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Title: CHM 434F/CHM 1206F SOLID STATE MATERIALS CHEMISTRY 2004


1
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-property-function 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.

2
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.

3
CHM 434F/CHM 1206FSOLID STATE MATERIALS
CHEMISTRY 2004
  • Solid-state materials synthesis methods
  • Combinatorial materials chemistry robotic
    synthesis
  • Contemporary issues in solid-state materials
    chemistry case histories
  • Recommended text A. R. West, Solid State
    Chemistry and its Applications, Wiley, 1997.
  • Reference texts D. W. Bruce, D. OHare,
    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.

4
COURSE EVALUATION 2004
  • Mid-term test 90 min (25)
  • Written term paper 3000 words (15)
  • Written/oral assignments (10)
  • Final examination 180 min (50)

5
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
    mid-term test
  • Assignment 4 25th November 2004 - term paper
  • Assignment 5 Final exam TBA - December 2004

6
PRIMER SOLID STATE MATERIALS CHEMISTRY
  • 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, space-filling 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

7
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.
8
BONDING IN MATERIALS SIMPLE OR COMPLEX?
  • IONIC COVALENT METALLIC VDW
  • IONIC NaCl K3C60 K2Pt(CN)4Br0.3.2H2O
    (RNH3)2MnCl4
  • COVALENT Si (SN)x
    C60
  • METALLIC Cu
    (TTF)2Br
  • VDW 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-proper
    ties relations.

9
PRIMER BLOCH-WILSON BAND DESCRIPTION OF SOLIDS
  • 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 es 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)

10
PRIMER BLOCH-WILSON BAND DESCRIPTION OF SOLIDS
  • 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, Guasss 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

11
SOLID STATE MATERIALS CHEMISTRY MEETS CONDENSED
MATTER PHYSICSOVERCOMING THE JARGON BARRIER
  • SOLID STATE BAND MOLECULAR ORBITAL
  • Valence band, VB, continuous HOMO, discrete
  • Conduction band, CB, continuous LUMO, discrete
  • Fermi energy, EF (Electro)chemical potential
  • Bloch orbital, delocalized Molecular orbital,
    localized/delocalized
  • Tight binding band calculation EH molecular
    orbital calculation
  • n-doping Reduction, pH scale base
  • p-doping Oxidation, pH scale acid
  • Band gap, Eg HOMO-LUMO gap
  • Direct band gap Dipole allowed
  • Indirect band gap Dipole forbidden
  • Phonon, lattice vibration/libration Molecular
    vibration/rotation
  • Peierls distortion, CDW Jahn Teller distortion
  • Polarons, magnons, plasmons No analogues in
    molecules

12
ASSIGNMENT 1 Due 14th October 2004SOLIDS THAT
INFLUENCED THE MATERIALS WORLD AND WHY?Give a
brief 1-3 line descriptor for each material in
the list that illuminates the key features of
each material that were responsible for the
impact that it had on the high technology world
of advanced materialsThis assignment is
intended to get you reading around the subject of
solid state materials chemistryIt is very
demanding to provide succinct answers to each
part of this question, it will take much reading
and thinking
  • ZrO2
  • Na1xAl11O17x/2
  • alpha-SiO2
  • Si
  • a-SiH
  • alpha-AlPO4
  • GaAs
  • Na56Al56Si136O384
  • (amine)xTaS2
  • BaPb0.8Bi0.2O3
  • SnFxO2-x

13
  • 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?
14
  • h-BN
  • PbMo6Se8
  • Y3Al5O12
  • K2Pt(CN)4Br0.3
  • (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?
15
  • (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?
16
ASSIGNMENT 2 CONTEMPORARY ISSUES IN MATERIALS
CHEMISTRY
  • 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

17
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?

18
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?

19
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 microelectro-mechanical
    machines MEMS?

20
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-to-electricity
    conversion efficiency of a photo-regenerative
    solar cell with the following construction
    ITOnc-TiO2, Ru(bipy)32I-, I2, CH3CNPt?
  • 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?

21
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?

22
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 Lords 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

23
ASSIGNMENT 3 INDEPENDENT WRITTEN PROJECT
SUGGESTED TOPICS
  • Focus your attention on materials design,
    synthesis, characterization, structure, property
    and function relations and the relevance of the
    materials to advanced technologies
  • 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
  • A typed version is required of not more than 3000
    words, not including figures and tables.
  • Hand in a bound copy to Professor Geoffrey A.
    Ozin before 25th November 2004

24
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?

25
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 Natures 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?

26
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?
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