Materials

Science &
Engineering
Session (3)
Directions in
crystal lattices
 Indices of Directions
Directions in crystals and lattices are labelled by

a) drawing a line (vector) passing through the origin, and parallel to the direction

b) noting the point of intersection of line with unit cell boundary (face, edge, corner)

c) write fractional co-ordinates of this ‘exit’ point

 Indices of Directions (continued)
• Convert to a set of whole numbers:

• Multiplying by lowest common denominator

• ½, 1, ½ becomes 1, 2, 1

• Place in square brackets, no commas [uvw]

• [121] = ‘ one two one direction’

• Other example: [110] = ‘the one one nought’ direction

Directions: examples
z

[111]
(iii)

y
(i) (ii)

[100] [110]
 [121] Direction
z

Exit point, side face-centre

Co-ordinates 1/2, 1, 1/2

y Multiply by x 2

x [121] direction
 Labelling directions of axes
• x axes (a edge of unit cell ): [100]
• y axes (b edge): [010]
• z axes (c edge): [001]

Recall Cartesian axes (x, y, z) coincide with (a, b, c) for orthogonal

crystal systems
 Negative Directions
[ 1 00 ] ‘bar one- nought-nought direction’

Negative x direction

x
 Symmetrically Equivalent Directions: <uvw>
• Indices of directions <uvw>

• angle brackets refer to set of directions equivalent through symmetry

• Shorthand notation

• For example, <100> for a cubic system expands to:

• [100], [010], [001], and their negative equivalents
 Exercise 1
• Sketch a unit cell of a cubic crystal system and indicate the following
directions:

[100] [111] [120]

 Answer
• Sketch a unit cell of a cubic crystal system and indicate the following
directions:

[100] [111] [120]

[100] [111] [120]

 Check: Apply rule
Directions: Divide by largest value

[1 2 0 ] [2 1 0 ]

Divide by two to get fractional coordinates at Divide by two to get fractional coordinates at
exit: exit:
= ½ , 1, 0 = 1, ½ , 0
½ along a 1 along a
1 along b ½ along b
0 along c 0 along c
 Exercise 2
• State the directions indicated below (i) [023]
(ii) [010]
(iii) [00]

(i)
(ii)
z

(iii) y
x
 Planes (hkl) vs Directions [uvw]

Planes (hkl) Directions [uvw]

Invert (1/h, 1/k, 1/l) to Divide by largest value

give fractions along a, b, (one common denominator)
c where plane intersects to give fractional coordinates
unit cell boundary where direction exits the unit
- three points cell
- one point
 Important Directions in Cubic Close
packing
• In CCP structures:
• CP layers with Miller Indices (111) are at right angles to the [111]
direction

• The equivalent relationship holds for other planes in the family {111} and the
directions in the family <111> with corresponding digits
• Note <111> represents the four body diagonals of cubic unit cell
 Close Packed planes in HCP
• In HCP the close packed planes coincide with the {00.2} planes, basically only one
set: (00.2)
• The close packed planes run at right angles to the c-edge of the unit cell, [001]
direction [001]

c/a = 1.6
a3
c
a
120º a3
a a2
a1
60º z || c
Plan down z Perspective a3
[100]
Plan down c view a2
a1 120º
More on Unit Cells
So far only considered unit cell of
metal crystal structures
(cubic and hexagonal unit cells)

In all crystals :

7 possible shapes of unit cell

7 crystal systems
 Crystal Systems
There are 7 crystal systems
i.e., 7 shapes of unit cell

Each with characteristic symmetry:

• Cubic
• Tetragonal
• Orthorhombic
• Hexagonal
• Rhombohedral (trigonal)
• Monoclinic
• Triclinic
x, y, & z axes convention
z

z
c

β α b y
y
a γ
x

α β γ are angles between axes ( unit cell edges)

x
 Seven Crystal Systems
System Name Cell Parameters

Cubic a=b=c
 =  =  = 90
Tetragonal a=b≠c
 =  =  = 90
Orthorhombic a ≠ b≠ c
 =  =  = 90
Rhombohedral a=b=c
 =  =   90
Hexagonal a=bc
 =  = 90,  = 120
Monoclinic a≠b≠c
 =  =90,  ≠ 90
Triclinic abc
      90
 Cubic Crystal System
• Many examples in preceding lecture notes

• Highest Symmetry of any System

(four 3-fold axes of rotation)

• a = b =c
•  =  =  = 90
 Tetragonal Crystal System
Square Prism z

a=b≠c
 =  =  = 90
c

Plan View
a(= b)
y
y a

x
 Orthorhombic System
• a ≠ b≠ c
z
•  =  =  = 90
• If a < b < c;
c
d (100) <d (01 0) <d (001)
b
a y
Side View
Plan View
b x

a c

b
• All angles 90° - Cubic, Tetragonal, Orthorhombic

• All Termed Orthogonal Crystal Systems

System Name Cell Parameters

Cubic a=b=c
 =  =  = 90
Tetragonal a=b≠c
 =  =  = 90
Orthorhombic a ≠ b≠ c
 =  =  = 90
Rhombohedral a=b=c
 =  =   90
Hexagonal a=bc
 =  = 90,  = 120
Monoclinic a≠b≠c
 =  =90,  ≠ 90
Triclinic abc
      90
 Hexagonal System
Plan View
b

a (b = a)
a a
120º
90º 90°

b
a 120º
Significance of planes in
crystal applications
 Crystal Structure and Mechanical
Properties
• Four times as many sets of close packed planes in CCP metal
structures compared to HCP

• Has consequences on mechanical properties:

deformation by slipping of adjacent layers of close packed atoms

• Expect CCP metals to be more ductile

Crystal Structure and Properties of
Particles Crystallised From Solution

Knowledge of lattice planes

(and surface energy of different planes) explains shapes of
precipitated particles in chemical reactions
 Production of ZnO microrods
• ZnO prepared by reaction at elevated temperature and pressure
• Zinc acetate starting reagent: hydrolysis reaction
Zn (CH3COO)2 , H20, NH4OH,
• Zn(OH)2 formed which dehydrates to ZnO particles
• Nucleation and Growth from solution
 Crystal Structure of Wurtzite ZnO
(Hexagonal)
• Oxygen ions in same position as atoms in HCP

• Hexagonal Unit Cell

• Oxygen ions: 0,0,0 and 1/3, 2/3, 1/2

• Zn ions in half the tetrahedral voids

ZnO
{10}

{0002}
ZnO
 Nucleation and Growth
• Crystal planes with lowest surface energy

• ‘control’ shape of macrocrystal as it grows from solution or vapour

phase

{100} and {0002} lowest energy planes: determine shape of crystal

ZnO rods grow along <0002> direction.

 Imaging of Crystal Lattice Planes
Transmission Electron Microscopy
d0002 <0002> Measured spacing of lattice fringes
= d-spacing 0002 planes of ZnO
(wurtzite - hexagonal)

Rods grow in c-direction

Interplanar spacings
 Interplanar Spacings (d-spacings)
• Perpendicular distance between lattice planes.
Miller Indices (hkl). Unit cell edge lengths: a, b, c
• For orthogonal crystal system (all 90° angles)

2 2 2
1 h k l
2
 2
 2
 2
d a b c
 Lists of d-spacings (pm or Å)
• Identifying feature of every crystalline material

• d-spacings of a given set of planes (hkl) depend on:

i) crystal system and
ii) unit cell dimensions and angles between axes

• Lattice parameters = dimensions + angles

 Sequence of planes of decreasing d-spacing
• First consider sequence of increasing values of the summation:

(h2 + k2 + l2)

• Then consider crystal system and relationship between planes within each (h2 + k2
+ l2) grouping.
• Which planes are equivalent?

• For a cubic system, the sequence of decreasing d spacing follows sequence of

increasing sum of (h2 + k2 + l2)
 Interplanar Spacings
d-spacings
For cubic crystal system: a = b = c
2 2 2
1 h +𝑘 +𝑙
2
= 2
𝑑 𝑎

For given crystal, a is constant

Sequence of decreasing d-spacing?
Sequence of increasing 1/d2
Sequence of increasing h2 + k2 + l2
 Sequence of planes
Σ= (h2 + k2 + l2 ) = 1, 2, 3, 4, 5, 6, …
Σ = 1 (100), (010), (001)

Σ = 2 (110), (011), (101)

Decreasing d-spacing
Σ = 3 (111)

Σ = 4 (200), (020), (002)

Σ=5 (210), (120), (201), (102), (012), (021)

 Cubic system (a = b = c)
d100
• d(100) = d(010) = d(001) d 110
d111 Decreasing d-spacing
• d(110) = d(011) = d(101) d200
d210
• d(111)

• d(200) = d(020) = d(002)

• d(210) = d(120) = d(201) = d(102) = d(012) = d(021)

Brackets for d-spacings optional ‘d100’ is normal

 Calculation of d-spacings
(up to Σ = 4)

Cubic system (a = b = c)

Copper: a = 362.5 pm
 Copper:
Cubic
a = 362.50 pm

z hkl 1/d2 d2 d pm dÅ
1 (100) 7.60999 x 10-6 131406.2 362.50 3.6250
2 (110) 1.52199 x 10-5 65703.4 256.32 2.5632
3 (111) 2.28299 x 10 -5 43802.16 209.29 2.0929
4 (200) 3.04399 x 10 -5 32851.6 181.25 1.8125

1 pm = 1 x 10 -12 m

1Å = 1 x 10 -10 m
 Calculation of d-spacings
• Tetragonal system (a = b < c)

2 2 2
1 h +𝑘 𝑙
2
= 2
+ 2
𝑑 𝑎 𝑐
 Relationships of d-spacings for tetragonal
system
a=b<c
d(100) = d(010) < d(001)

d(110) < d(011) = d(101)

d(111)

d(200) = d(020) < d(002)

List (hkl) corresponding to decreasing d spacings Tetragonal System
Assume a = 399.4 pm; c = 403.8
pm z hkl d pm dÅ
d(100) = d(010) < d(001) 1 (100) 399.4 3.994
d(200) = d(020) < d(002) 2 (001) 403.8 4.038
3 (200) 199.7 1.997
4 (002) 201.9 2.019
 Orthorhombic System
• a < b < c; α , β,  = 90°

z
d100 < d010 < d001

x
 Calculation of d spacings
up to Σ = 3
• Orthorhombic System (a < b < c)

• Assume a = 350 pm, b = 400 pm, and c = 500 pm

2 2 2
1 h 𝑘 𝑙
2
= 2
+ 2
+ 2
𝑑 𝑎 𝑏 𝑐
 Note here the ±1 x (hkl) pairs are always
equivalent so are not mentioned directly
Multiplicities to simplify the notation.

• Notice in cubic crystals (100), (010), and (001) gives:

• one set of d-spacings
• {100} represents all (100), (010), (001)

• For tetragonal crystals, (100), (010), and (001) gives two sets:
• {100} represents only (100) and (010) for tetragonal
• Recall d(100) = d(010) ≠ d(001)

• For orthorhombic crystals, (100), (010), and (001) gives three sets:
• d(100) ≠ d(010) ≠ d(001)
• {100} represents only (100)
Diffraction
and
Bragg’s law
 Diffraction gratings

Single slit experiment:

slit acts as secondary

scattering source for light
 constructive
interference

set of
constructive
interference broad
lines
constructive
interference
• two “slits”  broad lines
• many “slits”  narrower lines, patterns
• conditions  l  or < “slit” separation
 “slit” – same size, evenly spaced
(“slit” = source of secondary scattering for a wave)
 Constructive Interference
In phase: path difference = nλ (n = 0,1,2,3, …)
λ 1

Strong Scattered wave-diffraction

 Destructive Interference
½ λ out of phase

Peaks and troughs in successive waves cancel: zero

intensity results
X-Ray diffraction photograph of DNA (Rosalind Franklin)
Optical Diffraction Grating

.
.
.
.
 Crystal Lattice Planes are a
‘diffraction grating’ for X-rays
• Crystal lattice spacings are similar to wavelength of certain types of X-ray
(λ ~ 100 pm).
• Use fixed wavelength, and measure directions (angles) of diffracted X-ray
beam

• Different sets of planes have different d-spacings:

• different diffraction angles
 Bragg’s Law
Consider X-ray diffraction to be reflection of X-rays off a family of parallel planes

X-rays

q q
P1
A d C
q q
P2
B

For constructive interference between reflected X-rays the path

difference must be a whole number of wavelengths
i.e. AB + BC = nl
 AB + BC = nl
q q
AB = BC = dsinq
A d C
q q Hence nl = 2dsinq
B

Bragg’s Law: nl = 2dsinq

• Get same result by considering a scattering diffraction process

rather than reflection

• Family of planes are the lattice planes defined by Miller indices

 General form of Bragg’s Law
d hkl
Bragg’s law: nl = 2dsinq (1) d nh ,nk ,nl  (2)
n

d 
(1) Rearranges to   2  sin 
n
Substitute (2) to get :
l = 2dhklsinq (3)

This is the general form of Bragg’s Law for reflection of X-rays

from lattice planes within a crystal
• is the Bragg angle and is usually measured as 2
• Bragg’s Law is a strict requirement for diffraction – if
not met within 0.1° then get destructive interference

Incident
X-rays reflected
X-rays

 
 crystal plane

Main X-ray
beam path
 Non-Bragg angle
Move away from Bragg angle

1’

2’

3’

4’

5’

Beams 1’ + 5’= ½ λ path difference:

total destructive interference
 Example 1:
• The wavelength of the X-rays is 0.071 nm which is diffracted
by a plane of salt with 0.28 nm as the lattice constant.
Determine the glancing angle for the second-order
diffraction. Assume the value of the salt plane to be 110, and
the given salt is rock salt.
 Answer
Given:
• Wavelength of the X-rays = 0.071 nm
• Lattice constant = 0.28 nm
• Plane = 110
Substituting the values,
• Order of diffraction = 2
• Glancing angle =?
• Using Bragg’s law:
• 2d sin Ө = nλ Substituting in the Bragg’s equation,
• Rock salt has FCC, therefore, Ө = 21°
 Exercise 2
n = 1: λ = 1.5418 Å

Given:
d-spacing (002) = 2.8664Å

Calculate 2θ
Answer
θ =15.60°
2θ = 31.2°
 Exercise 3
n = 1: λ = 1.5418 Å

Given:
Peak at 2θ = 31.2°

Calculate d spacing
Answer
θ =15.60°
sinθ = 0.2689
d = 2.8664Å.
 Alternative representation

Recall that a general cosine function:

Scattering: Change in angle of incident

wave
(No change in wavelength)
Alternative representation sinθ : opposite over hypotenuse

1/ (2 𝑑) 𝜆
sin 𝜃 = =
1/ 𝜆 2𝑑

1/λ ½ (1/d) = 1/(2d)

1
𝑘=
𝑑
rearrange

1/λ 1/(2d)

λ =2 𝑑 sin 𝜃
Alternative representation
𝑛 𝜆=2 𝑑 sin ⁡(𝜃)
X-ray diffraction
 Background to X-ray Diffraction (XRD)
X-rays can be used to determine values of d-spacings.

• Lattice planes cause diffraction of X-rays

• Direct relationship between angle of a diffracted X-ray beam and the d-spacing of a
set of lattice planes

• A list of d-spacings* is an identifying feature of every crystalline material

*peak intensities are also important

 Diffraction from powders
A single (individual) crystal gives a single diffraction pattern as a
regularly spaced series of reflections or peaks

Incident X-ray
beam

crystal

diffraction pattern
 Diffraction from powders
• Many materials exist as powders rather than as large single crystals
• Crystalline powders have many very small crystallites
• Each crystallite in a sample will give its own diffraction pattern
• Hence many diffraction patterns are superimposed on each other
Diffraction from powders
With thousands of crystallites found in a typical sample, together
the scattering forms a pattern of concentric circles:
• 2q corresponds to the
radius of each circle (q is
Bragg angle of diffraction)

2
 Powder Diffractometer
• A diffractometer is an instrument that measures diffraction
• Sample is ground to a fine powder
• Measures 2q and intensity values (I) as I vs 2q
• Sample and/or detector are rotated to access different 2q values

x-ray source

detector
sample

2q
 Intensities
• Intensity of Diffracted Beam depends on:
Atomic number (number electrons)
Electron density in a solid scatters X-rays ​
higher atomic number gives more scattering

Number of atoms​​
​
Position of atoms in unit cell
Simple Cubic (4 unit cells
shown)
θ Plane 1

d 001
Plane 2

[100] perspective
direction (001) planes view along [100]
highlighted direction
z
z
y
y
x
x
XRD pattern (powder) - Cubic
each XRD peak corresponds to a set of planes (hkl)

{100}
intensity
(100) {110}
(010)
(001) (110)
(101)
(111)

angle
 XRD pattern (powder) - Cubic
each XRD peak corresponds to a set of planes (hkl)

nλ = 2dsinθ lowest angle peak = highest d spacing

intensity
{100} planes
Or 100
{111}
{110} planes
planes Or 111
Or 110

angle

Diffraction gives peaks: peak position (2θ) depends on interplanar d-spacing.

 d-spacing list from XRD experiments
Table of XRD data: indexed when hkl assigned to peak positions

2θ (°) d-spacing (pm) Intensity (hkl)

I/I max x 100

Smallest Largest
value of d-spacing
2θ

Increasing Decreasing
value of value of
2θ d-spacing
 Directions in unit cells [uvw]
• Use integer indices [uvw] to refer to a direction in the unit cell

• A direction is defined by a vector (arrow with magnitude and direction)

that intersects the boundary of the unit cell at one point

• Start at the origin

• Fractional coordinates of the ‘exit’ point

• Multiply by single lowest common denominator

• Negative directions:
• Choose alternative corners to keep the arrow in the unit cell
 Interplanar spacings (d-spacings)
(020)
Distance formula:
b

d(020)

a
0 0
2 2 2
1 h k l
2
 2
 2
 2
d a b c
Bragg’s law and X-ray diffraction: nλ = 2d
sinθB
2θ (°) d-spacing (pm) Intensity (hkl)
AB + BC = nl I/I max x 100
q q
AB = BC = dsinq
A d C Hence nl = 2dsinq
q q
B

λ
Body-centred
{100} planes Body-centred

Intensity
Or 100
{111}
Constructive interference: nλ
{110} planes
planes Or 111

Cubic: Or 110

Angle (2θB)
 Calculation 1
Consider the data below for an orthorhombic unit cell.
Determine the values of a, b, c.
No 0k0 or 00l values are available.
How can we calculate all lattice parameters a, b, c of this orthorhombic* unit cell?
Hint: use simple simultaneous equations involving interplanar spacing formulae.

*In this crystal the usual sequence of ascending values of lattice parameter (a<b< c does not apply)

hkl d pm
100 569.5
110 403.5
111 283.2
021 232.2
220 201.8
202 162.9
 Calculation 1
hkl d pm
Answer: when d spacings for all of h00, k00 and 001
100 569.5
are not available it is possible to calculate lattice 110 403.5
parameters using simple simultaneous equations 111 283.2
021 232.2
involving interplanar d spacing formula. In this
220 201.8
example: orthorhombic unit cell 202 162.9
Calculation of c
Interplanar d spacing equation for 111 minus equation for 110 will yield value of c lattice parameter.
1/d2111 = 1/a2 + 1/b2 + 1/c2
1/d2110 = 1/a2 + 1/b2
Thus (1/d2111 - 1/d2110 ) = ( 1/a2 + 1/b2 + 1/c2) – (1/a2 + 1/b2 ) = 1/c2
1/(283.2)2. - 1/(403.5)2. = 6.326 x 10 -6 = 1/c2
c = 397.6 pm

Determination of a
This is straightforward since 100 d spacing is given in Table 1.
a = 569.5 pm
 hkl d pm
100 569.5
Calculation 1 110 403.5
111 283.2
Calculation of b 021 232.2
220 201.8
Consider 110 and 100 data.
202 162.9
d- spacing equation for 110 minus d space equation for 100 yields value of lattice
parameter b.
1/d2110 = 1/a2 + 1/b2
1/d2100 = 1/a2
1/(403.5)2. - 1/(569.5)2 = 3.0587 x 10-6 = 1/b2
b = 571.8 pm
Another way of considering how to obtain b is to ‘substitute value of a ( from
100 d spacing ) into d space equation for 110’. In essence both approaches are the
same.
Full lattice parameters a = 569.5 pm; b = 571.8 pm; c = 397.4 pm
In this example the sequence of rising values of lattice parameters does not
follow the convention a< b< c for an orthorhombic crystal system.
 Calculation 2
For a Simple Cubic crystal structure with lattice parameter a = 392.3
pm:

a) Calculate the d-spacing and corresponding Bragg diffraction

angle (°2θ) for the three sets of planes of highest d-spacing. Label
the Miller Indices. X-ray wavelength Cu Kα, λ = 154.18 pm.

b) Will all of these peaks (reflections) appear in an experimental

diffraction pattern?
 Calculation 2
Peak list
No. h k l d [Å] 2Theta[deg] I [%]
1 1 0 0 3.92300 22.648 12.5
2 1 1 0 2.77400 32.244 100.0
3 1 1 1 2.26500 39.765 12.1
4 2 0 0 1.96150 46.246 52.5
5 2 1 0 1.75440 52.089 2.8
6 2 1 1 1.60160 57.496 28.5
7 2 2 0 1.38700 67.473 21.9
8 3 0 0 1.30770 72.179 0.8
9 3 1 0 1.24060 76.765 9.2
10 3 1 1 1.18280 81.272 1.4
11 2 2 2 1.13250 85.715 5.5
12 3 2 0 1.08800 90.144 0.2
13 3 2 1 1.04850 94.558 9.0
Thank
You