CHAPTER 2
CRYSTAL STRUCTURE
Contents
2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . 1
2.2 Space Lattice . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2.3 Lattice Parameters . . . . . . . . . . . . . . . . . . . . . . 3
2.4 Unit cell and Primitive Cell . . . . . . . . . . . . . . . . . 4
2.5 Crytsal Systems . . . . . . . . . . . . . . . . . . . . . . . . 6
2.6 Bravais Lattice . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.7 Miller Indices . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.8 Planes in a cubic crystal . . . . . . . . . . . . . . . . . . . 15
2.9 Interplanar distance, dhkl . . . . . . . . . . . . . . . . . . . 17
2.10 Coordination Number . . . . . . . . . . . . . . . . . . . . . 18
2.11 Atomic Packing Factor . . . . . . . . . . . . . . . . . . . . 20
2.12 NaCl Structure . . . . . . . . . . . . . . . . . . . . . . . . . 22
2.13 Diamond Structure . . . . . . . . . . . . . . . . . . . . . . 23
2.14 Bragg Law . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
2.15 Bragg’s X-ray Spectrometer . . . . . . . . . . . . . . . . . 25
2.1 Introduction
Crystal is defined as a solid material whose constituent atoms, molecules, or ions are
arranged in an ordered pattern extending in all three spatial dimensions. It is
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• a word derived from the Greek word Krystallos meaning frozen ice.
• a misnomer for what we now know today as ‘Quartz’
The scientific study of crystals and crystal formation is known as crystallography.
2.1.1 Characteristics
• They have a well defined shape.
• They show anisotropy with respect to physical properties.
• Some Crystals show polarization of light. (Ex. Sodium Chlorate (NaClO3 ))
• Pleochroism, the effect when a material appears to have different colors when
viewed in different directions.
• Fluorescence and Phosphorescence
• Magnetism
2.1.2 Occurrence
• found in nature (eg. diamond, graphite, quartz, etc)
• also grown in labs (eg. silicon, germanium, etc)
2.2 Space Lattice
A space lattice is a regular arrangement of geometrical points in space.
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2.2.1 One Dimensional Lattice
It is an array of points arranged such that the distance between any two successive
points is a constant, a.
a is called the lattice periodicity. ⃗a is called the basis vector. Position vector of any
lattice point with respect to an arbitrary origin is given as
⃗r = n × ⃗a; n∈Z
2.2.2 Two Dimensional Lattice
An one dimensional lattice repeated at a regular interval b in a non-collinear direction
gives a net of lattice points called the two dimensional lattice.
Position vector of any lattice point with respect to an arbitrary origin is given as
⃗r = p⃗a + q⃗b; p, q ∈ Z
2.2.3 Three Dimensional Lattice
A two dimensional lattice repeated at a regular interval c in a non-coplanar direction
gives rise to a three dimensional lattice.
A 3-dimensional lattice will have three basis vectors ⃗a, ⃗b and ⃗c.
Position vector of any lattice point with respect to an arbitrary origin is given as
⃗r = l⃗a + m⃗b + n⃗c; l, m, n ∈ Z
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2.3 Lattice Parameters
The crystal coordinate system is as shown. ⃗a, ⃗b and ⃗c are cell axes; α, β and γ are
the interaxial angles.
β The coordinate system, in general, is
γ
b not orthogonal
α
α ̸= β ̸= γ ̸= 90
a
c
If a, b and c are the reference axes and X, Y and Z
are the intercepts along the three axes respectively,
then Z
⃗b Y
⃗a ⃗c b
+ + =1
X Y Z
X
is the equation of the plane.
a
2.4 Unit cell and Primitive Cell
Given a lattice, the choice of a cell is arbitrary. Once can even choose a centered cell.
A cell with minimum area will generally be chosen unless the centered cell provides
additional benefits.
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2.4.1 Lattice Points per Cell
When one considers a lattice and an unit cell, how many lattice points are associated
with a cell?
One lattice point is associated with each cell.
An alternate view : Consider a lattice point as shown. It is shared between four cells.
Contribution of the lattice point to each cell is 1/4. From the four corners, we have
4 × 1/4 = 1 lattice point per cell.
≡ ≡
For a centered cell, it is 1 + 4 × 1/4 = 2 lattice points per cell.
2.4.2 Some definitions
Unit Cell A region of the crystal defined by three vectors, ⃗a, ⃗b and ⃗c, which when
translated by any integral multiple of those vectors, reproduces a similar region
of the crystal.
Primitive Cell A cell which has only one lattie point associated with it.
All primitive cells are unit cells, but all unit cells need not be primitive cells.
Basis Vector A set of linearly independent vectors, ⃗a, ⃗b and ⃗c,, which can be used
to define a unit cell.
Lattice Parameters The basis vectors, along with the angle between the three
vectors are called the lattice parameter.
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2.5 Crytsal Systems
2.5.1 Triclinic
Cell Parameters
a ̸= b ̸= c
α ̸= β ̸= γ ̸= 90◦ , 120◦
2.5.2 Monoclinic
Cell Parameters
a ̸= b ̸= c
α = γ = 90, β ̸= 90◦ , 120◦
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2.5.3 Orthorhombic
Cell Parameters
a ̸= b ̸= c
α = β = γ = 90◦
2.5.4 Tetragonal
Cell Parameters
a = b ̸= c
α = β = γ = 90◦
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2.5.5 Cubic
Cell Parameters
a=b=c
α = β = γ = 90◦
2.5.6 Hexagonal
Cell Parameters
a = b ̸= c
α = β = 90◦ , γ = 120◦
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2.5.7 Rhombohedral
Cell Parameters
a=b=c
α = β = γ ̸= 90◦ , < 120◦
2.6 Bravais Lattice
Auguste Bravais, a french physicist showed in 1845 that there are only 14 unique
lattices in three dimensional crystallographic systems.
“A Bravais lattice is an infinite set of points generated by a set of discrete
translation operations.”
The Bravais lattices are arrived at by combining one of the seven crystal systems with
one of the lattice centerings.
Primitive (P): Lattice points only at corners, or no centering.
Body Centered (I): P, with an additional point at the cell center.
Base Centered (C): P, with two additional points at the centers of opposite faces.
Face centered (F): P with one additional point at the centre of each face of the cell.
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2.6.1 Triclinic Bravais Lattices
2.6.2 Monoclinic Bravais Lattices
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2.6.3 Orthorhombic Bravais Lattices
2.6.4 Orthorhombic Bravais Lattices
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2.6.5 Tetragonal Bravais Lattices
2.6.6 Cubic Bravais Lattices
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2.6.7 Hexagonal Bravais Lattices
2.6.8 Rhombohedral Bravais Lattices
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2.7 Miller Indices
Miller indices may be defined as a set of lowest three integers, whose ratio is
taken in the order same as that of the reciprocals of the intercepts of the
planes on the corresponding axes in the same order.
2.7.1 Calculating the Miller Indices
The 3 steps are
• Choose a convenient origin and set up a coordinate axes in the direction of the
basis vectors.
• Find the intercepts of a plane belonging to the system, expressing them as
integral multiples of the basis vectors along the crystal axes.
• Write the equation of the plane in intercept form and simplify to obtain the
coefficients of a, b and c, namely h, k, and l as integers.
The quantity (hkl) is then the Miller indices of that system of planes.
2.7.2 Miller Indices: An example
c
1. We have drawn the coordinate axes
Z 2. x-intercept: 2 × ⃗a
y-intercept: 3 × ⃗b
z-intercept: 4 × ⃗c
Y b ⃗a ⃗b ⃗c
3. Plane: + + =1
2 3 4
X
Simplify: 6⃗a + 4⃗b + 3⃗c = 12
4. ∴ Miller indices ≡ (6 4 3)
a
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2.8 Planes in a cubic crystal
2.8.1 Drawing a plane
Drawing the plane represented by (643)
1. Draw the unit cell for a cubic crystal c
1 1 1
2. Compute , ,
h k l
1 1 1
≡ , ,
6 4 3
O b
3. Multiply by the lowest non-zero
number among (h, k, l)
a
1 3
, ,1
2 4
2.8.2 (643) family of planes
c You can observe that the first 6 planes
cut the a axis into 6 equal parts, the first
4 planes cut the b axis into 4 equal parts,
the first 3 planes cut the c axis into 3 equal
parts.
O b
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2.8.3 Planes in a cubic crystal
c c
(100) (010)
O b O b
a a
c c
(001) (110)
O b O b
a a
c c
(101) (011)
O b O b
a a
c
(111)
O b
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(13̄2) (1̄1̄0)
−b O −a
a −b O
2.9 Interplanar distance, dhkl
c c
Z Z
P γP
Y α β Y
b b
O
X X
a a
From △OP X
• ∠OP X = 90
• ∠P OX = α
• ⇒ OP = OX cos α OR
OP dhkl
• cos α = =
OX OX
From △OP Y and △OP Z
OP dhkl
cos β = =
OY OY
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OP dhkl
cos γ = =
OZ OZ
We know that, for an orthogonal coordinate system
cos2 α + cos2 β + cos2 γ = 1
Therefore,
2 2 2
dhkl dhkl dhkl
+ + =1
OX OY OZ
Also,
1 h 1 k 1 l
= , = , =
OX a OY b OZ c
This give us,
2 2 2 !
h k l
d2hkl + + =1
a b c
or
1
dhkl = s
2 2 2
h k l
+ +
a b c
2.10 Coordination Number
Coordination Number is defined as the number of nearest neighbors of the given atom.
2.10.1 Simple Cubic
Coordination number = 6
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2.10.2 Body Centered Cubic
Coordination number = 8
2.10.3 Face Centered Cubic
Coordination number = 12
2.11 Atomic Packing Factor
APF is defined as the ratio of the volume of all the atoms in the unit cell to that of
the unit cell. Mathematically,
n × 43 πr3
AP F =
a3
2.11.1 Simple Cubic
• Number of atoms per unit cell = 1
4
• Volume of one atom = πr3
3
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• Volume of one cube = a3 In terms of r, it is
a = 2r
4
1 × πr3 π
A.P.F = 3 =
(2r) 3 6
2.11.2 Body Centered Cubic
• Number of atoms per unit cell = 2
4
• Volume of one atom = πr3
3
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• Volume of one cube = a3 In terms of r, it is
4r
a= √
3
4 √
2 × πr3 3
A.P.F = 3 3 = π
4r 8
√
3
2.11.3 Face Centered Cubic
• Number of atoms per unit cell = 4
4
• Volume of one atom = πr3
3
• Volume of one cube = a3 In terms of r, it is
√
a = 2 2r
4
4 × πr3 1
A.P.F = √3 = √ π
(2 2r)3 3 2
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2.12 NaCl Structure
In solid sodium chloride, each ion is surrounded by six ions of the opposite charge as
expected on electrostatic grounds. The larger chloride ions are arranged in a cubic
array whereas the smaller sodium ions fill all the cubic gaps between them.
It can be represented as a face-centered cubic (fcc) lattice with a two-atom basis or
as two interpenetrating face centered cubic lattices. The first atom is located at each
lattice point, and the second atom is located half way between lattice points along
the fcc unit cell edge.
2.13 Diamond Structure
Diamond cubic follows the face-centered cubic bravais lattice. The lattice describes
the repeat pattern; for diamond cubic crystals this lattice is “decorated” with a motif
of two tetrahedrally bonded atoms in each primitive cell, separated by 1/4 of the
width of the unit cell in each dimension.
√
The atomic packing factor of the diamond cubic structure is π163 ≈ 0.34, signifi-
cantly smaller (indicating a less dense structure) than the packing factors for the
face-centered and body-centered cubic lattices.
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2.14 Bragg Law
W L Bragg considered diffraction as reflection from a set of parallel planes. A beam
not reflected at the top level is reflected at a deeper level. The two beams will have
a phase difference. Beams reflected off the same plane have no phase difference.
2.14.1 Derivation of Bragg’s Law
The path difference, δ, is the extra path CB + BD the second ray travels.
δ = CB + BD
From the △ABC and △ABD, we have
BC = AB sin θ = d sin θ
BD = AB sin θ = d sin θ
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θ
A
C
θ θ D
d
Therefore,
δ = d sin θ + d sin θ = 2d sin θ
We know that, there is constructive interference only when the path difference is an
integral multiple of the wavelength. That would mean that
δ = nλ
or
nλ = 2d sin θ
where, n is the order of diffraction.
2.15 Bragg’s X-ray Spectrometer
2.15.1 Construction
• Bragg’s X-ray Spectrometer consists of three parts
1. A source of X-rays (X-ray tube)
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Figure 2.1: Bragg’s X-Ray Spectrometer
2. A crystal held on a graduated circular turntable
3. A detector (ionization chamber)
• X-rays from an x-ray tube collimated by two narrow slits S1 , and S2 are allowed
to fall upon the crystal D.
• The crystal is mounted on the turn table which can rotate about a vertical axis
and its position can be determined from the graduations.
• The table is provided with a radial arm which carries the ionization chamber
which acts as the detector.
• The ionization chamber is connected to an electrometer to measure the ioniza-
tion current.
• The crystal table and the detector are mounted in such a way that when the
crystal turns through an angle θ, the detector rotates through an angle of 2θ.
2.15.2 Working
• To begin with the glancing angle θ is kept very small and corresponding ioniza-
tion current is noted.
• The glancing angle is increased in equal steps and in each case, ionization current
is noted down.
• The ionization current is plotted against the glancing angle.
• This graph is called x-ray spectrum.
• The peaks in the graph occur whenever Bragg’s law is satisfied.
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Unit 2. Crystal Structure 26
Figure 2.2: X-Ray Spectrum
2.15.3 Wavelength measurement
• To measure the wavelength we use a crystal of known lattice constant, say,
NaCl.
• Then from the X-ray spectrum, we can obtain the angle θ and the order n.
• From the Bragg’s law, we can obtain λ as
2d
λ= sin θ
n
2.15.4 dhkl measurement
• To measure the interplanar spacing we perform the spectrometry using x-rays
of known wavelength.
• Then from the X-ray spectrum, we can obtain the angle θ and the order n.
• From the Bragg’s law, we can obtain d as
nλ
d=
2 sin θ
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Unit 2. Crystal Structure 27
References
• Introduction to Solid State Physics, S O Pillai
• Elements of X-Ray Diffraction, B D Cullity
• Solid State and Semiconductor Physics, John P McKelevey
• Introduction to Solid State Physics, Charles Kittel
• [Link]
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