chm 434f/1206f 2007 solid state materials chemistry

CHM 434F/1206F 2007

SOLID STATE MATERIALS CHEMISTRY

Geoffrey A. Ozin

Materials Chemistry and Nanochemistry Research Group, Chemistry Department, 80 St. George Street, University of Toronto, Toronto,

Ontario, Canada M5S 3H6

Tel: 416 978 2082, Fax: 416 971 2011,

E-mail: [email protected]

Group web-page: www.chem.toronto.edu/staff/GAO/group.html

Password: GoMaterials

mailto:[email protected]

http://www.chem.toronto.edu/staff/GAO/group.html

CHM 434F/CHM 1206F

MATERIALS CHEMISTRY 2007

• Designed as follow-up to CHM 325, Polymer and Materials Chemistry, which focused on synthesis-structure-property-function relations of selected classes of low dimensional 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 and nanomaterials with properties that are intentionally tailored for a particular use.

• The lecture notes 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.

• Followed by a survey of archetype solids that have had a dramatic influence on the materials world.

• Strategies for synthesizing and understanding the formation of many different classes of materials and nanomaterials with intentionally designed structures and compositions, textures and morphologies, length scales and dimensionality are then explored emphasizing how to control relations between structure and property 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 and nanochemistry - emerging sub-disciplines of chemistry.

CHM 434F/CHM 1206F MATERIALS CHEMISTRY 2007

CHM 434F/CHM 1206FMATERIALS CHEMISTRY 2007

• RECOMMENDED TEXT: L. Smart and E. Moore, Solid State Chemistry, An Introduction, Chapman and Hall, London Third Edition

• REFERENCE TEXTS: A. R. West, Solid State Chemistry and its Applications, Wiley, 1997. 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. P. Ball, Made to Measure, New Materials for the 21st Century, Princeton University Press, 1997. G. A. Ozin, A. Arsenault, Nanochemistry: A Chemical Approach to Nanomaterials, Royal Society of Chemistry, 2005

COURSE EVALUATION 2007

• Mid-term test 90 min (25%)

• Written term paper 3000 words (15%)

• Written/oral assignments (20%)

• Final examination 180 min (40%)

SCHEDULE FOR TERM WORK

• Assignment 1: 4th October 2007 – bonding in materials• Assignment 2: 11th October 2007 - short answer paper • Assignment 3: 25th October 2007, oral presentation -

mini-symposium, 6-9 pm, Davenport East• Last day to drop course 4th November 2007 • Assignment 4: 8th November 2007 - 90 minute mid-

term test • Assignment 5: 22nd November 2007 - term paper • Assignment 6: Final exam TBA - December 2007

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

BONDING AND ELECTRONIC PROPERTIES OF SOLIDS

Eg

CB

EF

W

VB

Metal Semiconductor Insulator Semimetal

Bloch-Wilson description of electron occupancy of allowed energy bands for a classical metal, semiconductor, insulator and semimetal.

EF

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 off-diagonal (mixtures of bonding). Try to classify each of these in terms of structure-bonding-properties relations.

ASSIGNMENT 1 – DUE 4TH OCTOBER 2007

BONDING IN MATERIALS - SIMPLE OR COMPLEX?

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, Eg, 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) = 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, k = 0, kv = kc, conservation of momentum

• Indirect transitions, k 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/2)2/(d2E/dk2)

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, 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!!!

• PHYSICS - SOLID STATE BAND CHEMISTRY - MOLECULAR ORBITAL

• Valence band, VB, continuous HOMO, discrete• Conduction band, CB, continuous LUMO, discrete• Fermi energy, EF (Electro)chemical potential• Bloch orbital, localized/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

ASSIGNMENT 2: Due 11th October 2007

SOLIDS THAT INFLUENCED THE MATERIALS WORLD AND WHY?

Give a brief 1-3 line descriptor for 20 of the materials 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

• ZrO2

• Na1+xAl11O17+x/2

• alpha-SiO2

• Si• a-Si:H

• alpha-AlPO4

• GaAs

• Na56Al56Si136O384

• (amine)xTaS2

• BaPb0.8Bi0.2O3

• SnFxO2-x

• YBa2Cu3O7-x

• BaTiO3

• LiNbO3

• SrxLa1-xMnO3

• LixCoO2

• LaNi5

• Nb3Ge

• Ca10(PO4)6(OH)2

• TiS2

• ZnS• WC

• (Si,Al)3(O,N)4

ASSIGNMENT 2


• 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 2


• (SN)x

• HxWO3

• WO3-x

• CrxAl2-xO3

• AgBr

• Cu2HgI4

• gamma-AgI

• VO2

• CrO2

• AlxGa1-xPyAs1-y

• SmCo5

• Fe3O4

• PEO(LiClO4)

ASSIGNMENT 2


ASSIGNMENT 3

CONTEMPORARY ISSUES IN MATERIALS CHEMISTRY

• MINI-SYMPOSIUM 25th October 2007, 6-10 pm• ORAL PRESENTATION• MAXIMUM OF 3 TRANSPARENCIES• MAXIMUM 5 MINUTES

• First come first served – send your first three choices to First come first served – send your first three choices to [email protected]@chem.utoronto.ca

• 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 3: CONTEMPORARY ISSUES IN MATERIALS CHEMISTRY, MINI-SYMPOSIUM

1. Why would the MoS2 faux fullerenes make ideal solid lubricants? 2. How and why would you use chemistry to make water flow uphill ? 3. How and why 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? Herman

5. How and why would you solublize a single wall carbon nanotube? 6. How and why would you functionalize the tip of a single wall carbon nanotube? Ian7. How can an electroluminescent thin film device be made from monodispersed

surfactant-capped CdSe clusters? 8. How and why would you make thread from carbon nanotubes? 9. How and why might you synthesize a concrete spring? 10. How and why would you synthesize a zeolite-like material with a metal-organic

framework, called MOFs?


11. Why and how does the color and luminescence of monodispersed surfactant-capped CdSe clusters change with the size of the clusters? Anna

12. How would you make an abacus from C60?

13. How would you use a liquid crystal and a polymer to electrically control the

transmission of light through a glass window?

14. How would you use a liquid crystal to tune the optical Bragg reflection from a silica colloidal crystal

15. How and why does the magnetotactic bacteria synthesize a chain of ferromagnetic clusters? Leo

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. 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

microspheres22. Why is a membrane made out of Nafion, a perfluorosulphonic acid, the solid electrolyte-separator of choice in a hydrogen-oxygen fuel cell? 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 be made from a single 5 nm diameter CdSe cluster?

Steve25. 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}? What is this good for?


28. Why do green fluorescent 5 nm CdS nanoclusters blink? Jenny29. Why does nitric acid preferentially open the end of a closed carbon nanotube? 30. Why are Fe, Co, Ni the only ferromagnetic transition metals? Megan31. 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 ITO|nc-TiO2, Ru(bipy)3

2+|I-, I2, CH3CN|Pt? 32. Why is the fracture toughness of the calcite nacre shell of the mollusk 1000x that of calcite

itself? Trevor33. How and why would you tune the color of a colloidal crystal? Daniela34. Nanotetrapods – new nanoscale building block new opportunities?35. Carbon nanotubes or inorganic nanotubes – which way to go? Cindy36. Chemically powered nanomotors – dream nanomachines or nanomachine dreams?37. Bio-optics – nature did it first!38. Laser holographic and direct laser written materials – what are they good for?


39. 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?

40. Using porous silicon how would you build an array of color tunable LEDs on a Si wafer that could be used for a flat panel display?

41. 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 barcode nanoscale segments

42. How would you synthesize Ca2C60? Assuming a fcc arrangement of C60 molecules and Ca residing in octahedral interstices, explain why the material is semiconducting?

43. Given just a glass slide, curved lens, polarizers and cholesteryl esters, how would you make a clinical thermometer with a precision of ± 0.1oC?

44. Which materials are in the battle for control of the flat panel display market and what properties of the material will make it a winner?

45. How would you mimic biomineralization of magnetotactic bacteria in the laboratory to synthesize better data storage materials?

46. How might you make a buckyball switch?


47. Given Pt, how would you devise a resistless lithography for Si wafers?48. How would you synthesize and self-assemble semiconductor nanowires into

nanoscale devices like, lasers, LEDs, diodes, transistors, logic circuits? What would it take to synthesize a better computer than current state of the art ones? Jeff

49. How could you self-assemble micron diameter silica spheres into a micron scale checker board pattern?

50. Devise a way of synthesizing a micron scale checker board pattern of vertically aligned zinc oxide nanowires – can you think of a use??

51. How could you store large amounts of information in a fcc colloidal crystal array of microspheres?

52. How could you build a chemical sensor from monodispersed polymer spheres?53. What are the materials options for the safe storage of hydrogen for fuel cell

powered cars?54. Devise a way to synthesize a AuAg nanocluster inside a hollow AuAg nanosphere55. Buckyball or Buckytubes – which one fuels the nanotechnology revolution?

Stephan


56. How might you write the Lord’s prayer on the head of a gold pin?57. Devise means of synthesizing quantum confined silicon in the form of

nanoclusters, nanowires and nanosheets and proving the existence in these nanostructures of QSE in zero, one and two-dimensions.

58. Hello graphene – goodbye carbon nanotubes?59. How and why would you synthesize a superconducting MgB2 nanospring?60. How and why would you synthesize silicon diatoms?61. Evaluate the potential of the materials chemistry that founded Opalux Inc62. Which class of materials can slow the velocity of light to zero and how would

you use this property to build a better solar cell?63. Gold nanorods cure cancer – fact or fiction?64. Chalcogels – beyond silica gels?65. Light emitting electrochemical cells – what are they and do they have a future?66. Chemically smart Bragg mirrors – what are they good for?67. Dream up materials synthesis methods for making an antireflection coating68. Nanodiamonds are a girls best friend too? Pauline

ASSIGNMENT 4: INDEPENDENT WRITTEN PROJECT: SUGGESTED TOPICS

• First come first served – send your first three choices to First come first served – send your first three choices to [email protected]@chem.utoronto.ca

• 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 by 22nd Nov 2007


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? Cindy4. 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? Trevor 7. Plastic electronics for the next millennium- goodbye silicon? 8. Carbon nanotubes - better than Buckminsterfullerene C60? Stephan9. Capped semiconductor nanoclusters - what are they good for? 10. Capped gold nanoclusters - would Faraday be impressed? Jeff11. Electrides - chemistry with the electron – past, present and 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 - do they have a bright future?. 15. Nanoscale patterning and imaging with scanning probe microscopes - smaller, faster, better?16. High Tc superconductors - will they ever reach RT?17. Kinetics of intercalation - getting between the sheets as fast as possible - why do we need to do this?18. Layer-by-layer electrostatic self-assembly – designer thin films?


19. Alkane thiol self-assembled monolayers (SAMs) - what are they good for? Pauline

20. Biomimetic inorganic materials chemistry - why steal Nature’s best ideas? Jenny

21. Microgravity chemistry - 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?

24. Photonic band gap materials for a photonics revolution - trapping light - a new religion?.

25. Dye sensitized nanocrystalline semiconductors - high efficiency low cost solar cells – how are we doing?

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? Daniela

28. Forbidden symmetry - quasi-crystals for quasi-technologies?

29. Nanomaterials - 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 to NEMS – micro(nano)electromechanical 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. Nanosafety - a hot button scientific and political issue?

36. Materials self-assembly over “all” length scales – a panoscopic view of materials?

37. Electrophoretic, electrochromic, electrodewettable materials – battle for electronic paper?


38. Slow photons in photonic crystals - are they good for chemistry?39. Barcode nanorods - do they have a future in bio-nanotechnology?40. Dynamic self-assembly - towards complex systems in chemistry, physics and biology?41. Periodic mesoporous organosilicas - new generation low k microelectronic packaging?42. Molecular electronics - a problem without a solution?43. Spintronics - can we really compute with electron spin rather than charge?44. How would you write all the information in the library of congress on the head of a pin using a chemistry approach - was Richard Feynman right?

45. Nanotetrapods – building blocks for future nanotechnology?

46. Chemically powered nanomotors – dream nanomachines or nanomachine dreams?

47. Carbon nanotubes or inorganic nanotubes – seeing the light at the end of the nanotunnel? Leo

48. Nano: Top-down or bottom-up or an integration of both – which way to go?

49. The race for the hydrogen storage material – challenge for materials chemistry!

50. Bio-optics – helping the photonics revolution?

51. Binary nanocluster superlattices – a new periodic table of superatoms?

52. Elastic photonic crystals –stretching science and technology to new limits?

53. Luminescent nanoclusters - throwing light on living cells? Anna

54. Mesoporous carbons – better lithium solid state battery anodes – pores for thought?


55. Hello graphene – goodbye carbon nanotubes?

56. How and why would you synthesize a superconducting nanospring made of MgB2?

57. How and why would you synthesize silicon diatoms?

58. Evaluate the potential of the materials chemistry that founded Opalux Inc

59. Which class of materials can slow the velocity of light to zero and how would you use this property to build a better solar cell?

60. Gold nanorods cure for cancer – fact or fiction? Steve

61. Chalcogels – beyond silica gels?

62. Light emitting electrochemical cells – what are they and do they have a future?

63. Chemically smart Bragg mirrors – what are they good for?

64. How did the bio-optics of the mosquito eye enable a biomimetic synthesis of antifogging coatings? Megan

chm 434f/1206f 2007 solid state materials chemistry

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