Crystal 1
Crystal 1
Crystal 1
States of matter
Condensed matter physics
Condensed Matter
Melts and
Crystalline Non-crystalline Liquid Crystals
Solutions
Solids or Amorphous
Solids
Bio-matter
(proteins, DNA,
Single Crystalline Poly-crystalline Membranes)
Solids Solids
SSP
What is solid state physics (SSP)?
Solid-state physics is the study of rigid matter, or solids, through methods such as
quantum mechanics, crystallography, electromagnetism, and metallurgy. It is the
largest branch of condensed matter physics. Solid-state physics studies how the
large-scale properties of solid materials result from their atomic-scale properties.
Thus, solid-state physics forms the theoretical basis of materials science. It also
has direct applications, for example in the technology of transistors and
semiconductors (Wikipedia quoting)
Liquid: atoms are closely packed but don not form a rigid
structure. It has no atomic or molecular order and they
assume the shape of its containers. As the liquid is heated up
the up the atoms move around but without clear relation to
one another .
Mica mineral
Crystalline Si
Non-crystalline Si
Lattice
Lattice is an infinite set of regular geometric arrangement of points in the
crystal space.
Lattice point
Space lattice
Basis
An atom or group of atoms or molecules attach to each lattice point are called
basis or atomic pattern or building pattern of the crystal.
In a real crystal the lattice point is replaced by a basis and every basis is
identical in composition, arrangement and orientation.
The atoms do not necessarily lie at lattice points but basis must be in the same
orientation .
Thus, a crystal structure results when basis is added to each lattice points of
space lattice.
Lattice translation operation
The repetitive nature of the basis or atomic pattern is expressed by the fact
that displacement or translation of crystal parallel to itself by a translation
operator, 𝑇 given by 𝑟′
𝑇 = 𝑢𝑎 + 𝑣𝑏 + w𝑐………………………………(1)
𝑐 𝑎
𝑟
𝑏
This process of displacement of a crystal by an operation 𝑇 given by
equation (1) is known as lattice translation operation.
For a two dimensional lattice, the unit cells are of the form of a
parallelogram and for a three dimensional lattice, the unit cells are of the
form of a parallelepiped.
𝑎2
𝑏2 𝑎3
𝑎1 𝑏3
𝑐
𝑏1 𝑎4
𝑎
𝑏
𝑏4
Fig. In 2 dimension Fig. In 3 dimension
Primitive and non-primitive unit cells:
A unit cell that contains only one lattice point is called a primitive unit cell
(P), which is made up from the lattice points at each of the corners.
In case of non-primitive unit cells, there are additional lattice points, either
on a face of the unit cell or with in the unit cell. It is also known as a
centered unit cell.
The three edge lengths of the unit cell a, b and c are called lattice constants.
Bravais lattices or space lattices in three dimension
In 1850, Auguste Bravais showed that there
are only 14 different ways of arranging
identical points in 3D space so that the points
are equivalent in their surroundings. These
arrangement are later called the Bravais
Lattices.
A Bravais Lattice is defined as an infinite array
of points which appears exactly the same
Auguste Bravais when viewed from any one of the lattice
points.
For example, the coordination number of carbon atom in CH4 is four, because it
has four hydrogen atoms around it.
Coordination number for cubic system
Simple cubic
BCC FCC
Number of atoms per unit cell
For simple cubic
In the primitive cubic unit cell, the atoms are only located on the corners. That means
8 atoms are located on 8 corners of the lattice. Each atom located on the corner
contributes 1/8th of the original volume of the cell. So number of atoms per unit cell
is
1
8× = 1 𝑎𝑡𝑜𝑚
8
In a body-centred unit cell, 8 atoms are located on the 8 corners and 1 atom is present at
the center of the structure. 1 corner shares 1/8th volume of the entire cell. Also, the
atom at the centre is wholly present at the centre of the cell and can’t be shared.
1
(8 × 8) + 1 = 2 𝑎𝑡𝑜𝑚𝑠
•Each corner atom will be shared equally among 8 adjoining unit cells, therefore, each
corner will get 1/8 part of atom
1
8× = 1 𝑎𝑡𝑜𝑚
8
•There are six faces and each phase atom will be shared between 2 adjoining unit
cells. So each face gets 1/2 part of atom then
1
6× = 3 𝑎𝑡𝑜𝑚𝑠
2
Total atoms present in a face-centred unit cell = 1 + 3 = 4 atoms
No. of atoms per unit cell in hexagonal close packed (HCP) structure:
𝑁𝑐 𝑁𝑓 𝑁𝑖
𝑁= + +
6 2 1
12 2 3
= + +
6 2 1
=2+1+3
= 6 𝑎𝑡𝑜𝑚𝑠
We can also calculate the no. of atoms per unit cell in SC, BCC, and FCC structure using
the following formula:
𝑁𝑐 𝑁𝑓 𝑁𝑖
𝑁= + +
8 2 1
To perform this calculation, we need to know the volume of a cube and the volume of
a sphere.
For simple cubic system
In case of SC structure, atoms are closely packed along the cube
edges.
If ‘a’ is the lattice parameter and ‘r’ is the atomic radius, then
𝑎
a= 2𝑟 Or, r= 2
4
Volume of an atom = π𝑟 3
3
4 𝑎 3 4π𝑎3
= π =
3 2 3×8
4π𝑎3 /3×8 𝜋
APF = = 6 = 0.52
𝑎3
Or, 4𝑟 2
= 𝑎2 + 𝑎2 Or, 16𝑟 2 = 2𝑎2
2𝑎2 𝑎 2 A B
Or, r= =
16 4
3
4 3 4 𝑎 2 4𝜋×2 2𝑎3
Volume of an atom = 𝜋𝑟 = 𝜋 =
3 3 4 3×64
4𝜋×2 2𝑎3
4× 4×4𝜋×2 2𝑎3
3×64
Therefore, APF = = = 0.74
𝑎3 3×64
From ∆BEC,
𝐵𝐸 2 = 𝐵𝐶 2 + 𝐶𝐸 2
= 𝑎2 + 𝑎2 = 2𝑎2
So, 𝐵𝐸 = 𝑎 2
Again from ∆BFE,
𝐵𝐹 2 = 𝐵𝐸 2 + 𝐸𝐹 2
2
Or, 4𝑟 2 = 𝑎2 + 𝑎 2
Or, 16𝑟 2 = 𝑎2 + 2𝑎 2
Or, 3𝑎2 𝑎 3
r= =
16 4
3
4 3 4 𝑎 3
So, volume of an atom= 𝜋𝑟 = 𝜋
3 3 4
3
4 𝑎 3
2×3𝜋 4
Therefore, APF=
𝑎3
𝜋 3
= = 0.68
8
Crystal directions and planes are described using 3 integers -- Miller indices.
Many material properties vary with direction in the crystals, such as:
o Electrical conductivity
o Thermal conductivity
o Elastic modulus
o Polarizability
William Hallowes Miller (1801-1880)
Miller indices were introduced by the British mineralogist William Hallowes Miller.
Miller indices for crystal planes
Miller indices are sets of integers obtained from the reciprocals of fractional intercepts
which the plane makes with the crystallographic axes, enclosed in parentheses used
to specify the positions and the orientation of the plane of a crystal.
1) Find the intercepts of the plane on the three axes a, b, c in terms of the lattice
constants.
4) The result enclosed in parentheses as (hkl) and is known as the Miller indices of the
plane.
For example
Axes X Y Z
Intercepts 1 2 3
Reciprocals 1/1 1/2 1/3
Reduction 1 1 1
×6=6 ×6=3 ×6=2
1 2 3
If a plane cuts an axis on the negative side of the origin, the corresponding index is
negative and is indicated by a minus sign above the index such as ℎ 𝑘 𝑙 or ℎ 𝑘 𝑙 etc.
The brackets { } are used to refer to all the sets of a given type, e.g., {100} refers to the
sets of (100), (010), (001). Such an arrangement constitutes a family of planes.
A family of equivalent sets of directions, such as [100], [100], [010], [010], [001] and
[001] is designated as angle bracket <100>.
Miller indices of some planes in cubic crystals
Directions of planes
Important features of Miller indices
Miller indices do not define a particular plane but asset of parallel planes
All equally spaced parallel planes have the same index numbers h, k, l.
It is only the ratio of indices that is important. Thus the (422) planes are the
same as the (211) planes.
Miller indices are especially useful for cubic crystals:
The angle θ between two directions [ℎ1 𝑘1 𝑙1 ] and [ℎ2 𝑘2 𝑙2 ] can be obtained
from the following expression
ℎ1 ℎ2 + 𝑘1 𝑘2 + 𝑙1 𝑙2
cos 𝜃 = 1 1
(ℎ12 +𝑘12 + 𝑙12 ) 2 (ℎ22 +𝑘22 + 𝑙22 ) 2
The distance ‘d’ between two adjacent parallel planes with index (ℎ 𝑘 𝑙) is
given by
𝑎
𝑑= 1
(ℎ2 + 𝑘 2 + 𝑙 2 ) 2
Crystal Planes
Let us take any lattice point ‘O’ as the origin. Axes are taken in the a, b, c directions and
OP is the perpendicular distance between the origin ‘O’ and the plane ABC. Let h, k, l are
the Miller indices of the plane ABC.
Let us denote the angles between the normal OP and crystal axes respectively by α, β,
and γ.
The intercepts of the plane ABC on the three axes are OA, OB, and OC.
𝑎 𝑏 𝑐
𝑂𝐴 = ℎ , 𝑂𝐵 = 𝑘 and 𝑂𝐶 = 𝑙
𝑎 𝑏 𝑐
d = OP= ℎ cosα= 𝑘 𝑐𝑜𝑠𝛽 = 𝑐𝑜𝑠𝛾 −−−−−−−− −(1)
𝑙
In an orthogonal lattice, taking the X-axis along a, the Y-axis along b and Z-axis along
𝑎 𝑏 𝑐
c, the equation of (ℎ 𝑘 𝑙) plane whose intercepts are ℎ , 𝑘 , 𝑙 is
𝑥 𝑦 𝑧
𝑓 𝑥, 𝑦, 𝑧 = = = =1
𝑎/ℎ 𝑏/𝑘 𝑐/𝑙
ℎ 𝑘 𝑙
Or, 𝑓 𝑥, 𝑦, 𝑧 = 𝑎 𝑥 + 𝑏 𝑦 + 𝑐 𝑧 = 1
Since f(x, y, z) = constant, is the equation of a surface and the unit normal vector 𝑛 𝑖𝑠
∆𝑓
𝑛= Where, ∆𝑓 𝑖𝑠 𝑎 𝑣𝑒𝑐𝑡𝑜𝑟 𝑛𝑜𝑟𝑚𝑎𝑙 𝑡𝑜 𝑡ℎ𝑒 𝑝𝑙𝑎𝑛𝑒.
∆𝑓
ℎ 𝑘 𝑙
𝑖 + 𝑖 +
𝑎 𝑥 𝑏 𝑦 𝑐 𝑖𝑧
=
2 2 2
ℎ 𝑘 𝑙
+ + 𝑐
𝑎 𝑏
The spacing ‘d’ between (ℎ 𝑘 𝑙) plane a parallel plane passing through the origin ‘O’ is
ℎ 𝑘 𝑙
𝑖𝑥 + 𝑖𝑦 +
𝑛. 𝑎 𝑎 𝑏 𝑐 𝑖𝑧 . 𝑎 𝑖𝑥
𝑑= =
ℎ 2 2 2
ℎ 𝑘 𝑙
ℎ + + 𝑐
𝑎 𝑏
ℎ
.𝑎
𝑑= 𝑎
ℎ2 𝑘 2 𝑙 2
ℎ 2+ 2+ 2
𝑎 𝑏 𝑐
1 ------------------------(3)
=
ℎ2 𝑘 2 𝑙 2
+ +
𝑎2 𝑏 2 𝑐 2
It is evident from equation (3) that as the value of one or more of Miller indices
is increased, the distance between the successive planes is reduced.
𝑎
For a cubic lattice: 𝑑 =
ℎ2 +𝑘 2 +𝑙 2
Symmetry operations in crystal
A symmetry operation is that transformation through which crystal remains invariant.
These operations are translation, rotation, reflection and inversion. The translation
operation applies to lattices only while all the remaining operations and their
combinations apply to all objects and are collectively known as point symmetry
operations. The inversion operation is applicable only to 3-dimensional crystals.
𝑇 = 𝑢𝑎 + 𝑣𝑏 + w𝑐………………………………(1)
where u, v, w are arbitrary integers and 𝑎, 𝑏, 𝑐 are translational vectors. This process
of displacement of a crystal parallel to itself by the crystal translational operation T is
called lattice translation operation and application of this operation to any point 𝑟 in a
crystal lattice result in a point 𝑟 ′ .
𝑟′ = 𝑟 + 𝑇
Which is identical in all respects to the original point 𝑟 and thus this is an equivalent
point.
2. Rotational symmetry or rotational operation
A body is said to possess the rotational symmetry about an axis if the rotation of the body
about this axis by some angle θ leaves the body invariant.
Lattice always remains invariant by a rotation of 2π. So for truly invariant of the body,
there must be an integral number of such rotations in one complete revolution of the body
2𝜋
i.e., 2π=nθ or 𝜃 = 𝑛 , where n is an integer. The integer n is called the multiplicity of
rotation axis.
Thus, one-, two-, three-, four-, and six- fold rotation axes carry the lattice into itself and
corresponds to rotation by
2𝜋 2𝜋 2𝜋 2𝜋 2𝜋
, , , &
1 2 3 4 6
In fact only 1-, 2-, 3-, 4- and 6- fold rotation axes can exist in a lattice and a 5-fold
rotation axis is impossible.
Rotational symmetry about an axis
3. Reflection symmetry
A body is said to possess reflection symmetry if a plane can be drawn in the body
dividing it into two exactly similar parts, so that one half is the reflection of the other
half which are mirror images of each other. Such a plane is known mirror reflection
plane and is represented by m.
4. Inversion symmetry
Similarly, let the vector 𝑎 be rotated about an axis passing through the lattice point B
2𝜋
and perpendicular to the plane of the paper through the same angle 𝜃 = 𝑛 in the clock
wise direction so that it produces a new lattice vector 𝑂𝐵′ = 𝑅2′
So, 𝐴𝐴′ = 𝐵𝐵 ′ = 𝑎
and ∠𝐵𝐴𝐴′ = ∠𝐴𝐵𝐵′ = 𝜃
The quadrilateral 𝐴𝐵𝐵′ 𝐴′ is a trapezium with 𝐴′ 𝐵′ parallel to AB. Further 𝐴′ 𝐵′ must be
an integral multiple of the primitive translation vector 𝑎
Or 𝐴′ 𝐵′ = 𝑞 𝑎 , where q is an integer.
1−𝑞 𝜋
∴ q = 1 − 2 cos 𝜃 or cos 𝜃 = 𝜃−
2 2
Thus we find that a crystal can have only 1-, 2-, 3-, 4- and 6-fold axis of rotation or
symmetry and cannot have five fold symmetry.
Fig.: Ten two dimensional point groups consisting of rotation and reflection symmetry operations illustrated
using notched wheel [Coefficient represent rotational symmetry and the fist m represents reflection symmetry
(plane parallel to the rotation axis) and the 2nd m represents another reflection symmetry (plane perpendicular to
the rotation axis)]
Bragg’s law
W.H. Bragg and W.L. Bragg studied the diffraction of X-rays in detail. W.L.
Bragg considered that when monochromatic X-rays impinge upon the atoms
in the crystal lattice, each atom acts as a source of scattered radiation of the
same wavelength.
The crystal acts as a series of parallel reflecting planes. Thus X-rays would
be reflected according to ordinary laws of reflection and the planes would
reflect X-rays at all angles. X-rays that penetrate more deeply into the
crystal are reflected from the lower planes and thus several beams of X-rays
reflected from various planes are obtained.
Let the crystal spacing between the two planes be 𝑑 and 𝜃 the glancing angle.
The path difference between the reflected waves along BC and EF
= 𝐶𝐵 + 𝐵𝐷
𝐶𝐵
In the ∆ 𝐴𝐶𝐵, sin 𝜃 = , 𝑂𝑟, 𝐶𝐵 = 𝐴𝐵 sin 𝜃 = 𝑑 sin 𝜃
𝐴𝐵
Similarly, 𝐵𝐷 = 𝑑 sin 𝜃