CRYSTAL STRUCTURE

Introduction


A crystal is a solid composed of atoms or other microscopic particles arranged in an orderly repetitive array. Further Solids can be broadly classified into Crystalline and Non-crystalline or Amorphous. In crystalline solids the atoms are arranged in a periodic manner in all three directions, where as in non crystalline the arrangement is random. Non crystalline substances are isotropic and they have no directional properties i.e., the magnitude of specific property does not change with the change of direction. Crystalline solids are anisotropic and they exhibit varying physical properties with directions. Crystalline solids have sharp melting points where as amorphous solids melts over a range of temperature.

Space lattice
An infinite array of points in three dimensions in which every point has surroundings identical to that of every other point in the array is known as Space lattice. lattice. X X X X X

X Where a and b are X called the repeated translation vectors. X

b
X X X X

a
X X X X

Three dimensional lattice

Lattice planes

Lattice lines

Lattice points

UNIT CELL The minimum fundamental pattern or the smallest block or minimum geometrical pattern which exists in a crystal is called Unit cell. Note: When unit cell is repeated indefinitely, in all three dimensions a crystal is generated. BASIS A group of atoms or molecules identical in composition is called the Basis. Lattice + basis = Crystal structure

CRYSTALLOGRAPHIC AXES
The lines drawn parallel to the lines of intersection of any three faces of the unit cell which do not lie in the same plane are called Crystallographic axes. PRIMITIVES: Intercepts made by the unit cell along the crystallographic axes are called Primitives. These are represented by the notations a, b and c. INTERFACIAL ANGLES The angles between three crystallographic axes are known as Interaxial angles or Interfacial angles and are denoted by the symbols , and .

X c a b X X X

NOTE

1. Primitives decides the size of the unit cell. 2. Interfacial angles decides the shape of the unit cell.

PRIMITIVE CELL
The unit cell is formed by primitives is called primitive cell. cell. A primitive cell will have effectively only one lattice point.
Z

LATTICE PARAMETERS
c

The primitives and interfacial angles together are called lattice parameters. parameters.

a b

X X X X X

X X X X X

X X X X X

X X X X X

X X X X X

X X
Example for 2D lattice

X X X

BRAVIAS LATTICES
There are only fourteen distinguishable ways of arranging the points independently in three dimensional space and these space lattices are known as Bravais lattices and they belong to seven crystal systems

CRYSTAL TYPE

BRAVAIS LATTICE

1. Cubic

Simple Body centered Face centered

2. Tetragonal

Simple Body centered Simple Base centered Body centered Face centered Simple Base centered Simple Simple Simple

3. Orthorhombic

SYMBOLS Simple Cubic Base Centered P C I F

4. Monoclinic

5. Triclinic 6. Trigonal 7. Hexgonal

Body Centered Face Centered

Crystal System


Unit Vector
a=b=c a=bc abc a=b=c a=bc abc abc =

Angles
= = = = = = 90 90 = = 90 90
r

Cubic Tetragonal Ortho rhombic

Rhombohedral or Trigonal

= = 90 90 = 90 90

Hexagonal Mono clinic Triclinic

= 90, =120 90, =120 = = 90 90 90

Cubic Crystal System

6

1 2 3 4

a=b=c &

=90

Cubic Crystal System

6

1 2 3 4

a=b=c &

=90

Tetragonal Crystal System

a=bc &

=90

Ortho Rhombic Crystal System

6 1 3 5

abc &

=90

Monoclinic Crystal System

abc &

= 90

Triclinic clinic Crystal System

abc &

90

Trigonal Crystal System

a=b=c &

90

Hexagonal Crystal System

a=bc &

=90, =120

NEAREST NEIGHBOUR DISTANCE The distance between the centers of any two nearest neighboring atoms is called nearest neighbor distance.

ATOMIC RADIUS
Half the distance between any two nearest neighbors is called atomic radius

CO ORDINATION NUMBER The number of nearest equidistant neighbors that an atom has in a given structure is known as Co-ordination CoNumber. Number.

ATOMIC PACKING FACTOR

Atomic packing factor is the ratio of volume occupied by the effective no. of atoms in a unit cell to that of the total volume of the unit cell. It is also called packing fraction.
Vol occupied by the atoms in an unit cell Atomic Packing factor ! Total volume of a unit cell

PF = nv / V

Void Space


Vacant space left or unutilized space in unit cell is called void space and more commonly known as interstitial space. Void space = ( 1-APF ) X 100

SIMPLE CUBIC STRUCTURE - PACKING FACTOR 1. Each corner is shared by eight identical unit cells. Thus every unit cell contributes 1/8th of atom to the corner. Hence effective number of atoms per unit cell (8 x 1/8) =1 2. Atomic radius r = a / 2 3. Nearest neighbor distance 2r = a 4. Co-ordination number = 6; Coi.e., four will lie in the same plane, 1 above the plane and 1

5. Atomic packing factor

4 3 1v T r 3 ! a3 wherea ! 2r

4 3 1v T r 3 6.Void space = (1-APF) X 100 ! (13 (2r ) = (1-0.52)X 100 (1= 48% Example: Polonium. Polonium. ! 0.52 ! (52%)

BCC STRUCURE PACKING FACTOR

1. Effective number of atoms per unit cell (8 x 1/8) + 1 =2 i.e., 1 from corners and one from center of the cube 2. Atomic radius r = 3a /4 3. Nearest neighbor distance 2r =3a/2 4. Co-ordination number = 8 i.e., Coall corner atoms are at the equidistance from center atom or 8 body centered atoms are at the equidistance from the corner atom

3a

4r

a
C

2a

a
B

5.Atomic packing factor

4 3 2v T r 3 ! a3 3 wherer ! a 4

6.Void space = (1-APF) x 100 (1= (1-0.68) x 100 (1= 32%



4 3 3 2 v T ( a) 3 4 ! 3 (a) ! 0.68 ! (68%)

Ex: Na, lithium and Chromium.

FCC Crystal Structure APF

1. Effective number of atoms per unit cell (8 x 1/8) + 1/2 X 6 = 4 2. Atomic radius r = a / 22 3. Nearest neighbor distance 2r = a /2 4. Co-ordination Number = 12 Coi.e., 4 in the same plane, 4 above the plane and 4 below the plane. All these are represented at face centers and are at the equidistance from

5.Atomic packing factor

4 3 4v T r 3 ! a3 r! a 2 2

4 a 3 4v T ( ) 3 2 2 ! ( a )3

6.Void space = (1-APF) X 100 (1= (1-0.74) X 100 (1= 26%

! 0.74 ! (74%)

Ex: Cupper , Aluminum, Silver and Lead

Diamond Structure:
Diamond is a combination of two interpenetrating Fcc - sub lattices along the body diagonal by 1/4th Cube edge.

4 1 3 2

Diamond - APF
1. It is the combination of interpenetration of two FCC sub lattices along the body diagonal by th cube edge. One sub lattice say x(0,0,0), has its origin x and the other sub lattice y(a/4, a/4, a/4). y(a 2.Effective number of atoms per unit cell (8 x 1/8) + 1/2 X 6 + 4 = 8. 3. Atomic radius r = 3a / 8. 4. Nearest neighbor distance 2r = 3a / 4. 5. Co-ordination number = 4. Cox a/4 y

a/4 2r

z a/4 p

a/4 z x a/4 p a/2 a

5. Atomic packing factor

4 3 8v T r 3 ! a3 3 r! a 8 4 3 3 a) 8v T ( 3 8 ! ( a )3 ! 0.34 ! (34%)

6. Void space = (1-APF) x 100 (1= (1-0.34) x 100 (1= 66% Ge, Ge, Si and Carbon atoms are possess this structure

Structure of a Zinc Sulphide:

ZnS structure is interpenetration of two FCC sub lattices where One of zinc and other is of Sulphur atoms. This structure is identical to that of the Diamond structure except that the two interpenetrating sub lattices are occupied by two different elements. i.e., Zinc and sulphur.
Zn

Zinc sulphide structure results when Zn atoms are placed on one FCC lattice and S atoms on the other FCC lattice as shown in figure below.
6

Zn

4 1 3

S
5

Effective no . of atoms per unit cell are 8. i.e., 4 Zinc atoms and 4 Sulphur atoms or Effective no . of molecules is 4 . The co-ordination Number is 4. Packing fraction is 34 % The other examples are InSb2, GaAs, and CuCl.

Hexagonal Close Packed Structure 1. Effective number of atoms per unit cell 2 x (6x 1/6) + 2 x 1/2 + 3 = 6. 2. Atomic radius r = a / 2. 3. Nearest neighbor distance 2r = a 4. Co-ordination number = 12. Coi.e., 6 in the same plane 3 above the plane and 3 below the plane.

5.Volume of the HCP unit cell



The volume of the unit cell determined by computing the area of the base of unit cell and then by multiplying it with height of the unit cell. Volume = (Area of the base) x (height of the Unit cell) Area of the hexagon
! 6 v ((ABC ) 1 ! 6 v ( a )(a sin 600 ) 2 ! 3a 2 sin 600 3 3a ! 2
2

60 A

If c is the height of the unit cell

3 3 2 V! ac 2

c/a ratio: The three middle layer atoms lie in a horizontal plane at a height c/2 from the base or at top of the Hexagonal cell.

c (2r ) 2 ! x 2  ( ) 2 2 2 x ! AN 3 a 2 3 x ! (a )! 3 2 3

2r c/2 A 30 a B o x N a

a2 ! (

a 2 c )  ( )2 2 3

c2 a2 2 !a  4 3 c2 8 ! 2 a 3 c ! a 8 3

5. Atomic packing factor

4 6 v T r3 3 ! 3 2a 3 a r! 2

6. Void space = (1-APF) x 100 (1= (1-0.74) x 100 (1= 26% Ex: Mg, Cd and Zn.

a 3 4 6v T ( ) 3 2 ! 3 2 ( a )3 ! 0.74 ! (74%)

Sodium Chloride Structure



Nacl Crystal is an ionic crystal. It consists of two crystal. FCC sub lattices. lattices. One of the chlorine ion having its origin at the (0 0 0) point and other of the sodium ions having its origin at (a/2 0 0). (a/2 Each ion in a NaCl lattice has six nearest equidistant opposite ions at a distance a/2. i,e its Co-ordination a/2 Conumber is 6.

Sodium Chloride structure

Cl

Na

Each unit cell of a sodium chloride has four sodium ions and four associated chlorine ions. Thus there are ions. four molecules in each unit cell. cell. The ionic radius of chlorine is about 1.81 AU and for sodium, it is about 0.98 AU. AU. The other examples of this structure are KCl, KBr, KCl, KBr, MgO, MgO, AgBr etc. etc.

Structure of Cesium chloride:

It is an ionic Crystal. It is the result of interpenetration of two simple cubic sub lattices. One sub lattice is occupied by cesium ions and the another one is occupied by Cl ions. Both ions have almost same size The co-ordinates of the ions are coCs : (000),(100),(010),(001),(110), (110),(011),(111). Cl : (1/2,1/2,1/2). The other examples are RbCl and LiHg. LiHg.
Cs

Cl

Some important directions in Cubic Crystal



Square brackets [ ] are used to indicate the directions The digits in a square bracket indicate the indices of that direction. A negative index is indicated by a bar over the digit . Ex: for positive x-axes for negative x-axes [ 100 ] [ 100 ]

Fundamental directions in crystals

z [001]

[000] x [100]

[010] y

Crystal planes & Miller indices



Reciprocals of intercepts made by the plane which are simplified into the smallest possible numbers or integers and represented by (h k l ) are known as Miller Indices. (or) The miller indices are the three smallest integers which have the same ratio as the reciprocals of the intercepts having on the three axes. These indices are used to indicate the different sets of parallel planes in a crystal.

Procedure for finding Miller indices

Find the intercepts of desired plane on the three Co-ordinate axes. Let they be (pa, qb, rc). Express the intercepts as multiples of the unit cell dimensions i.e. p, q, r. (which are coefficients of primitives a, b and c) Take the ratio of reciprocals of these numbers i.e. a/pa : b/qb : c/rc. which is equal to 1/p:1/q:1/r. Convert these reciprocals into whole numbers by multiplying each with their L.C.M , to get the smallest whole number. These smallest whole numbers are Miller indices (h, k, l) of the crystal.

Important features of miller indices



When a plane is parallel to any axis, the intercept of the plane on that axis is infinity. Hence its miller index for that axis is zero. When the intercept of a plane on any axis is negative a bar is put on the corresponding miller index. All equally spaced parallel planes have the same index number (h, k, l). If a plane passes through origin, it is defined in terms of a parallel plane having non-zero intercept.

The numerical parameters of the plane ABC are (2,2,1). The reciprocal of these values are given by (1/2,1/2,1). LCM is equal to 2.

Multiplying the reciprocals with LCM we get Miller indices [1,1,2].

2 y

Construction of [100] plane

z

Intercepts of the Plane are ! (1, g, g) 1 1 1 R`eciprocals of intercepts are ! ( , , ) 1 g g Miller indices : (1,0,0)

x y [1 0 0] plane

x y

Set of [100] parallel planes

Intercepts of the Plane are ! (g,1, g) 1 1 1 R`eciprocals of intercepts are ! ( , , ) g 1 g Miller indices : (0,1,0)

x [010] y plane.

Set of ( 0 1 0 ) parallel planes

Intercepts of the Plane are ! (g, g,1) 1 1 1 R`eciprocals of intercepts are ! ( , , ) g g 1 Miller indices : (0,0,1)

[ 001 ]

plane

Set of ( 0 0 1 ) parallel planes

z

[ 001 ]

x y

Construction of [110] plane

Intercepts of the Plane are ! (1,1, g)
z

1 1 1 R`eciprocals of intercepts are ! ( , , ) 1 1 g Miller indices : (1,1,0)

[110] x

x [110] y

Set of [110] parallel planes

Construction of ( 0 0) Planes
Intercepts of the Plane are ! (1, g, g) 1 1 1 R`eciprocals of intercepts are ! ( , , ) 1 g g Miller indices : (1,0,0)

x y

Intercepts of the planes are 1,1,1

z

Reciprocals of intercepts are 1/1,1/1,1/1 Miller indices:(111)

x (111) y plane

Inter planner spacing of orthogonal crystal system:

 

Let ( h ,k, l ) be the miller indices of the plane ABC. Let ON=d be a normal to the plane passing through the origin 0. Let this ON make angles , and with x, y and z axes respectively. Imagine the reference plane passing through the origin o and the next plane cutting the intercepts a/h, b/k and c/l on x, y and z axes.

Z c C l

Ko
a h

B
b k

OA = a/h, OB = b/k, OC = c/l A normal ON is drawn to the plane ABC from the origin o. the length d of this normal from the origin to the plane will be the inter planar separation. from ONA from ONB from ONC
ON d cos E ! ! OA ( a ) h ON d cos F ! ! OB ( b ) h ON d cos K ! ! OC ( c ) h

Where cos , cos ,cos are directional cosines of , , angles.

According to law of directional cosines

cos 2 E  cos 2 F  cos 2 K ! 1 d 2 d 2 d 2 [ ] [ ] [ ] !1 a b c ( ) ( ) ( ) h k l h2 k 2 l 2 d 2{ 2  2  2 } ! 1 a b c d! 1 h2 k 2 l 2  2 2 2 a b c

This is the general expression for inter planar separation for any set of planes. In cubic system as we know that a = b = c, so the expression becomes

d!

a h k l
2 2 2