Crystallography

A solid consists of a large number of closely packed atoms or molecules. The physical
structure of a solid and its properties are related to the arrangement of molecules or
atoms with in the solid. The study of crystal geometry helps to understand the diverse
behaviour of solids in their mechanical, metallurgical, electrical, magnetic and optical
properties. For structural investigations of solids we use X-rays, neutron beams or
electron beams.
Solids are classified into two categories based on the arrangement of atoms or molecules:
1. Crystalline solids 2. Amorphous solids
Crystalline solids Amorphous solids
1. In a crystalline solid, the atoms or 1. In amorphous solids, the atoms or
molecules have regular periodic molecules are not arranged in a regular
arrangements periodic manner. They have random
2. They exhibit different magnitudes of arrangement
physical properties in different 2. They exhibit same magnitudes of physical
directions. properties in different directions.
3. They are anisotropic in nature 3. They are an isotropic in nature
4. They exhibit directional properties 4. They do not exhibit directional properties
5. They have sharp melting points 5. They do not possess sharp melting points
6. Crystal breaks along regular planes 6. When amorphous solid breaks, the broken
and hence the crystal pieces have pieces have irregular shape due to lack of
regular shape crystal plane
Eg: Copper, silver, aluminium, etc. Eg: Glass, Plastic, Rubber, etc.
Space lattice or Crystal lattice:
Consider a two dimensional crystal structure, which consists of a regular periodic
arrangement of atoms along x and y directions. The distance between any two atoms
remains same and each atom is surrounded by equal number of neighbouring atoms,
i.e., in crystal structure, each atom will have an identical environment w.r.t other atoms.
This crystal structure can be studied in terms of an idealised geometrical concept called
space lattice, devised by Bravais. “According to this concept, each atom in the structure
can be replaced by a point in the space. This points will have a regular periodic
arrangement and each point will have an identical environment w.r.t. other points. This
array of lattice points in space which resembles the atoms in a crystal is known as space
lattice or crystal lattice. A three dimensional space lattice consists of an array of lattice
points in three dimensions (x,y and z).”

Lattice point
Consider a lattice point at ‘O’ as origin and join
the origin to a successive lattice point along x and
Q
y directions. Let the position vectors of these
lattice points be and . When is repeated
regularly, then it gives the positions of lattice
P points along the x direction, i.e., , , .....
Similarly, if is repeated periodically then it gives
O the positions of lattice points along the y
direction, i.e., , , .....
Fig: Space lattice or crystal lattice
Since and when repeated regularly give the array of lattice points in space lattice,
they are known as fundamental translational vectors or basis vectors or primitive vectors.
Now the position vector of the lattice point ‘P’ is given by
Similarly, for the lattice point ‘Q’ is given by
For a two dimensional space lattice, the position vector of any lattice point is represented
by
where n1 and n2 are integers
For a three dimensional space lattice, the position vector of any lattice point is
represented by
where n1 ,n2 and n3 are integers and , and are the translational vectors along x, y
and z- directions.
Basis associated with each lattice point
Basis:
Since a lattice point is an infinitesimal point in
space, it is an imaginary concept. When each
atom of the crystal is replaced by a lattice
point, we are left with an infinite array points in
space. Now the crystal structure is formed by
associating with every lattice point and a set of
assembly of atoms or molecules or ions
identical in composition, arrangement and
orientation called as the Basis as shown in fig.
Fig: Basis structure
This unit assembly indicated in previous figure is called the Basis. When this basis is
repeated with periodicity (a,b,c) along x, y and z directions, we get the actual crystal
structure.
Space lattice+Basis =crystal structure
In crystalline solids like Al, Cu, Ag, Na the basis contains single atom. In case of NaCl, NaBr,
KCl, CsCl the basis contains two atoms and in some cases the basis may also contains more
atoms. A basis is an assembly of atoms identical in composition, arrangement and
orientation.
Unit cell and lattice parameters
Consider a two dimensional crystal with periodic arrangement of atoms as shown in fig.
(a). The smallest geometrical figure which we get by joining the successive atoms along x
and y directions is ABCD (square). When this figure is repeated regularly along x and y-
axis, we get the actual crystal structure. Thus, “the smallest possible geometrical figure
which repeated regularly gives the crystal structure is known as the unit cell”.
z

Unit Cell
D C

 
y
O
A B 
Figure.(a): Two and (b) three dimensional crystal structure x
For a three dimensional crystal, the unit cell may be cubic or parallel piped. Consider a
cubic unit cell with crystallographic axes x, y and z. Let Oa, Ob and Oc be the intercepts
made by the unit cell along the crystallographic axes. These intercepts giving the
concurrent edges of the unit cell are represented by , and are known as
primitives. The angles between x, y and z axes are called interaxial or interfacial angles.
To represent a lattice unit cell, we require the six parameters, i.e., a,b,c and ,,.
These quantities are known as lattice parameters. The lattice parameters a, b and c may
or may not be equal and ,, may or may not be right angles. Based on the value of
the lattice parameters, we have different crystal systems.

• • •
• • • =
• • •
Space Lattice + Basis = Crystal Structure

Figure: 3D Cubic unit cell

Crystal systems:
Crystals are classified into seven systems on the basis of the shape and of the unit cell or
lattice parameters. These are classified in terms of lengths of unit cells and the angle of
inclination between them. These seven crystal systems are shown below:
THREE DIMENTIONAL UNIT CELLS / UNIT CELL SHAPES
1 7

3 1. Eg. for cubic: Cu, Ag and NaCl

2. Eg. for tetragonal: TiO2 and SnO2
3. Eg. for Orthorhombic: BaSO4
4
4. Eg. For Hexagonal: Quartz, Zn and Cd

5. Eg. for Monoclinic: CaSO4

5 6. Eg. for Triclinic: K2Cr2O7
7. Eg. for Trigonal or Rhombohedral:
As, Bi and Sb.

6
Bravais Lattices:
Bravais showed that there are 14 different types of unit cells under the seven crystal
systems as discussed earlier. They are commonly called Bravais Lattices. The
classification of the Bravais Lattices is based on the following crystal lattices.
1. Primitive Lattice (P): In this lattice, the unit cell consists of eight corner atoms and
all these corner atoms contribute only one effective atom for the cell.
2. Body centred lattice (I): In addition to the eight corner atoms, it consists of one
complete atom at the center
3. Face centered lattice (F): Along with the corner atoms, each face will have one
centre atom
4. Base centred lattice (C): The base and opposite face will have center atoms along
with the corner atoms.

Figure: Lattice types

BRAVAIS LATTICES

7 UNIT CELL TYPES + 4 LATTICE TYPES

= 14 BRAVAIS LATTICES
 Rhombohedral

Figure: Fourteen Bravais lattices

 Expression for lattice constant:
Consider a cubic unit cell with lattice parameters a=b=c and == =90o. Let ‘’ be the
density of the cell. Since the edges of the cube are equal and constant, it is known as
lattice constant, i.e., a=b=c=lattice constant (a).
Volume of cubic unit cell= a3 [density=mass/volume]
Mass of the cubic unit cell= a3 ...................................(1)
Let ‘M’ be the molecular weight of the cell and NA be the Avagadro’s number.
Mass of each atom in unit cell =M/NA
If there are ‘n’ number of atoms in a unit cell, then
mass of the cubic unit cell = nM/NA ...........................(2)
From equations (1) and (2), we have
a3 = nM/NA  a3 = nM/NA  a = [nM/NA]1/3
The above expression represents the expression for lattice constant.
Basic definitions
1. Effective number of atoms per unit cell: The effective number of atoms per unit cell
is the total number of atoms in a unit cell by considering the contribution of corner
atoms, centre atoms and face centered atoms.
2. Atomic radius (r): It is half the distance between any two successive atoms in a
crystal lattice.
3. Coordination number (N): The number of equidistant neighbours that an atom has
in a crystal lattice is known as coordination number.
4. Nearest neighbour distance (2r): The distance between two nearest neighbouring
atoms in a crystal lattice is known as the nearest neighbour distance (2r).
5. Atomic packing factor: It is the ratio between the total volume occupied by the atoms
or molecules in a unit cell to the volume of the unit cell.
 Atomic packing factor= Total volume occupied by atoms in a unit cell/volume of the
unit
cell
6. Interstitial space or Void space: The empty space available in a crystal lattice with
atoms occupying their respective positions is the interstitial or void space.
7. Density: Density of crystal lattice=  = nM/a3NA
where, n=number of atoms in a unit cell
M=molecular
SIMPLE CUBIC CRYSTALweight ; NA = Avogadro number; a=lattice constant.
STRUCTURE:
A simple cubic unit cell consists of eight
corner atoms as shown in figure.

Figure : Simple cubic unit cell, Coordination Number = 6 (equidistant nearest neighbors
The lattice parameters for simple cubic structure are a=b=c (lattice constant=a) and
== =90o . Thus, it is a primitive lattice.
Effective number of atoms in the unit cell: In actual crystals, 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 one unit cell. Hence, the effective number of atoms present
in a unit cell is= 8 x 1/8 =1.
Coordination number (N): For the corner atom there are four nearest neighbours in a
plane which lies just above this atom and yet another nearest neighbour in another
plane which lies just below this atom. Therefore, the total number of nearest neighbours
is six and hence the coordination number is six.
Nearest neighbour distance (2r): Let ‘r’ be the radius of spherical corner atom. From the
figure the nearest neighbour distance=2r=a.
Atomic radius: Atomic radius, r =a/2
Atomic packing factor: For simple cubic, the total number of atoms present is one.
Therefore, the atomic packing factor of the simple cubic can be written as follows.
Volume of one atom(sphere) = 4 p (r)3
Volume of unit cell=a3 3
Number of atoms present in the unit cell=1 4
4
1 p (r) 3 p (a/2)3
Atomic packing factor= 3 3 where , r =a/2
=
a3 a3
 Atomic packing factor= π/6 = 0.52
Thus 52 % of the volume of the simple cubic unit cell is occupied by atoms. The empty or
interstitial space is 48 %. The density is =  = nM/a3NA = M/a3NA . ( Hence, n=1)
 BODY CENTERED CUBIC (BCC) CRYSTAL STRUCTURE:
A body centred cubic cell consists of one body centred atom in addition to eight corner
atoms as shown in below figure.

Lattice parameters: The lattice parameters for simple cubic structure are a=b=c (lattice
constant=a) and == =90o. Thus, as it consists of a centre atom along with corner atoms,
it is not a primitive cell.
Effective number of atoms in unit cell: In a bcc unit cell, each and every corner atom is
shared by eight adjacent unit cell. So, the total number of atoms contributed by the corner
atom is (1/88)=1. Also, a bcc unit cell has one full atom at the centre of the unit cell.
Therefore, the effective number of atoms present in a bcc unit cell is 2.
Coordination number (N): Let us consider a body centred atom. The nearest neighbour for
a body centred atom is a corner atom. A body centred atom is surrounded by eight corner
atoms. Therefore, the coordination number of bcc unit cell is “8”.
 Atomic radius: For a body centred cubic unit cell, the atomic radius can be calculated
from the figure as shown below.
From the figure, AH=4r and DH=a
From the triangle AHD, AD2+DH2=AH2 .........(1)
To find AD, consider the triangle ABD,
From the triangle ABD, we can write
AB2+BD2=AD2 or a2+a2=AD2 i.e, AD2=2a2
Therefore, AD= (2)1/2a
Substituting AD, AH and DH values in equation (1), we
get, AD2+DH2=AH2
(or) 2a2+a2=(4r)2, 3a2=16r2, r2 = (3/16).a2, r=(3/4).a
Figure: calculation of atomic radius
Atomic packing factor: The atomic packing factor of a body centred unit cell can be
calculated as follows:
Number of atoms present in the unit cell=2
4
Volume of one atom= p (r)3 , Volume of unit cell=a 3
3 4
2  p (r)3
Atomic packing factor= 3 ; where r=(3/4).a
a3
4 3
2  p (3/4)3.(a )
Atomic packing factor= 3 = 3π/8=0.68
a3
This shows that 68 % of the volume of the body centred cubic unit cell is occupied by
atoms. It is closely packed structure compared to simple cubic structure.
Interstitial spacing= 32 %
Density: As n=2, for BCC,  = nM/a3NA = 2M/a3NA; Example: Na, Cr and W.
 FACE CENTRED CUBIC TRUCTURE

Fig: Arrangement of
atoms in FCC unit
cell
Face centred cubic structure consists of atoms at eight corners and each face has a centre
atom.
Lattice parameters: The lattice parameters for face centred cubic structure are a=b=c
(lattice constant=a) and == =90o.
Primitive cell: In addition to corner atoms, it consists of face centred atoms, hence it is
not a primitive cell.
Effective number of atoms in unit cell: A FCC unit cell consists of eight corner atoms and
six face centred atoms as shown in figure. Each and every corner atom is shared by eight
adjacent unit cell. Therefore, each and every corner atom contributes 1/8 of its part to
one unit cell. The total number of atoms contributed by the corner atom is (1/8)8=1.
Each and every face centred atom is shared by two unit cells. Therefore, a face centred
atom contributes half of its part to one unit cell. The total number of atoms contributed
by face centred atom is (1/2)6=3. Therefore, the total number of atoms present in FCC
unit cell is 4.
Coordination number: Let us consider a corner G H
atom. In its own plane, that corner atom has four
face centred atoms. These face centred atoms are C
its nearest neighbours. In a plane which lies just D 4r a
above this corner atom, it has four more face
centred atoms as nearest neighbours. Moreover, in
a plane which lies just below this corner atom, it E F
has yet four more face centred atoms as its nearest a
neighbours. Therefore, for an atom in an FCC unit A B
cell, the number of nearest neighbours is ’12’. a
Atomic Radius: The atomic radius can be calculated from the above figure.
From the triangle ABC, AC2=AB2+BC2, (4r)2=a2+a2, 16r2=2a2, r=(a/22)
Nearest neighbour distance (2r): r=(a/22), 2r=(a/2).
Atomic packing fraction: The number of atoms present in an FCC unit cell are 4.
4
Volume of one atom= p (r)3, Volume of unit cell=a 3
3 4 4 3
4  p (r)3 4  p (a/22)
3 3
Atomic packing factor= a 3
= a3  where r=(a/22)

 packing density=π/32=0.74
That is, 74 % of the volume of an FCC unit cell is occupied by atoms. It is a very closely
packed structure then the simple cubic and body centred cubic.
3 3
 MILLER INDICES-CRYSTAL PLANES
The crystal lattice may be regarded as made up of an
infinite set of parallel equidistant planes passing through the
lattice points which are known as lattice planes.
In simple terms, the planes passing through lattice points
are called ‘lattice planes’.
The perpendicular distance between two adjacent crystal
planes is called interplanar spacing (d). The crystal plane can
have different orientation.
 For a given lattice, the lattice planes can be chosen in a d
different number of ways.
The orientation of planes or faces in a crystal can be FIGURE: DIFFERENT LATTICE OR
described in terms of their intercepts on the three axes.
Miller derived a method of representing the orientation of a CRYSTAL PLANES IN A
TWO DIMENSIONAL
crystal plane. The crystal plane is represented by three CRYSTAL LATTICE
smallest integers known as miller indices.

“The Miller indices are the three smallest possible integers which have the same ratios as
the reciprocals of the intercepts of the crystal plane concerned on the three axes”.
Procedure for finding miller indices:
1. First, determine the intercepts of the plane along X, Y and Z axes in terms of lattice
constants a, b and c.
2. Determine the reciprocals of these intercepts.
3. Find the least common factor (LCM) and multiply each by the LCM.
4. Write the result in the form of (hkl) and is called the Miller indices of the plane.
 Defining Crystallographic Planes:
Example:1 a b c
1. Intercepts 1/2 1 3/4
2. Reciprocals 1/½ 1/1 1/¾
2 1 4/3
3. Reduction 6 3 4
4. Miller Indices (634)

Example:2 a b c
1. Intercepts 1 1 
2. Reciprocals 1/1 1/1 1/
3. Reduction 1 1 0
4. Miller Indices (110)
z
 Miller indices (200)
c

Application: In Materials Science it is important to

y have a notation system for atomic planes, since,
a b these planes influence, Optical properties,
Reactivity, Surface tension and Dislocations
x
 IMPORTANT FEATURES OF MILLER INDICES
A plane passing through the origin is defined in terms of a parallel plane having non
zero intercepts.
Any plane which is parallel to any one of the co-ordinate axes has an intercept of
infinity (). Therefore the Miller index for that axis is zero; i.e. for an intercept at
infinity, the corresponding index is zero.
All equally spaced parallel planes have same ‘Miller indices’ i.e. the Miller indices do
not only define a particular plane but also a set of parallel planes.
It is only the ratio of the indices which is important in this notation. The (622) planes
are the same as (311) planes.
If a plane cuts an axis on the negative side of the origin, corresponding index is
negative. It is represented by a bar, like (100). i.e. Miller indices (100) indicates that the
plane has an intercept in the negative X –axis.
 If (hkl) is the Milller indices of a crystal plane, then the intercepts made by the plane
with the coordinate axes are a/h, b/k and c/l where a, b, c are the lattice parameters or
primitives.
 For a cubic crystal, the interplanar spacing between the adjacent parallel plane is
given by a
d 
h 2  k 2  l2
where ‘a’ is the lattice constant and (hkl) is the miller indices of the crystal plane.
 For a cubic crystals, h:k:l=a/p:a/q:a/r , where a=b=c.
 For any crystal, h:k:l=a/p:b/q:c/r
Miller indices of the crystal planes in a unit cubic cell

z (211)

y
a b
x

Z
(100)

x
 z
(112) (111)

y
z (110)
c xx
(110) z

y
a b
x y

x
Plot the plane (110)
The reciprocals are (1,-1, ∞)
The intercepts are x=1, y= -1 and z= ∞
(parallel to z- axis)
To show this plane in a single unit cell,
the origin is moved along the negative
direction of y-axis by 1 unit.
 Z

X
 Miller indices-Crystal Directions
o In crystal analysis, it is essential to indicate
certain directions inside the crystal.
o A direction, in general may be represented in
terms of three axes with reference to the origin. In
crystal system, the line joining the origin and a
lattice point represents the direction of the lattice
point.
o To find the Miller indices of a direction, choose a
perpendicular plane to that direction. Find the
Miller indices of that perpendicular plane. The
perpendicular plane and the direction have the
same Miller indices value.

Therefore, the Miller indices of the perpendicular plane is written within a square
bracket to represent the Miller indices of the direction.
 Negative values are written with a bar over the integer.
 The direction [hkl] is perpendicular to the plane (hkl).
 The angle ‘’ between the two directions [h1k1l1] and [h2k2l2] is given by
 Z
Separation between two
successive planes:
Consider a plane ABC intercepting all C1
three axes at distances OA, OB and 2c
OC (a/h, b/k, c/l) as shown in figure. l
Let the normal to the plane from the C
origin intercepts the plane at N.
Distance of the normal from the c N1
origin is the interplanar spacing ‘d’ l N 2d
i.e, [ON].  d
Let the angles made by the normal to  Y
the X, Y and Z axes be , , , O  b B 2b
respectively. Then the interplanar a k k B1
distance ‘d’ between the origin and h
A
the plane is derived as follows. 2a
Let OA, OB and OC be the intercepts h A1
made on the orthogonal axes OX, OY
and OZ
ON= the perpendicular distance from X
the origin to the plane
d= the interplanar distance Figure: Separation between two
, ,  are the angles between ON
and X, Y and Z axes respectively. successive planes.
From the figure OA=a/h, OB=b/k, OC=c/l
From  ONA, cos=ON/OA=d/(a/h)= d(h/a);
From  ONB, cos=ON/OB=d/(b/h)= d(k/b);
From  ONC, cos =ON/OC=d/(c/l)= d(l/c);
We know form the law of direction cosines that

Since a=b=c for cubic system


 ‘d’ is the perpendicular distance between the origin and the 1 st plane ABC.
Now, let us consider the next parallel plane A1B1C1. Let ON1=2d be the perpendicular
distance of this plane from the origin ‘O’. The intercepts of this plane along the three
axes are OA1=2a/h, OB1=2b/k, OC1=2c/l. 2
2

Hence the interplanar distance between the two planes is given by (ON1 – ON=2d-d).
Therefore,
2d-d = where ‘d’ is the interplanar distance
between the two planes
•Amorphous: An amorphous solid does not have a well-defined structure; it is formless. There
is no recognizable long-range order in the positioning of atoms within the material (Fig. (a)).

• Polycrystalline : In a polycrystalline solid there are many small regions each having an well-
organized structure but differing from its neighboring regions and separated by grain
boundaries (see Fig. (b)).

• crystalline: A unit cell when repeated by itself produces a crystalline solid. In a crystalline
solid atoms are arranged in an orderly array that defines a periodic structure called the lattice.