Week 2 Crystallography

Video 6 Stacking sequences

Miller Indices
Bravais lattices
Classification system
 SIMPLE CUBIC STRUCTURE (SC)

• Rare due to poor packing (only Po has this structure)

• Close-packed directions are cube edges.

• Coordination # = 6
(# nearest neighbours)

SC elements:

Polonium (Po)

APF 0.52
BODY CENTERED CUBIC STRUCTURE (BCC)
• Close packed directions are cube diagonals.
--Note: All atoms are identical; the center atom is shaded
differently only for ease of viewing. BCC elements:
· Barium (Ba)
• Coordination # = 8 · Cesium (Cs)
· Chromium (Cr)
· Europium (Eu)
· Iron (Fe)
· Lithium (Li)
· Manganese (Mn)
· Molybdenum (Mo)
· Niobium (Nb)
· Potassium (K)
· Radium (Ra)
· Rubidium (Rb)
· Sodium (Na)
· Tantalum (Ta)
APF 0.68 · Tungsten (W)
· Vanadium (V)
HEXAGONAL CLOSE-PACKED STRUCTURE (HCP)
HCP elements:
• ABAB... Stacking Sequence · Beryllium (Be)
· Cadmium (Cd)
· Cobalt (Co)
• 3D Projection • 2D Projection · Dysprosium (Dy)
· Erbium (Er)
Atoms fill the gaps · Gadolinium (Gd)
· Hafnium (Hf)
A sites · Holmium (Ho)
Top layer · Lutetium (Lu)
· Magnesium (Mg)
B sites Middle layer · Osmium (Os)
· Rhenium (Re)
A sites Bottom layer · Ruthenium (Ru)
· Scandium (Sc)
Adapted from Fig. 3.3, · Technetium (Tc)
Callister 6e. · Terbium (Tb)
Sequence: · Thallium (Tl)
• Coordination # = 12 A  B plus 120 rotation · Thulium (Tm)
B  A minus 120 rotation · Titanium (Ti)
· Yttrium (Y)
APF 0.74 · Zinc (Zn)
· Zirconium (Zr)
 The ABABAB
stacking sequence
of close-packed
planes produces
the HCP structure.

Atoms fill the gaps

(c) 2003 Brooks/Cole Publishing / Thomson

Learning™
 FACE CENTERED CUBIC STRUCTURE (FCC)

• Close packed directions are face diagonals.

--Note: All atoms are identical; the face-centered atoms are shaded
differently only for ease of viewing.
FCC elements:
• Coordination # = 12 · Aluminium (Al)
· Calcium (Ca)
· Copper (Cu)
· Gold (Au)
· Iridium (Ir)
· Lead (Pb)
· Nickel (Ni)
· Palladium (Pd)
· Platinum (Pt)
· Rhodium (Rh)
APF 0.74 · Silver (Ag)
· Strontium (Sr)
But it is important to note the FCC structure is built up from a hexagonal · Thorium (Th)
platform. Hence the coordination number is the same as HCP · Ytterbium (Yb)
 FCC STACKING SEQUENCE
• ABCABC... Stacking Sequence
• 2D Projection
Atoms fill the gaps

A
B B
C
A
A sites B B B
C C
B sites B B
C sites

A
• FCC Unit Cell B Sequence:
C A  B plus 120 rotation
B  C plus 120 rotation
C  A plus 120 rotation
 (c) 2003 Brooks/Cole Publishing / Thomson
Learning™

The ABCABCABC stacking sequence of close-packed

planes produces the FCC structure.
 Describing directions in a crystal
c P Generally lattices have only three axes and in the case
of the cubic lattice these are mutually perpendicular.
The direction OP in a lattice is labelled by locating where
the vector intersects a lattice point and noting the integer
steps of lattice points along the a, b & c axes.
Recording directions is important as the properties of many
O crystals are anisotropic.
b aka Young’s modulus
a
Unit side length cube
Anisotropy in
some metals

The direction OP is labelled [111] and the square brackets are used by convention to indicate a
vector from a known starting point or origin O.

In practice in crystallography it is enough to know the general direction indicated by OP

through the bulk of the crystal and the family of these directions is given by <111> using corner
brackets.
 Negative directions in a crystal

c
P Directions with -ve directions are labelled with a bar

Similarly the complete set of directions given

by OP follows the labelling convention

O
b
a
 Describing atomic planes in a crystal – Miller Indices

The planes in a crystal are labelled in a similar way to

directions.

z The plane obviously extends across the whole of the

crystal so it is helpful to show where the plane
c intercepts the axes close to an assumed origin.

The following steps yield the Millar indices

a b c
y
a b 1. Intercepts 1 1 
2. Reciprocals 1/1 1/1 1/
x 1 1 0
3. Reduction 1 1 0

4. Miller Indices (110)

The round brackets (110) signify a single plane whereas as curly brackets {110} is
used for the family of planes
 Atomic planes in a crystal

z
a b c
c 1. Intercepts 1/2  
2. Reciprocals 1/½ 1/ 1/
2 0 0
y 3. Reduction 1 0 0
a b
4. Miller Indices (100)
x

(100) Single plane or {100} family of planes

 Equivalent directions and planes

Turn 90⁰
The symmetry of the cubic structure
and can give rise to a large number
of indices describing basically the
same direction or plane within the
crystal.

(c) 2003 Brooks/Cole

Publishing / Thomson
Learning™

For example - Directions

Similar idea applies to

planes

In this case the simplest form <110> is adopted to describe the direction in the crystal
 Point coordinates in a lattice

z
111 Point coordinates for unit cell
c center are
a/2, b/2, c/2 ½½½

000
y
a b
x 
Point coordinates for unit cell
z (body diagonal) corner are 111
2c


  Translation: integer multiple of

b y lattice constants  identical
position in another unit cell
b
 Calculating the spacing of crystal planes

1. The Miller Indices system allows for the easy calculation of separation d of the crystal planes

Cubic crystals 𝑎𝑜
𝑑=
√( 𝑎 2
+ 𝑏2 +𝑐 2 )

Where ao is the unit cell lattice spacing and the plane is defined as {a b c}

2. Angle  between planes and directions can also be calculated as follows:

Cubic crystals
𝑎1 𝑏1 +𝑎 2 𝑏 2 +𝑎 3 𝑏3
𝑐𝑜𝑠 ∅ =
√( 𝑎 + 𝑏 +𝑐 ) √ ( 𝑎 +𝑏
2
1
2
1
2
1
2
2
2
2 +𝑐 2 )
2

For the plane indices )

 Bravais lattice constructions
Bravais (c1850) was a French crystallographer who
observed naturally occurring minerals, with crystal
structure, fall into 7 primitive classes.

Some of these primitive classes could be extended

to include Body Centred, Face Centred & Base
Centred lattices.

The Bravais lattice is a construction of points to

hang an atom or group of atoms. These points are
linear translations in three-dimensional space and
describe the macroscopic form of the crystal.
Auguste Bravais (1811-1863)
The sub classes were labelled according:

P - Primitive or Simple
I – Body or Volume centred ( innenzentriert - German)
C – Base centred
F – Face centred
The Seven known Crystal Systems

Rhombohedral
Bravais Lattices Extended to include SC, BCC & FCC sub classes

The general lattice is called triclinic

and are another 13 special lattices.
Triclinic – meaning ‘Having three
unequal axes all intersecting at
oblique angles’ – (The catch all
crystal structure!)

The 13 special cases have either

some/all of the internal angles and
axis lengths within the unit cell
equal.
This distinction is important in
crystallography as the special
cases exhibit symmetry.
Many crystalline solids have
different properties depending
on the orientation in the
crystal. This is called anisotropy
and is linked to symmetry.
 Crystal Systems – Introduction to classification

Unit cell: smallest repetitive volume which contains the complete

lattice pattern of a crystal.

The crystal systems are built by

changing the lattice parameters:

a, b, and c are the edge lengths

, , and  are interaxial angles

Fig. 3.4, Callister 7e.

 Bravais lattice Table Crystal family

* a Triclinic
m monoclinic
o orthorhombic
t tetragonal
h hexagonal
c cubic

Pearson
Lattice
Crystal family symbol
symbol
letters
Triclinic P aP
Monoclinic P mP
S mS
Orthorhombic P oP
S oS
F oF
I oI
Tetragonal P tP
I tI
Hexagonal P hP
R hR
Cubic P cP
F cF
*from innenzentriert (German))
I cI
 Crystals using the Pearson Symbol classification

Materials in reference books can summarise the crystal structure in a simplified format:

Sodium forms a body centred cubic crystal with a coordination number of 8 (8

surrounding atoms in the unit cell)

Sodium cI8 – Cubic, Body centred with 8 surrounding atoms

Sodium chloride cF8 – Cubic, Face centred with 8 surrounding atoms

Caesium chloride cP2 – Cubic, Primitive (Simple) with 2 surrounding atoms
Chemically these salts are similar but because the ratio of the size of the metal
ions and ionic chlorine are significantly different the resulting crystal is different

cF8 is called the “Rock salt structure” and cP2 the “Caesium chloride”
structure no matter what atoms form the ionic compound

NB. Diamond (carbon) is also cF8 but there are two interleaved FCC lattices giving rise
to a new structure of tetrahedral bonds forming the “Diamond structure”
 Diamond structure

Tetrahedral bonds* at 109.47⁰ formed by 2 interleaved Cubic FCC Bravais lattices

Carbon (diamond) unit cell

The two Cubic FCC lattices are shifted by a

vector [1/4, 1/4/,1/4] i.e. along the diagonal
of the unit cell
APF = 0.34

* The tetrahedral covalent bond results from hybridisation of the carbon orbitals from 1s 22s22p2 to
1s22s12p3. Spatially the “sp3” shells are positioned to minimise free energy at an angle of 109.47 ⁰ to
each other. The other elements, Si, Ge, Sn in Column 4 of the periodic table also form sp3 bonds.