Miller Indices

• Miller Indices are the convenient way to define the various planes in a crystal.
• Miller Indices are a symbolic vector representation for the orientation of an
atomic plane in a crystal lattice and are defined as the reciprocals of the fractional
intercepts which the plane makes with the crystallographic axes.
 Miller indices are denoted by hkl and written in parentheses (hkl) without any
comma i.e. (100).

To determine Miller indices of a plane, take the following steps;

1) Determine the intercepts of the plane along each of the three

crystallographic directions.

2) Take the reciprocals of the intercepts.

3) Find the least common multiple (LCM) of the denominator

and multiply this LCM to above ratios yields set of three integers
h, k and l referred as Miller indices. 1
Example-1

Axis X Y Z
Intercept
points 1 ∞ ∞
Reciprocals 1/1 1/ ∞ 1/ ∞
Smallest
Ratio 1 0 0

Miller İndices (100)

2
Example-2

Axis X Y Z
Intercept
points 1 1 ∞
Reciprocals 1/1 1/ 1 1/ ∞
Smallest
Ratio 1 1 0

Miller İndices (110)

3
Example-3

Axis X Y Z
Intercept
points 1 1 1
Reciprocals 1/1 1/ 1 1/ 1
Smallest
Ratio 1 1 1

Miller İndices (111)

4
Example-4

Axis X Y Z
Intercept
points 1/2 1 ∞
Reciprocals 1/(½) 1/ 1 1/ ∞
Smallest
Ratio 2 1 0

Miller İndices (210)

5
Axis X Y Z

Intercepts points 0.5 1 1

Reciprocals 1/2 1/1 1/1

Smallest Ratio 2 1 1

Miller indices (211)

Example-5

Axis a b c
Intercept
points 1 ∞ ½
Reciprocals 1/1 1/ ∞ 1/(½)
Smallest
Ratio 1 0 2

Miller İndices (102)

7
 Miller Indices
Z
(233)

Plane intercepts axes at3a , 2b , 2c

2
1 1 1
Reciprocal numbers are: , ,
c 3 2 2
b 2
Indices of the plane (Miller): (233)
a Y

3
X

(200)
(111)
(110) (100)

(100) 8
 Bragg’s law
Sir William Henry Bragg: Noble
prize
• William Henry and William 1915!
Lawrence Bragg
• (father and son) found a simple
interpretation of von Laue’s
experiment.
• They assume that each crystal
plane reflects radiation as a mirror
and analyze this situation for cases
of constructive and destructive
interference.

Conditions for 2d sin θ = nλ

reflection:
 Derivation of Bragg’s law
Braggs assumed that
1) Crystal contains parallel plans.
2) X-Ray is reflected by parallel planes.
3) If the path difference between two rays is
integral multiple of wavelength: constructive
interference
Path difference = nλ,
 nλ = AB + BC
We also know that AB = BC
nλ = 2AB……. (1)
 d is the hypotenuse of the right triangle ABZ.
AB is the opposite of the angle θ.
AB = d sinθ ……(2)
Substituting equation 2 in equation 1
nλ = 2d sinθ
The above equation is Bragg’s law expression.
n = order of reflection, λ= wavelength of X-ray
d= interplanar spacing

λ ≤ 2d, If , sin 𝜽𝜽 ≤ 1
11
 x
sin(θ ) =
d hkl θ

⇒ x = d hkl sin(θ ) θ
dhkl
θ x

 Path difference Δ= 2x => phase shift

 Constructive interference if Δ=nλ
 This gives the criterion for constructive interference:

⇒ ∆ = 2d hkl sin(θ ) = nλ
 Bragg’s law tells you at which angle θB to expect maximum
diffracted intensity for a particular family of crystal planes.

 For large crystals, all other angles give zero intensity.

12
 Determination Of Crystal Structure by Powder
method

Detector
X-
ray
tube
ω θ 2θ

13
 There are three major components in Bragg diffractometer namely X-ray generator, sample
holder and a detector. A beam of electron is accelerated through a potential difference in
the range 10–50 kV.

 The accelerated electron beam is made to fall on metal target T, which is typically made up
of Cu, Mo, W, Co or Cr, where the kinetic energy of the accelerated electrons are converted
into X-rays and heat.

 The incident angle, ω, is defined between the X-ray source and the sample.

 When a sample rotates by an angle of θ, the detector rotates around the same axis by an
angle of 2θ to collect the Bragg reflection.

 This experimental configuration is known as a θ – 2θ diffractometer.

 The detector measure the number of X-ray photon (intensity) I which are scattered from the
sample over an angle of 2θ with respect to incident X-ray beam direction.

 In a θ:2θ instrument (e.g. Rigaku RU300), the tube is fixed, the sample rotates at θ °/min and
the detector rotates at 2θ °/min.
 In a θ:θ instrument (e.g. PANalytical X’Pert Pro), the sample is fixed and the tube rotates at a
rate -θ °/min and the detector rotates at a rate of θ °/min.
14
 A single crystal specimen in a Bragg-Brentano diffractometer
would produce only one family of peaks in the diffraction
pattern.

2θ

At 20.6 °2θ, The (110) planes would diffract at 29.3 °2θ; The (200) planes are parallel
Bragg’s law however, they are not properly aligned to to the (100) planes. Therefore,
fulfilled for the produce a diffraction peak (the they also diffract for this
(100) planes, perpendicular to those planes does not crystal. Since d200 is ½ d100,
producing a bisect the incident and diffracted beams). they appear at 42 °2θ.15
diffraction peak. Only background is observed.
A polycrystalline sample should contain thousands of
crystallites. Therefore, all possible diffraction peaks should be
observed.

2θ 2θ 2θ

• For every set of planes, there will be a small percentage of crystallites that are properly
oriented to diffract (the plane perpendicular bisects the incident and diffracted beams).

• Basic assumptions of powder diffraction are that for every set of planes there is an equal
number of crystallites that will diffract and that there is a statistically relevant number
16
of
crystallites, not just one or two.
 Example: Diffraction Patterns
• Each peak represents
the solution to Bragg’s
law for known
radiation wavelength
(λ = 0.154 nm)
• The unique
relationship between
such patterns and
crystal structures
provide a powerful
tool for identification
of the phase
composition of
powders and
polycrystalline
materials.
17
18
19
d = interplanar spacing
hkl = miller indices
a = lattice parameter/constant

20
d = interplanar spacing
hkl = miller indices
a,b,c = lattice parameters/constants