I.

Structure of Solids
1. Crystalline, polycrystalline and amorphous materials
2. Defect in crystals
3. Lattice Dynamics
4. Miller indices, Reciprocal lattice
5. Diffraction condition (Bragg’s Law)
6. Acoustic and Optical phonons

Matter is anything that occupies space and has the attribute of gravity and inertia. There are three
states of matter: Solid, Liquid and Gas. [Plasma is the fourth state of matter]

Solid is characterized by resistance to any change in shape, caused by strong attraction between
the molecules of which it composed.

Liquid does not resist forces that act to change its shape, because molecules are free to move
with respect to each other.

In case of gases molecules are widely dispersed and move freely, offer no resistance to change of
shape and little resistance to change of volume.

According to the atomic arrangement, solids are of three types:

(i) Crystalline
(ii) Amorphous
(iii) Pollycrystalline

Crystalline:

In a crystalline solid atoms are arranged in a periodic fashion. That means there is some basic
arrangement of atoms, which is repeated throughout the entire solid.

Fig 3.1: Atomic arrangement in case of crystalline solids

Properties
  Crystalline solids have different physical properties (thermal conductivity, electrical
conductivity, refractive index etc.) in different direction i.e. they are anisotropic.
 Cooling curve of crystalline substance has breaks. The middle of which corresponds to
the process of crystallization. In case of crystalline solids two break points ‘a’ and ‘b’
appears. These points indicate the beginning and end of the process of crystallization. In
this time interval temperature remains constant. This is due to the fact that during
crystallization process energy is liberated which compensate the loss of heat, thus
temperature remains constant.

Fig 3.2: Cooling Curve of crystalline solids

 Melting point of crystalline solid is very sharp.

 Some crystals, when compressed develop electrical changes at their ends; other crystals
develop similar changes when heated. These properties, called piezoelectricity and
pyroelectricity, are shown to a marked degree by quartz.

Amorphous:

Solids in which atoms do not have any geometrical regularity or periodicity are said to be
amorphous solids.

Fig 3.3: Atomic arrangement in case of amorphous solids

Properties
  Amorphous solids have their physical properties (thermal conductivity, electrical
conductivity, refractive index etc.) same in all direction i.e. they are isotropic.
 The cooling curve of amorphous solid is smooth.

Fig 3.4: Cooling Curve of amorphous solids

 Amorphous solids do not have sharp melting point.

 An amorphous solids do not generally posses elasticity but shows only plasticity.

Polycrystalline:

Polycrystalline materials are composed of many small regions of single crystal material. In a
macroscopic piece small crystals are called as grain or crystallites. The grain size can be varying
from few nanometers to several millimeters.

Each grain in polycrystalline aggregate is connected to its neighborhood by a grain boundary

which is generally of irregular shape and bears no relation to the internal symmetry of the
crystal. Orientation of the crystal axis in different grain is usually random, although in certain
cases there is a preferred distribution of the orientation.

Fig 3.5: Atomic arrangement in case of polycrystalline solids

Properties

 Due to random orientation of the individual crystal in a polycrystalline material,

properties in all direction are same i.e. they are isotropic

Factor affecting the properties of polycrystalline material

 Properties of crystal themselves i.e. their size etc.
 Arrangement of their crystal whether random or ordered.
 Interference between crystal or their action on each other.
 Phenomenon at the grain boundaries of crystalline grain such as those, which cause hot
shortness# and inter crystalline corrosion.
 The impurities present at the grain boundaries.

[# Hot shortness means formation of liquid phase at grain boundary or grain boundary
precipitation can lead to low strength and ductility]

Defect in crystals:

Real crystals are never perfect; there are always imperfections or defects in the ideal arrangement
of atoms in a crystal. Presence of a relatively small number of defects has a profound impact on
the macroscopic properties of materials, and control of defect is important in many kinds of
material processing.

Importance in semiconductor technology:

Production of advanced semiconductor devices requires not only a rather perfect Si crystal as
starting material, but also involves introduction of specific defect in small areas of the sample.

There are three basic classes of defect in crystals

(i) Point defects

(ii) Linear defects
(iii) Planar defects

(i) Point defects:

If the atoms are missing or placed irregularly in the lattice then those are said to be point defects.
There are always defects in a crystal, and the most common defects are point defects. Point
defects can be categorized as

 Vacancies
 Interstitials
 Frenkel defect
 Schottky defect
Fig 3.12: Schematic representation of different point defects in a crystal, (1) vacancy (2) self-
interstitial (3) interstitial impurity (4),(5) substitutional impurities. The arrows show the local
stresses introduced by the point defect.
 At high temperature when the atoms are frequently and randomly changes their positions
leaving behind empty lattice site, called vacancies.
 Interstitial atoms that are squeezed in between regular lattice site
 Self-interstitial- Interstitial atom is of same species.
 Interstitial impurities- Interstitial atoms are foreign atom.
 Substitutional impurity-If foreign atom replaces or substitute for a matrix atom.

In ionic crystals the bonding is provided by columbic forces between positively and negatively
charged ions. To maintain charge neutrality several point defect can be created.

 A Frenkel defect is a pair of cation (+ve ion) vacancy and cation interstitial or it may
also be an anion (-ve ion) vacancy and anion interstitial.
 A schottky defect is a pair of anion and cation vacancy
Fig 3.13: Schematic representation of (1) Frenkel defect (vacancy-interstitial pair) and (2)
Schottky defect (a pair of cation and anion vacancies) in an ionic crystal

Linear Defect:

If the groups of atoms are in irregular positions then it is said to be linear defect. Dislocations are
linear defect around which some of the atoms of crystal lattice are misaligned. The direction and
magnitude of dislocation can be expressed in terms of Burgers Vector (𝒃 ⃗ ). To find the Burgers
vector, we should make a circuit from atom to atom counting the same number of atomic
distances in all directions. If the circuit encloses a dislocation it will not close. The vector that
closes the loop is the Burgers vector𝒃 ⃗ . Based on the direction of Burgers Vector dislocation are
of two types: Edge dislocation and Screw dislocation
 If the Burger Vector is directed perpendicular to the dislocation line, then these
dislocations are called Edge Dislocation.
 If the Burger Vector is directed parallel to the dislocation line, then these dislocations are
called Screw Dislocation.

(a) (b)
Fig 3.14: Burgers vector in case of (a) Edge dislocation (b) Screw dislocation
Planar Defects:

If the defects are caused at the interface between homogeneous regions of the material then it is
said to be planar defect. Planar defects are generally found in case of polycrystalline materials.
Types of planar defect are

(i) Grain Boundaries

(ii) Stacking Fault

 Grain boundaries are interfaces where crystals of different orientations meet. These
regions are less densely packed as compared to the bulk of the grain.
 Stacking fault is another type of surface defect within lattice where the sequence of atom
planes has an error. Twin boundaries are similar, and may be produced by deformation of
materials. This gives rise to shape memory metals, which can recover their original shape
if heated to a high temperature.

(a) (b)

Fig 3.15: (a) Grain boundaries (b) Twin boundaries

Space Lattice, Basis and Translation Vector:

An ideal crystal is constructed by the infinite repetition of identical groups of atom. A group is
called the basis. The set of mathematical points to which the basis is attached is called the space
lattice. The lattice in three dimensions may be defined by three primitive translation vectors ⃗⃗⃗⃗
𝑎1 ,
𝑎2 , ⃗⃗⃗⃗
⃗⃗⃗⃗ 𝑎3 such that the arrangement of atoms in the crystal looks the same when viewed from the
point 𝑟 as when viewed from every point 𝑟⃗⃗⃗′ translated by an integral multiple of a’s.

⃗⃗⃗
𝑟 ′ = 𝑟 + 𝑢1 ⃗⃗⃗⃗
𝑎1 + 𝑢2 ⃗⃗⃗⃗
𝑎2 + 𝑢3 ⃗⃗⃗⃗
𝑎3 ---------------------------------------------- (1)
Where 𝑢1 , 𝑢2 , 𝑢3 are arbitrary integers. The set of points ⃗⃗⃗
𝑟 ′ define by eq. 1 for all 𝑢1 , 𝑢2 ,
𝑢3 define the lattice.

Fig 3.6: The crystal structure is formed by the addition of the basis (b) to every lattice point of
the space lattice (a). By looking at (c), one can recognize the basis and one can abstract space
lattice.

Unit Cell:

Unit cell is the smallest geometrical figure the repetition of which in 3-D will give the actual
crystal structure.
 (a) (b)

Fig 3.7: (a) Unit cell with lattice parameters (b) Mathematical point lattice with a unit cell
outlined.
An arbitrary arrangement crystallographic axis (Marked X,Y,Z) defining a unit cell is shown in
figure. A unit cell is completely defined if the distance between two neighboring lattice point
(i.e. edges) along the three directions and the angle between the three axes are called interfacial
angle and are denoted by α, β, γ. The intercepts a, b and c define the dimension of unit cell.

Unit cell where the atoms are present at the vertex of the cell are called Primitive Unit Cell. Non-
primitive unit cell contain extra lattice point at the corners. In 3D non-primitive cells are of three
kinds

 Base centered: an extra lattice point is centered in each of the two opposing face of the
cell
 Face Centered: an extra lattice point is centered in every face of the cell
 Body Centered: an extra lattice point is centered in the exact middle of the cell.

Fig 3.8: Unit Cells

Three Dimensional Lattice Types:

In three dimensions, point symmetry groups require fourteen different lattice types- one general
(triclinic lattice) and thirteen special collectively called as Bravais lattice.

These fourteen lattice types are conventionally grouped seven crystal systems according to seven
type of conventional unit cell. They are

1. Triclinic 5. Cubic
2. Monoclinic 6. Trigonal
3. Orthorhombic 7. Hexagonal
4. Tetragonal
 Fig 3.9: Fourteen Bravais Lattices

System No. of Lattice Restriction on conventional Example

in System cell axes and angle
Triclinic 1 a ≠ b ≠ c, α ≠ β ≠ γ Potassium dichromate (K2Cr2O7)
Monoclinic 2 a ≠ b ≠ c, α = γ= 900 ≠ β Borax (Na2B4O710H2O)
Orthorhombic 4 a ≠ b ≠ c, α = β = γ =900 Oivine (Mg2SiO2)
Tetragonal 2 a = b ≠ c, α = β = γ =900 Cassiterite (SnO4)
Cubic 3 a = b = c, α = β = γ =90 0
Diamond
Trigonal 1 a =b=c, α = β= γ≠900 <1200 Quartz
 Hexagonal 1 a =b ≠ c, α = β=900, γ=1200 Ice (H2O)

Lattice Planes & Miller Indices:

Crystal is made up of a large number of parallel equidistant planes (passing through lattice
points) called the lattice planes. The lattice planes can be chosen in different numbers of ways, as
shown in fig 1.14 (a), (b), (c), (d). The perpendicular distance between adjacent planes is called
interplanar spacing. A given space lattice may have an infinite set of lattice planes each having
its characteristic spacing. The direction of these planes are specified by Miller indices h,k,l.
Miller indices are defined as the reciprocals of the intercepts made by the plane on the three
rectangular axes.

Fig 3.10: Different Lattice Planes

The Miller indices (hkl) for any plane (say cutting intercepts of 2, 3 and 6 units along three
crystallographic axes) can be obtained by following procedure:

(1) Find the intercepts on the three crystallographic axes OX, OY and OZ theses are
2, 3, 6
(2) Note their reciprocals
1/2, 1/3, 1/6
(3) Clear the fractions (it is done by multiplying the reciprocal by L.C.M. of their denominator)
3, 2, 1
For an intercept at infinity the corresponding index is zero. The indices of some of the important
planes in a cubic crustal are illustrated in figure. The indices (hkl) may denote a single or a set of

Fig 3.11 : Indices of important planes in a cubic crystal. The plane (200) is parallel to (100) and
to (1̅00)

parallel planes. If a plane cut an axis on the negative side of the origin, the corresponding index
is negative, indicated by placing a minus sign above the index: (h𝑘̅l). The cube faces of a cubic
crystal are (100), (010), (001), (1̅00), (01̅0) and (001̅). Planes equivalent by symmetry can be
denoted by curly brackets (braces) around indices: the set of cube faces is {100}. When we spick
of the (200) plane we mean a plane parallel to (100) cutting the X axis at (½)*a.

Reciprocal lattice:

In a crystal, there exist many sets of planes with different orientations and spacing. These planes
can cause diffraction. If we draw normal to all set of planes from a common origin, then the end
points of the normal form a lattice which is called as reciprocal lattice

Diffraction Condition :( Bragg’s Law)

Bragg presented a simple explanation of the observed angles of the diffracted beams from a
crystal. Consider a series of parallel rows in which the atoms are arranged in a given plane of the
crystal. Suppose parallel beam of x-ray is incident in a direction making a glancing angle θ with
the surface of the plane. Each atom act as a center of disturbance and send spherical waves fronts
by Huygens construction. There will be however, no diffraction beam unless the waves reflected
from different planes are exactly in phase. Now they will reinforce themselves and an intense
reflected beam will result. The condition that the reflected waveform be in same phase, is that
path difference between the reflected wave from one layer and that from the next must be an
exact wavelength, or an integral multiple of it.

Fig 3.16: Illustrating the derivation of Bragg’s Law

Let us consider two parallel rays LMN and PQR, which are reflected by two atoms M and Q in
adjacent layers as shown in figure. The atom Q is vertically below M. The length of the path
PQR is greater than the length of the path LMN. The path difference is AQ+QB and according to
the condition of reflection we have
AQ+QB=nλ

Since AQ=QB=d sin θ

=>2d sin θ= nλ

This is known as Bragg’s Law and gives the condition for the reflection of x-ray from series of
atomic layer in a given plane.

Crystals can diffract X-ray because the interplaner spacing in a crystal lattice is of the same order
as that of wavelength of X-ray.
Bragg’s Spectrometer

For the structural study of different crystalline material Bragg’s Spectrometer is a very important
instrument. In this apparatus X-ray generated in X-ray tube are passed through a series of slits to
give a sharp and monochromatic beam. The beam is then directed to strike the face of the crystal
which is mounted on a graduated rotating table. The rays reflected from the crystal are then
allowed to pass through a detector known as an ionizing chamber filled with vapours of methyl
bromide. The chamber is rotated coaxially with the crystal table. The crystal table and the
chamber are so adjusted that when the crystal rotates through any angle, the chamber rotates at
twice the angle so that the reflected rays always enter the chamber. The position of the table is
noted on a circular vernier scale. The extent of ionization produced by the diffracted beam is
measured by the electrometer.

Fig 3.17 : Bragg’s Spectrometer

The value of glancing angle is gradually increased by rotating the table. The intensities of the
reflected X-rays for various angles are determined. Strong diffractions are obtained from those
planes which contain large no of atoms and for those value of θ which satisfy the Bragg’s
equation
2d sin θ= nλ

Therefore, by measuring the glancing angles at which reflections occurs, we can determine the
inter-planer spacing knowing the wavelength of X-rays. For example structure of rock salt(NaCl)
was studied by using the Bragg’s Spectrometer. If a graph is plotted between the ionization
current and the glancing angle as shown in figure, some peaks are obtained, which represent the
value of glancing angles satisfying Bragg’s law.

Fig 3.18: Ionization Current Vs. glancing angle

Phonon

The energy of lattice vibration is quantized. The quantum of energy is called a phonon in
analogy with the photon of electromagnetic wave.

Crystal has two types of lattice vibration. The types of vibration are called

(i) Acoustic Mode

(ii) Optical Mode

If the frequency of vibration (ω) is relatively independent of propagation constant (k) of the
wave then that type of lattice vibration is said to be acoustic mode.

If the frequency of vibration (ω) is proportional to the propagation constant (k), in the range of
small k value, then that type of lattice vibration is said to be optical mode.

Fig 3.19: Illustration of the movement of ions in the transverse acoustical and optical mode.