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# 27/07/16

CHEE 4301
Nanomaterials and
their characterisation

## Why Study Crystal Structures

Traditionally, metals and ceramics are crystals and
their crystalline nature affects their properties.
The earliest crystallographers discovered that the
naturally developed external facets of substance
were related to the regularity of their internal
structures.

Lecture 2
Crystal Structure 1
Professor Jin Zou
Contact details: Office Room 75-108
Telephone: 3346 3195
Email: j.zou@uq.edu.au

Lithium Pegmatite

## A crystal consists of identical structural units, consisting

of one or more atoms, which are regularly and
periodically arranged in three dimensions. This
regularity extends over thousands and millions of
molecular dimensions.
crystal structure = lattice + basis
Note:
The smallest building
basis
blocks of a crystal are
referred to as the basis,
the periodic arrangement
is described by the lattice.

lattice
points

crystal structure

## To describe a crystal, it is convenient to ignore the basis

and to focus on the lattice.
The lattice is a three-dimensional array of points (lattice
points), each of which has identical surroundings.
Notes on Unit Cells:
[a Unit Cell represents a small
volume of a lattice
[the whole lattice can be
reconstructed by repeating this unit
cell without empty space in
between
[the unit cell is defined by three
independent unit vectors, a, b, and c
[the direction of the unit vectors a, b,
and c defines the direction of the x, y
and z axes, called the crystal axes

Primitive Cells

Multiple Cells

## Parallelogram cells can be either primitive or

multiple. In general, there are infinite
number of parallelogram cells for a given
lattice.

## A three dimensional Unit Cell can be

described by the relative lengths of three
independent unit vectors (a, b, and c) and
three independent angles between them (,
, and ).
is angle between b and c
is angle between c and a
is angle between a and b

In 2D case

b 3 variables
0

6 variables

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## Unit Cells & Lattice Parameters

For a given lattice, an Unit Cell is defined as the
smallest parallelogram cell that contains less
variables (representing the highest symmetry of
the lattice). - 90 and 120 do not count as
variables.
Lattice parameters a & b are lengths of independent
sides of an Unit Cell.

Triclinic System

## Seven Crystal Systems

Seven distinct Unit Cells can be recognised
for all possible crystalline materials. The
seven Unit Cells are associated with seven
systems of crystal axes called the seven
Crystal Systems.
z
Triclinic system
Monoclinic system
Orthorhombic system
Tetragonal system
Cubic system
Hexagonal system y
Rhombohedral system

Monoclinic System

## In the monoclinic system, a b c, 90 .

6 variables

4 variables

Orthorhombic System

Tetragonal System

## In the tetragonal system, a b c, 90.

3 variables

2 variables

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Cubic System

Hexagonal System
In the hexagonal system,
a b c, 90 and 120.

c
b

1 variable

2 variables

Crystal
systems
Triclinic
Monoclinic
Orthorhombic
Tetragonal
Cubic
Hexagonal
Rhombohedral

Necessary
conditions
a b c,
a b c, 90
a b c, 90
a b c, 90
a b c, 90
a b c, 90, 120
a b c, ( 90)

2 variables

## Fourteen Bravais Lattices

14 Bravais lattices

## Within some Crystal Systems, different lattice

types are possible to represent the highest
symmetry of the lattice. These types are

Why cubic
does not
have a Ccentred
lattice?

P = primitive
I = body-centred

F = face-centred
C = base (one pair of parallel sides)-centred

## Altogether there are fourteen different ways of

distributing lattice points to make 3D lattices.

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## Nearest Neighbours/Coordination Number

Each atom has neighbours
The coordination number (Z) is the number of first
nearest neighbours
In the case of the 2D square lattice, Z = 4
In turn, second nearest neighbours can be
determined

Lattice Parameter
In the simple case, the lattice parameter of an
unit cell is determined by the size of atom
In the square lattice, the lattice parameter is the
length of the side of the unit cell a=2Ratom

a
First nearest
neighbours
Second nearest
neighbours

## The atomic packing fraction (APF) is the fraction of

unit cell occupied by atoms
Assume that atoms are spheres with a specific
radius, the APF can be calculated.
For the case of (2-D) simple
squared unit cell

APF( area ) =

2
Ratom
1 4
4

a2

and a = 2 Ratom
Ratom

APF( area ) =

= 0.79 = 79%

Simple Cubic
Z= 6
a = 2R
V =a3 = 8R3
APF=0.57=57%
1 atom/unit cell

## Body Centre Cubic (BCC)

Z= 8
a = (4/ 3)R
V =a3 = (64/3 3 )R3
APF=0.68=68%
2 atom/unit cell

Ratom

## Number of atoms inside an unit cell (for the given case):

8 corner atoms = 81/8 = 1,
6 face atoms = 61/2 = 3,
so that total number of atoms = 4 atoms

## Volume of 4 atoms = 4x(4/3)r3

Volume of unit cell = a3=(2 2 r)3
4 3 1
r
8 + 1 6
8
2
APF( vol ) = 3
a3

and a = 2 2r
APF( vol ) =

3 2

= 0.74 = 74%

Packing Structures
What is the APF
of close-packed
layer (assuming
2D)?

Z= 12
a = (2 2)R
V =a3 = (16 2)R3
APF=0.74=74%
4 atom/unit cell

Z= 12
a = 2R
V = (8 2)R3
APF=0.74=74%
2 atom/unit cell
c/a=1.633

Simple Cubic

Simple
Hexagonal

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## Two Common Close-Packed Layers

Face-centred cubic
structure

## Two Common Close-Packed Layers

Hexagonal close-packed
structure

B
A

http://www.physics-in-a-nutshell.com/article/11#the-hcp-structure

## What Determines Crystal Structure

Chemical bonding
Size of atoms in structure (especially in
compounds)
Temperature
The crystal structure is the lowest energy
configuration of atoms.
As temperature varies, this can change
For example - Fe (Iron)

## Summary of the Lecture

Concept of lattices and unit cell
7 crystal systems and 14 Bravais lattices
Concepts of
nearest neighbours
coordination number (Z)
lattice parameters (a)
atomic packing fraction (APF)

## At high T, Fe has a BCC structure (T>1394C): -Fe

For 912C < T < 1394C, Fe structure is FCC: -Fe
For T < 912C, Fe structure is BCC (again): -Fe
Below 600C, -Fe becomes magnetic

Homework
Many elements, such as C, Si and Ge, have a
special structure Diamond structure, a special FCC
structure containing 8 atoms (of the same kind) in
each unit cell. As a result, there are two atoms relate
to each lattice point.
Do your literature search (from internet) to find out
and draw the diamond structure.
Based on the obtained structure, determine
the numbers of first and second nearest neighbours
the lattice parameter (assume r is the radius of the
atom)
the atomic packing fraction

## References & Useful Websites

Books
Crystallography, W. Borchardt-Ott
Crystallography and Crystal Defects, A. Kelly, G.W.
Groves, and P. Kidd
The Basics of Crystallography and Diffraction, C.
Hammond
The Structure of Materials, S.M. Allen and E.L.
Thomas

Websites
http://www.matter.org.uk/matscicdrom/manual/xl.html
http://www.msm.cam.ac.uk/phase-trans/2001/
intro.cryst.pdf