CHEM0013

Introduction to Solid
State Chemistry

Prof Ben Slater

b.slater@ucl.ac.uk

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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