CHEM 340-3

Dr. Hamel Tailor

E-mail: hntailor@sfu.ca
Office: C-9033

Fall 2016

This set of notes is copyright protected

and is not meant for public distribution.
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Dr. H. N. Tailor

BSc: Department of Chemistry, Simon Fraser University.

PhD: Department of Chemistry, Simon Fraser University.
Supervisor: Dr. Zuo-Guang Ye , Professor, Department of Chemistry.

Research Interests: (i) Growth and characterization of relaxor-based

piezo- and ferroelectric single crystals, (ii) Dielectric Spectroscopy (iii)
solution processing and (iv) Highly birefringent and polar inorganic
crystals.
Manager, Laboratory Operations
2010 Faculty of Science Excellence in Teaching Award Recipient

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 -I
Lectures (T & R, 8:30am 10:20am, @ AQ 5037)
Notes: Principles, Concepts & Guidelines (via e-mail or Website)
Tutorials (T or R, 8:30am 10:20am, @ AQ5037)
Questions / Discussion / Problem Sets / Exam Reviews
Solid State Chemistry and Its
Applications nd Edition, Student Edition, Wiley, 2013
[+ ]
Reference Books (Reserved at Library)
[
nd Ed.), Wiley, 1999

Chapman & Hall, 1995.

[3]
[ISBN: 0198557981 (pbk.)]

[4] C.N.R. Rao & B. Raveau -VCH, 1998.

[6] Z.-
Ferroelectric Materials Woodhead
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Publishing Ltd., UK, 2008.

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Evaluation/Marking/Grading
Two Quizzes: 2 x 10% =20 %
Midterm: 30 %
50 %
Important Dates (* Tentative date) :
Quiz #1: Tuesday, Oct 2 9:30 10:20 am
Midterm Exam #1: Oct 27th 9:30am 10:30pm*
Quiz #2: Tuesday, Nov 10/15 9:30 10:20 am*
Final Exam: Thurs Dec 8 8:30 11:30 am
Office Hours:
Time TBA or by email appointment: C9033 , unless otherwise stated.

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 CHEM 340 -

The chemistry of solid state inorganic materials in terms of:

1. Crystal structures, symmetry and properties.
2. Bonding in solids, molecular orbitals & band structures.
3. Basic crystallography
4. X-ray diffraction technique
5. Non-Stoichiometry & Solid solutions
6. Electronic and ionic properties.
7. Applications of inorganic functional materials in
advanced technology
8. Selected topics on structure property relations

1) Functional Materials
Human Civilization & Materials

The growth of civilization has been dependent on materials

The ages of human-kind have been designated based

Iron & Steel Age

Bronze Age
Stone Age
 Semiconductors
Element/Compound SCs
Electronic & Ionic (High-TC)
LS Integrated Circuits
Conductors Superconductors
Optoelectronic Devices
Oxide Transparent Electrodes Cupprate Family
Rechargeable Batteries Iron-Based Supercond.
SOFC New Supercond.

Magnetic Materials Optical Materials

Ferro-/Antiferromagnets Luminescence/Phosphors
(White) LEDs
Magnetoresistance (GMR/CMR)
Laser / Non-linear Optics
Magnetic Data Storage
Ferroelectric Materials
Dielectrics
Piezoelectrics
Pyro-/Ferroelectrics

1. Materials Science and Materials Chemistry

Materials Substances having properties which make them useful in

machinery, structures, devices and properties.
Materials Functions (Properties) Utility (Applications)
Materials & civilization eras:
Stone Age Bronze Iron Synthetic mat. Advanced (smart) mater.
( )
Classification of Materials (on chem. constitution & typical properties)
Metallic materials (metals & alloys):
Metallic bonding, close-packed structures
Delocalized (free) e-s, good electric & thermal conductor, non-transparent to visible light
(luster)
Ductile & malleable for structural applications
Ceramics and (non-metallic) crystalline & non-crystalline materials:
Compounds formed betw. metallic & non-metallic elements
Metal oxides, sulfides, fluorides, nitrides & carbides
Ionic and/or extended covalent bonding
Mostly insulators to electricity & heat, high mech. resist. for ceramics
Variety of structures and compounds numerous8 functional properties for structural,
optical and electronic applications
Semiconductors:
Elements (gr. IV), binary or ternary compounds of (III-V, II-VI)
Extended covalent bonding
Electronic properties betw. insulators and conductors
Very sensitive to trace impurity controlled doping properties
Advent of integrated circuits revolution of -electronics & computers
Polymers:
Macromolecules ranging from linear polymers (amorphous or
quasicrystalline strs.) to extended cross-linked networks.

Functional: e-conductors ( -conjugated), ionic, luminescence, photo-

resistance (lithography), thermoplastic (ductility & formability), e-active
Molecular and Biological Materials:
Materials comprised of discrete molecules bonded by mol. forces.
Functional properties: ferromagnetism, luminescence, catalysis, conductors
& supraconductors..

Weak in strength, unstable at high temperatures

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Composite Materials:
Combinations of two or more different materials
Synergetic combinatn of the best characteristics of each component
Reinforcement of properties (1+1>2)
Ceramics (glass or carbon fibers) embedded with a polymeric matrix

- Functional hybridization: e.g. Magnetic & electric ordering effects

Metals & Ceramics Semi-

Alloys & Crystals conductors

Polymers Molecular
Materials
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 An interdisciplinary area involving materials chemistry, materials physics,
crystallography, processing, manufacturing & applications of materials.

Design of materials with functional properties

Bonding of atoms or mol. groups, crystal field approach;

Anisotropic atomic groupings and symmetry arguments.
Synthesis of functional materials
In the forms of powders, ceramics, single crystals, glasses, thin and thick films
and composites:
Determination of structural properties
Crystal, magnetic and microstructures
Characterization of the physical properties
Electronic, ionic, dielectric, magnetic, optical properties for applications
Understanding the structure property relations
Tailoring the properties for specific applications

Innovative materials, New materials design,

and Novel synthetic strategies
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Functional materials or systems

Normally macroscopic function
Often microscopic mechanism
Design & Synthesis
Often Nanostructured or composite

Bonding & Properties &

Microstructures Applications

Chemistry of solid state inorganic materials in terms of crystal structures, bonding,

preparative methods, analytical and characterization techniques, mixed valence states,
solid solutions, defects and non-stoichiometry, molecular mechanisms of the optical,
electronic, ionic, magnetic and dielectric properties, and materials applications in
advanced technology.
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Materials of interest
Inorganic solids, mostly non-molecular
Structures from 3D packing of atoms & ions collective properties
Variety & complexity of strs central to the appreciation
More sophisticated synthesis methods
Solid state reactions, vapor phase transport, inorganic precursors, crystal growth,

Interpretation and applications of phase diagrams

Many of the synthesis methods are unique to solid state chemistry
Characterization techniques
More emphasis on a variety of diffraction (X-ray, neutron, synchrotron, etc.) and
microscopic (optical and electron) techniques, rather than spectroscopy
Bonding, structures and properties
Ionic models corrected by covalent character; lattice energy
Crystal field theory
Extended covalent model; band structures
Physical properties and applications
Great diversity in the range of properties and applications
Analysis profound of structure-property relations

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Applications of Materials in
Advanced Technology

MP3 Player

Electronics- silicon, Al, Cu

Memory- magnetic,
ferroelectric, optical
Battery Li+-intercalation;
solid state electrochemistry
Case- polymer
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 F1 Helmet
Formula One helmets weighing ca 1.25 kg.
Helmets are constructed from several separate layers,
offering a combination of strength and flexibility.
Fibre reinforced resin, carbon fibre, Kevlar
Polystyrene based deformable layer, flame proofing
Visor clear polycarbonate, anti fogging chemicals,
transparent tear offs
Integrated air intakes with filters
Despite the cutting edge materials used in their
construction Formula One helmets15 are still painted by
hand.

Electronic Article Surveillance

Transmitter yields pulse at 58 kHz for 2ms

Induces resonance in amorphous metal plate
Resonance transmits signal to receiver after
excitation is stopped (like a tuning fork)
Demagnetization of
underlying magnet
renders device inactive.

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 Micro Electro-Mechanical Systems
(MEMS)
Active sensing,
actuating & switching
Must be made in a
way compatible with
other process steps

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Solid Oxide Fuel Cell - Principle

18 Ref.
Development of ( ) Superconducting Materials

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Nobel Prize 1987

Berdorz & Muller
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Multilayered Materials (GMR)

Discovered by Albert Fert and coworkers in 1988
The application of magnetic fields to super lattices of
Fe/Cr greatly reduced their electrical resistivity

Fe
Cr Nobel Prize in Physics
Low High
Fe 2007
Resistivity
Cr
Albert Fert and Peter Grnberg
Fe

N S
MR ratio
80 % at 4K
20 % at 300K
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 Profs. Akasaki, Amano and Nomura for Red Green

Nobel Prize in Physics

2014

Blue
one red + one green + one blue
= white light!
the blue
was really missing. Thanks to the blue LED, we can now get white light

20% of the world's electricity used for lighting, it's been

calculated that optimal use of LED lighting could reduce this to 4%
By Dr Frances Saunders, President, Institute of Physics.

Ye Lab @ SFU
Advanced Materials: Structure, Properties & Applications

Ferroelectrics for
Relaxor-based
non-volatile
piezo-/ ferroelectric
random access
single crystals
1
P, M, S
memories (FeRAM)

E, H,

Lead-free high TC
0

Magnetically piezoelectrics &

ordered ferroelectric crystalline oxides
/ ferroelastic high-K gate
materials dielectrics
 Piezoelectric Materials
Direct Effect:
D3=d33X3
d33: piezoelectric coefficient
D: electrical displacement
X: mechanical stress

Converse Effect:
S3=d33E3
d33: piezoelectric coefficient
E: electric field
S: mechanical strain
Need non-
centrosymmetric
point group kp: planar coupling constant
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P iezoelectric Devices Us ed in the E lectronic Equipment

C eramics
C eramics res onator for
res onator for time counting
CPU

ceramics filter
Mobile phone
Fujitsu Laboratories, Ltd.

CPU
(c)1996 2002 WANI3/T.Kitajima/ WANILAND
Inkjet printer head ceramics r
NG K INSULATOR S , LTD.
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S. Wada
 Ye Lab @ SFU
Piezoelectric Single Crystals as Ultrasound Transducer

( ( (c
a) b) )
Meso- to micro-
scopic domain
structure/Symmetry
Composition -
property relations,
temperature
dependences.
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History of Piezoelectric Materials Development*

3000

PMN-PT/PZN-PT
2500

Single Crystals
2000

PMN-PT
1500
PZN-PT

1000

PZT+
PZT
500 Ternary
BaTiO3

0
1930 1940 1950 1960 1970 1980 1990 2000 2010

Year

*Z.-G. Ye, "High-Performance Piezoelectric Single Crystals of Complex Perovskite

Solid Solutions", , Vol. 34, No. 4 (April 2009) pp. 277-283.
 Chem: Jan. 22, 2016 @ 4:00pm
https://www.sfu.ca/dean-gradstudies/awards/undergraduate-
awards/undergraduate-research-awards.html

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NSERC & VPR USRA information can be found here

NSERC USRA Process (for Students & Supervisors)

- Interested eligible students should contact the proposed Supervisor in the

department at which they would like to hold the award.

- Students must create an NSERC Online Account and complete the application
for an Undergraduate Student Research Award Form 202 Part I.

- The student must request the supervisor to complete Form 202 Part II and
submit it online (the supervisor needs to know the "reference
number" to do so).

- The student verifies their application and submits it online, including uploading
transcripts to NSERC by February 4, 2015.

*********************************************************

Students must submit to the Chair's Office (C9040) by Jan 22 by 4:00 pm:

1. Paper application as follows:

- Form 202 (Part I) (student)
- Form 202 (Part II) (supervisor)
2. Photocopies of transcripts
********************************************************
VPR Sciences Process

- Interested eligible students should contact the proposed supervisor in the

department at which they would like to hold the award.

- Students complete the application form, print it and attach an up-to-date

unofficial transcript (not an advising transcript).

- This must be submitted to the Chair's Office (C9040) by Jan 22 by 4:00 pm:

Eligibility Quick Summary

NSERC VPR
Can International students apply? No Yes

Can non SFU students apply? Yes No

Does funding held by the Supervisor have to Yes No
be an NSERC grant? 30
Can the student take courses while holding No
award?