CHEM0013
Introduction to Solid
State Chemistry
Prof Ben Slater
[email protected] Room 343
Kathleen Lonsdale Building
Gower Place
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Recommended reading
Inorganic Chemistry, CE Housecroft & AG Sharpe
Inorganic Chemistry, D Shriver, PW Atkins & CH Langford
Basic Inorganic Chemistry, FA Cotton, GE Wilkinson & PL Gauss
Three topics : Solid state (BS),
Transition metal chemistry (AS) and
Main group chemistry (CEK)
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CHEM0013: Introduction to Solid State Chemistry
Introduction
Types and properties of inorganic crystalline materials: Metals, Covalent
solids, Molecular solids, Ionic systems, Molecular-ionic solids,
Periodicity, crystal systems and unit cells: Bravais lattices, Miller planes and
indices
Crystal structure determination: X-ray diffraction, Bragg's law
Structures of solid elements: Hexagonal and cubic close packed structures
Binary ionic solids: Packing of cations into hcp and fcc arrays of anions. Derivation of
structures of binary compounds: NaCl, NiAs, ZnS, CsCl, CaF2, CdI2. Examples of ternary
compounds.
Solid hydrides: Rationalising stability trends in hydrides
Radius ratio rules for predicting crystal structure: Coordination number,
tolerance factors
Energies of ionic solids: Calculation of lattice energies, Born-Haber cycles, Hess's law,
Kapustinskii’s equation
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CHEM0013: Introduction to Solid State Chemistry
Time
Ore extraction - gold, silver
Democritus proposes matter
is made of atoms (~370 BCE) but did not comment on the arrangement of
atoms
Alchemy - amongst the earliest targeted solid state experiments
The discovery of x-rays (Rontgen) and their harnessing (Bragg) revealed the
regular structure of materials (20th century)
Simple crystals - DNA - complex proteins
Neutron diffraction to "see" hydrogen atoms
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~70% surface area of earth is water
~20% surface area is rocky mass
~10% of the surface of earth is ice (12,600,000 km2)
Image c/o NASA Apollo 17
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8 Hurricane Isabel 2003
cirrus clouds
Ice
particulates
catalyse
production of
Cl which
destroys
ozone
contrails
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CHEM0013: Introduction to Solid State Chemistry
Why study the solid state?
Solid chemical compounds are ubiquitous in daily life. All elements and compounds are solid for
some range of pressure and temperature. Very many compounds are solid at ambient temperature
and pressure and hence they are the basis of much of inorganic and organic chemistry as well as a
host of technological applications. Often solidity gives rise to a useful property:
• Mechanical properties:
Cement (CaSO4.2H2O and various other minerals), Diamond - used as an abrasive e.g. drill
tips, Lonsdaleite, BN, Lubrication - Graphite, talc Mg3(OH2)Si4O10!
• Electrical properties
Electrical wiring(Cu), circuitry(Au)- semiconductors for computer processors (Si) -
superconductors YBa2Cu3O7 - batteries e.g. mobile phones (Li-ion). Solid state disks.
• Magnetism Magnetic audio/data tape CrO2. Magnetic hard drive.
• Optical properties
Lasers (Al2O3 ruby laser) - Pigments - TiO2, GaP LED’s. OLEDs. (Display devices)
• Catalysis
Zeolites(fine chemicals), Ice, Pt, Pd, Metal Organic Frameworks
• Smart properties
Sensing (gas sensors e.g. H2 on SnO2), filtering air O2/N2 (zeolites)
• Decorative appeal Gemstones - Al2O3 - Ruby (Cr impurities), Sapphire (Ti/Fe impurities)
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CHEM0013: Introduction to Solid State Chemistry
ZIF-8
1.7nm
Metal
Organic
Framework
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CHEM0013: Introduction to Solid State Chemistry
Why study the solid state?
Solid chemical compounds are ubiquitous in daily life. All elements and compounds are solid for
some range of pressure and temperature. Very many compounds are solid at ambient temperature
and pressure and hence they are the basis of much of inorganic and organic chemistry as well as a
host of technological applications. Often solidity gives rise to a useful property:
• Mechanical properties:
Cement (CaSO4.2H2O and various other minerals), Diamond - used as an abrasive e.g. drill
tips, Lonsdaleite, BN, Lubrication - Graphite, talc Mg3(OH2)Si4O10!
• Electrical properties
Electrical wiring(Cu), circuitry(Au)- semiconductors for computer processors (Si) -
superconductors YBa2Cu3O7 - batteries e.g. mobile phones (Li-ion). Solid state disks.
• Magnetism Magnetic audio/data tape CrO2. Magnetic hard drive.
• Optical properties
Lasers (Al2O3 ruby laser) - Pigments - TiO2, GaP LED’s. OLEDs. (Display devices)
• Catalysis
Zeolites(fine chemicals), Ice, Pt, Pd, Metal Organic Frameworks
• Smart properties
Sensing (gas sensors e.g. H2 on SnO2), filtering air O2/N2 (zeolites)
• Decorative appeal Gemstones - Al2O3 - Ruby (Cr impurities), Sapphire (Ti/Fe impurities)
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Zeolite
ZSM-5
SiO2-xAlxMx
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http://www.nrel.gov/ncpv/images/efficiency_chart.jpg
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MAPI Perovskite
20% efficient
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CHEM0013: Introduction to Solid State Chemistry
Why study the solid state?
Solid chemical compounds are ubiquitous in daily life. All elements and compounds are solid for
some range of pressure and temperature. Very many compounds are solid at ambient temperature
and pressure and hence they are the basis of much of inorganic and organic chemistry as well as a
host of technological applications. Often solidity gives rise to a useful property:
• Mechanical properties:
Cement (CaSO4.2H2O and various other minerals), Diamond - used as an abrasive e.g. drill
tips, Lonsdaleite, BN, Lubrication - Graphite, talc Mg3(OH2)Si4O10!
• Electrical properties
Electrical wiring(Cu), circuitry(Au)- semiconductors for computer processors (Si) -
superconductors YBa2Cu3O7 - batteries e.g. mobile phones (Li-ion). Solid state disks.
• Magnetism Magnetic audio/data tape CrO2. Magnetic hard drive.
• Optical properties
Lasers (Al2O3 ruby laser) - Pigments - TiO2, GaP LED’s. OLEDs. (Display devices)
• Catalysis
Zeolites(fine chemicals), Ice, Pt, Pd, Metal Organic Frameworks
• Smart properties
Sensing (gas sensors e.g. H2 on SnO2), filtering air O2/N2 (zeolites)
• Decorative appeal Gemstones - Al2O3 - Ruby (Cr impurities), Sapphire (Ti/Fe impurities)
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CHEM0013: Introduction to Solid State Chemistry
Solids : crystalline versus the amorphous state
We first need to distinguish between two distinct types of solid
Crystal: atoms are Amorphous: Short range
arranged periodically. A sub-unit can order but no long range
be used to tesselate the full structure. order. No unique sub-unit to
Short and long range order. generate the full structure
Translational order No translational order
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Quasicrystals
Prof Dan Schechtman wins 2011 Nobel prize for Chemistry
No translational order but rotational order
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CHEM0013: Introduction to Solid State Chemistry
Solids : crystalline versus the amorphous state
n(r) n(r)
r r
Crystalline Amorphous
Why are some solids amorphous?
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CHEM0013: Introduction to Solid State Chemistry
Solids : crystalline versus the amorphous state
n(r) n(r)
r r
Crystalline Amorphous
Why are some solids amorphous?
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CHEM0013: Introduction to Solid State Chemistry
Solids : crystalline versus the amorphous state
n(r) n(r)
r r
Crystalline Amorphous
Why are some solids amorphous?
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CHEM0013: Introduction to Solid State Chemistry
Solids : crystalline versus the amorphous state
n(r) n(r)
r r
Crystalline Amorphous
Why are some solids amorphous?
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CHEM0013: Introduction to Solid State Chemistry
Solids : crystalline versus the amorphous state
n(r) n(r)
r r
Crystalline Amorphous
Why are some solids amorphous?
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CHEM0013: Introduction to Solid State Chemistry
Families of crystalline solids
We can group solids into distinct families with broadly similar bonding.
a) Metallic
- -
Bonding in metals is reasonably
strong (evidenced by high melting + + +
points). Atoms are immersed
- -
in a sea of electrons.
+ + +
- -
Ag - CCP
b) Covalent solids
A solid in which all bonding is covalent in nature Diamond
(characterised by a build up of electron density
between atoms).
Graphite
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CHEM0013: Introduction to Solid State Chemistry
c) Ionic
Here the solid contains ions rather than uncharged atoms and hence the predominant
interaction between the ions is electrostatic. A most ubiquitous example is salt, NaCl.
+ - +
- + -
hexagonal
d) Molecular
Discrete, uncharged and covalently
bonded molecules held together by
van der Waals forces and perhaps
hydrogen bonds. Bonding typically
weak and hence melting temperatures
are usually low.
Cubic ice
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