CHM 434F/CHM 1206F
SOLID STATE MATERIALS CHEMISTRY 2004
• This course is designed as a follow-up to CHM 325, Polymer and
Materials Chemistry, which focused on structure-propertyfunction relations of selected classes of polymeric and inorganic
materials.
• In this course we will be concerned with a comprehensive
investigation of a wide range of synthetic methods for preparing
diverse classes of inorganic materials with properties that are
intentionally tailored for a particular use.
• The lectures begin with a primer that covers key aspects of the
background of solid-state materials, electronic band description of
solids, and connections between molecules and bonds in materials
chemistry and solids and bands in solid-state physics.
CHM 434F/CHM 1206F
SOLID STATE MATERIALS CHEMISTRY 2004
• This is followed by a survey of archetype solids that have had a
dramatic influence on the materials world, new and exciting
developments in materials chemistry and a look into the crystal ball at
perceived future developments in materials research, development
and technology.
• Strategies for synthesizing many different classes of materials with
intentionally designed structures and compositions, textures and
morphologies, length scales and dimensionality are then explored in
detail emphasizing how to control the relations between structure and
property of materials and ultimately function and utility.
• A number of contemporary issues in materials research are critically
evaluated to introduce the student to recent highlights in the field of
materials chemistry - an emerging sub-discipline of chemistry.
CHM 434F/CHM 1206F
SOLID STATE MATERIALS CHEMISTRY 2004
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Solid-state materials – synthesis methods
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Combinatorial materials chemistry – robotic synthesis
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Contemporary issues in solid-state materials chemistry – case histories
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Recommended text: A. R. West, Solid State Chemistry and its Applications,
Wiley, 1997.
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Reference texts: D. W. Bruce, D. O’Hare, Inorganic Materials, Second Edition,
Wiley, 1997. L. V. Interrante, M. J. Hampden-Smith, Chemistry of Advanced
Materials, Wiley-VCH, 1998. C. N. R. Rao, J. Gopalakrishnan, New Directions in
Solid State Chemistry, Second Edition, Cambridge University Press, 1997. L.
Smart and E. Moore, Solid State Chemistry, An Introduction, Chapman and Hall,
London, Second Edition. P. Ball, Made to Measure, New Materials for the 21st
Century, Princeton University Press, 1997.
COURSE EVALUATION 2004
• Mid-term test 90 min (25%)
• Written term paper 3000 words (15%)
• Written/oral assignments (10%)
• Final examination 180 min (50%)
SCHEDULE FOR TERM WORK
• Assignment 1: 14th October 2004 - short answer paper
• Assignment 2: 28th October 2004, oral presentation mini-symposium, 6-9 pm
• Last day to drop course 3rd November 2004
• Assignment 3: 11th November 2004 - 90 minute midterm test
• Assignment 4: 25th November 2004 - term paper
• Assignment 5: Final exam TBA - December 2004
PRIMER: SOLID STATE MATERIALS CHEMISTRY
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Bonding in solids, ionic and covalent
Most solids are not purely ionic or covalent, polarization, dipolar,
dispersion, Van der Waals forces
Close packing concepts, hard spheres, coordination number,
substitutional-interstitial sites
Primitive unit cell, standard crystal systems (seven), lattices (fourteen
Bravais), translational and rotational symmetry (230 space groups)
Factors controlling structure, stoichiometry, stability (charge, size, spacefilling concepts) of solids
Basic concepts in bonding and electronic properties of solids
Defects, doping, non-stoichiometry, effect on properties
Electronic, optical, magnetic, charge-transport behavior of solids
BONDING AND ELECTRONIC PROPERTIES OF SOLIDS
CB
Eg
EF
EF
VB
W
Metal
Semiconductor
Insulator
Semimetal
Bloch-Wilson description of electron occupancy of allowed energy bands for a
classical metal, semiconductor, insulator and semimetal.
BONDING IN MATERIALS
SIMPLE OR COMPLEX?
IONIC
COVALENT
METALLIC
VDW
IONIC
COVALENT METALLIC
VDW
NaCl
K3C60
K2Pt(CN)4Br0.3.2H2O (RNH3)2MnCl4
Si
(SN)x
C60
Cu
(TTF)2Br
C6H6
The bonding in these materials range from the simplest ones on the diagonal of the
matrix (single type of bonding) to more complex of diagonal (mixtures of bonding).
Try to classify each of these in terms of structure-bonding-properties relations.
PRIMER: BLOCH-WILSON BAND DESCRIPTION OF SOLIDS
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Free electron traveling wave exp(ikx)
Electron l, wave vector k = 2p/l, p = h/l = (h/2p)k quasi-momentum
Description of electrons in solids
Modulated electron waves in a periodic crystal potential U(x)
Bloch orbitals (x) = exp(ikx)U(x)
Electron wavelengths from  to lattice spacing 2a
Scattering of e’s by nuclei, standing waves at Bragg condition nl = 2a
Gives rise to forbidden energy band gap, Eg, and VB and CB
First Brillouin zone runs from k = p/a
Band description in terms of density of states (DOS), n(E)
Density of occupied and unoccupied states, n(E) = fFD(E)N(E)
Fermi Dirac distribution of electrons fFD(E) = 1/(1 + exp(EF-E)/kBT)
EF chemical potential of metal essentially highest occupied level of VB
EF chemical potential of electrons, pinned for intrinsic SCs 1/2(Ev + Ec)
Electronic selection rules, optical transitions, momentum k, electric dipole m
Direct transitions, Dk = 0, kv = kc, conservation of momentum
Indirect transitions, Dk  0, kv + kph = kc, conservation of momentum
Doping, H impurity model, n/p-doping, radius and energies of electrons/holes
Effective mass of electrons/holes in solids, me,h* = (h/2p)2/(d2E/dk2)
PRIMER: BLOCH-WILSON BAND DESCRIPTION OF SOLIDS
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Tight binding description of bands k = 1nexp(ikna)n, periodic SALCAO Bloch orbitals
Essentially EHMO approximation for solids, Hii coulomb, Hij resonance integrals, yields E(k) vs k
dispersion plots
Useful relations, orbital overlap, band width, delocalization, band gap, band curvature, m*,
mobility, conductivity
Junctions between SCs, Guass’s theorem, contact potential, band bending
Semiconductor np-junction diodes, M-SC junctions, Schottky barriers/diodes, ohmic contacts
Photovoltaics, photodetectors
Semiconductor-liquid junctions
Solar cells and photoelectrochemical cells
Semiconductor pnp and npn-junction bipolar transistors, amplifiers, switches
Metal-oxide-semiconductor junction field effect transistor, MOS-FET
Semiconductor LEDs, lasers, detectors
Organic LEDs, FETs
Quantum confined semiconductors, sheets, wires, dots
Quantum superlattices
Quantum devices, electronic/optical switches, MQW lasers, SETs
Nanomaterials, nanoelectronics, nanophotonics, nanomachines, nanofuture
SOLID STATE MATERIALS CHEMISTRY MEETS
CONDENSED MATTER PHYSICS
OVERCOMING THE JARGON BARRIER
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SOLID STATE BAND
Valence band, VB, continuous
Conduction band, CB, continuous
Fermi energy, EF
Bloch orbital, delocalized
Tight binding band calculation
n-doping
p-doping
Band gap, Eg
Direct band gap
Indirect band gap
Phonon, lattice vibration/libration
Peierls distortion, CDW
Polarons, magnons, plasmons
MOLECULAR ORBITAL
HOMO, discrete
LUMO, discrete
(Electro)chemical potential
Molecular orbital, localized/delocalized
EH molecular orbital calculation
Reduction, pH scale base
Oxidation, pH scale acid
HOMO-LUMO gap
Dipole allowed
Dipole forbidden
Molecular vibration/rotation
Jahn Teller distortion
No analogues in molecules
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ZrO2
ASSIGNMENT 1: Due 14th October 2004
Na1+xAl11O17+x/2
SOLIDS THAT INFLUENCED THE
alpha-SiO2
MATERIALS WORLD AND WHY?
Si
Give a brief 1-3 line descriptor for each material in the
a-Si:H
list that illuminates the key features of each material
that were responsible for the impact that it had on the
alpha-AlPO4
high technology world of advanced materials
GaAs
Na56Al56Si136O384 This assignment is intended to get you reading around the
subject of solid state materials chemistry
(amine)xTaS2
It is very demanding to provide succinct answers to each
BaPb0.8Bi0.2O3
part of this question, it will take much reading and
SnFxO2-x
thinking
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YBa2Cu3O7-x
BaTiO3
LiNbO3
SrxLa1-xMnO3
LixCoO2
LaNi5
Nb3Ge
Ca10(PO4)6(OH)2
TiS2
ZnS
WC
(Si,Al)3(O,N)4
ASSIGNMENT 1
SOLIDS THAT INFLUENCED THE
MATERIALS WORLD AND WHY?
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h-BN
PbMo6Se8
Y3Al5O12
K2[Pt(CN)4]Br0.3
(CH)n
TTF(TCNQ)
c-C, h-C
C60
K3C60
SiOPc
MgB2
Porous Si
nc-Si
nc-TiO2
ASSIGNMENT 1
SOLIDS THAT INFLUENCED THE
MATERIALS WORLD AND WHY?
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(SN)x
HxWO3
WO3-x
CrxAl2-xO3
AgBr
Cu2HgI4
gamma-AgI
VO2
CrO2
AlxGa1-xPyAs1-y
SmCo5
Fe3O4
PEO(LiClO4)
ASSIGNMENT 1,
SOLIDS THAT INFLUENCED THE
MATERIALS WORLD AND WHY?
ASSIGNMENT 2
CONTEMPORARY ISSUES IN MATERIALS CHEMISTRY
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MINI-SYMPOSIUM 28th October 2004, 6-9 pm
ORAL PRESENTATION
MAXIMUM OF 3 TRANSPARENCIES
MAXIMUM 5 MINUTES
• Note that these questions will require considerable
background reading and thought and may not be able to
be addressed until well into the course
• Also this type of oral presentation is amongst the hardest
to prepare and most demanding in terms of successfully
delivering the main message
ASSIGNMENT 2: CONTEMPORARY ISSUES IN
MATERIALS CHEMISTRY, MINI-SYMPOSIUM
1. Why would the MoS2 faux fullerenes make ideal solid lubricants?
2. How would you use chemistry to make water flow uphill?
3. How would you synthesize hexagonal mesoporous silica from a lyotropic liquid crystal?
4. Why does nanocrystalline TiO2 enhance the RT Li+ ionic conductivity of the polymer
electrolyte PEO-LiClO4 in a solid state Li intercalation battery?
5. How and why would you solublize a single wall carbon nanotube?
6. How and why would you functionalize a single wall carbon nanotube?
7. How can an electroluminescent thin film device be made from monodispersed
surfactant-capped CdSe clusters?
8. What are the advantages of using a single walled carbon nanotube as the tip in an
atomic force microscope?
9. How and why might you synthesize a concrete spring?
10. How would you synthesize a zeolite-like material with a framework based upon either
a metal sulfide or metal-ligand complex rather than an aluminosilicate?
ASSIGNMENT 2: CONTEMPORARY ISSUES IN
MATERIALS CHEMISTRY, MINI-SYMPOSIUM
11. Why and how does the color and luminescence of monodispersed surfactant-capped CdSe
clusters change with the size of the clusters?
12. How would you make an abacus from C60?
13. How would you use a thermotropic liquid crystal and a polymer to electrically control the
transmission of light through a glass window?
14. How would you use a thermotropic liquid crystal to tune the optical Bragg reflection from
a silica colloidal photonic crystal
15. How and why does the magnetotactic bacteria synthesize a chain of ferromagnetic
clusters?
16. How could you build a chemical sensor from monodispersed latex spheres?
17. How does the intermetallic LaNi5Hx function as a cathode in an alkaline-nickel hydroxide
battery?
18. How would you use a combinatorial materials chemistry approach to find a better lithium
solid state battery cathode or anode?
ASSIGNMENT 2: CONTEMPORARY ISSUES IN
MATERIALS CHEMISTRY, MINI-SYMPOSIUM
19. How can information be stored in CoCuCo metal magnetic multilayers?
20. How would you synthesize a plastic light emitting diode?
21. How and why would you synthesize a colloidal crystal with a diamond lattice of silica
microspheres
22. Why is a membrane made out of Nafion, a perfluorosulphonic acid, the solid
electrolyte-separator of choice in a hydrogen-oxygen fuel cell? Could you find a new
material to make a better membrane than Nafion?
23. Why does the Tc of BiSrCuO type ceramic superconductors not change on intercalating a
5 nm thickness (cetylpyridinium)2HgI4 bilayer between the BiO layer-planes?
24. How can a single electron transistor (SET) be made from a single 5 nm diameter CdSe
cluster?
25. How can a transistor be made from just one single walled carbon nanotube?
26. Why does the jewelers chisel preferentially cleave diamond along {111}?
27. Why does single crystal Si display chemical anisotropic etching in alkaline solutions that
is faster along {111} than {100}? How is this attribute used to make microelectromechanical machines MEMS?
ASSIGNMENT 2: CONTEMPORARY ISSUES IN
MATERIALS CHEMISTRY, MINI-SYMPOSIUM
28. Why does an ensemble of monodisperse 5 nm CdS nanoclusters, excited with UV
light, display continuous bright green-blue luminescence, whereas a single
nanocluster shows flashing green?
29. Why does nitric acid preferentially open the end of a closed carbon nanotube?
30. Why are Fe, Co, Ni the only ferromagnetic transition metals?
31. Why does dye-sensitized nanocrystalline nc-TiO2 greatly enhance the light-toelectricity conversion efficiency of a photo-regenerative solar cell with the following
construction ITO|nc-TiO2, Ru(bipy)32+|I-, I2, CH3CN|Pt?
32. Why is the fracture toughness of the calcite nacre shell of the mollusk 1000x that of
calcite itself?
33. How many ways can you think of tuning the wavelength of an optical Bragg
reflector built of a face centered cubic colloidal crystal array of silica spheres? Why
would you want to do this?
ASSIGNMENT 2: CONTEMPORARY ISSUES IN
MATERIALS CHEMISTRY, MINI-SYMPOSIUM
34. How does the anodic oxidation of a wafer of p-Si in aqueous HF, lead to self-limiting
monodispersed pore formation and a novel material that is photo- and
electroluminescent? With this knowledge how would you build an array of wavelength
tunable, individually addressable LEDs on a Si wafer based on this chemistry, that could
be used for an active matrix flat panel display?
35. How would you make an alumina or silicon thin disc with a hcp array of parallel nanoscale
channels starting with an aluminum disc or silicon wafer and then use it to make free
standing nanorod replicas comprised of Ag and Au bar coded nanoscale segments
36. How would you synthesize Ca2C60? Assuming a fcc arrangement of C60 molecules and Ca
residing in octahedral interstices, explain why the material is semiconducting?
37. Given just a glass slide, curved lens, polarizers and cholesteryl esters, how would you make
a clinical thermometer with a precision of ± 0.1oC?
38. Which organic, inorganic and polymeric materials are in the global battle for control of
the electroluminescent, electrochromic, electrophoretic and liquid crystal flat panel
display market, and what properties of the material will make it a winner?
ASSIGNMENT 2: CONTEMPORARY ISSUES IN
MATERIALS CHEMISTRY, MINI-SYMPOSIUM
39. How would you mimic biomineralization of magnetotactic bacteria in the laboratory to
synthesize better data storage materials?
40. How might you make a buckyball switch?
41. Given Pt, how would you devise a resistless lithography for Si wafers?
42. How would you synthesize and self-assemble semiconductor nanowires into nanoscale
devices like, lasers, LEDs, diodes, transistors, logic circuits? Can you use this
knowledge to synthesize a better computer than current state of the art ones?
43. How could you self-assemble micron diameter silica spheres into a micron scale checker
board pattern?
44. How might you write the Lord’s prayer on the head of a gold pin?
45. Devise a way of synthesizing a micron scale checker board pattern of vertically aligned
carbon nanotubes or zinc oxide nanowires?
46. How could you store large amounts of information in a fcc colloidal crystal array of
microspheres?
47. How could you build a chemical sensor from monodispersed polymer spheres?
48. Materials options for the safe storage of hydrogen for fuel cell powered cars
49. Devise a way to synthesize a AuAg nanocluster inside a hollow AuAg nanosphere
ASSIGNMENT 3: INDEPENDENT WRITTEN
PROJECT: SUGGESTED TOPICS
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Focus your attention on materials design, synthesis, characterization,
structure, property and function relations and the relevance of the
materials to advanced technologies
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High marks for this assignment will require more than just a written
representation of what you find in books, reviews and papers - it will also
require some evidence of creative ideas, original thinking and critical
commentary
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A typed version is required of not more than 3000 words, not including
figures and tables.
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Hand in a bound copy to Professor Geoffrey A. Ozin before 25th
November 2004
ASSIGNMENT 3: INDEPENDENT WRITTEN
PROJECT: SUGGESTED TOPICS
1. Evoking light emission from silicon - LEDs and lasers made of silicon - science fiction or reality?
2. Endohedral and exohedral fullerenes - what are they good for?
3. Inorganic polymers - materials for the next century?
4. Non-oxide open-framework materials - past, present and do they have a future?
5. Materials harder than diamond - can they be made and why do we need them?
6. Supramolecular templating of mesostructured inorganics - a solution looking for a problem?
7. Plastic electronics for the next millenium- goodbye silicon?
8. Carbon nanotubes - better than Buckminsterfullerene C60?
9. Capped semiconductor nanoclusters and nanocluster superlattices - what are they good for?
10. Capped gold nanoclusters and gold nanocluster superlattices - would Faraday be impressed?
11. Electrides - chemistry with the electron - do they have a future?
12. Magic of magnetic multilayers - giant magnetoresistance data storage materials - can they compete?
13. Molecular magnetism - a basis for new materials?
14. Photorefractive materials for manipulating light - do they have a bright future?.
15. Nanoscale patterning and imaging with scanning probe microscopes - smaller, faster, better things?
16. High Tc superconductors - will they ever reach RT and be useful?
17. Kinetics of intercalation - getting between the sheets as fast as possible - why do we need to do this?
18. Layer-by-layer assembly of inorganic thin films - why do we need such designer multilayers?
ASSIGNMENT 3: INDEPENDENT WRITTEN
PROJECT: SUGGESTED TOPICS
19. Alkane thiol self-assembled monolayers (SAMs) - what are they good for?
20. Biomimetic inorganic materials chemistry - why steal Nature’s best ideas?
21. Why grow inorganic crystals in space?
22. Information storage materials - how dense can you get?
23. Microelectrochemical transistors and diodes - materials chemistry on a chip that did not make it, why?.
24. Photonic band gap materials for a photonics revolution - trapping light - a new religion?.
25. Dye sensitized nanocrystalline semiconductors - towards high efficiency solar cells?
26. Fuel cell materials - future of the electric vehicle - science fiction or reality?
27. Smart window materials - energy conservation and privacy - how do they work?
28. Forbidden symmetry - quasi-crystals for quasi-technologies?
29. Nanocrystalline materials - will they really impact science and technology?
31. Silica film must be at least 4-5 atoms thick to be an insulator - end of the road for silicon electronics?
32. MEMS - microelectromechanical machines - can they really do big things?
33. Nanowire nanocomputer - science fiction or reality?
34. On-chip lithium solid state microbatteries - towards on board power?
35. Why has the subject of nanosafety recently become a hot button scientific and political issue?
36. Materials self-assembly over “all” scales - panoscopic view of materials?
37. Electrophoresis, electrochromicity, electrodewettability materials – battle for electronic ink?
ASSIGNMENT 3: INDEPENDENT WRITTEN
PROJECT: SUGGESTED TOPICS
38. Slow photons in photonic crystals, what are they good for?
39. Barcoded nanorods - do they have a future in bionanotechnology?
40. Dynamic self-assembly - towards complex systems in chemistry, physics and biology?
41. Periodic mesoporous organosilica materials - could they make it as a new generation of low
dielectric constant materials for microelectronic packaging.
42. Molecular electronics - a problem without a solution?
43. Materials for a spintronic revolution - can we really compute with electron spin rather than
charge?
44. How would you prove Richard Feynmann right and write all the information in the library of
congress on the head of a pin using a chemical approach?