiO2 164-169, 175
Nanotribology 88
Nanowhiskers 90, 95, 96, 100, 103, 107
Nonlinear Medium 492
Nonlinear Schrdinger Equation (NLSE) 492, 493,
496-498, 501-504
Nucleation 105, 110, 129, 130
O
Open Circuit Voltage 182, 195, 247, 278, 389
Opsonization 149, 157, 162, 163
Optical Fiber 492-504
Index
Oxides 101, 104, 116, 183, 190, 199, 205, 212-217,

224, 230, 253, 319, 328, 334, 353, 385-393,
396, 402, 408, 432, 443-446
P
PBPK Modeling 151, 163
Pharmacokinetics 146, 147, 150-154, 157-163, 456,
458, 489
Photovoltaics 111, 121, 191, 251-255, 262, 265-268,
286, 298-301, 304-308, 311, 402
Plasma Enhanced Chemical Vapor Deposition
(PECVD) 68, 87, 130
Polymer 1-25, 28, 29, 35-38, 42, 44, 47-61, 90, 98107, 150, 156, 157, 161, 173, 175, 247, 261,
265, 276, 288-290, 293, 294, 298-308, 344362, 367-374, 378, 379, 402, 403, 407-410,
426, 456, 468, 469, 476, 480, 484, 485, 489
Polymer Encapsulation 90, 98, 99, 107, 276
Power Density 65, 178, 179, 190, 195, 213, 390
Pozzolanic Reaction 166, 175
R
Raman Spectroscopy 52, 57, 60, 131, 132, 141-145,
199, 242, 272, 273, 300, 301, 310
Rayleighs Dissipation Function 492, 493, 498, 503
Ribozymes 414-430, 460, 472
RNA 28, 414-430, 460, 469, 472-474, 487
RNA Aptamers 417, 430, 469
ROMP Reaction 1
Ruthenium Complex 26, 38, 42, 44, 53, 61, 388
S
Schottky Diode 177, 195
Self-Healing Materials 1, 2, 10, 13, 19-25
Self Lubrication Film 88
Short Circuit Current 178, 195, 246, 286, 289, 290,
389
Solar Cell 28, 40, 120-122, 125, 128, 177-184, 190195, 214, 215, 220, 229, 231, 246-249, 254,
259, 261, 265-268, 275-278, 282, 286, 292,
299, 303-308, 311, 372, 373, 376, 388, 389,
400, 403, 404, 407, 408, 413
Solitons 493-504
Space Conditions 25
Space Debris 1, 25
Supercapacitor 178, 179, 185, 190, 192, 214, 221,
225, 376, 411, 413
Synthesis 13, 22, 30, 31, 35, 38, 39, 47, 53-61, 8997, 100-110, 125-128, 131, 143, 181, 184-186,
192, 195-199, 202-210, 213, 216-225, 228,
230, 236, 252-258, 264, 268, 270, 276, 280,
284, 296-303, 308, 309, 320, 334-341, 347,
392, 393, 398-404, 408, 411-413, 424, 451,
465, 466, 485-488, 491
T
Targeted Therapy 460, 483-485, 491
Terpridine 26, 61
Thermodynamics 260, 312, 313, 335, 342
Thermosetting 1, 3, 6, 25
Thin Films 55, 62, 63, 85, 88, 166, 226-267, 281,
292, 311, 333, 342, 349, 408, 444-446
Tunneling 57, 139, 271, 275, 345, 346, 353-359,
368, 374
U
Ultra High Vacuum Chemical Vapor Deposition
(UHVCD) 130
V
Vacancy Defects 446
Vapor-Liquid-Solid (VLS) Growth Method 108-114,
122, 123, 126, 129, 130
W
Work Function 178, 181, 183, 192, 193, 214, 290,
291, 348, 374
617

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Handbook of Research

A volume in the Advances in Chemical

Published in the United States of America by

British Cataloguing in Publication Data

IGI Global is currently accepting manuscripts

Titles in this Series

For a list of additional titles in this series, please visit: www.igi-global.com

Handbook of Research on Nanoscience, Nanotechnology, and Advanced Materials

701 E. Chocolate Ave., Hershey, PA 17033

Editorial Advisory Board

Sevdalin Georgiev, Sofia University, Bulgaria

Assa, Brahim / MPB Technologies Inc., Canada . ........................................................................ 1, 108

Sarfraz, Mansoor / King Saud University, Saudi Arabia .................................................................. 376

Compilation of References . .............................................................................................................. 505

About the Contributors .................................................................................................................... 605

Index ................................................................................................................................................... 615

Detailed Table of Contents

Ruthenium bipyridine or terpyridine complexes functionalized carbon-based nanocomposites have special

Compilation of References . .............................................................................................................. 505

About the Contributors .................................................................................................................... 605

Index ................................................................................................................................................... 615

Self-Healing Materials Systems

structural materials become damaged, there are

one mode might be completely useless for another.

microcracks within the structure during its service

terization of the self healing of the thermosetting

Table 1. Non exhaustive main developments in self-healing polymer composites

(Trask, & Bond,

(Lin, Lee, & Liu,

There are different methods to effect healing

where K1C virgin is the fracture toughness of the virgin

2.1. Self-Healing Efficiency

Figure 2. (Left) Schematic of the TDCB-based

ics, and the rest periods employed (Brown, White,

2.3. Self-Healing Efficiency

=KIC healed/KIC Virgin

2.2. Self-Healing Efficiency

where N healed is the total number of cycles to failure

A tear test utilizes a rectangular coupon of

two pieces of the same polymer are brought into

4.1. Hollow Glass Fibres Systems

composite (Trask, Williams & Bond, 2007). These

by vacuum, which is now the main commonly used

ing plastic deformation and delamination and will

4.2. Systems Based on

surface morphology that aids in the adhesion of

formaldehyde microcapsules have shown concrete

4.2.1. Size and Material

average thicknesses) and display good thermal

been used in the paper industry for a range of

4.2.2. Fatigue Cracks Retardation

were attributed mainly to the crack closure, which

4.2.3. Delaminating Substrate

reinforced epoxy composite. Low velocity impact

(White et al., 2001)

(Lee et al., 2004)

(Liu et al., 2006)

Mixture of hydroxyl end

(Cho et al., 2006)

(Yuan et al., 2006)

agent has been widely reported as we mentioned

(Wu et al., 2008)

more reactive healing system with acceptable