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Diunggah oleh MuthuLakshmi Rajendran

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Introduction:

We know that elements and chemical compounds occur in three states

viz., gas, liquid and solid.

Solids are broadly classified as Crystalline, polycrystalline and

Amorphous depending on the extent to which atoms or molecules are arranged in a

regular, periodic manner.

Crystalline solids have a regular geometrical shape. This regular shape is a

manifestation of the regular, periodic arrangement of atoms, or molecules, which

make up the solid. In a crystal, the atoms or molecules are arranged in a regular and

periodic pattern. When this periodic arrangement of constituent particles extends

throughout the solid, it is known as a ‘single crystal’. There is a long range order

throughout the single crystal.

A polycrystalline solid is an aggregate of many small crystals separated by

well-defined boundaries; the orientations of the adjacent single crystals across these

boundaries are random. In other words, the orientation of the periodic arrangement

of atoms in adjacent small crystals of the polycrystalline solid is changed abruptly

into an arbitrary orientation at these boundaries. Though crystal grains are small,

there is a long range order of atomic arrangements within each crystal grains.

In an or molecules are not arranged in a regular fashion they are said to be

‘amorphous’. When the atoms, molecules, or ions of a solid are arranged in a

regular and periodic pattern, they are called ‘crystalline’.

In a crystal, each atom or ions are bound to each other more strongly

than in liquids and gases. The interatomic distances between them are smaller than

that in liquids and gases. The study of the ‘solid state physics’ aims to interpret the

macroscopic bulk properties of a solid in terms of its constituent microscopic

particles.

CRYSTAL STRUCTURE:

A crystal is a three dimensional body made up of a regular array of

atoms (or ions) in all directions. It is called as the ‘crystal structure’. The crystal

2

lattice’. It is an array of points in space such that the environment about each point

is the same. A three dimensional space lattice may be defined as an infinite array of

points in three dimension in which every point has an identical environment as any

other point in the array.

EXAMPLE:

Consider the points shown in the diagram, which represent a two

dimensional space lattice.

Along the X-axis, distance between each constant points is ‘a’, while

along Y-axis it is ‘b’. This can be extended infinitely along both x and y directions.

Y-axis . . . . . . . .

. . . . . . . .

. . . . . . . .

b . . . . . . . .

b . . . . . . . .

a a

X- axis

then it represents a three dimensional array.

Extension of atoms in any or all direction is by the repeated movement in

steps of a particular unit. For example, here at every distance of ‘a’ along x axis we

have an atom. The repeated movement is called ‘translation’. A translation can be

represented by a vector.

3

→ → →

In the figure translational grid lines a , b , c are three non-coplanar

ranslational vectors. By repeated action (i.e., translational), they are sufficient to

→ → →

repeat the origin at every point in the ‘space lattice’. These a , b , c vectors are

known as ‘three unit translations’.

THE BASIS:

Every lattice point in a crystal structure is associated with one or more atoms

or ions called the ‘basis’. When the basis is repeated with correct periodicity in all

directions, it gives the actual crystal structure. In a crystal, the basis is identical in

composition, arrangement, and orientation. The basis can be mono atomic (Na, Fe

etc), diatomic (KCl), triatomic (Ca F2) etc.

. . . . .. .x .x .x .x

. . . . . .x .x .x .x

. . . . . .x .x .x .x

a c a c a c a c a c a c

b b b b b b

a c a c a c a c a c a c

b b b b b b

4

Thus in general, when the basis is repeated in the lattice, crystal structure is

obtained.

UNIT CELL:

Consider a two dimensional space lattice. Construct a parallelogram with

sides ABCD, AB = a and AD = b. by translating (i.e, by shifting) the parallelogram

by any integral multiples of vector a and b, the whole crystal structure may be

obtained in two dimensions. This can be extended to three dimensions also. The small

parallelepiped built upon the three translations selected as unit translations is known

as the ‘unit cell’.

The unit cell, though imaginary, has an actual shape and a definite minimum

volume. The entire crystal structure is obtained by the geometrical repetition of the

unit cell.

. . . . . .. . . .

. . . . . . . . .

. . . . . . . . .

. . . . . .. . . .

. . . . . . . . .

. . . . . . . . .

It must be noted that the choice of unit cell is not unique. For example,

consider parallelogram PQRS in the above diagram. By shifting this appropriately the

crystal structure can again be obtained. Therefore this can also be considered as a unit

cell. However if the unit cell of a crystal occupies a minimum volume, then it is

called as ‘primitive cell’.

A primitive unit cell has lattice points only at the corners of the unit cell.There

are no additional atoms at the interior of the unit cell or on the faces of the unit cell.

5

A ‘non-primitive unit cell’ has additional lattice points at the Face centres or at Body

centre in addition to the corner points.

→ → →

The volume of the primitive cell is given by | a x b . c | . A primitive cell

may be constructed by the following way.

1. Draw lines to connect a given lattice point to all the nearby lattice

points.

2. At the mid point and normal to these lines draw new lines or planes.

The smallest volume enclosed in this way is called a primitive cell. This

method is due to WINGNER and SEITZ.

In general, the unit cell may be defined as the smallest volume of a crystal from

which the entire crystal may be constructed by translational repetition in three

dimension.

(a) PRIMITIVE LATTICE:

→ → →

The lattice and the translational vectors a ,b , c are said to be primitive if any two

points r and r ' , from which the atomic arrangement looks the same, always satisfy the relation

→ → →

r ' = r + n1 a + n2 b − n3 c where n1,n2 and n3 are suitable integers.

It is found that there are seven systems of primitive lattices with lattice points

only at the corners of the unit cell. They are classified on the basis of the lengths

→ → →

( i.e, translational vectors a , b , c ) and directions of the axis of the symmetry

(i.e, angles α , β , γ between the axes) as given below. It should be noted that ,

6

→ →

→ →

;

→ →

;

b

→

α γ a

→ β

c

i. Cubic ii.Tetragonal iii Orthorhombic

iv. Rhombohedral v. Hexagonal vi. Monoclinic

vii. Triclinic

BRAVAIS LATTICES:

In 1848, Bravais showed that there are only 14 ways of arranging points in

space, so that the environment looks the same from each point. In the primitive

lattices, lattice points are considered only at the corners of the unit cell. But in the

monoclinic, orthorhombic, tetragonal and cubic systems, there are also seven other

lattices which have more symmetry than the primitive lattices. In these seven

additional types, there are faces or at the body diagonal in addition to those at the

corners. These seven types of lattices are known as centered lattices. Thus totally, 7

primitive type + 7 centered = 14 type of crystal lattices are there. These are known as

Bravais lattices. All these fourteen types are conventionally grouped into seven

systems according to the conventional unit cells.

7

lattices symbol On convention cells

I(bcc) α = β = γ =90

F(fcc) Na, W, Ag, Au, Pb

α = β = 90 ≠ γ

γ < 120

Tetragonal 2 P,I a=b ≠c Indium

α = β = γ =90

(C=base- α = β = γ =90 Olivine

centered) Mg 2 SiO4

α = β = 90 ≠ γ

γ = 120

Monoclinic 2 P,C a≠b≠c Borax,CaSO4.2H2O

α = γ = 90 ≠ β

α ≠ β ≠γ

There are three types of cubic lattices namely, simple cubic (sc), body centered

Cubic (bcc), face centered cubic (fcc).

a. Simple cubic or Primitive cubic (Sc) (cubic P):

There is one lattice point at each of the eight corners of the unit cell and there

is no lattice point inside the unit cell. Thus the primitive cell of SC (which is primitive to other cubic

systems, too) consists of only one lattice point.

8

There is one lattice point at each of the eight corners and one lattice point at each of the six

faces of the cubic cell. Thus an fcc consists of a 4 lattice points.

c. Body centered (Bcc) (cubic I):

There is one lattice point at each of the eight corners and one lattice point at the body centre of

the cell. Thus a Bcc consists of 2 lattice points.

2.TRIGONAL: (I)

Here a Rhombohedron is chosen as the primitive cell. This lattice itself is primitive.

3.TETRAGONAL: (2 types, P and I)

Here the simple unit cell is a right square prism. A second tetragonal lattice type is body

centered.

4. ORTHORHOMBIC: (4 types, P, C, I and F)

In this system there are four types of lattices, namely 1.primitive(P), 2.base centered( C)

3.body centered (I) and 4. face centered (F).

5.HEXAGONAL:(I)

The conventional cell chosen is a right prism based on a rhombus with an angle of 600 .

The lattice is primitive.

6.MONOCLINIC: (2 types, P and F)

There are two types. 1. primitive cell (P) and 2. face centered (F) with lattice points at the

centers of the rectangular faces in the ab plane.

7. TRICLINIC: (I)

This is a primitive cell. It consists of three axes of unequal lengths and unequal angles.

SIMPLE CUBIC (P) LATTICE

There are eight atoms at the eight corners of the cube. Each corner atom is shared by eight

adjacent unit cells surrounding that atom. Therefore only 1/8th of an atom belongs to a given unit cell.

1

∴ Contribution from all the 8 corner atoms to one Simple Cubic unit cell = 8 x = one atom.

8

∴ TOTAL NUMBER OF ATOMS/ UNIT CELL OF SIMPLE CUBIC LATTICE = 1 ATOM.

9

B.C.C. ( I LATTICE)

There are eight atoms at eight corners of the cube and one atom at the body centre of the

cube. Each corner atom is shared by eight unit cell.

1

∴ Contribution to one unit cell from all the corner atoms = 8 x = one atom

8

In addition to this, each unit cell has one atom at the body center which belongs to that unit

cell completely.

∴ Total number of atoms in a BCC unit cell =1+1= 2 atoms.

F.C.C. ( F LATTICE)

It consists of 8 atoms at eight corners of the cube + one atom at the centre of each of the six

1

cube faces. Contribution from corner atom/cell = 8 x = one atom

8

Each face centered atom is shared by two adjacent unit cells.

1

∴ Contribution from face centered atoms = 6 x =3 atoms

2

∴ Total number of atoms/unit cell = 1+ 3 = 4 atoms.

---------------------------------------------------------------------------------------------------

COORDINATION NUMBER:

Every atom in a crystalline structure is surrounded by other atoms. The number of equidistant

nearest neighbors that an atom has in a given crystal structure is called the ‘coordination number’.

When the coordination number is large, the crystal structure is more closely packed.

COORDINATION NUMBER:

The number of equidistant nearest neighbor atoms that a given atom has in a given crystal

structure is known as ‘coordination number’.

If the atoms of a crystal lattice are assumed to be hard spheres arranged in a repeated regular

pattern, a given atom will touch all its nearest neighbor atoms.

ATOMIC RADIUS:

When any two identical spheres touch each other, the distance between their centers will be

equal to twice their radius.

10

Hence, atomic radius may be defined as half the distance between any two nearest neighbor

atoms in a given crystal structure.

A cubic unit cell of edge ‘a’ has a volume a 3 . If the lattice points of a unit cell are assumed to

be occupied by spherical atoms at corners, and body or face centers, the entire volume of the unit cell

is not occupied by the lattice atoms.

The atomic packing factor (or packing density) is defined as the ratio of total volume

occupied by the atoms or molecules in a unit cell to the volume of the unit cell.

Total volume occupied by atoms in a unit cell

i.e. Atomic Packing Factor = ------------------------------------------------------

Volume of the unit cell.

= ------------------------------------------------------

volume of the unit cell

¾ SIMPLE CUBIC: A simple cubic lattice has atoms at eight corners only. Each corner

atom is surrounded by 4 other corner atoms in a horizontal plane. In addition to this, there is one atom in a

plane above this plane and another atom in a plane below this. So there are six nearest neighbors to an

atom in a simple cubic lattice. They lie along the cube edges.

¾ FACE CENTERED CUBIC: A FCC unit cell has eight corner atoms as well as an atom

at the centre of each of the six cubic faces. The nearest neighbors of a corner atom are the face centered

atoms surrounding it and vice versa.

In a given plane (say XY plane) containing the given corner atom O, it has

four nearest neighbor face centered atoms in the four adjacent unit cells. Similarly, when we consider the

other two perpendicular planes (say, XZ and YZ planes) containing the atom O, it has four more nearest

neighbors in each of these two planes. Hence totally, there are 12 nearest neighbor face centered atoms to

a corner atom. In a similar manner it can be shown that there are 12 nearest neighboring corner atoms to

each of the face centered atoms. So coordination number for FCC is 12.

11

¾ BODY CENTERED CUBIC: In a BCC structure, in addition to the eight corner atoms, there is

a body centered atom along the body diagonal. Each body centered atom is surrounded by eight nearest

neighbor corner atoms and vice versa. Hence coordination number for a BCC structure is 8.

___________________________________________________________________________________

1. The simple cubic lattice: The front view of a simple cubic lattice is shown fig.

2r There are eight atoms per unit cell situated at the eight corners. If a is the

side of the unit cell and r be the radius of the atom, then from fig.,

a

2r = a or r =

2

2. Body centered cubic (bcc) lattice: In the unit cell of bcc lattice there are eight atoms

at corners each forming a member of eight cells and one atom per cell at the body centre. The

calculation of r can be made with the help of fig. From the figure, the nearest neighbors of a body

centered atom lie along the body diagonal, DF (say). If ‘a’ is the cube edge, then AB= AD = BF = a and

DF = 4r; where r is the atomic radius.

In ∆ABF, AF = √[ (AB)2 + (BF)2 ] = √ ( a2 + a2 ) = a√2

H G

A F

B

12

In ∆ADF,

DF 2

= ( DA ) 2 + ( AF ) 2

(4 r )2 = a 2 + (a 2 )2

( 4 r ) 2 = 3 .a 2

3

r = a

4

3. Face centered cubic (fcc) lattice: In the face centered cubic lattice, there are eight corner atoms

in the unit cell and one atom at the centre of each face. Fig. shows the front view of fcc structure unit

cell while fig shows its cut view.

From the fig we have the nearest neighbour of a Face centered atom lie along the Face

centered DB. If r is the atomic radius,

B

A

D C

DB = 4r

( BD ) 2 = ( DC ) 2 + (CB ) 2

i.e, ( 4r ) 2 = a 2 + a 2

= 2a 2

2

r = .a

4

4

(or) a = r

2

a = 2 2r

------------------------------------------------------------------------------------------------------

PACKING DENSITY (or) PACKING FACTOR:

Packing density or packing factor is defined as the ratio of the volume of the atoms per unit cell to

the total volume of the unit cell.

13

i.e. Atomic Packing Factor = ------------------------------------------------------

Volume of the unit cell.

= ------------------------------------------------------

volume of the unit cell

If n be the number of atoms in a unit cell each with radius r and if a be edge of the cubic unit cell,

3

⎛ a ⎞

3

4 ⎛ 3 ⎞

⎜ ⎟ π 2 × π ⎜ .a ⎟

3 ⎝ 4 ⎠ = 3π =

then the packing factor (APF) = ⎝ 3 ⎠ = =

2 2

a 6 a3 8

Here we shall calculate the packing density in the following cases:

(1) Simple Cubic Lattice:

Number of atoms per unit cell, n=1

Atomic radius r in terms of cube edge a is r = ( ½ )a

(No. of atoms/unit cell). (Volume of one atom)

Atomic Packing factor = ------------------------------------------------------

volume of the unit cell

3

4 4 ⎛a⎞

n × π r3 1× π ⎜ ⎟

3 3 ⎝ 2⎠ π

i.e., APF = = = =

a3 a3 6

Number of atoms per unit cell, n=2

3

Atomic radius r in terms of cube edge a is r= a

4

3

4 ⎛ 3 ⎞

4

n × π r3 2× π ⎜ .a ⎟

3 3 ⎝ 4 ⎠ 3

∴ APF = = = π=

a3 a 3

8

14

Number of atoms per unit cell, n=4

⎛ a ⎞

Atomic radius r in terms of cube edge a is r= ⎜ ⎟

⎝2 2⎠

3

4 4 ⎛ a ⎞

n × π r3 4× π ⎜

3 3 ⎝ 2 2 ⎟⎠ π

∴ APF = = 3

= =

a3 a 3 2

Name of Cubic Number of Coordination Atomic radius Atomic Packing

Unit Cell atoms/unit cell Number r Factor

Simple Cubic 1 6 a/2 π

6

Body Centered 2 8 3 3

a π

Cubic 4 8

Face Centered 4 12 ⎛ a ⎞ π

⎜ ⎟

Cubic ⎝2 2⎠ 3 2

Let ‘a’ be the lattice constant (cube edge) of the cubic unit cell. Let ρ be the density.

∴ Volume of one unit cell = a3

Mass of one unit cell = volume x density = ρ.a3 ---------- (1)

Let there be n number of atoms or molecules per unit cell. If M be the molecular weight and N be the

Avogadro number, then,

Mass of each molecule (or atom) = M / N

∴Mass of one unit cell = number of atoms ( or molecules) per unit cell x volume of each

atom (or molecule)

nM

= -------------------- (2)

N

nM

Comparing eqns. (1) and (2) we have, ρ.a3 =

N

1 1

⎛ nM ⎞ 3 nM ⎛ nM ⎞ 3

i.e., .a3 =⎜ ⎟ (or) a = ⎜ ⎟

⎝ Nρ ⎠ Nρ ⎝ Nρ ⎠

With the help of the above equation, lattice constant a can be obtained.

15

The crystal structure may be considered as made up of a set of parallel, equidistant planes passing through

one or more lattice points. For a given crystal system these lattice planes may be chosen in different ways.

(Planes marked as A, A.., B,B.., C,C… etc. in the figure)

Miller devised a method to index the lattice planes of a crystal structure. The lattice planes of a

crystal structure are designated by three numbers, h, k, l within parenthesis.

The three numbers h, k and l are written within parentheses without commas between them as (hkl) are

known as Miller Indices and they represent a set of parallel planes.

Miller Indices of a lattice plane may be defined as the three smallest integers which have the same

ratio as the reciprocals of the intercepts of the plane on the three axes.

The procedure for finding the Miller Indices of a plane is described below.

To find the Miller Indices of Plane PQR,

1) Find the intercepts (n1a, n2b, n3c) of the plane on the three axes defined by the basis vectors, a, b,

and c.

G G G

⎛ n1a n2b n3c ⎞

⎜ 1

n = G , n2 = G n3 = G ⎟

⎝ a b c ⎠

3) Find the reciprocals of these numbers; i.e., find 1/n1, 1/n2, 1/n3.

4) Multiply the reciprocals by their Least Common Multiplier (LCM). The resulting set of three

numbers h = (1/n1).LCM, k = (1/n2).LCM and l = (1/n3).LCM are written within

parenthesis as (hkl). (hkl) is called Miller Indices of the given plane.

Thus a plane satisfying the equation h : k : l = 1/n1 : 1/n2 : 1/n3 is said to have the

Miller Indices of (hkl).

Example:

To find the miller indices of a plane making intercepts 2a, 3b and 4c with the axes.

Intercepts of the plane on the three axes Æ 2a, 3b, 4c

Coefficients of intercepts = 2, 3, 4

Reciprocals of coefficients = ½, 1/3, ¼

LCM of reciprocals = 12

16

∴Miller indices (hkl) of the given plane is (643)

Salient Features of Miller Indices:

1. The Miller Indices represents not a single plane but a family of parallel planes. (200) , (100) etc are

parallel planes and both can be represented by (100)

Similarly (111), (222) … etc are also a family of parallel planes. In general, (hkl) and (nh nk nl) = n

(hkl) for any n belong to a family of parallel planes.

2. If a plane cuts any of the three axes on the negative side of the origin, then, the intercept and hence

the corresponding Miller index for the axis will be negative. A negative Miller index is written

with a “bar” over it.

Thus in the above example, if the intercepts are 2a, 3b, -4c, then the corresponding Miller indices

would be h = 6, k = 4 and l = -3 and therefore, Miller Indices of the given plane is (6 4 3).

3. A plane parallel to a particular axis has an intercept of ∞ and hence the corresponding Miller index

would be zero. Thus Miller indices (100) of a plane mean that the plane is parallel to both y and z-

axes.

4. the normal to the plane (hkl) is the direction [hkl] within the crystal

5. The normal distance d between the adjacent neighboring planes of the family (hkl) in a cubic

a

crystal with cube edge ‘a’ is given by d= . d is the interplanar spacing.

( h2 + k 2 + l 2 )

--------------------------------------------------------------------------------------------------------

Reciprocal Lattice

The concept of reciprocal lattice was introduced by Ewald. A crystal may be considered as made

up of a number of interpenetrating lattice planes. These lattice planes can be represented conveniently by a

set of lattice points in a space known as ‘reciprocal space’. Vectors in reciprocal space have unit of length-1.

Let a, b and c be the basis vectors in direct lattice. The basis vectors a*, b* and c* of the reciprocal

lattice are defined by assuming the following:

a*.a = 2π; b*.b = 2π; c*.c = 2π …….(1)

a*.b = a*.c = 0; b*.c = b*.a = 0 and c*.a = c*.b = 0

These equations imply that the vector a* in reciprocal lattice is perpendicular to the plane containing both

the vectors b and c of direct lattice and so on. Thus a* is a vector perpendicular to the bc plane of the

direct lattice and so on. The basis vectors of the reciprocal lattice are defined using the above assumptions

17

as a ∗ = 2π . b ∗ = 2π . c ∗ = 2π . …….(2)

a.b × c b.c × a c.a × b

The denominators of the set of equations (2) represent the volume of the unit cell.

The lattice points in a direct lattice are defined by the vector R from the origin as

R = n1a + n2b + n3c. ……..(3) Similarly, the reciprocal lattice points are given by the reciprocal lattice

vector G = ha* + kb* + lc*…….. (4) . Here, n1, n2 and n3 and h,k and l are integers; h, k, l are the Miller

indices of the plane (hkl).

Properties:

1. An important property of the reciprocal lattice is that the reciprocal lattice vector G= ha* + kb*

+ lc* is normal to the crystal lattice plane with Miller indices (hkl).

2. The spacing between adjacent (hkl) plane of the direct lattice is given by

d hkl = (n.2π) / |G| where n is an integer.

3. The direct lattice is the reciprocal of its own reciprocal lattice. The reciprocal lattice of simple

cubic is simple cubic; The reciprocal lattice of body centered cubic is face centered cubic and vice versa.

Significance and applications:

1. The orientations of different sets of direct lattice planes (two dimensional) are very conveniently

represented by one dimensional vectors in reciprocal space.

2. If K and K’ are the wave vectors of the incident and diffracted X-rays, and

if ∆K = K’-K, then it can be shown that the Bragg’s diffraction condition (2dsinθ=nλ) is satisfied when

∆K = G , where G is a reciprocal lattice vector.. Thus the concept of reciprocal lattice provides an easier

way of interpreting the X-ray diffraction data.

K K’

∆K = Ghkl

|K| = 2π / λ = |K’| θ θ . (hkl) plane

(for elastic scattering) θ

λ Æ wavelength of X-ray used for K

x-ray diffraction

understood in terms of the reciprocal lattice. This is because, the wave vector space (K

space) of the electrons in a crystal is periodic in reciprocal lattice.

18

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