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Nanotechnology

Engineering Physics

Nanotechnology

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Nanotechnology

Engineering Physics

1. Introduction
Nanotechnology
Study of structures with at least one characteristic dimension measured in
nanometer range
Range: Atomic size (10-9m) to Bulk macroscopic materials (10-7m), i.e. 1-100nm
Physical properties of nano-materials are different from atoms or bulk materials
Some nano-materials could harm human health or environment

Short History
Michael Faraday (1857)
Discovery of colloidal gold particles

Karl Wilhelm Wolfgang Ostwald (1917)

Book Welt der vernachlaessigten Dimensionen or the World of negligible
dimensions
Study of colloidal state of matter

Richard Feynman (1950)

Lecture at American Physical Society: There is plenty of room at the bottom

On manipulating miniscule bits of condensed matter

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2. Classification

Nanostructures confined in 3D: 3 dimensional nanostructures

Nanostructures confined in 2D: 2 dimensional nanostructures

Nanoparticles
Nanopores
Quantum dots
Nonowires
Nanorods
Nanofilaments
Nanotubes (Carbon nanotubes, Silicon nanotubes)

Nanostructures confined in 1D: 1 dimensional nanostructure

Nanodiscs
Nanoplatelets

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Nanorings

Zinc Oxide Nanoring (2004)

The first nanoring by Georgia Institute of Technology, USA

A single-crystal seamless nano-ring
Made of piezoelectric zinc oxide of diameter of about 3 microns and thickness 15nm
Made by a new crystal growth process: Spontaneous self-coiling process of nanobelts

Other examples

Layers of nanobelts are rolled together as coils, layer-by-layer

Silver nanoring
Gold nanoring
Carbon nanoring

Applications of nanorings

Real-time monitoring of blood pressure

Measurement of blood flow rate
Measurement of stress at the a single cell scale
Micro-and nano-electromechanical systems (MEMs NEMs)

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Nanorods

General Method of Preparation

Direct chemical synthesis in the presence of a shape control agents, like ligands
Ligand: Ion or molecule that binds to a central metal atom to form a coordination complex
Different faces of nanorod grows at different rates, producing rod-like elongated object

Diamond Nanorods or Nanodiamond or hyper diamond (2003)

Made by compression of graphite or fullerene

The hardest and least compressible known material

Isothermal bulk modulus of 491 GPa , in contrast to diamond with 442-446 Gpa.
0.3% denser than regular diamond
Nanodiamond
Hardness and Young's modulus comparable to that of natural diamond, but with "superior wear
resistance

Gold Nanorods

ZnO Nanorod

Preparation: Photochemical method employing UV-irradiation to facilitate slow growth of rods

Gold Nanorod
Uses: In vitro and in vivo biomedical applications
Minimal inherent cytotoxicity

Silicon Nanorods

Si Nanorod

Silicon nanorod solar cell: Developed by the California Institute of Technology in Pasadena
The nanorods are assembled into a carpet and embedded into a transparent polymer
Flexible solar cells that use only 1% of the material as conventional silicon cells
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Nanoparticles
Magnetic nanoparticle

Definition

Particles sized between 1-100 nm, characterized by size-dependent properties

Reason for Nano effects

Gold Nanoparticles

Due to significant percentage of atoms at the surface of a material

Due to the large surface area per weight of the material, which make them more reactive

Examples

Iron Oxide nanoparticles: Improves MRI (Magnetic Resonance Imaging) images of cancer
tumors
Palladium nanoparticles: Detection of Hydrogen
Iron Nanoparticles: Clean up CCl4 pollution in ground water
Silicon nanoparticles: Increase battery power and reduce recharge time
Gold Nanoparticles: Allow heat from infrared lasers to be targeted on cancer tumors
Silicate nanoparticles: Stops gasses or moisture in plastic films used for packing
Zinc oxide nanoparticle: Coating on wood, plastic and textiles to protect them from UV rays
Silver nanoparticles: Kills bacteria making clothing making it odor-resistant

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Nanoshells

Nanoshells

Spherical nanoparticle, consisting of a dielectric core covered by a thin metallic shell (usually
gold)
Nanoshells involve a quasiparticle called plasmon
Plasmon oscillation: A collective excitation where the electrons simultaneously oscillate
with respect to all the ions
Plasmon oscillation is tunable
Thickness of the shell and overall particle radius determines which wavelength of
light it couples with
Interacts with a broad range of the light spectrum that spans the visible and near
infrared regions depending on the shape

Synthesis

Gold Nanoshell

E.g. Gold nanoshell: Reduction using tetrachloroauric acid

Applications

Biomedical imaging: E.g. Cancer treatment using gold nanoshells

Fluorescence enhancement of weak molecular emitters
Surface enhanced Raman spectroscopy
Surface enhanced infrared absorption spectroscopy
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Fullerenes and Nanotubes

Buckminster Fullerenes (C60)
History
Kroto and Smalley (1985): Strange results in mass spectra of evaporated carbon samples
Name: A homage to Richard Buckminster Fuller, whose geodesic domes it resembles

Definition
Fullerenes are a class of allotropes of carbon which conceptually are graphene sheets of
linked hexagonal/pentagonal /heptagonal rings rolled into tubes or spheres.
Spherical and ellipsoidal carbon nanomaterials are referred to as fullerenes or bucky balls
Cylindrical ones are called nanotubes or buckytubes

Properties

High tensile strength

High ductility
High electrical conductivity
High heat conductivity
Relative chemical inactivity (as it is cylindrical and "planar" that is, it has no "exposed"
atoms that can be easily displaced).

Applications
Electronics: Organic solar cells, Transistors
Medicine: Antioxidants and biopharmaceuticals; Controlling neurological damage due to
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Fullerenes and Nanotubes

Carbon Nanotubes (CNTs) or Bucky tubes
Discovery: Sumio Iijima and co., 1991
Large length (~microns) and small diameter (~nm)
spect ratio (132,000,000:1) : Near 1D form of Fullerenes

Types:
Single-walled CNT: Zig-zag, Armchair and Chiral
Band gap: 0-2 eV: Metallic/semiconducting behavior

Multi-walled CNT: Multiple rolled layers of concentric tubes: Inter-layer distance ~3.4 A
Zero band gap

Properties
Electronic
Efficient electrical conductors

Mechanical

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Strongest in terms of tensile strength and stiffest in terms of elastic modulus

Single wall CNT: Y = ~1054 Gpa; Tensile Strength (150 Gpa), (1.3-1.4 g/cm3)
Multiwall CNT: Y = ~1200 Gpa; Tensile Strength (150 Gpa), (2.6 g/cm3)
Steel: Y = 208Gpa; Tensile Strength ( 0.4Gpa), (7.8 g/cm3)
Reason: Sp2 bonds formed between the individual carbon atoms
Thermal
Thermal conductivity along the axis of SWNT: ~3500 W/m.K (Copper: 385 W/m.K)
Thermal conductivity across the axis of SWNT: ~1.52 W/m.K ~ that of soil

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Nanocomposites
Nanocomposites
Solid combination of a bulk matrix and nano-dimensional phase(s)
Matrix: Leads to superior overall properties compared to constituent properties e.g.
optical clarity, strength, stiffness, permeability

Size limits for different properties:

<5 nm: Catalytic activity
<20 nm: To make a hard magnetic material soft
<50 nm: For refractive index changes
<100 nm: For achieving super-paramagnetism, mechanical strengthening or restricting
matrix dislocation movement.

Preparation:
Incorporation of additive to a ceramic/metallic matrix leading to intra-granular
dispersions
Generate and fix dislocations during processing: annealing, cooling,

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Nanocomposites
Types
Ceramic-matrix nanocomposites

Matrix of ceramic material (Al2O3, MgO, Si3N4, SiC, etc.)

Al2O3 /W, Mo, Ni, Cu, Co, Fe; ZrO2 /Ni, Mo; MgO/Fe, Co, Ni, etc.
Homogeneous dispersions of metallic particles within the ceramic matrices
Improves optical, electrical and magnetic properties as well as tribological, corrosion-resistance and
other protective properties, Fracture strength, toughness, hardness, etc.

Metal-matrix nanocomposites

E.g.: Carbon nanotube metal matrix composites (TNCMMC)

Economically viable
Provides for a homogeneous dispersion of nanotubes in the metallic matrix
Leads to strong interfacial adhesion between the metallic matrix and the carbon nanotubes

Properties: Improved wear resistance, friction coefficient, or thermal conductivity

Polymer-matrix nanocomposites (PNC)

Polymer nanocomposites (PNC)

Combination of polymer or copolymer matrix and additives of nanosize.
1D (Nanotubes, fibers), 2D (Layered minerals like clay) and 3D (spherical particles)
Polymer: E.g. Polyamide (Nylon): a thermoplastic polymer, glass fiber, carbon fiber, etc.
E.g. Reinforce a polymer matrix by much stiffer nanoparticles of ceramics like clays, or carbon
nanotubes.

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Nanocomposites
PNC Properties
High strength
Because of the higher surface area of the nano-particles, the interaction with the
other particles within the mixture is more
E.g. silicon nanospheres which show quite different characteristics; their
size is 40 100 nm and they are much harder than silicon, their hardness
being between that of sapphire and diamond

Heat resistance
Reduction in heat resistance
E.g. Dispersion of metal nanoparticles within the polymer matrix, enhance
the conductivity of the polymers.

Polymer-carbon nanotube composite

Improved electrical conductivity

Enhancement of thermal conductivity and thermal stability, fire retardancy
Enhancement of oxidation stability
Outstanding mechanical properties : Elastic stiffness, strength, barrier resistance,
scratch/wear resistance
Excellent optical, magnetic and electrical properties
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Properties of Nanoparticles
Optical Properties
Fundamental reasons for unique optical properties
Size of nanoparticle is comparable to the size of EM radiation, or
Elastic light scattering, absorption, reflectance and transmittance, second
harmonic generation, nonlinear optical properties, surface enhanced Raman
scattering, etc. are size-dependent properties for nanomaterials

Labors of the Months

(Norwich, England, ca.
1480). Ruby color
probably due to gold
nanoparticles

The Lycurgus Cup (glass;

British Museum; 4th century A.
D.)
Lycurgus: A Tarcian King
When illuminated from outside,
it appears green.
Shorter wavelengths are not
absorbed

When illuminated from within,

the Lycurgus cup glows red.
The red color is due to tiny
gold particles embedded in
the glass (about 40 parts per
million). Absorption peak at
around 520 nm

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Optical Properties of Nanoparticles

Different Optical Properties

Change in colour
E.g. Gold nanoparticles appear deep red to black in colloidal solution
E.g. Silicon (Gray) Nanoparticles are red in color

Absorption properties
Greater absorption of solar radiation
Absorption of nanoparticle photovoltaic cells is greater than that of thin film solar
cells
Since the smaller the particles, the greater the solar absorption
E.g. Silver nanoparticles: For efficient harvest of light
E.g. Silver nanoparticles in Metal-enhanced fluorescence (MEF) and in surfaceenhanced Raman scattering (SERS)

Superior UV blocking properties

E.g. Zinc oxide nanoparticles
E.g. ZnO nanoparticles: Due to photostability ZnO is used in the preparation of sunscreen
lotions

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Electrical Properties of Nanoparticles

Electrical Resistivity

Larger Resistivity
E.g. Ni-P alloy (363 Ohm-cm) v/s Ni-P nano-crystal (622 Ohm-cm)
Size-dependent electrical resistivity
Increase in both resisitivity and in residual resistivity (T->0) with decreasing size
Due to increased volume fraction of atoms lying in the grain boundaries
Electrical conductivity is proportional to the grain size

Temperature coefficient of resistance (TCR)

TCR decrease with a reduction in size

Due to enhanced scattering from grain boundaries
Grain boundaries are modelled as potential barriers of certain height and width

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Electrical Properties of Nanoparticles

Ballistic Conduction in Carbon and Silicon nanowires

Ohms law is not valid for nanowires

Strictly linear relationship between current and voltage is replaced by a nonlinear law
Explanation
Electrical conductivity of metal is characterized by the free mean path of electrons
Diffusive conductance: Scattering of free electrons in the conductor causes resistance
Ballistic Conductance: Characterized by unimpeded flow of charge or energy carrying
particles over relatively long distances in a material
If the geometric dimensions reach the mean free path length of electrons, the mechanism of
conduction changes from a diffusive to a ballistic

Superconduction

Weak-coupling Type I superconductors (Al, Sn)

Increase in Tc with decrease in size
Due to softening of surface phonon modes
Strong-coupling Type-I superconductor (Pb)
Doesnot change Tc down to particle size of ~6nm

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Magnetic Properties of Nanoparticles

Reason for special magnetic properties

Magnetic properties of a single isolated particle are strongly influenced by the particle size
Magnetic moment per atom increases as size of the nanoparticle decreases
Number of surface atoms increases as cluster size decreases

Ferromagnetism as universal feature of nanoparticles

Ferromagnetism is exhibited by nanoparticles of intrinsically non-magnetic materials

CeO2, TiO2, Al2O3, and MgO

Nitrides such as GaN and chalcogenides such as CdS and CdSe

Ferromagnetism of the nanoparticles is confined to the surface

For nanoparticle, coercivity or remanence increases with decrease in size

Super paramagnetism

Further decrease in particle size leads to zero remanence and coercivity called
Superparamagnetism
E.g. SPIONS: Super Paramagnetic Iron Oxide Nanoparticles (Biomedical application)

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Magnetic Properties of Nanoparticles

Applications
Giant Magnetic Resistance

Albert Fert and Peter Grnberg: Nobel Prize in 2007 for the discovery of GMR
Change in the electrical resistance depending on whether the magnetization of
adjacent ferromagnetic layers are in a parallel or an anti-parallel alignment.
The overall resistance is relatively low for parallel alignment and high for antiparallel alignment
Commercial application in production of hard disk drives (CD)

Magnetic Nanocomposites
Magnetic nanocomposites finds applications in the areas of heath care, catalysis, and
environmental separation

Magnetic nanoparticles with core/shell structures

Biomedical applications: Useful due to their tailored dimensions and compositions
affecting magnetic behavior
Size, shape and biochemical coating could be controlled
Used in magnetic bio-sensing, Cell separation, Contrast enhancement in MRI, cell
labeling, targeted drug delivery, Hyperthermia (cancer treatment)

Magnetic tapes
Reducing the magnetic grain size and narrowing the size distribution are two key issues in
high density magnetic recording.
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Mechanical Properties of Nanomaterials

Reason for enhanced mechanical properties

Reduced imperfections
The small size either renders nanomaterials free of internal structural imperfections such
as dislocations, micro twins, and impurity precipitates
The few defects or impurities present can not multiply sufficiently to cause mechanical
failure
Self-purification process : The imperfections within the nano dimensions are highly
energetic and will migrate to the surface to relax themselves under annealing, purifying
the meterial and leaving perfect material structures inside the nanomaterials
The external surfaces of nanomaterials also have less or free of defects compared to bulk
materials, serving to enhance the mechanical properties
E.g. Superior mechanical properties of carbon nanotubes

High density of grain boundaries

50% or more atoms are situated in the grain boundaries
Two types of atomic arrangements
Crystalline arrangement: All atoms located in the lattice of the crystallite
Interfacial arrangement: All atoms situated in the grain or interface boundaries
between the crystallte

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Mechanical Properties of Nanomaterials

Hardness

Youngs Modulus

Super-hard composites made of nitrides, borides and carbides by plasma-induced chemical and
physical vapor deposition
E.g. Nanocomposites ~50GPa, though individual nitrides has hardness ~21GPa
Nearly spherical, defect-free silicon nanospheres with diameter 20-50 nm has hardness
~50GPa (4 times greater than the bulk silicon)
Single wall carbon nanotube: Y~1000 GPa
Multiwall carbon nanotube: Y ~ 500-6000 Gpa
Steel: ~200GPa

Tensile Strength

Measured by checking Sword-in-sheath failure

Failure mode corresponding to the sliding of the layers within the concentric MWNT assembly
~11-63 Gpa (Steel ~1-2 Gpa)

Applications: High frequency electro-mechanical resonators from carbon nanotubes

and nanowires

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Mechanical Properties of Nanoparticles

Diffusion and sintering

Self-Cleaning effect

Clay nanoparticles when incorporated into polymer matrices increase reinforcement, leading to
stronger plastics, verifiable by a higher glass transition temperature

Melting point

E.g. Presence of titanium dioxide nanoparticles imparts self-cleaning effect

Stronger plastics

The high surface area to volume ratio of nanoparticles provides a tremendous driving force for
diffusion, especially at elevated temperatures
Sintering can take place at lower temperatures, over shorter time scales than for larger
particles.

Gold nanoparticles melt at much lower temperatures (~300 C for 2.5 nm size) than the gold
slabs (1064 C)

Larger Glass Transition temperature

These nanoparticles are hard, and impart their properties to the polymer (plastic).
Nanoparticles have also been attached to textile fibers in order to create smart and functional
clothing

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Quantum Confinement

Quantum Confinement effects

Size-dependent property of nanomaterials
A particle behaves as if it were free when the confining dimension is large compared to the
wavelength of the particle
During this state, the band-gap remains at its original energy due to a continuous
energy state
As the confining dimension decreases and reaches a certain limit, typically in nanoscale,
the energy spectrum turns to discrete
Diameter of the particle is of the same magnitude as the wavelength of the electron
wave function
Band-gap becomes size-dependent

Blue shift in optical illumination as the size of the particles decreases

The smaller the size of the nanoparticle, the larger the band gap, the greater the
difference in energy between the highest valence band and the lowest conduction band
becomes
More energy is needed to excite the dot, and concurrently, more energy is released when
the crystal returns to its resting state
Their electronic and optical properties deviate substantially from those of bulk materials

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Quantum Confinement

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Quantum Confinement

Exciton Bohr Radius

Electrons and electron holes being squeezed into a dimension that approaches a critical
quantum measurement, called the exciton Bohr radius.
3D confinement: Quantum dot
2D confinement: Quantum wire
1D confinement: Quantum well

Applications

Fluorescent dye applications

Higher frequencies of light emitted after excitation of the dot as the crystal size grows
smaller, resulting in a color shift from red to blue in the light emitted
Because of the high level of control possible over the size of the crystals produced, it is
possible to have very precise control over the conductive properties of the material
Other Applications
Nanoparticles act as artificial, man-made atoms with discrete electronic spectra
Enhanced Lasers
Discrete components in nanoelectronics, qubits for quantum information processing
Enhanced ultra-stable fluorescent labels for biosensors to detect, for example, cancers,
malaria or other pathogens, and to do cell biology

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Applications
Areas of applications
In materials science, nanoparticles allow for the making of products with
new mechanical properties, including surface friction, wear resistance,
and adhesion.
The smallest components of a computer chip are on a nanoscale.
In biology and medicine, nanomaterials are used to improve drug design
and targeting. Others are being developed for analytical and
instrumental applications.
Consumer products such as cosmetics, sunscreens, fibres, textiles,
dyes, and paints already contain nanoparticles.
In electronic engineering, nanotechnologies are used for instance to
design smaller, faster, and less consuming data storage devices.
Optical devices such as microscopes have also benefited from Logic
circuits, magneto-electronic devices, magnetic data storage, medicine,
biotechnology
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Applications
Uses of Nano-powder:
Particle of size ~100nm

High-density magnetic recording materials

Absorbing stealth materials
Magnetic fluid materials
Radiation shielding material
Silicon and precision optical polishing materials
Micro-chip thermal conductivity of the substrate and the wiring material
Microelectronic packaging materials
Optoelectronic materials
Advanced battery electrode materials
Solar cell materials
Efficient catalyst
Efficient accelerant
Sensitive components
High toughness ceramic material (not crack the ceramic fell for ceramic engines, etc.)
Body repair materials
Anti-cancer agents.
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Applications
Nano-fiber
Micro-conductors
Micro fiber (future quantum computer) materials
New laser or light-emitting diode materials

Nanofilms

Gas catalyst (such as automotive exhaust gas) materials

Filter material
High-density magnetic recording materials
Photosensitive material
Flat panel display materials
Superconducting materials

Nanoblocks
High strength materials
Intelligent metal materials

Semiconductor nanostructures
Nanostructures in the emitting region of injection laser reduces threshold current
requirement and decreases the device temperature
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Applications of Nanotechnology
Medicine
Biomedical nanotechnology, nano biotechnology, nano medicine
Size of nanomaterials are comparable to biological molecules
In vivo and in vitro biomedical applications

Diagnosis
Nanotechnology-on-a-chip is one more dimension of lab-on-a-chip
technology
Magnetic nanoparticles are used to label specific molecules,
structures or microorganisms
Gold nanoparticles are used to detect of genetic sequence
Multicolor optical coding for biological assays by embedding
different-sized quantum dots into polymeric microbeads
Nanopore technology for analysis of nucleic acids converts strings
of nucleotides directly into electronic signatures
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Applications of Nanotechnology
Medicine
Drug Delivery
The overall drug consumption and side-effects can be lowered
significantly by depositing the active agent in the morbid region only
and in no higher dose than needed

Reduces costs and human suffering

Dendrimers, Nanoporous material, Block co-polymers
Nano Electromechanical systems (NEMS) for active release of drugs
Implantable drug delivery systems

Cancer treatment with iron nanoparticles or gold shells

Gold nanoparticles with a polyelectrolyte coating can make smaller
tumors more visible through X-ray

Buckyballs can "interrupt" the allergy/immune response

Tissue Engineering
Bones regrown on carbon nanotube scaffolds
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Applications of Nanotechnology
Environment
waste-water treatment, air purification and energy storage
devices
Nanoporous membranes are suitable for a mechanical filtration
with extremely small pores smaller than 10 nm (nanofiltration)
and may be composed of nanotubes
Ultrafiltration, which works down to between 10 and 100 nm
Renal dialysis

Magnetic nanoparticles offer an effective and reliable method to

remove heavy metal contaminants from waste water
Using nanoscale particles increases the efficiency to absorb the
contaminants and is comparatively inexpensive compared to
traditional precipitation and filtration methods
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Applications of Nanotechnology
Energy
Themes: Storage, conversion, manufacturing improvements by
reducing materials and process rates, energy saving (by better
thermal insulation for example), and enhanced renewable
energy sources
Reduction of energy consumption
Nanotechnological approaches like light-emitting diodes (LEDs) or
quantum caged atoms (QCAs) could lead to a strong reduction of
energy consumption for illumination

Increasing the efficiency of energy production

Nanotechnology could help increase the efficiency of light
conversion by using nanostructures with a continuum of bandgaps
Spray-on nanoparticle substance as a solar collector (Uty of
Toronto)

Recycling of batteries
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Rechargeable batteries or supercapacitors with higher rate of

recharging using nanomaterials

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Applications of Nanotechnology
Information and Communication
Memory Storage
carbon nanotube based crossbar memory called Nano-RAM
(Nantero)
use of memristor material as a future replacement of Flash memory
(HP)

Novel semiconductor devices

Based on spintronics
Based on GMR - Giant Magneto-Resistance
Hard discs of gigabyte range

Based on Tunneling magnetoresistance (TMR)

Non-volatile main memory for computers, such as the so called
magnetic random access memory or MRAM

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Applications of Nanotechnology
Novel optoelectronic devices
photonic crystals and quantum dots
Photonic crystals
Photonic crystals are materials with a periodic variation in the refractive
index with a lattice constant that is half the wavelength of the light used

Displays
displays with low energy consumption could be accomplished using
carbon nanotubes (CNT)
CNT as as field emitters with extremely high efficiency for field
emission displays

Quantum computers
The Quantum computer has quantum bit memory space termed
"Qubit" for several computations at the same time

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Applications of Nanotechnology
Heavy Industry
Aerospace
Nanotech is lowering the mass of supercapacitors
Reduce the size of equipment and there by decrease fuelconsumption

Catalysis
Extremely large surface to volume ratio
Platinum nanoparticles as automotive catalytic converter

Construction
Nano-cement, nano-steel, Nanoparticles in Glass, Nanoparticles in
coatings, Nanoparticles in fire protection and detection, etc.

Consumer Goods, etc.

Nanofood, self-cleaning or easy-to-clean surfaces on ceramics
or glasses, Nanooptics, Nanotextiles, Nanocosmetics,
Agriculture
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