PX3012

The Solid State

CM3020
Solid State Chemistry

Course coordinator:
Dr. J. Skakle

Course coordinator:
Dr. J. Feldmann

SOLID STATE
Crystals

Crystal structure basics

unit cells
symmetry
lattices

Diffraction
how and why - derivation
Some important crystal structures and properties
close packed structures
octahedral and tetrahedral holes
basic structures
ferroelectricity

Objectives
By the end of this section you should:
be able to identify a unit cell in a symmetrical
pattern
know that there are 7 possible unit cell shapes
be able to define cubic, tetragonal,
orthorhombic and hexagonal unit cell shapes

Why Solids?
most elements solid at room temperature
atoms in ~fixed position
simple case - crystalline solid
Crystal Structure
Why study crystal structures?
description of solid
comparison with other similar materials classification
correlation with physical properties

Crystals are everywhere!

More crystals

Early ideas
Crystals are solid - but solids are not
necessarily crystalline
Crystals have symmetry (Kepler) and long
range order
Spheres and small shapes can be packed to
produces regular shapes (Hooke, Hauy)

Group discussion
Kepler wondered why snowflakes have 6 corners,
never 5 or 7. By considering the packing of
polygons in 2 dimensions, demonstrate why
pentagons and heptagons shouldnt occur.

Definitions

1. The unit cell

The smallest repeat unit of a crystal structure, in 3D,
which shows the full symmetry of the structure

The unit cell is a

box with:
3 sides - a, b, c
3 angles - , ,

 Seven unit cell shapes

Cubic
a=b=c ===90
Tetragonal a=bc ===90
Orthorhombic
abc ===90
Monoclinic abc
==90, 90
Triclinic abc
90
Hexagonala=bc ==90, =120
Rhombohedral a=b=c ==90

Think about the shapes that these define - look at the

models provided.

2D example - rocksalt
(sodium chloride, NaCl)

We define lattice points ; these are points

with identical environments

Choice of origin is arbitrary - lattice points need not be

atoms - but unit cell size should always be the same.

This is also a unit cell it doesnt matter if you start from Na or Cl

- or if you dont start from an atom

This is NOT a unit cell even though they are all the
same - empty space is not allowed!

In 2D, this IS a unit cell

In 3D, it is NOT

All M.C. Escher works (c) Cordon Art-Baarn-the Netherlands.

All rights reserved.

Examples
The sheets at the end of handout 1 show examples of
periodic patterns. On each, mark on a unit cell.
[remembering that there are a number of different
(correct) answers!]

Summary
Unit cells must link up - cannot have gaps

between adjacent cells

All unit cells must be identical
Unit cells must show the full symmetry of
the structure next section