Engineering Physics Unit - II Crystallography and X-ray Diffraction

Crystallography: Space lattice, Basis, Unit Cell and lattice parameters – Bravais Lattices – crystal systems
(3D) – coordination number - packing fraction of SC, BCC & FCC - Miller indices – separation between
successive (hkl) planes.

X-ray diffraction: Bragg’s law - X-ray Diffractometer – crystal structure determination by Laue’s and
powder methods.
Introduction: Many of the properties of solid materials depend mainly on their crystal structures.
Based on the arrangement of atoms and molecules, the solid material classified as follows

Crystalline Material: The periodic arrangement of atoms in all three dimensions space is called
crystal. It has regular shape and when it is broken, all broken pieces have the same regular shape. It
has sharp melting point. The physical properties of the crystal vary with direction and therefore they
are called anisotropic substances. It may be made up of metallic crystals or non-metallic crystals.
Examples: Cu, Al, W, Mg, Carbon, crystallized polymer and plastics.
Crystalline Material are classified into two types. They are, 1. Single Crystal 2. Polycrystalline
Material.
1. Single Crystal: The entire crystalline material consists of only one crystal is known as single
crystal. Example: KDP, ADP.
2. Polycrystalline Material: A collection of many small crystals are separated by well-defined
boundaries is called polycrystalline materials.
Example: GaP, GaAs, ZnO and ZnS.
Non-Crystalline Material: Random arrangement of atoms in all three dimensions space is called
non-crystalline material or amorphous. They have no directional properties and therefore they are
called isotropic substances. They do not possess any regular shape and they have a wide range of
melting points.
Examples: Glass and Rubber.
Space Lattice: A regular and periodic arrangement of infinite number of points in three dimensions
space is known as space lattice. Every point in this arrangement is identical to that of every other
point.

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 Engineering Physics Unit - II Crystallography and X-ray Diffraction

Basis (Motif): A group of atoms in every lattice point is called basis or motif.

Crystal: A crystal is defined as regular and periodic arrangements of atoms or molecule in three
dimensional spaces.
Space lattice + Basis = Crystal

Fundamental translation vector: Mathematical representation of position vector in the space

lattice is called fundamental translation vector. In two dimension R = n1a + n2b
In three dimension R = n1a+ n2b + n3c Where, a, b and c are the fundamental translation vectors and
n1, n2 and n3 are the integers.

Interfacial angles: The angles between the three crystallographic axes are known as interfacial
angles. Generally it’s are represented as α, β and γ respectively.

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 Engineering Physics Unit - II Crystallography and X-ray Diffraction

Unit Cell: The unit cell is a smallest geometric volume containing one or more atoms arranged in
three dimension. And also, it is called fundamental building block of a crystal structure.

Primitive cell: Primitive cell is the smallest volume unit cell which contains the lattice points at the
corner only.

Lattice Constant: The distance between any two successive lattice points along any three
dimensional directions is called lattice constant.
Properties of the Unit cell: Let us discuss some of the important parameters which are used to
describe the crystal structure.
1. Number of atoms per unit cell or Effective number: The total number of atoms present in or
shared by a unit cell is known as number of atoms per unit cell.
2. Atomic radius: Atomic radius is defined as half of the distance between any two nearest
neighbour atoms which have direct contact with each other, in a crystal of a pure element. It is
usually expressed in terms of cube edge a.
3. Co-ordination number: Co-ordination number is the number of nearest neighbouring atoms to a
particular atom (or) Coordination number is the number of nearest neighbours directly surrounding a
given atom.
4. Atomic packing factor or packing density or density of packing: Atomic packing factor is
defined as the ratio between the volumes occupied by the total number of atoms per unit cell (u) to
the total volume of the unit cell (v).
࢛
APF = Where, u = Total number of atoms per unit cell x volume of one atom, v = Total
࢜
volume of the unit cell.

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Seven Crystal Systems: Based on the fundamental translation vector and interfacial angle, the
crystal classified in to seven types. They are,
1. Cubic
2. Triclinic
3. Monoclinic
4. Orthorhombic
5. Tetragonal
6. Rhombohedral
7. Hexagonal.

Bravais Space Lattice: A three dimensional space lattice is generated by repeated translation of
three non-coplanar vectors a, b and c. In 1848, Bravais showed that there are 14 distinguishable
ways of arranging points in three dimensional spaces. These fourteen space lattices are known as
Bravais space lattices. The different Bravais space lattices and their crystal systems are listed in
given table.
In general, there are 4 types of lattice symbols or arrangements. They are,
P-Simple or Primitive: Lattice points only at the corners of the unit cell.
C-Base centered: Lattice points at the corners + at the centre of two opposite faces of the unit cell.
I-Body centered: Lattice points at the corners + at the body centre of the unit cell.
F-Face centered: Lattice points at the corners + at the centers of all the six faces.

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STRUCTURE OF CUBIC:
Cubic system: The cubic crystal structure is the simplest type and the atoms can take positions at
the corners, faces and also at the centre of the cube. Based on the positions of the atom in the cubic
system, it can be classified in to three types. They are, 1. Simple Cubic (SC) or Primitive (P) 2.
Body Centered Cubic (BCC) and 3. Face Centered Cubic (FCC).
1. Simple Cubic Structure (SC): A simple cubic unit cell consists of eight corner atoms as shown in
given figure. Example: polonium

Number of Atoms per unit cell: In actual crystal, each and every corner atom touches with each
other and is shared by eight adjacent unit cells. Therefore, one corner atom contributes 1/8 of its part
to one unit cell.
ଵ ଵ
Hence, Total number of atoms per unit cell is = × (total number of corner atoms) = × 8 = 1
଼ ଼
In other words, the effective number of lattice points in a simple cubic structure is one. Thus, simple
cubic is a primitive cell.

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Atomic Radius: In simple cubic (SC) structure the corner atoms touch each other along the edges.
Let us consider one face (front face) of the simple cubic structure as shown in figure. Here, the
௔
nearest neighbour distance is the lattice constant a = 2r. Atomic radius r = .
ଶ

Co-ordination Number: Simple cubic unit cell consists of eight corner atoms. Let us consider any
one corner atom say X, shared by 8 unit cells as shown in figure.

For this particular atom ‘X’ there are four nearest neighbour atoms, shown as 2, 3, 4 and 5 in its own
plane (horizontal plane) and there are two more nearest atoms, one directly above (atom 1) and the
other one directly below (Atom 6). All the atoms, other than these six atoms lie at greater distances
from the X atom. The total number of nearest neighbours for X-atom is 4+2= 6. Hence, the
coordination number for simple cubic is six.

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Packing factor:

Therefore, we can say that 52% volume of the unit cell of SC is occupied by atoms and remaining
48% volume is vacant. Thus, the packing density is 52%. Since the packing density is very low, SC
has loosely packed structure.

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2. Body Centre Cubic Structure (BCC): A body centered cubic structure has eight corner atoms and
one body centered atom. The diagrammatic representation of a body centered cubic structure is
shown in given figure. Examples: Tungsten, Chromium, Molybdenum, etc.

Number of Atoms per unit cell: In a body centered crystal structure, the body centered atom touch
along the diagonal of the body. In bcc unit cell, each and every corner atom is shared by eight
ଵ
adjacent unit cells. The total number of corner atoms per unit cell is = × 8 = 1
଼
The number of body centred atoms per unit cell is = 1 × 1 = 1
Total number of atoms per unit cell in BCC is = 1 + 1 = 2
Atomic Radius: In BCC structure, the corner atoms do not touch each other. But each corner atom
touches the body centered atom along the body diagonal as shown in figure. Therefore the two
corner atoms (A and D) situated at the opposite ends can be joined by drawing a diagonal as shown
in figure.

From the geometry of the figure, we can write (AD)2 = (AC)2 + (CD)2

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Co-Ordination Number: In BCC structure, there will be one body centered atom at the centre of the
unit cell and eight atoms at the 8 corners of the unit cell as shown in figure.

The corner atoms do not touch each other. But each corner atom touches the body centered atom
along the body diagonal. Thus, the body centre atom has eight nearest neighbour atoms (corner
atoms). Hence, the co-ordination number body centered cubic structure is eight.
Packing Factor:

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 Engineering Physics Unit - II Crystallography and X-ray Diffraction

Therefore, we can say that 68% volume of the unit cell of BCC is occupied by atoms and remaining
32% volume is vacant. Thus the packing density is 68%. Since the packing density is greater than
simple cubic, it has tightly packed structure, when compared to SC.
3. Face Centered Cubic Structure (FCC): A face centered cubic (FCC) structure unit cell consists
of eight corner atoms and six face centered atoms. A face centered cubic unit cell is shown in given
figure.

Number of atoms per unit cell: Each and every corner atom is shared by eight adjacent unit cells.
Therefore, each and every corner atom contributes 1/8 of its part to unit cell. Hence, the total number
ଵ
of atoms contributed by the corner atom is = × 8 = 1 Each and every face centered atom is shared
଼
by two unit cells. Therefore, a face centered atom contributes half of its part to one unit cell.
ଵ
Hence, the total number of atoms contributed by the face centered atom is = × 6 = 3
ଶ
Total number of atoms per unit cell in FCC is = 1 + 3 = 4
Atomic Radius: In FCC structure, the corner atoms do not touch each other. But each corner atom
touches the face centered atoms along the diagonal of the face of the cube as shown in figure.

Therefore, the two corner atoms (A and C) situated at the opposite ends of the same face can be
joined by drawing a diagonal as shown in above figure. From the geometry of the figure, we can
write

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Co-Ordination Number: In this system, there are eight corner atoms, and six face centered atoms,
one at the centre of each face. To calculate the coordination number, for FCC, let us consider a
corner atom (X) as shown in figure.

In its own plane it has four face centered atoms (1, 2, 3 and 4) as nearest neighbours. In a plane
which lies just above this corner atom, it has four more face centered atoms (5, 6, 7 and 8) as nearest
neighbours. And, similarly in a plane which lies just below this corner atom it has four more face
centered atoms, (9, 10, 11 and 12) as nearest neighbours. The total number of nearest atoms to any
corner atom is 4+4+4+4= 12. Hence, the coordination number is 12.
Packing Factor:

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Therefore, we can say that 74% volume of the unit cell of FCC is occupied by atoms and remaining
26% volume is vacant. Thus, the packing density is 74%. Since the packing density is very high, the
FCC structure has closely or tightly packed structure.
Comparison for SC, BCC and FCC structures
The parameters determining the crystal structure of SC, BCC and FCC are given for comparison, in
table.

Relation between lattice constant and density:

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Lattice planes: A crystal lattice is considered as a collection of a set of parallel equidistant planes
passing through lattice points. These planes are known as lattice planes.

Miller Indices: In 1839 W.H. Miller derived a method for representing the orientation of crystal
planes. Miller indices are a set of smallest integers (h k l) which indicate the direction of a set of
parallel planes in a crystal. It is defined as the reciprocal of the fractional intercepts which the plane
makes with the crystallographic axes.
Procedure for finding Miller indices:
1. Find the intercepts of the plane along the co-ordinate axes X, Y and Z.
2. Take reciprocal of these intercepts.
3. Reduce the reciprocals into whole numbers using least common multipliers (LCM).
4. Write these integers within parentheses to get Miller indices.
For example, consider a crystal plane as shown in given figure.

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Features of Miller indices:

1. Plane passing through the origin has non zero intercepts.
2. All equally spaced parallel planes have same Miller indices.
3. Miller indices do not define a particular plane, but it defines a set of parallel planes.
4. If the plane is parallel to any one of the coordinate axes, then its intercepts will be at infinity.
Therefore, the miller index of that particular axis is zero.
5. If a plane cuts the axis on the negative side, then the corresponding Miller indices will be
negative, is represented by a bar over it. i.e.,
Procedure for sketching intercepts of a plane for a given Miller indices (h k l)
1. Sketch the unit cell in the coordinate system x y z with the given lattice constants a, b, c.
2. If the lattice constants are not given, then we can consider a cubic unit cell.
3. Consider the given Miller indices (h k l).
ଵ ଵ ଵ
4. Get the reciprocals of the indices, i.e. ௛ , ௞ , ௟ .

5. These give us the intercepts of the desired plane on the axes, respectively.
6. These intercepts are marked in the unit cell and the plane is drawn.
7. If the intercept is ∞ on any axis, then the plane drawn will be parallel to that axis.
Example of Planes

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Interplanar distance (or) separation between successive (hkl) planes (or) d spacing in cubic
lattice:
The distance between any two successive planes is called d spacing or interplanar distance.

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 Engineering Physics Unit - II Crystallography and X-ray Diffraction

X-Rays:
German physicist Wilhelm Röntgen is typically credited for the discovery of X-Rays in 1895
because he was the first to comprehensively study them.
1. X-rays are part of electromagnetic radiation with wavelengths between about 0.01A0-10A0.
2. They are part of the electromagnetic spectrum which includes electromagnetic radiation called
visible light.
3. X-rays have wavelengths similar to the size of atoms, they are useful to explore within the crystals.
4. The energy of X-rays, like all electromagnetic radiation, is inversely proportional to their
wavelength as given by the Einstein equation E= hν = hc/λ.
5. Since X-rays have smaller wavelength than visible light, they have higher energy, hence they can
penetrate matter more easily than visible light.
Diffraction of X-rays by Crystal Planes
W.L. Bragg, observed X-ray diffraction when X-rays are incident on the crystal surface nearly at
Bragg’s angles. Bragg’s angle or glancing angle means the angle between incident ray and crystal
plane at which diffraction occurs.
Bragg’s Law: Bragg’s law states that X-rays reflected from different parallel planes of a crystal
interfere constructively when the path difference is an integral multiple of the wavelength of X-rays.
Bragg’s law is a consequence of the periodicity of the crystal lattice.
Explanation: Consider a crystal made up of equidistant parallel planes of atoms with interplanar
spacing dhkl, as shown in Fig. Let the wave front of monochromatic X-rays of wavelength λ incident
at an angle θ on these atomic planes. θ is called the Glancing angle or Bragg’s angle. The planes are
called the Bragg’s planes. Each atom scatters the x-rays in all directions.

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In certain directions, these scattered or reflected radiations are in phase. This means they
interfere constructively, while in all other directions, there is destructive interference. Consider the
x-rays AB and DE falling at an angle θ on the planes 1 and 2. They are scattered (reflected) along
BC and EF at an angle θ to plane 1 and plane 2, respectively. BM and BN are the normals drawn to
DE and EF.
The path difference between the incident and reflected waves is given by Δ = ME+EN

This condition is known as Bragg’s law.

From Bragg’s law nλ = 2d sin θ, since maximum possible value for sin θ is 1, nλ/2d ≤ 1 or
λ ≤ 2d. This sets the limitation on the wavelength, i.e. in order to get the diffraction pattern by a
crystal; the wavelength of X-rays should not exceed twice the inter-planar spacing.
Importance of Bragg’s law:
1. Bragg’s law is the essential condition to be satisfied by crystal planes in order to get
diffraction pattern from a crystal.
2. It is used to calculate inter-planar spacing. Knowing the values of inter-planar spacing, lattice
parameters can be determined.

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Bragg’s X-Ray spectrometer

Bragg’s X-ray spectrometer can be used to determine the type of lattice in a cubic crystal. When
once the lattice type is known, the lattice parameters can be easily obtained.
Experimental Setup: The schematic diagram of Bragg’s x-ray spectrometer is shown in fig. It has
x-ray source, a crystal fixed on a circular table provided with scale and ionization chamber.

Working: A collimated beam of x-rays after passing the slits S1 and S2 is allowed to fall on a
crystal C mounted on a circular table. An ionization chamber is fixed to the longer arm attached to
the table. An electrometer is connected to the ionization chamber to measure the ionization current
produced by diffracted x-rays from the crystal. S3 and S4 are the lead slits to limit the width of the
diffracted beam. Here we can measure the intensity of the diffracted beam. If x-rays incident at an
angle ‘θ’ on the crystal, then reflected beam makes an angle 2θ with the incident beam. Hence the
ionization chamber can be adjusted to get the reflected beam till the ionization current becomes
maximum. A plot of ionization current for different incident angles to study the x-ray diffraction
spectrum is shown in fig.

The rise in Ionization current for different values of ‘θ’ shows that Bragg’s law is satisfied for
various values of ‘n’. i.e. 2dsinθ = λ or 2λ or 3λ etc. Peaks are observed at θ1, θ2, θ3 etc. with
intensities of P1, P2, P3 etc. i.e. 2dsinθ1 : 2dsinθ2 : 2dsinθ3 = λ : 2λ : 3λ The crystal inter-planer
spacing ‘d’ can be measured using 2dsinθ = nλ.

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 Engineering Physics Unit - II Crystallography and X-ray Diffraction

Example: Consider NaCl crystal. The first order reflection maxima for it occur at 5.90, 8.40 and 5.20
for (100), (110), and (111) planes, respectively. If d1, d2, d3 be the inter-planar spacing for the planes
(100), (110) & (111) respectively. It can be shown
ଵ ଵ ଵ
d1:d2:d3 = : :
ௌ௜௡ହ.ଽ ௌ௜௡଼.ସ ௌ௜௡ହ.ଶ

Hence NaCl crystal has FCC lattice.

X-ray Diffraction Methods for Crystal Analysis
Laue method- It is used for analyzing the structure of single crystals.
Debye-Scherrer method (or) Powder method-It is used to analyze the structure of polycrystalline
materials in powder form. All these methods, for their working, essentially depend on Bragg’s law.
LAUE METHOD: The Laue method was the first diffraction method developed by Max Von Laue
in 1913. This method is used to study the orientation of single crystals and to verify crystal
symmetry.
In this method a single crystal specimen is held stationary and it is irradiated with a fine beam
of white X-radiation (λ 0.2 to 2A0).
Experimental Setup: Laue experimental setup contains X-ray tube, lead sheets as narrow slits, ZnS
single crystal and a photographic plate.

Working: The X-rays after passing through the crystal get diffracted by different sets of parallel
planes with different orientations and different values of interplanar spacing’s. The diffracted beams
are recorded on a photographic plate. The plate is held perpendicular to the central beam of X-rays.
The X-ray beam selects different sets of parallel planes for different wavelengths and diffracts to any
angle θ, wherever the two parameters θ and d satisfy the Bragg’s condition for a wavelength λ.
For every value of λ, the d and θ values are fixed to satisfy the Bragg’s reflection condition
2 d sin θ= n λ. Each family of atomic planes picks out the wavelength λ which it can diffract at the
angle at which it finds itself. Fig. shows the Laue pattern for a cubic structure. Each dot is called a
Laue spot and the pattern of spots is called Laue pattern. Each Laue spot represents a set of Miller
indices (h k l) of planes in the crystal.

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Merits: This method is essentially employed to evaluate (h k l) values of various planes from
different Laue spots. The shape of unit cell can be established from the symmetry of the Laue
pattern.
Demerits: Since λ values for different reflections are not known, the determination of unit cell
dimensions is not possible. This method is not very useful in the overall study of the crystal
structure.
POWDER METHOD (Debye-Scherrer Method): The Powder method was developed by Debye
and Scherrer in 1961. X-ray powder method is usually carried for polycrystalline materials.
Therefore, the sample used is in the form of a fine powder containing a large number of tiny
crystallites with random orientations.
Experimental Setup: Powder method setup contains X-ray tube, collimator, powder sample in a
capillary tube, Debye-Scherrer camera and a screen as shown in Fig.

Working: The given polycrystalline material is ground to fine powder and this powder can be taken
either in a capillary tube made up of non-diffracting material and fixed at the centre of cylindrical
Debye-Scherrer camera as shown in above Fig. A stripe of X-ray photographic film is arranged
along the inner periphery of the camera. A beam of monochromatic X-rays is passed through the
collimator to obtain a narrow fine beam of X-rays. This beam falls on the polycrystalline specimen
and gets diffracted. The specimen contains very large number of small crystallites oriented in
random directions. So, all possible diffraction planes will be available for Bragg reflection to take

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place. Such reflections will take place from many sets of parallel planes lying at different angles to
the incident X-ray beam. Also, each set of planes gives not only first-order reflections but also of
higher orders as well. Since all orientations are equally likely, the reflected rays will form a cone
whose axis lies along the direction of the incident beam and whose semi-vertical angle is equal to
twice the glancing angle (θ), for that particular set of planes. For each set of planes and for each
order, there will be such a cone of reflected X-rays. There intersections with a photographic film sets
with its plane normal to the incident beam, form a series of concentric circular rings. In this case, a
part of the reflected cone is recorded on the film and it is a pair of arcs, the resulting pattern is shown
in Fig.(c). Diameter of these rings or corresponding arcs is recorded on the film, and using this
glancing angle and inter planar spacing of the crystalline substance can be determined. Figure (b)
shows the film mounted in the camera and the X-ray powder pattern obtained. The film on spread-
out is shown in Fig (c). The distance between any two corresponding arcs on the film is indicated by
the symbol S.
In case of cylindrical camera, the diffraction angle θ is proportional to S. Then,

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