CRYSTAL STRUCTURE NOTES

1. Explain the following terms briefly.

a. Space Lattice - It is a geometrical representation of a crystal structure, by means of set of points
arranged regularly in a space having identical surroundings where each point represents position of a
atom in a crystal.

b. Unit Cell - It is a part of a space lattice which when repeated in 3 co-ordinate directions generates
entire space lattice or is also a building block of a space lattice. For a given space lattice, choice of unit
cell is not unique but the volume covered by the unit cell remains same.

c. Primitive Cell - It is a minimum volume unit cell which contains lattice points only at the corner or
number of lattice points per unit cell is one. for eg: simple cubic unit cell.

d. Non-Primitive Cell – Unit cell in volume it is integral multiple of primitive cell volume which is
considered for the easy visualization of the crystal structure. Number of lattice points per unit cell in this
case will be more than one. for e.g.; body centered cubic unit cell and face centered cubic unit cell.

e. Bravais lattice and Non Bravais Lattice - It is a Space lattice which contains only one set of identical
points which is required to represent crystals like sodium, nickel, etc. In fig ABCD are identical points.

If space lattice contains

more than one set of
identical points, it is
called as non Bravais
lattice which is required
to represent crystal
structures like sodium
chloride, cesium
chloride.etc. In figure 2 (A C) is one set of identical points and (b d) is another set.

f. Lattice Parameters - A set of 3 basis vectors (a,b,c) & 3 interfacial angles α β and γ which are required
to represent a complete unit cell in 3 dimension are called as lattice parameters. Here vectors a, b & c
are position vectors of a lattice point along X, Y, & Z axis respectively and α β and γ are the angl es
between the vectors b & c, c & a and a & b respectively.

2. What is crystal system? Explain crystal systems and Bravais lattices in 3 dimensions.

Crystal system is a coordinate system required to explain different ways of regular arrangement of
points (atoms) in three dimensions. The crystal systems are a grouping of crystal structures according to
the axial system used to describe their lattice. Each crystal system consists of a set of three axes in a
particular geometrical arrangement. There are seven unique crystal systems. They are given below.

1. Cubic crystal system

2. Tetragonal crystal system
3. Orthorhombic crystal system
4. Monoclinic crystal system
5. Triclinic crystal system
6. Rhombohedral crystal system
7. Hexagonal crystal system
3. What do you mean by crystal directions? Explain with examples.

Crystal Direction is a position vector of any given lattice point in 3 dimensions & is given by

⃗ ⃗
Where n1 , n2, n3 are integers. , ⃗ , are basis vectors. Hence it helps to find a position & direction of a
given lattice point.Integers n1, n2, n3 written under square brackets i.e [n1 , n2, n3] are called as direction
indices.In the figure given below direction of the points A and B with direction indices [111],[101] is
shown.

4. What are Miller indices? Explain with examples.

These are the set of 3 whole numbers which determines the position and direction of set of
parallel planes in a crystal. generally written as (hkl).Here h, k & l are equal to the reciprocal of the ratios
of the intercepts made by the crystal plane w.r.to coordinate axes x, y & z respectively taken in order.

Steps to find Miller Indices for a given crystal plane

1. Find the intercepts made by the plane w.r.t X, Y & Z axes in terms of length of the basis vectors, say
a,b,c.
2. Express intercepts as ratios, say , &
3. Find the reciprocal of the ratios, say , &
4. Express above reciprocals to the smallest whole numbers in the same ratio by taking LCM. Then it
 reduces to , &
Examples.
1) Find miller indices of the palne if it makes intercepts 1a,2b and 3c.

Solution: Here x = 1a, y = 2b, z = 3c

x/a = 1, y/b = 2, z/c = 3
a/x = 1, b/y = ½, c/z = 1/3
Multiplying by 6 we get a/x = 6, b/y = 3, c/z = 2
Therefore millerindices are (h k l) = (6 3 2)

5. Derive an expression for interplanar spacing for a given set of parallel planes in terms of Miller
indices.
As shown in figure below abc and ABC are two parallel planes with miller indices (hkl), plane ABC
is intersecting coordinate axes X,Y,Z and origin of the coordinate system O is laying on the plane abc.

Let OA = x, OB = y and OC = z which are the intercepts made by ABC w.r.to X,Y & Z axis respectively.
Draw a perpendicular OP to the plane ABC from O,here OP= interplanar distance=d(hkl).
Let α, β and γ be the angle made by OP w.r.to X,Y& Z axis respectively.
From right angled triangle OPA, cosα = OP/ OA= ,
From right angled triangle OPB, cosβ = OP/ OB=
From right angled triangle OPC, cos γ = OP/ OC=
Here cosα, cosβ & cos γ are direction cosines of line OP,
therefore cos2α + cos2β + cos2 γ = 1,
i.e ( ) ( ) ( )

√[ ]

By using the miller indices (h= a/x, k= b/y, l= c/z) , and substituting 1/x= h/a, 1/y = k/b, 1/z= l / c in above
relation we get.
 √[ ]

for cubic system a = b = c,

√[ ]

6. What do you mean by atomic packing factor? Find the atomic packing factor for simple cubic, body
centered cubic and face centered cubic structures.
In crystallography, atomic packing factor (sometimes called a packing fraction) is the
fraction of volume occupied by atoms in a unit cell. That, It is dimensionless and always less than unity.
For practical purposes, the APF of a crystal structure is determined by assuming that atoms are rigid
spheres. It is represented mathematically by

Let there are ‘n’ number of the atoms in a unit cell and are sprherical in shape then, volume of atom is
given by . As the cubic unit cell has a = b = c. Then the volume of the unit cell is

Therefore

PF for Simple cubic system:

For a simple cubic system, The number of atoms per unit cell is n = 1 and the relation between lattice
constant and inter atomic radiur is a= 2r

Therefore
 ( )

Hence, Only 52% of the unit cell is occupied by the atoms

PF for Body centered cubic system:

The number of atoms per unit cell is n = 2 and the relation between lattice constant and inter atomic
radiur is
√

( )
√

Hence, Only 68% of the unit cell is occupied by the atoms

PF for face centered cubic system:

The number of atoms per unit cell is n = 4 and the relation between lattice constant and inter atomic
radiur is
√
 ( )
√

Hence, Only 74% of the unit cell is occupied by the atoms

7. Explain the crystal structure of diamond with a neat diagram.

The Diamond lattice can be regarded as the result of the interpenetration of two fcc lattices
formed by carbon atoms, they are superposed in such a way that carbon atoms belonging to two fcc
lattices are along the body diagonal with shortest distance equal to ¼ th the length of the body diagonal.
Unit cell of Diamond structure is shown in fig-1 given below. If we calculate number of carbon atoms per
unit cell it is 8 implies there are 4 carbon atom pairs. Thus if we consider pair of carbon atom as basis it
is characteristic of fcc bravais lattice. Fig-2 shows part of the unit cell with position coordinates of each
atom & formation of tetrahedral structure by joining position of each carbon atom.
Radius of carbon atom here is R = √3/8 a ( 2R = √3/4 a)
APF for diamond structure is 34%.

8. Explain the perovskite crystal structure with a neat diagram.

The mineral perovskite (CaTiO3) is named after a Russian mineralogist, Count Lev Aleksevich von
Perovski, and was discovered and named by Gustav Rose in 1839. If the large oxide ion is combined with
a metal ion having a small radius the resulting crystal structure can be looked upon as close packed
oxygen ions with metal ions in the interstitials. This is observed for many compounds with oxygen ions
and transition metals of valence +2, e.g. NiO, CoO, and MnO. In these crystal structures the Oxygen ions
form a cubic close packed lattice (ccp) with the metal ion in octahedral interstitials (i.e.the rock salt
structure). Replacing one fourth of the oxygen with a cation of approximately the same radius as oxygen
(e.g.alkali, alkali earth or rare earth element) reduces the number of octahedral voids, occupied by a
small cation, to one fourth.where 'A' and 'B' are two cations of very different sizes, and O is an anion.
The 'A' atoms are larger than the 'B' atoms. The perovskite structure is adopted by many oxides that
have the chemical formula ABO3. The chemical formula can be written as ABO3 and the crystal structure
is called perovskite. O is often oxygen but also other large ions such as F – and Cl –are possible.

Although the most common perovskite compounds contain oxygen, there are a few perovskite
compounds that form without oxygen. Fluoride perovskites such as NaMgF 3 are well known. A large
family of metallic perovskite compounds exists and among them MgCNi 3 compound has received a lot of
attention because of its superconducting properties.

APPLICATIONS OF PERVOSKITES:
Perovskites have a wide range of applications in technology. Perovskites are currently used in
sensors, memory devices (RAM), amplifiers, fuel cells, superconductors, and electroptical devices.
Orthorhombic perovskites such as BaZrO3 and SrZrO3 are currently being developed as the electrolyte
material for solid oxide fuel cells. Solid oxide fuel cells (SOFC) are electrochemical devices that convert
chemical energy of a fuel and oxidant directly into electrical energy. Since SOFCs produce electricity
through an electrochemical reaction and not through a combustion process, they are much more
efficient and environmentally friendly than conventional processes.

Another current area of research involving perovskites is high-temperature superconductors

(HTSCs). The cuprate-perovskite type is a specific kind of superconducting material that could operate
under STP in the future. Cuprate-perovskites are related to CaTiO3 type perovskites. Starting from the
CaTiO3 prototype and going to YBa2Cu3O7, Ba and Y substitute for Ca, while Cu substitutes for Ti. Some
cuprate-perovskite ceramic HTSCs currently have an operating temperature of 90K, which is significantly
higher than most other superconducting materials. However, much work needs to be done before a
superconductor can operate at 273 K. Photovoltaic is another application of perovskites which has been
identified as possible inexpensive base materials for high-efficiency commercial photovoltaic. They
showed conversion efficiency up to 15% and is manufactured using the same thin-film manufacturing
techniques as that used for thin film silicon solar cells.

9. State & derive Bragg's law of X-ray diffraction.

Bragg’s law states that for x-rays of wavelength λ when incidents on crystal planes of interplanar
distance d will under go constructive interference if angle of incidence satisfies the relation nλ = 2dsinθ,
where n is the order of diffraction.
 In figure given below XY AND X’Y’ are two parallel crystal planes with interplanar spacing d. Let
AO & A’O’ be the two parallel beams of x-rays which are incident on crystal planes with angle of
incidence θ and OB&O’B’ be the emergent rays at an θ w.r.to the planes.

Draw perpendiculars and ON from O to the ray A’O’B’.

Here OO’= d, triangles OO’M and OO’N are right angled triangles with MOO’= θ = NOO’.
From fig. path difference between the rays AO & A’O’= MO+ON
For the constructive interference of the rays path difference MO+ON = nλ………..(1)
Where n=1,2,3…
From right angled triangles OO’M and OO’N,
OM = d sinθ and ON = d sinθ ………..(2) Substituting 2

From right angled triangles OO’M and OO’N,

OM = d sinθ and ON = d sinθ ………..(2) Substituting 2 in 1 nλ = 2d sinθ which is nothing but Bragg’s
law of x-ray diffraction.
Here θ is called as bragg’s angle, angle of incidence and reflection angle also, which is
related to diffraction angle Φ by relation Φ = 2θ.

10. Explain construction and working of Bragg's X-ray spectrometer and hence determination of wave
length of X-rays, interplanar spacing of the crystal and verification of Bragg’s law.

Bragg’s spectrometer ( x-ray diffractometer) consists of X-ray source, Collimating slits S1S2,Circular
turn table,Ionization chamber and Electometer as a main parts as shown in fig. given below.
X-ray source emits monochromatic x-rays. S1,S2 are collimating slits made up of lead blocks with
fine holes which allows pencil beam of x-rays to pass through it. Circular turn table graduated with
main scale consists of sample holder at the center which rotates with turntable. V1 V2 are fixed
vernier scales that helps to measure angle on main scale through which the turn table is rotated.
Ionization chamber consists of metallic chamber filled with gas which undergoes ionization (emits
electrons), when x-rays enters the chamber. Anode fixed inside the chamber collects these
electrons and builds current in the electrometer. Ionization chamber is mounted on the mechanical
arm which is internally coupled to sample holder in such a way that when sample holder rotates by
an angle θ ionization chamber moves by angle 2θ (as crystal planes acts like a mirror for the
incident x-rays).
Working;` When X-ray source is switched on, the collimated beam of X-rays falls on the crystal
placed in sample holder. By rotating turn table slowly different crystal planes makes different angle
with the incident X-rays. For particular angles which satisfy Bragg’s law, X-rays after diffraction
enter the ionization chamber constituting current in the electrometer. Rotate the turn table
through 0’ to 360’ and note down the angles for which we find the current I in the electrometer.
Plot the graph between bragg’s angle θ and current I, nature of the graph for particular set of
planes will be as shown in fig. Angle θ1 corresponding to maximum intensity will be first order
bragg’s angle ,same way second and third order angles θ2& θ 3can be identified comparing relative
decrement in the peaks intensity.

Determination of Interplanar distance(d): To determine d use x-rays of known wavelength say λ.

Now place crystal whose d is to find in the sample holder and turn the turn table in the same time
note down the angles for which electrometer shows current. By plotting graph between I and θ find
the bragg’s angles for 1,2nd and 3rd order diffraction θ1, θ2& θ3 respectively. By using bragg’s law nλ
= 2d sinθ we can calculate d = λ/2sin θ1= λ/ sin θ2= 3λ/2sin θ3…= n λ / 2sinθn
Determination of wavelength of the x-rays (λ): To calculate λ of the x-rays use these rays as a
source in bragg’s spectrometer and by using crystal planes whose d is known one can find bragg’s
angles for 1,2nd and 3rd order diffraction θ1, θ2& θ3 respectively.
Now using Bragg’s law we can calculate λ = 2dsinθ1= d sinθ2 = 2dsin θ3/ 3= 2dsinθn/n.
Verification of Bragg’s law: Use x-rays of known wavelength λ and crystal whose d is known.Find
out bragg’s angles for 1,2nd and 3rd order diffraction θ1, θ2& θ3 respectively using above method.
Bragg’s law says nλ = 2d sinθ that is for 1st order diffraction 1λ = 2dsinθ1,for 2nd order 2λ = 2dsinθ2
and for 3rd order 3λ = 2dsinθ3.
If we take ratio sinθ1 : sinθ2 : sinθ3 should equal to 1 : 2 : 3 according to bragg’s law.
To verify Bragg’s law use θ1, θ2& θ3 experimentally observed and take ratio of sinθ1 : sinθ2 : sinθ3
which will be equal to 1 : 2 : 3 satisfying Bragg’s law.

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