Materials Science & Engineering

Session (2)
 Exercise 1
a) Sketch a plan view of a tetrahedral void.

b) Describe in words how a tetrahedral void is formed in close packing (HCP

and CCP).

c) Sketch a plan view of an octahedral void.

d) Describe in words how an octahedral void is formed in close packing

(HCP and CCP).
 (1a)

Plan View of Tetrahedral Void in CP

(note inverted voids also exist)

(1b) Tetrahedral void is formed by an atom in one CP layer nestling in

the gap between three atoms in an adjacent CP layer.

(1c)
Plan View of Octahedral void in CP

(1d) Octahedral void is formed by a group

of 3 atoms in one layer and a ‘rotated’
group of 3 atoms in an adjacent layer
Dashed and solid lines represent
different layers of CP
 Exercise 2
e) State the stacking sequence of: (i) HCP and (ii) CCP.

f) State the co-ordination number of: (i) HCP and (ii) CCP.

g) State the ratio of tetrahedral voids to atoms in HCP and CCP.

h) State the ratio of octahedral voids to atoms in HCP and CCP.

(1e) HCP = AB ; CCP = ABC

(1f) C.N.= 12 for both HCP and CCP

(1g, 1h) 1 octahedral void per atom

2 tetrahedral voids per atom
 Exercise 4

a) From theorem of Pythagoras, calculate the cube unit cell edge length (in
CCP) expressed in units of r (where r is the radius of an atom in a CP
structure).

b) Calculate the Packing Density of CCP (base your calculations on the unit
cell).
Geometry of a cube: edge length = 1/(√2 face diagonal)

r= radius of CP atom

Edge = 1 /√2 . (Face diagonal)

√2
1
1

We know that face diagonal = 4r in CCP

Edge of CCP Unit Cell = 1 /√2 . (4r)
= 2.828 r
Packing Density = (vol. of atoms in unit cell)/(volume of unit cell).

Edge length of CCP unit cell = 2.828 r.

√2
1
Vol. cell = (2.828r)3 = 22.62 r3
1

4 atoms per cell. Total volume atoms = 4 x (4/3πr3) =

16.755r3
Packing Density = 16.755r3 / 22.62 r3 = 0.74 ( 74%)
 Fractional
coordinates
 Recap: Coordination = 12 in CCP
Colour shading indicates depth
(all atoms identical in CCP)

Coordination number:
A coordination number
can be defined as the
number of neighboring
atoms or ions that
closely surrounding a
central atom or ion in a
complex or crystal.
Coordination number refers to nearest neighbours
In CCP, it is helpful to draw a second cell to see all neighbours
Atom and Oct Void Sites in CCP

CCP – atom positions CCP-Oct Void sites

 Tetrahedral Voids in CCP

Tetrahedral voids at centre of the 8 sub-cubes

CCP Atom Positions CCP: Tetrahedral Void Sites & Atoms

Tetrahedral Voids in CCP

Plan View
NOTE: TWO Tetrahedral voids are
superimposed
(one below the other) in plan view
 x, y, & z axes convention
z

x
 x, y, & z axes convention
z

c z

β α b y
γ y
a
x

x
Origin = back bottom left corner
α β γ are angles between axes (unit cell edges)
 Fractional co-ordinates
label any position using fractions of a, b, c edge lengths : translation from origin

Example 1
Bottom face centre X:
c
½, ½, 0
‘half, half, nought’
½a
y
X
½b

Commas, but NO brackets

x
 Fractional co-ordinates
z

Example 2
c

x
½c
½a y

½b

x
Body Centre of cube X
lies at: ½, ½, ½
 Fractional Co-ordinates
• If atoms are being labelled,
use the term’ atomic co-ordinates’ or ‘fractional atomic co-ordinates’

• Atomic co-ordinates of atoms in cubic close packing:

• 0, 0 ,0 ½, ½, 0 0, ½, ½ ½, 0, ½

these are the four ‘Non-equivalent ‘atom positions

Atomic Co-ordinates in CCP unit cell

y
x

In CCP, an atom coincides

with a lattice point.
1 lattice point = 1 atom
0,0,0

face-centred cubic
 Equivalent Atom Positions
• 2 atoms are equivalent if they lie on opposite faces of the unit cell

• e.g. bottom face centre ½, ½, 0

and top face centre ½, ½, 1

• Think of the next unit cell sitting above the one drawn in previous slide.
Within this next unit cell above, the fractional co-ordinates of ‘top’ atom
would be ½, ½, 0 (periodic structure).
 Equivalent Atom Positions

• Normally only label co-ordinates of Non-equivalent atoms

– e.g. the 4 coloured atoms in previous diagram of CCP unit cell

• If correctly selected, no fractional co-ordinates of non-equivalent atoms

should contain the number 1.
 Sharing of Atoms
Corners, faces or edges of unit cell
• One unit cell is somewhat artificial

• Crystal is extended structure of repeating unit cells

• Faces, corners and edges are shared with neighbouring cells

• Atom on a face centre belongs to two-unit cells corner atom belongs to eight cells
– an edge belongs to 4-unit cells
 Atoms per Unit cell
• Atoms per cell are calculated as follows
• Count number of corner atoms: multiply the total by 1/8
(sharing factor = 1/8)
• Count number of face centre atoms: multiply by ½
(sharing factor = ½)
• Thus, four atoms per unit cell of CCP
• Sharing rule only applies to atoms with centre points on the surface of the
cell
 Number of Atoms in BCC Cell
• a) 8 corners × 1/8 per corner atom = 8 × 1/8 = 1 atom
b) 6 face-centered atoms × 1/2 atom per unit cell = 3 atoms

• Hence, the total number of atoms in a unit cell = 4 atoms

• Thus, in a face-centered cubic unit cell, we have:

• 8 corners × 1/8 per corner atom = 8 × 1/8 = 1 atom

• 6 face-centered atoms × 1/2 atom per unit cell = 3 atoms

• Therefore, the total number of atoms in a unit cell = 4 atoms.

 Atom Positions CCP
z=0 z = 0.5 z=0
z
y

z=0
c z = 0.5 z = 0.5

b
y
a
z=0 z = 0.5 z=0
x x

Plan View Atoms in Unit Cell CCP;

Perspective View viewed down z axis (c edge ) to
Unit Cell CCP show xy (ab) plane in projection
 Octahedral Voids CCP
z

0.5 0 0.5

0.5
0 0

0.5 0 0.5

x
Plan xy plane
 Tetrahedral voids CCP

5 6
0.25 & 0.75 0.25 & 0.75
8 7

1 2

4 3
0.25 & 0.75 0.25 & 0.75

y
Plan xy plane

x
 Tetrahedral voids CCP
1) ¼, ¼, ¼ Centre of Td void
5) ¼, ¼, ¾

2) ¼, ¾, ¼
5 6
6) ¼, ¾, ¾
8 7

1 2
3) ¾, ¾ , ¼ z
7) ¾, ¾ , ¾ 4 3

4) ¾, ¼ , ¼ y
8) ¾, ¼ , ¾
x
 Fractional co-ordinates
Label any position using fractions of a, b, c edge lengths

b
a y

x
Origin = back bottom left corner
 Exercise 3
a) Sketch a perspective view of the CCP unit cell, indicating the centre of
atoms.

b) Label the axes, cell edges, and angles.

c) Indicate a direction along which atoms would touch along their

diameters.

d) If an atom has radius r, what is the length of a face diagonal?

 z

b
y
a

x
2b) continued
z

c z

β α b y
γ y
a
x

x Origin = back bottom left corner

α β γ are angles between axes (unit cell edges)
 z
2c) In real unit cell atoms
touch ‘diameter to
diameter’ along a face
diagonal
c (example highlighted)

b
y
a

2d) Face diagonal = 4r

x
 Unit cell of
Hexagonal
Close Packing
HCP - side view ABA
Unit Cell Hexagonal Close Packing

A
 Plan view HCP
Plan Unit Cell highlighted
 Hexagonal Unit Cell
z

b ( = a) c/a = 1.6
y
120º
a

60º c
Plan down z
Plan down c b ( = a) y
a
x
c || z
Plan shows regular x
parallelogram Perspective view 90º 90°
b
a 120º
a=b≠c γ = 120º, α= 90º, β = 90º
 Hexagonal Unit Cell
Solid circle height 0 (1)
Dashed circle height 1/2

c/a = 1.6

a c
a
γ
90°
90º
Plan shows regular
parallelogram b
Perspective view 120º
a
a=b≠c γ = 120º, α = 90º, β = 90º
 Unit Cell HCP - centres of atoms
Atom at
height ½ c

c/a = 1.6
a

a 1/3, 2/3, 1/2

c

0,0,0 a
Plan down z c
a
Plan down c
90°
90º
Plan shows regular b
parallelogram Perspective view 120º
a
a=b≠c γ = 120º, α= 90º, β = 90º
Two non-equivalent atom positions: 1/3, 2/3,1/2
 Unit Cell HCP - centres of atoms
Fractional co-ordinates

c/a = 1.6

1/3,2/3,1/2
c

0,0,0 a c
a
90°
90º
b
Perspective view 120º
a

a=b≠c γ = 120º, α= 90º, β = 90º

Plan Unit Cell HCP showing x, y co-ordinates
atoms

1/3 a
2/3 b ½c

1/3, 2/3, 1/2

 Hexagonal Close Packed

• Each atom is coordinated by 12 nearest neighbours

Repetition of Hex Unit Cell

Basal plane
Generates 6-fold rotational symmetry-HCP

Every 360°/6=
coincident image
 Summary HCP Unit Cell
• One set of CP layers in HCP
(in contrast to Four sets in CCP)
• Simple or Primitive Hexagonal Bravais Lattice*

One lattice point per unit cell

(1 lattice point = 2 atoms in HCP)
 Learning Points : Unit Cell HCP
• Shape = Rhombus Prism (or Parallelogram Prism)
• Atom on corners, 0,0,0 and 1/3, 2/3, 1/2
• 2 atoms per cell
• CP layers run parallel to top and bottom faces of Hexagonal unit cell
– Another CP layer includes the atom at 1/3, 2/3, 1 /2
– Every ½ c edge encounter a CP layer

• c/a ratio = 1.6

Other Metal Structures

Not close packed

Body Centred Cubic Packing

Simple Cubic Packing

 Body Centred Cubic
Non-CP metal structure

• Packing density 68 %

• Atoms at 0,0,0 and ½, ½, ½

• 2 atoms per cell

• Atom diameters touch along body diagonal

Example: α- Fe
Simple Cubic Packing
Non-CP metal structure

• Packing Density- 52 %

• Atom diameters touch along edges of cubic unit cell

• Atom at 0,0,0 only

• 1 atom per cell

Unusual structure- Example Polonium

 Exercise 4
a. State the Packing Density of Body Centred Cubic Packing (BCC)

b. State the co-ordination number of BCC

c. Sketch the unit cell of BCC

 Answers
a. Packing density BCC = 68%
b. CN = 8
c.
 Exercise 5
a) Sketch a plan view of the unit cell of CCP showing atom positions and label their
fractional heights.
b) Sketch a plan view of the unit cell of CCP showing positions of centres of
Octahedral voids and label their fractional heights.
c) Sketch a plan view of the unit cell of CCP showing positions of centres of
Tetrahedral voids and label their fractional heights.
d) Sketch a perspective view of the Unit Cell of HCP showing atom positions (always
label 60° and 120° angles)
e) Sketch a plan view of the unit cell of HCP showing atom positions and centres of
octahedral voids. Label the fractional heights of atoms and Octahedral voids.
 Answers
z=0 z = 0.5 z=0
y

z=0
z = 0.5 z = 0.5

z=0 z = 0.5 z=0

x

a. Plan View Atoms in Unit Cell

CCP; viewed down z axis (c edge ) to
show xy (ab) plane in projection
 Answers

0.5 0 0.5

0.5
0

0.5 0

b. Plan xy plane
Answers

0.25 & 0.75 0.25 & 0.75

0.25 & 0.75 0.25 & 0.75

c. Plan xy plane
 Answers

d. 120°
60°
c/a = 1.6

1/3, 2/3, 1/2

c

0,0,0 a c
a
 Answers
Tetrahedral
e.
0, 0, 3/8
3/8 & 5/8
0, 0, 5/8
1/8 & 7/8
1/3, 2/3, 1/8
1/3, 2/3, 7/8
1/4 & 3/4

120º
60º Octahedral

2/3, 1/3, 1/4

2/3, 1/3, 3/4
 c

a
a

1/3, 2/3,1/2
c

0,0,0 a
a

The half-diagonal of the sub-cube is shown in the purple double-ended arrows,

 Exercise 6

• Sketch a plan view of the unit cell of body centred cubic packing; label
the fractional heights of atoms

• Note positions of distorted octahedral voids

 Answers
0, 0, 0
½
Fractional coordinates of
atom positions

Distorted octahedral
½, ½, ½ voids in BCC
½ ½ (at face centres)
0&1

½, ½, 0 0, ½, ½ ½, 0, ½
½
Plan xy plane
 A look ahead on multi-element structures
ZnS and ZnSe can both adopt the zincblende structure – notice the FCC-like positions of Zn.
The stoichiometry is 1:1, but are they equal parts by weight in each case?

S: 32.06 g/mol
Se: 78.971 g/mol
Zn: 65.38 g/mol

For AxBy with molar masses MA and MB

Wt%(x) =
Wt%(Zn in ZnSe):
65.38/(65.38+78.971) = 0.45 = 45%

Wt%(Zn in ZnS):
65.38/(65.38+32.06) = 0.67 = 67%
Lattice planes
and Miller
indices
x, y, & z axesz convention

c z

β α b
y
a y
γ
x

Origin = back bottom left corner

x α β γ are angles between axes ( unit cell edges)
 Crystal Lattice Planes
• Crystal structures may be considered in terms of sets of parallel planes

– Provide a reference grid to which atoms in the structure may be referred

• Some structures (e.g. CP structures) are composed of layers of atoms

– These layers coincide with certain lattice planes.

• However, most structures are not composed of layers of atoms.

• Lattice planes do not always coincide with layers of atoms.

 Unit Cell of CCP
highlighting one set CP planes

CP planes at right angles

to body diagonals

x
 Unit Cell of CCP
highlighting one set CP planes

x
 Unit Cell of CCP
another set of close packed planes

CP planes at right angles

to body diagonals

x
 Unit Cell of CCP
highlighting one set CP planes

x
 Rules for Assigning Miller Indices
• Planes are labelled with respect to the unit cell
• Select a plane in the set which lies closest to origin but does not pass through
• Note the points where the selected plane intersects each edge of the unit cell (some
planes do not intersect all three edges)
• Determine the distance of each intersection from the origin (in terms of fractional
lengths of each unit cell edge)
– e.g. ½ a ½ b ½ c
• Take reciprocals of these fractions
– e.g. 1/2 → 2
 Rules for Assigning Miller Indices
• Place the resulting whole numbers in curved brackets
• Do not use commas
• For example (222) the 'two two two planes‘.
– The (222) planes intersect
a edge at ½ a
b edge at ½ b
c edge at ½ c
• If a plane is parallel to a unit cell edge
– 'it intercepts at infinity ∞’
– Miller index 1/∞ = 0
Example: Determining Miller Indices
(2 2 2) planes
Intercept Reciprocal
½ a 2
½ b 2
½ c 2

(2 2 2) z
y

x
 Examples of Lattice Planes

Top and
bottom faces (001) planes

b
a

x
 Examples of Lattice Planes

Front and
(100) planes
rear faces

c
b
a z

x
 Examples of Lattice Planes

Side faces (010) planes

x
 Examples of Lattice Planes

(222) planes

Shaded
Plane used Try to show more
for indexing than one plane
The (110) set of planes

x
 General Case (hkl) planes
A set of planes (h k l) intercept

a edge of unit cell at a/h

b edge of unit cell at b/k
c edge of unit cell at c/l
Try to illustrate the length of the intercepts on your diagrams (show more than one
plane)

e.g. (0 2 0) planes should intercept the b edge EVERY ½ b.

Always a parallel plane through origin

Common mistake: (020) Planes

Two unit cells shown

y
x
Incorrect
Wrong inter-planar spacing
 Correct (020) Planes
d020
Two unit cells shown

z
Correct interplanar spacing (d-spacing) y
x
(020) planes
d020

y
x
 Planes Equivalent by Symmetry
Cubic System (100), (010), (001) {hkl}
These 3 sets of planes are symmetrically equivalent. Rotation inter-converts the planes
( same spacing)

(100) (010) (001)

c
b
a

{100} planes x
y
 Equivalent sets of planes
Braces or curly brackets {hkl} is shorthand for sets of
equivalent planes

For cubic system {100} represents the following specific sets of planes:
(100)
(010)
(001)
Miller indices
of
closed packed
planes
in CCP
 Close packed planes in CCP
• In CCP, the close packed planes coincide with the {111} planes:

– Four sets of planes

– The close packed planes lie at right angles to the <111> directions

(see notes below on directions)

• For example (111) planes lie at 90° to the [111] direction

Miller indices of closed packed planes in CCP

(111) planes

x
 Negative Miller indices
Bar above index

• Certain planes do not conform to previous rules for assignment of

Miller indices (back bottom left corner = origin)

• Need to use a different corner of unit cell

(1 1 1 )
one – bar one – one

x
( 11 1 )
one – one – bar one
z
‘Origin’
Planes run normal (90º) to
body diagonal indicated

z
-x

y -y y

x
-z

x
( 1 11 ) z
bar one – one – one

‘Origin’ z
-x
y
-y

x
y
x -z
Miller Indices of
Close Packed
Planes in HCP
 Plan view HCP unit cell

0,0,0
a

a ``````````` ```````````
1/3, 2/3, 1/2 `` ``

Plan down z ```````````

Plan down c ``

Ht ½ atom ( average one per unit cell).

Total 2 atoms per unit cell.
 (002) Planes in HCP
(0002) or (00.2) for hexagonal system: 4 indices

B
c
d 002 A

a
a c
90°
90°
b
Perspective view 120°
a
Hexagonal Unit Cell: Four Miller Indices
(h k i l)
z || c

a3

a c/a = 1.6
120º
c
a

60º
a3
Plan down z a2
a1
Plan down c z || c
Plan shows regular
parallelogram Perspective view
a2
4th axis used in indexing system a1 120°
 Hexagonal Unit Cell: (110) planes

a3

a c/a = 1.6
120º
c
a

60º
a3
Plan down z a2
a1
Plan down c z || c
Plan shows regular
parallelogram Perspective view a3
a2
4th axis used in indexing system a1 120º
 Hexagonal Unit Cell: (100) planes

a3

a c/a = 1.6
120º
c
a

60º a3
a2
Plan down z a1
Plan down c z || c
Plan shows regular
parallelogram Perspective view a3
a2
4th axis used in indexing system a1 120º
 Hexagonal Unit Cell: (010) planes

a3

a c/a = 1.6
120º
c
a

60º a3
a2
Plan down z a1
Plan down c z || c
Plan shows regular
parallelogram Perspective view a3
a2
4th axis used in indexing system a1 120º
 Miller indices for lattice planes (hkl)

• Use integer indices (hkl) to refer to sets of planes

• A plane can be defined by ≤3 points of intersection at the unit cell boundary
• Select a plane not through the origin
• Identify fractions of the lattice parameters a, b, c for the intersections
• Take reciprocals of the fractions
• If a plane is parallel to a unit cell edge:
'it intercepts at infinity ∞’. Miller index 1/∞ → 0
• Negative values of (hkl) marked with bar above index:
planes can be defined by a surface normal (vector ⊥ plane) – 2 sides!
 Exercise

• State the Miller indices of planes represented in the following

images.
(a)
(b)
z z

y y

x x
 Answer
(a)
(b)
z z

y y

x x

(211)
 Exercise
• Sketching planes from known Miller indices: Using
appropriate diagrams, illustrate how the following planes
intersect a cubic unit cell.
a) (200)
b) (020)
c) (002)
d) (121)*
e) (212)*
f) (111)
 Answer

(121)
(212)
(111)

Tip: To insert a second plane think of multiplying each index by -1.

This rule works for {111} planes.
1 11 )

Showing two planes:

• Directions: Sketch the following directions in a cubic unit cell:
a) [110] *
b) [111]
c) [120] *
d) <100>
e) ]
a) [110]
b) [111]
z
c) [120]
d) <100>
e) ]

z z y

b) d)
z
y y
a) c)

e) y
Thank
you