Crystal Structure

Semester 6: Core Course 14

Syllabus: Solids: Amorphous and Crystalline Materials. Lattice Translation Vectors. Lattice with a
Basis; Central and Non-Central Elements. Unit Cell. Miller Indices. Reciprocal Lattice. Types of
Lattices. Brillouin Zones. Diffraction of X-rays by Crystals. Laue and Bragg’s Law and their
equivalence. Atomic and Geometrical Structure Factor. Basic idea of crystal indexing: examples with
SC, BCC, FCC structure.

References:
1. Solid State Physics, R. K. Puri & V. K. Babbar (S. Chand)
2. Introduction to Solid State Physics, C. Kittel (John Wiley & Sons)
3. Solid State Physics, A. J. Dekker (Prentice Hall India)
4. Solid State Physics, S. O. Pillai (New Age International)
 Crystal Structure

Crystal structure is one of the most important aspects of materials science and engineering as many
properties of materials depend on their crystal structures. The basic principles of many materials
characterization techniques such as X-Ray Diffraction (XRD), Transmission Electron Microscopy
(TEM) are based on crystallography. Therefore, understanding the basics of crystal structures is of
paramount importance.

NPTEL
 Crystal Structure
Matter

Solid Liquid Crystal Liquid Gas

Crystalline – periodic & ordered arrangement of

Crystalline Amorphous atoms: definite repetitive pattern

Quasicrystals – ordered but not periodic

Quasicrystals
arrangement of atoms

Amorphous – random arrangement of atoms

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Crystal Structure

❑ Basis: Identical group of atoms having

infinite repetition within an ideal crystal

❑ Lattice: Set of mathematical point to which

the basis is attached

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 Crystal Structure

❑ Periodicity of atoms in crystalline solids can be described by a network of points in space called
lattice
❑ A space lattice can be defined as a three-dimensional array of points, each of which has identical
surroundings
❑ If the periodicity along a line is 𝑎, then position of any point along the line can be obtained by a
simple translation, 𝑟𝑢 = 𝑢𝑎 (𝑢 is an integer)

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 Crystal Structure

❑ Similarly, 𝑟Ԧ𝑢𝑣 = 𝑢𝑎Ԧ + 𝑣𝑏 will repeat the lattice points in a 2D plane, where u and v are integers

Space Lattice
Space lattice is arrangement of lattice points with each point having exactly same surroundings

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 Crystal Structure
❑ Lattice in three dimensions may be defined by three translational vectors 𝑎,
Ԧ 𝑏, 𝑐Ԧ such that the
arrangement of atoms in the crystal looks the same when viewed from the point 𝑟Ԧ as when viewed

from every point 𝑟Ԧ ′ = 𝑟Ԧ + 𝑢𝑎Ԧ + 𝑣𝑏 + 𝑤𝑐Ԧ for arbitrary integers 𝑢, 𝑣 and 𝑤.

❑ If any two points from which the atomic arrangement looks the same always satisfy the relation

𝑟Ԧ ′ = 𝑟Ԧ + 𝑢𝑎Ԧ + 𝑣𝑏 + 𝑤 𝑐Ԧ with a suitable choice of the integers 𝑢, 𝑣 and 𝑤, 𝑎,

Ԧ 𝑏, 𝑐Ԧ are called the
primitive translation vectors and the lattice is said to be primitive.

❑ No cell of volume smaller than 𝑎Ԧ ∙ (𝑏 × 𝑐)

Ԧ can serve as a building block of the crystal structure.
❑ Primitive translation vectors are often used to define the crystal axes, which form three adjacent
edges of the primitive parallelopiped.
❑ Nonprimitive axes are often used as crystal axes when they have simple relation to the symmetry of
the structure.
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Introduction to SSP: C. Kittel
 Crystal Structure
❑ Unit Cell: The structure of a crystal can be seen to be composed of a repeated element in three
dimensions. This repeated element is known as the unit cell. It is the building block of the crystal
structure. We define the unit cell in terms of the lattice.
❑ Primitive Unit Cell: contain only one lattice point, which is made up from the lattice points.
❑ Non-primitive Unit Cell: contain additional lattice points, either on a face of the unit cell or within
the unit cell, and so have more than one lattice point per unit cell.

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 Crystal Structure
❑ Wigner-Seitz Cell: Primitive unit cell choosing in a particular way.

1. Choose a lattice point

2. Draw lines to all nearby lattice points

3. At the midpoint of each line, draw another line normal to

each of the first set of lines

4. The smallest area enclosed in this way is called the Wigner–

Seitz primitive cell

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 Symmetry
❑ Symmetry refers to certain pattern or arrangement. A body is symmetrical when it is reproduced by
certain operation

❑ In the picture below the plane looks identical after a 90o rotation. The plane has 4-fold rotational
symmetry as it repeats itself 4 times (shown by the red dot) in a full 360o rotation.

❑ Symmetry Operations:
1) Translation
2) Rotation
3) Reflection
4) Inversion

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 Translation Symmetry

The first point is repeated at equal distances along a line by a translation 𝑢𝑡1 , where 𝑡1 is the translation
vector and u is an integer.
Translation on a point with coordinates 𝑥, 𝑦, 𝑧 → (𝑥 + 𝑎, 𝑦 + 𝑏, 𝑧 + 𝑐) where, 𝑎, 𝑏 and 𝑐 are the unit
vectors in 𝑥, 𝑦 and 𝑧 directions respectively

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 Crystal Systems
In geometry and crystallography, a Bravais lattice, named after Auguste Bravais (1850), is an infinite
array of discrete points generated by a set of discrete translation operations described in three
dimensional space by 𝑅 = 𝑢𝑎Ԧ + 𝑣𝑏 + 𝑤 𝑐Ԧ where 𝑢, 𝑣, 𝑤 are integers and 𝑎,
Ԧ 𝑏, 𝑐Ԧ are primitive vectors
which lie in different directions (not necessarily mutually perpendicular). Based on the length equality
or inequality of the primitive vectors and their orientation (the angles between them, 𝛼, 𝛽 and 𝛾) a total
of 7 crystal systems can be defined. With the centering (face, base and body centering) added to these,
14 kinds of 3D lattices, known as Bravais lattices, can be generated.

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 Crystal Systems
(1) Cubic: 𝑎 = 𝑏 = 𝑐 & 𝛼 = 𝛽 = 𝛾 = 90°

(2) Tetragonal: 𝑎 = 𝑏 ≠ 𝑐 & 𝛼 = 𝛽 = 𝛾 = 90°

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 Crystal Systems
(3) Orthorhombic: 𝑎 ≠ 𝑏 ≠ 𝑐 & 𝛼 = 𝛽 = 𝛾 = 90°

(4) Monoclinic: 𝑎 ≠ 𝑏 ≠ 𝑐 & 𝛼 = 𝛾 = 90° ≠ 𝛽

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 Crystal Systems
(5) Trigonal or Rhombohedral: 𝑎 = 𝑏 = 𝑐 & 𝛼 = 𝛽 = 𝛾 ≠ 90°

(6) Hexagonal: 𝑎 = 𝑏 ≠ 𝑐 & 𝛼 = 𝛽 = 90°, 𝛾 = 120°

(7) Triclinic: 𝑎 ≠ 𝑏 ≠ 𝑐 & 𝛼 ≠ 𝛽 ≠ 𝛾 ≠ 90°

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 Crystal Systems
Bravais Lattices: Summary

Wikipedia & Essentials of SSP: S. P. Kuila

 Cubic Structures
Some Terminologies:

(1) Coordination Number: Number of equidistant nearest atoms relative to a particular atom in
a unit cell
(2) Nearest Neighbour Distance: The center-to-center distance between two nearest atoms in
a unit cell = 2𝑟 (𝑟 = atomic radius)
2𝑟

(3) Atomic Packing Factor:

Volume of the unit cell occupied by the atoms

Volume of the unit cell

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 Cubic Structures
Simple Cubic (SC):
1. Coordination Number (𝑁) = 6
2. Nearest Neighbour Distance (2𝑟) = 𝑎
3. Atomic Radius (𝑟) = 𝑎/2
1
4. Number of atoms per unit cell (𝑛) = 8 × 8 = 1
4
5. Volume of the unit cell occupied by the atoms 𝑣 = 1 × 𝜋𝑟 3
3

6. Volume of the unit cell 𝑉 = 𝑎3 = 2𝑟 3

a
7. Atomic Packing Factor:
𝑣 4 𝜋𝑟 3 𝜋
APF = = 3
= = 52%
𝑉 3 2𝑟 6 a a

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 Cubic Structures
Body Centered Cubic (BCC):
1. Coordination Number (𝑁) = 8
3
2. Nearest Neighbour Distance (2𝑟) = 𝑎
2
4 a
3. Dimension of unit cell (𝑎) = 𝑟
3
1
4. Number of atoms per unit cell (𝑛) = 8 × 8 + 1 = 2
4 3
5. Volume of the unit cell occupied by the atoms 𝑣 = 2 × 𝜋𝑟
3
64 3 a
6. Volume of the unit cell 𝑉 = 𝑎3 = 𝑟 a
3 3
7. Atomic Packing Factor:
𝑣 4 3 3 3 3𝜋
APF = = 2 × 𝜋𝑟 × 3
= = 68%
𝑉 3 64𝑟 8

4𝑟 = 3𝑎

© Dr. P. Mandal
 Cubic Structures
Face Centered Cubic (FCC):
1. Coordination Number (𝑁) = 12
2
2. Nearest Neighbour Distance (2𝑟) = 𝑎
2
4 a
3. Dimension of unit cell (𝑎) = 𝑟
2
1 1
4. Number of atoms per unit cell (𝑛) = 8 × 8 + 2 × 6 =4
4 3
5. Volume of the unit cell occupied by the atoms 𝑣 = 4 × 𝜋𝑟 a
3 a
64 3
6. Volume of the unit cell 𝑉 = 𝑎3 = 2 𝑟
2
7. Atomic Packing Factor:
𝑣 4 3 2 2 2𝜋
APF = = 4 × 𝜋𝑟 × 3
= = 74%
𝑉 3 64𝑟 6

© Dr. P. Mandal 4𝑟 = 2𝑎
 Cubic Structures
Summary
 Cubic Structures
NaCl structure

❑ Ionic bonding between Na+ and Cl–

❑ FCC structure – number of molecules per unit cell 𝑛 = 4

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 Cubic Structures
Diamond structure
❑ The diamond lattice can be viewed as a pair of intersecting
face-centered cubic (fcc) lattices, with each separated by 1/4
of the width of the unit cell in each dimension.
❑ There are 8 atoms in 8 corners, 6 face-centered atoms and four
more atoms inside the unit cell. Thus, a unit cell contains
1+3+4=8 atoms.
Source: Wikipedia
Blue circles: (a) The lattice points of a face-centered cubic (fcc) lattice
and (b) Carbon atoms sitting on the lattice points.
Green circles: Carbon atoms but not lattice points
Red lines: Strong bonds between carbon atoms. All atoms are strongly
bonded to 4 neighbors and that's why it is difficult to rip them apart.
(Diamond is very hard!)
Black lines: Only to guide the eye in seeing the cubic lattice.
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 Cubic Structures
Calculation of lattice constant from density:
Consider 𝑛 number of molecules (or, atoms) per unit cell, 𝑀 is the molecular (or, atomic) weight
Mass of a single molecule = 𝑀/𝑁𝐴 where 𝑁𝐴 is the Avogadro number
𝑀
Mass of each unit cell 𝑚 = 𝑛 × 𝑁
𝐴

Assuming the unit cell of cubic structure, the volume of the cell V = 𝑎3
𝑚 𝑛𝑀
Hence the density is given by 𝜌 = 𝑉 = 𝑁 𝑎3
𝐴
1/3
3
𝑛𝑀 𝑛𝑀
⇒𝑎 = ⇒𝑎=
𝑁𝐴 𝜌 𝑁𝐴 𝜌

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 Cubic Structures
Problem:
Calculate the lattice constant of NaCl. Given, NaCl has FCC structure and the density of NaCl is
2.17 g/cc [CU – 2017]

FCC structure – number of molecules per unit cell 𝑛 = 4

Molecular weight 𝑀 = 23 + 35.5 g = 58.5 g
Density 𝜌 = 2.17 g/cc
Avogadro number 𝑁𝐴 = 6.626 × 1023
1/3 1/3
𝑛𝑀 4 × 58.5
Lattice constant 𝑎 = = cm = 5.64 Å
𝑁𝐴 𝜌 6.626 × 1023 × 2.17

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 Crystal Planes: Miller Indices
Locations in Lattices: Point Coordinates
z
111
c Position of any point in a unit cell is given by its coordinates or
distances from the x, y and z axes in terms of the lattice vectors a, b
and c

000
y
a b Point coordinates for unit cell (body diagonal) corner are 111
x •
z 2c Translation: integer multiple of lattice constants → identical
• position in another unit cell

• •
b y
b
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 Crystal Planes: Miller Indices
Planes in a crystal are described by notations called Miller indices. Miller indices of a plane, indicated by
(h k l), are given by the reciprocal of the intercepts of the plane on the three axes
How to find Miller Indices?
❑ Determine the intercepts of the plane along the crystal axes – 𝑝𝑎, 𝑞𝑏, 𝑟𝑐
❑ Take the reciprocals – 1/𝑝, 1/𝑞, 1/𝑟
❑ Clear fractions
❑ Reduce to lowest terms and enclose in brackets (ℎ 𝑘 𝑙)
Example: 𝑝 = 4, 𝑞 = 3, 𝑟 = 3
1 1 1
ℎ∶ 𝑘∶ 𝑙= ∶ ∶ =3∶4∶4
4 3 3
Miller Indices (ℎ 𝑘 𝑙) = (3 4 4)

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 Crystal Planes: Miller Indices
Few more examples:

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 Crystal Planes: Miller Indices
❑ Miller indices define a set of parallel planes
❑ If a plane passes through the origin its Miller indices are determined in terms of a parallel plane
having non-zero intercepts
❑ Planes can also have negative intercept e.g., 1, −1/2, 1 ⇒ (ℎ 𝑘 𝑙) = ( 1 − 2 1).
This is denoted as ( 1 2ത 1 )
❑ Family of planes: ℎ 𝑘 𝑙
Planes having similar indices are equivalent, e.g., faces of the cube (1 0 0), (0 1 0) and (0 0 1). This is
termed as a family of planes and denoted as {1 0 0} which includes all the (1 0 0) combinations
including negative indices. Some other equivalent planes are shown in the next slide

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 Crystal Planes: Miller Indices
Equivalent planes:

𝟏𝟎𝟎

𝟏𝟏𝟎

𝟏𝟏𝟏
 Crystal Planes: Inter-planar Spacing
Consider a set of parallel planes having Miller indices (ℎ 𝑘 𝑙)
Equation of the plane nearest to the origin
𝑥 𝑦 𝑧
+ + =1
(𝑎/ℎ) (𝑏/𝑘) (𝑐/𝑙)

Draw a normal OP from the origin to this plane – length 𝑑 of this

normal is the spacing between adjacent parallel planes in the set. The
direction cosines of OP (= 𝑑) are

𝑑 ℎ𝑑 𝑘𝑑 𝑙𝑑
cos 𝛼 = = , cos 𝛽 = , cos 𝛾 =
(𝑎/ℎ) 𝑎 𝑏 𝑐

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 Crystal Planes: Inter-planar Spacing

cos2 𝛼 + cos2 𝛽 + cos2 𝛾 = 1

ℎ2 𝑘 2 𝑙 2 2
⇒ 2+ 2+ 2 𝑑 =1
𝑎 𝑏 𝑐
1
⇒ 𝑑 ≡ 𝑑ℎ𝑘𝑙 =
ℎ/𝑎 2 + 𝑘/𝑏 2 + 𝑙/𝑐 2

For cubic crystals, 𝑎 = 𝑏 = 𝑐

𝑎
𝑑ℎ𝑘𝑙 =
ℎ2 + 𝑘 2 + 𝑙 2

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 Crystal Planes: Normal

Equation of the plane having Miler indices (ℎ 𝑘 𝑙)

𝑥 𝑦 𝑧 ℎ 𝑘 𝑙
𝑓= + + =1 ⇒𝑓 = 𝑥+ 𝑦+ 𝑧=1
(𝑎/ℎ) (𝑏/𝑘) (𝑐/𝑙) 𝑎 𝑏 𝑐

𝛻𝑓 ℎ/𝑎 𝑖Ƹ + 𝑘/𝑏 𝑗Ƹ + 𝑙/𝑐 𝑘෠

Direction of the normal to the plane 𝑛ො = =
𝛻𝑓 ℎ/𝑎 2 + 𝑘/𝑏 2 + 𝑙/𝑐 2

ℎ𝑖Ƹ + 𝑘𝑗Ƹ + 𝑙𝑘෠

For a cubic structure 𝑎 = 𝑏 = 𝑐: 𝑛ො =
ℎ2 + 𝑘 2 + 𝑙 2

© Dr. P. Mandal
 Crystal Planes: Angle
ℎ1 𝑖Ƹ + 𝑘1 𝑗Ƹ + 𝑙1 𝑘෠
Direction of normal to (ℎ1 𝑘1 𝑙1 ) plane for cubic structure 𝑛ො1 =
ℎ12 + 𝑘12 + 𝑙12

ℎ2 𝑖Ƹ + 𝑘2 𝑗Ƹ + 𝑙2 𝑘෠
Direction of normal to (ℎ2 𝑘2 𝑙2 ) plane for cubic structure 𝑛ො 2 =
ℎ22 + 𝑘22 + 𝑙22

Angle 𝜃 between the planes is given by

ℎ1 ℎ2 + 𝑘1 𝑘2 + 𝑙1 𝑙2
cos 𝜃 = 𝑛ො1 ∙ 𝑛ො 2 =
ℎ12 + 𝑘12 + 𝑙12 ℎ22 + 𝑘22 + 𝑙22

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 Crystal Planes
Inter-planar Spacing 𝑎
Crystal Structures Lattice Planes (ℎ 𝑘 𝑙) 𝑑ℎ𝑘𝑙 =
(𝒅𝒉𝒌𝒍 ) ℎ2 + 𝑘 2 + 𝑙 2
100 𝑎
SC 110 𝑎/ 2
111 𝑎/ 3
100 𝑎/2
BCC 110 𝑎/ 2
111 𝑎/2 3
100 𝑎/2
FCC 110 𝑎/2 2
111 𝑎/ 3

Lattice Planes: SC
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 Reciprocal Lattice
Definition
Starting with a Bravais lattice, the reciprocal lattice is the set of all wave vectors 𝐺Ԧ that give plane waves
Ԧ 𝑟Ԧ
𝑒 𝑖𝐺∙ with the periodicity of the Bravais lattice. If the Bravais lattice is given by points 𝑅, one thus have
Ԧ 𝑟+𝑅) Ԧ 𝑟Ԧ Ԧ
𝑒 𝑖𝐺∙( Ԧ
= 𝑒 𝑖𝐺∙ ⇒ 𝑒 𝑖𝐺∙𝑅 = 1 = 𝑒 𝑖2𝜋 ⇒ 𝐺Ԧ ∙ 𝑅 = 2𝜋
Ԧ
The 𝐺-vectors correspond to the reciprocal lattice points. The reciprocal lattice is also a Bravais lattice
Vector in direct lattice space is defined as 𝑅 = 𝑝𝑎Ԧ + 𝑞𝑏 + 𝑟𝑐Ԧ 𝑏 × 𝑐Ԧ
∗
𝑎Ԧ = 2𝜋
Vector in reciprocal lattice space is defined as 𝐺Ԧ = 𝑙𝑎Ԧ ∗ + 𝑚𝑏∗ + 𝑛𝑐Ԧ∗ 𝑎Ԧ ∙ 𝑏 × 𝑐Ԧ
𝑐Ԧ × 𝑎Ԧ
𝑎Ԧ𝑖∗ ∙ 𝑎Ԧ𝑗 = 2𝜋𝛿𝑖𝑗 𝑏∗ = 2𝜋
𝑎Ԧ ∙ 𝑏 × 𝑐Ԧ
𝑎Ԧ𝑖∗ = 𝑎Ԧ ∗ , 𝑏 ∗ , 𝑐Ԧ∗
𝑎Ԧ × 𝑏
𝑎Ԧ𝑗 ≡ 𝑎,
Ԧ 𝑏, 𝑐Ԧ 𝑐Ԧ∗ = 2𝜋
𝑎Ԧ ∙ 𝑏 × 𝑐Ԧ

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 Reciprocal Lattice
Reciprocal Lattice to SC:
Primitive translation vectors of a simple cubic lattice: 𝑎Ԧ = 𝑎𝑖,Ƹ 𝑏 = 𝑏𝑗,Ƹ 𝑐Ԧ = 𝑐 𝑘෠ and 𝑎 = 𝑏 = 𝑐
Volume of a unit cell: V = 𝑎Ԧ ∙ 𝑏 × 𝑐Ԧ = 𝑎3 𝑖Ƹ ∙ 𝑗Ƹ × 𝑘෠ = 𝑎3
Reciprocal lattice vectors to the SC lattice are
𝑏 × 𝑐Ԧ 𝑎 ෠
2 𝑗Ƹ × 𝑘 2𝜋
∗
𝑎Ԧ = 2𝜋 = 2𝜋 = 𝑖Ƹ
𝑎 3 𝑎
𝑎Ԧ ∙ 𝑏 × 𝑐Ԧ
𝑐Ԧ × 𝑎Ԧ 𝑎 ෠ × 𝑖Ƹ
2 𝑘 2𝜋
∗
𝑏 = 2𝜋 = 2𝜋 = 𝑗Ƹ
𝑎 3 𝑎
𝑎Ԧ ∙ 𝑏 × 𝑐Ԧ
2 𝑖Ƹ × 𝑗 Ƹ
𝑎Ԧ × 𝑏 𝑎 2𝜋
∗
𝑐Ԧ = 2𝜋 = 2𝜋 3
= 𝑘෠
𝑎Ԧ ∙ 𝑏 × 𝑐Ԧ 𝑎 𝑎

⇒ Reciprocal lattice also simple cubic with lattice constant 2𝜋/𝑎.

Volume of the primitive cell of reciprocal lattice 𝑉 ′ = 2𝜋/𝑎 3

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 Reciprocal Lattice
Reciprocal Lattice to BCC:
Primitive translation vectors of a BCC lattice are: 𝑎
𝑎Ԧ ′ = 𝑖Ƹ + 𝑗Ƹ − 𝑘෠
2
𝑎
𝑏 ′ = −𝑖Ƹ + 𝑗Ƹ + 𝑘෠
2
𝑎
𝑐Ԧ = 𝑖Ƹ − 𝑗Ƹ + 𝑘෠
′
2

Volume of a unit cell: V = 𝑎Ԧ ′ ∙ 𝑏′ × 𝑐′

Ԧ
𝑎 𝑎2
= 𝑖Ƹ + 𝑗Ƹ − 𝑘෠ ∙ −𝑖Ƹ + 𝑗Ƹ + 𝑘෠ × 𝑖Ƹ − 𝑗Ƹ + 𝑘෠
2 4
𝑎 𝑎2 𝑎3
= 𝑖Ƹ + 𝑗Ƹ − 𝑘෠ ∙ 𝑖Ƹ + 𝑗 Ƹ =
2 2 2

© Dr. P. Mandal
 Reciprocal Lattice
Reciprocal Lattice to BCC:
Reciprocal lattice vectors to the BCC lattice are

𝑏′ × 𝑐′
Ԧ (𝑎 2 /4) −𝑖Ƹ + 𝑗Ƹ + 𝑘෠ × 𝑖Ƹ − 𝑗Ƹ + 𝑘෠ 2𝜋
∗
𝑎Ԧ = 2𝜋 = 2𝜋 = 𝑖Ƹ + 𝑗 Ƹ
(𝑎 3 /2) 𝑎
𝑎′
Ԧ ∙ 𝑏′ × 𝑐′
Ԧ
𝑐′
Ԧ × 𝑎′
Ԧ (𝑎 ෠ × 𝑖Ƹ + 𝑗Ƹ − 𝑘෠
2 /4) 𝑖Ƹ − 𝑗Ƹ + 𝑘 2𝜋
∗
𝑏 = 2𝜋 = 2𝜋 = 𝑗 Ƹ + ෠
𝑘
𝑎′
Ԧ ∙ 𝑏′ × 𝑐′
Ԧ (𝑎3 /2) 𝑎

𝑎′
Ԧ × 𝑏′ (𝑎 ෠ × −𝑖Ƹ + 𝑗Ƹ + 𝑘෠
2 /4) 𝑖Ƹ + 𝑗Ƹ − 𝑘 2𝜋
∗
𝑐Ԧ = 2𝜋 = 2𝜋 3
= 𝑘෠ + 𝑖Ƹ
𝑎′
Ԧ ∙ 𝑏′ × 𝑐′
Ԧ (𝑎 /2) 𝑎
⇒ Reciprocal lattice is FCC.

Volume of the primitive cell of reciprocal lattice 𝑉 ′ = 𝑎Ԧ ∗ . 𝑏 ∗ × 𝑐Ԧ∗ = 2 2𝜋/𝑎 3

© Dr. P. Mandal
 Reciprocal Lattice
Reciprocal Lattice to FCC:
Primitive translation vectors of a FCC lattice are: 𝑎
𝑎Ԧ ′= 𝑖Ƹ + 𝑗 Ƹ
2
𝑎
𝑏′ = 𝑗Ƹ + 𝑘෠
2
𝑎
𝑐Ԧ′ = 𝑘෠ + 𝑖Ƹ
2

Volume of a unit cell: V = 𝑎Ԧ ′ ∙ 𝑏′ × 𝑐′

Ԧ
𝑎 𝑎2
= 𝑖Ƹ + 𝑗 Ƹ ∙ 𝑗Ƹ + 𝑘෠ × 𝑘෠ + 𝑖Ƹ
2 4
𝑎 𝑎2 𝑎3
= 𝑖Ƹ + 𝑗 Ƹ ∙ 𝑖Ƹ + 𝑗Ƹ − 𝑘෠ =
2 4 4

© Dr. P. Mandal
 Reciprocal Lattice
Reciprocal Lattice to FCC:
Reciprocal lattice vectors to the FCC lattice are

𝑏′ × 𝑐′
Ԧ (𝑎 ෠ × 𝑘෠ + 𝑖Ƹ
2 /4) 𝑗Ƹ + 𝑘 2𝜋
∗
𝑎Ԧ = 2𝜋 = 2𝜋 = 𝑖 Ƹ + 𝑗 Ƹ − ෠
𝑘
𝑎′
Ԧ ∙ 𝑏′ × 𝑐′
Ԧ (𝑎3 /4) 𝑎

𝑐′
Ԧ × 𝑎′
Ԧ (𝑎 ෠ + 𝑖Ƹ × 𝑖Ƹ + 𝑗 Ƹ
2 /4) 𝑘 2𝜋
∗
𝑏 = 2𝜋 == 2𝜋 = −𝑖 Ƹ + 𝑗 Ƹ + ෠
𝑘
𝑎′
Ԧ ∙ 𝑏′ × 𝑐′
Ԧ (𝑎3 /4) 𝑎

𝑎′
Ԧ × 𝑏′ (𝑎 ෠
2 /4) 𝑖Ƹ + 𝑗Ƹ × 𝑗Ƹ + 𝑘 2𝜋
∗
𝑐Ԧ = 2𝜋 == 2𝜋 3
= 𝑖Ƹ − 𝑗Ƹ + 𝑘෠
𝑎′
Ԧ ∙ 𝑏′ × 𝑐′
Ԧ (𝑎 /4) 𝑎
⇒ Reciprocal lattice is BCC.

Volume of the primitive cell of reciprocal lattice 𝑉 ′ = 2𝜋/𝑎 3

© Dr. P. Mandal
 X-Ray Diffraction
❑ In order to probe the crystal structure, we require waves that interact with atoms and have
wavelength comparable with the interatomic spacing in crystal (𝜆~1 Å)
❑ The interaction should be weak enough so that the incident wave can penetrate in a coherent
fashion into the crystal at least for a distance of the order of 1000 lattice constants
❑ X-ray is the most convenient wave suitable for probing crystal structure. Other waves are those
associated with electron beam or neutron beam (energies ~100 eV and ~0.1 eV respectively for
which 𝜆~1 Å)
❑ X-ray diffraction technique was first suggested by von Laue in 1912 and was later further
developed by W. H. Bragg and W. L. Bragg (father & son, Nobel Laurate – 1915, W. L. Bragg
youngest Nobel Laurate in Physics)
❑ When an atom is exposed to electromagnetic radiation, the atomic electrons are accelerated, and
they radiate at the frequency of the incident radiation in all directions (elastic scattering)

© Dr. P. Mandal
 X-Ray Diffraction
❑ The superposition of waves scattered by individual atoms in a crystal results in the ordinary
reflection
❑ If the wavelength of the incident radiation is comparable with or smaller than the lattice constant,
we will have diffraction of the incident beam under certain conditions
❑ At optical frequencies (~1015 Hz) only refraction occurs; at X-ray frequencies (~1018 Hz)
diffraction becomes important

© Dr. P. Mandal
 Bragg’s Law
Path difference δ = GE + EH

From Δ BEG, sinθ = GE/BE = GE/d

or, GE = d sinθ
Similarly, from ΔBEH, EH = 𝑑 sinθ

⸫ δ = 2𝑑 sin θ
For constructive diffraction, δ = 2𝑑 sin θ = 𝑛λ

𝑛 = 0, 1, 2, 3, ….

© Dr. P. Mandal
 Bragg’s Law
𝟐𝒅𝒉𝒌𝒍 𝐬𝐢𝐧 𝜽 = 𝒏𝝀

❑ This condition immediately shows that for a given value of 𝑑ℎ𝑘𝑙 and 𝜆, and n having integer
values, only a particular angle 𝜃 would produce such a reflection

❑ Thus, a beam of monochromatic X-rays incident on a crystal with an arbitrary angle 𝜃 is, in
general, not reflected

❑ Also, because sin 𝜃 ≤ 1 and 𝑑 ≈ 1 Å, we see that reflection can be observed only for 𝜆 of the order
of 1 Å or less

© Dr. P. Mandal
 Bragg’s Law
2𝑑ℎ𝑘𝑙 sin 𝜃 = 𝑛𝜆
𝑎
𝑑ℎ𝑘𝑙 =
ℎ2 + 𝑘 2 + 𝑙 2

Bravais Lattices Examples Allowed Forbidden

Reflections Reflections
Simple Cubic (sc) Po any h, k, l N/A

Body-Centered Fe, Cr etc. h + k + l = even h + k + l = odd

Cubic (bcc)
Face-Centered Cu, Al, Ni, NaCl, h, k, l all even or h, k, l mixed odd
Cubic (fcc) LiH etc. all odd and even

© Dr. P. Mandal
 Bragg’s Law
Prob.: In a powder diffraction experiment with X-rays of wavelength 1.54 Å, the first order Bragg
reflections occur from a monoatomic crystal for θ-values 17.4°, 20.3°, 29.3°, 35.1° and 36.9°.
Determine the Miller indices of diffraction planes, (ii) the crystal structure and (iii) the lattice parameter

For first order reflection from a plane with Miller indices (h k l) in a cubic crystal with lattice
parameter a, we have from Bragg’s law
2𝑑ℎ𝑘𝑙 sin 𝜃 = 𝜆
𝑎
⇒2 sin 𝜃 = 𝜆
2
ℎ +𝑘 +𝑙2 2
2
𝜆
⇒ sin2 𝜃 = 2 ℎ2 + 𝑘 2 + 𝑙2
4𝑎
⇒ sin 𝜃 ∝ ℎ2 + 𝑘 2 + 𝑙2
2

For θ-values 17.4°, 20.3°, 29.3°, 35.1° and 36.9°, values of sin2 𝜃 are 0.09, 0.12, 0.24, 0.33 and 0.36
i.e. sin2 𝜃 are in the ratio 3 : 4 : 8 : 11 : 12

© Dr. P. Mandal
 Bragg’s Law
𝜃 sin 𝜃 sin2 𝜃 ℎ2 + 𝑘 2 + 𝑙 2 (h k l)
17.4° 0.299 0.09 3 (1 1 1)
20.3° 0.347 0.12 4 (2 0 0)
29.3° 0.489 0.24 8 (2 2 0)
35.1° 0.575 0.33 11 (3 1 1)
36.9° 0.6 0.36 12 (2 2 2)
Since the Miller indices (h k l) are either all odd or all even, the crystal has fcc structure
To calculate the lattice parameter a, take θ = 20.3° and (h k l) = (2 0 0)
𝑎
2𝑑ℎ𝑘𝑙 sin 𝜃 = 𝜆 ⇒ 2 sin 𝜃 = 𝜆
2
ℎ +𝑘 +𝑙2 2

𝜆 2 2 2
1.54
⇒𝑎= ℎ +𝑘 +𝑙 = 22 + 02 + 02 Å = 4.46 Å
2 sin 𝜃 2 sin 20.3°

© Dr. P. Mandal
 Bragg’s Law
Prob.: In a powder diffraction experiment with X-rays of wavelength 1.54 Å, the first order Bragg
reflections occur from a monoatomic crystal for θ-values 5.22°, 7.30°, 9.05°. Determine the Miller
indices of diffraction planes and hence (ii) the crystal structure.

𝜃 sin 𝜃 sin2 𝜃 ℎ2 + 𝑘 2 + 𝑙 2 (h k l)
5.22° 0.091 0.008 1 (1 0 0)
7.30° 0.127 0.016 2 (1 1 0)
9.05° 0.157 0.024 3 (1 1 1)
The crystal has sc structure

© Dr. P. Mandal
 Laue Diffraction Equation
Now, consider the nature of the diffraction pattern
produced by identical atoms located at the corners (lattice
points) of the primitive cells of a space lattice
First, look at the scattering from two lattice points P1 and
P2 separated by 𝑟. Ԧ The unit incident wave normal is 𝑠Ԧ0
and the unit scattered wave normal is 𝑠Ԧ
The path difference between two scatted waves is

𝛿 = 𝑃1 𝐵 − 𝑃2 𝐴 = 𝑟. 𝑠Ԧ − 𝑟. 𝑠Ԧ0 = 𝑟. 𝑠Ԧ − 𝑠Ԧ0 = 𝑟. 𝑆Ԧ

© Dr. P. Mandal
 Laue Diffraction Equation
The vector 𝑆Ԧ = 𝑠Ԧ − 𝑠Ԧ0 has a simple interpretation as the direction of the normal to a plane that would
reflect the incident direction into the scattering direction – reflecting plane
𝑆 = 2 sin 𝜃

2𝜋 2𝜋
The phase difference 𝜙= 𝛿= 𝑟. 𝑆Ԧ
𝜆 𝜆

For maxima of scattered wave amplitude, the phase

difference is integral multiple of 2π

© Dr. P. Mandal
 Laue Diffraction Equation

h, k, l are integers

or

𝛼, 𝛽, 𝛾 are the direction cosines

Laue equations

© Dr. P. Mandal
 Laue Diffraction Equation
❑ In a given direction (θ) and for a given wavelength (λ), the direction
cosines 𝛼, 𝛽, 𝛾 are proportional to h/a, k/b and l/c respectively

❑ If (h k l) are the Miller indices representing a set of parallel lattice

planes, they intersect the axes at intervals a/h, b/k, c/l so that the
direction cosines of the normal to the plane are proportional to h/a, k/b
and l/c
𝑎𝛼 𝑏𝛽 𝑐𝛾
𝑑ℎ𝑘𝑙 = = =
ℎ 𝑘 𝑙

From Laue equations, 2𝑑ℎ𝑘𝑙 sin 𝜃 = 𝑛𝜆 Bragg equation

© Dr. P. Mandal