2. 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.

3. 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.

4. CHM 434F/CHM 1206F SOLID 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. 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 21 st Century, Princeton University Press, 1997.

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

6. 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

7. 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

8. BONDING AND ELECTRONIC PROPERTIES OF SOLIDS EgEg CB EFEF W VB Metal Semiconductor Insulator Semimetal Bloch-Wilson description of electron occupancy of allowed energy bands for a classical metal, semiconductor, insulator and semimetal. EFEF

9. IONICCOVALENT METALLIC VDW IONIC NaClK 3 C 60 K 2 Pt(CN) 4 Br 0.3.2H 2 O (RNH 3 ) 2 MnCl 4 COVALENT Si (SN) x C 60 METALLIC Cu (TTF) 2 Br VDW C 6 H 6 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. BONDING IN MATERIALS SIMPLE OR COMPLEX?

10. PRIMER: BLOCH-WILSON BAND DESCRIPTION OF SOLIDS Free electron traveling wave exp(ikx) Electron, wave vector k = 2  /, p = h/ = (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 n = 2a Gives rise to forbidden energy band gap, E g, and VB and CB First Brillouin zone runs from k =  /a Band description in terms of density of states (DOS), n(E) Density of occupied and unoccupied states, n(E) = f FD (E)N(E) Fermi Dirac distribution of electrons f FD (E) = 1/(1 + exp(E F -E)/k B T) E F chemical potential of metal essentially highest occupied level of VB E F chemical potential of electrons, pinned for intrinsic SCs 1/2(E v + E c ) Electronic selection rules, optical transitions, momentum k, electric dipole m Direct transitions,  k = 0, k v = k c, conservation of momentum Indirect transitions,  k  0, k v + k ph = k c, conservation of momentum Doping, H impurity model, n/p-doping, radius and energies of electrons/holes Effective mass of electrons/holes in solids, m e,h * = (h/2  ) 2 /(d 2 E/dk 2 )

11. PRIMER: BLOCH-WILSON BAND DESCRIPTION OF SOLIDS Tight binding description of bands  k =  1 n exp(ikna)  n, periodic SALCAO Bloch orbitals Essentially EHMO approximation for solids, H ii coulomb, H ij 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

12. SOLID STATE MATERIALS CHEMISTRY MEETS CONDENSED MATTER PHYSICS OVERCOMING THE JARGON BARRIER SOLID STATE BANDMOLECULAR ORBITAL Valence band, VB, continuousHOMO, discrete Conduction band, CB, continuousLUMO, discrete Fermi energy, E F (Electro)chemical potential Bloch orbital, delocalizedMolecular orbital, localized/delocalized Tight binding band calculationEH molecular orbital calculation n-dopingReduction, pH scale base p-dopingOxidation, pH scale acid Band gap, E g HOMO-LUMO gap Direct band gapDipole allowed Indirect band gapDipole forbidden Phonon, lattice vibration/librationMolecular vibration/rotation Peierls distortion, CDWJahn Teller distortion Polarons, magnons, plasmonsNo analogues in molecules

13. ASSIGNMENT 1: Due 14th October 2004 SOLIDS 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 materials This assignment is intended to get you reading around the subject of solid state materials chemistry It is very demanding to provide succinct answers to each part of this question, it will take much reading and thinking ZrO 2 Na 1+x Al 11 O 17+x/2 alpha-SiO 2 Si a-Si:H alpha-AlPO 4 GaAs Na 56 Al 56 Si 136 O 384 (amine) x TaS 2 BaPb 0.8 Bi 0.2 O 3 SnF x O 2-x

14. YBa 2 Cu 3 O 7-x BaTiO 3 LiNbO 3 Sr x La 1-x MnO 3 Li x CoO 2 LaNi 5 Nb 3 Ge Ca 10 (PO 4 ) 6 (OH) 2 TiS 2 ZnS WC (Si,Al) 3 (O,N) 4 ASSIGNMENT 1 SOLIDS THAT INFLUENCED THE MATERIALS WORLD AND WHY?

15. h-BN PbMo 6 Se 8 Y 3 Al 5 O 12 K 2 [Pt(CN) 4 ]Br 0.3 (CH) n TTF(TCNQ) c-C, h-C C 60 K 3 C 60 SiOPc MgB 2 Porous Si nc-Si nc-TiO 2 ASSIGNMENT 1 SOLIDS THAT INFLUENCED THE MATERIALS WORLD AND WHY?

16. (SN) x H x WO 3 WO 3-x Cr x Al 2-x O 3 AgBr Cu 2 HgI 4 gamma-AgI VO 2 CrO 2 Al x Ga 1-x P y As 1-y SmCo 5 Fe 3 O 4 PEO(LiClO 4 ) ASSIGNMENT 1, SOLIDS THAT INFLUENCED THE MATERIALS WORLD AND WHY?

17. 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

18. ASSIGNMENT 2: CONTEMPORARY ISSUES IN MATERIALS CHEMISTRY, MINI-SYMPOSIUM 1. Why would the MoS 2 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 TiO 2 enhance the RT Li + ionic conductivity of the polymer electrolyte PEO-LiClO 4 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?

19. 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 C 60 ? 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 LaNi 5 H x 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?

20. 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) 2 HgI 4 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?

21. 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-TiO 2 greatly enhance the light-to- electricity conversion efficiency of a photo-regenerative solar cell with the following construction ITO|nc-TiO 2, Ru(bipy) 3 2+ |I -, I 2, CH 3 CN|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?

22. 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 Ca 2 C 60 ? Assuming a fcc arrangement of C 60 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 ± 0.1 o C? 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?

23. 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

24. 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

25. 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?

26. 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?

27. 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? ASSIGNMENT 3: INDEPENDENT WRITTEN PROJECT: SUGGESTED TOPICS