BANSAL ACADEMY CHANDIGARH

SCF-19, Sector 16-D, Chandigarh

Condensed Matter Physics

Notes

Solid State Physics

1. Unit Cell:- Smallest unit of the crystal, which on continuous repetition generates the whole crystal.
2. Lattice:- Lattice is periodic arrangement of imaginary points in the space.
* Distance between two successive points is known as lattice parameters or lattice constant.

Bravais lattice or space lattice:- A lattice will be bravais lattice if each lattice point has identical surrounding.
Basis (Motif):- Basis is an atom or group of atoms. By attaching the basis to each lattice point, a crystal structure is formed.
Lattice  Basis  Crystal
* Basis  contain one atom  monoatomic atom basis
* Basis  contain two atoms  diatomic or two atom basis

For example:-
NaCl  two atom basis
CsCl  two atom basis
Diamond  two atom basis.
* If we do not attach basis to lattice, then it will be unit cell of lattice.
* After attaching basis to lattice, it will be unit cell of crystal.

Types of unit cell:-

Primitive unit cell Non-Primitive unit cell
Effective number of lattice point in the Effective number of lattice points in
cell is 1 or one lattice point in the cell the cell is more than 1

It can contain more than one atom It also contain more than one atom

  
Volume of the unit cell 
 a bc 
Bravais lattice in 2-dim  5

Sr. No. Crystal system Bravias lattice Condition

1. Square  
a b
  90

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2. Rectangular  
a b
primitive
  90
3. Rectangular non-  
a b
primitive
  90
4. Hexagonal  
a b
  120

5. Oblique  
a b
  90

**  Honeycomb lattice is not a bravais lattice.

Any point in a lattice is described by Translation vector T which is given by
  
T  n1 a  n2 b  n3 c  3  D
 
T  n1 a  n2 b  2  D
where n1 , n2 , n3  0,  1...............
  
a, b, c  Primitive lattice vectors
C TOM THR
C  cubic, T  tetragonal, O  orthorhomic, M  monoclinic, T  triclinic,
H  Hexagonal, R  Rhombohedral

Bravais lattice in 3-D  14

Sr. No. Crystal system Bravias lattice Conditions

1. Cubic (i) Simple cubic a  b  c,       90
(ii) Body centred
(iii) Face centred
2. Tetragonal (i) Simple tetragonal a  b  c,       90
(ii) Body centred
3. Orthorhombic (i) Simple a  b  c,       90
(ii) Body centred
(iii) Face centred
(iv) Base centred
4. Monoclinic (i) Simple a  b  c,     90,   90
(ii) Base centred
5. Triclinic (i) Simple cubic a  b  c,       90
6. Hexagonal (i) Simple cubic a  b  c,     90,   120
7. Rhombohedral (i) Simple cubic a  b  c,       90  120
(Trigonal)

Crystal structure:-
(I) Simple cubic (Primitive cubic):- SCC
Atoms are placed at each corner of cube

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internal angle
Sharing:-
360

45 1
Sharing at each corner atom  
360 8
1
Total number of atoms in unit cell  8   1
8
n 1
(i) First nearest neighbour distance = a
No. of first nearest neighbours atom = 6.
(ii) Second nearest neighbour distance from one reference atom (let assume a corner atom)  2a
No. of second nearest neighbour atom = 12.
(iii) Third nearest neighbour distance  3a
No. of third nearest neighbour atom = 8.
Volume of atoms in unit cell
Packing fraction 
Volume of unit cell
No. of atoms Volume of one atom in unit cell
PF 
Volume of unit cell
4
1  r 3
P  F  33
a
First nearest neighbour distance
2r  a

4
1  r 3
So P.F  3 3
 2r 
 P.F  0.52 or 52%  loosly packed structure
So 52% part of crystal is occupied by atoms and 48% part is empty.
Volume of unit cell
Volume of primitive unit cell 
No. of atoms
a3
  a3
1

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No. of atoms in a unit cell 1

Atomic density   3
Volume of unit cell a
(II) Body Centred Cubic (BCC):- (atoms present at corner) + (atom at body centred position)

1
Total no. of atoms in the unit cell  8  1
8
n2
3 3
(i) First nearest neighbour distance  a  2r  a
2 2
No. of first nearest neighbour atoms = 8.
(ii) Second nearest neighbour distance [imagine this from one reference point (corner atoms)] = a
No. of second nearest neighbour atoms = 6.
(iii) Third nearest neighbour distance  2a
No. of third nearest neighbour atoms = 12.
No. of atoms  Volume of one atoms in unit cell
Packing fraction 
Volume of unit cell
4
2   r3
PF  3
a3

3
Here 2r  a
2
4
ra
3
4
2   r3
So P.F  3
3
 4r 
 
 3
 P.F  68%  loosly packed structure
Volume of unit cell
* Volume of primitive unit cell 
No. of atoms
a3

2

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No. of atoms in a unit cell 2

Atomic density   3
Volume of unit cell a
(III) FCC:- (atoms are placed on each corner atom + atoms at each face of the cube)

1 1
Total no. of atoms in a unit cell  8 
 6
8 2
 1 3
n4
0.707

2
(i) First nearest neighbour distance  2r   a
2
No. of first nearest neighbour atoms = 12.
(ii) Second nearest neighbour distance = a
No. of second nearest neighbour atoms = 6.
(iii) Third nearest neighbour distance  2a
No. of third nearest neighbour atoms = 12.
No. of atoms  Volume of atoms in unit cell
Packing fraction 
Volume of unit cell
4
4   r3
PF  3
a3

2 a
 2r  a
2 2
2 2r  a
4
4   r3
So P.F  3
 
3
2 2r
 P.F  0.74  74%  closely packed structure
Volume of unit cell
Volume of primitive unit cell 
No. of atoms in unit cell
a3

4
No. of atoms 4
Atomic density   3
Volume of cell a
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{* When phase transition take place from one crystal to another crystal, then number density (Atomic density) remains
same}
(IV) Hexagonal structure:-
In 2 – D:- In structure

{Hexagonal = 6 (equilateral triangles)}

{For equilateral triangle each side is equal and angle  60 }
Now to find area of equilateral triangle

h 3
sin 60   h a
a 2
1
Area of equilateral   base  height
2
1 3 3 2
 a a a
2 2 4
3 2
Total area of hexagonal unit cell  6 a
4
3 3 2
 a
2
1
Now total number of atoms in the unit cell   6  1 {6 atoms at each corner + one atom at centre}
3
 n3
First nearest neighbour distance  2r   a
No. of atoms  area of one atom
Packing fraction 
area in  2  D  of unit cell
3 r 2
P.F 
3 3 2
a
2

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a
 r
2
a2
3
P.F  4  90%
3 3 2
a
2
P.F  90%  closely packed structure
In 3-D structure:

Place A atoms, then put B atoms on alternate void we get layer B, now void will be at the centre of atoms of layer A.
1 2 1
1st atom occupies (0, 0, 0) position then 2 nd atom occupies  , ,  position.
3 3 2
So hexagonal close structure is ABAB…….. type
for Hexagonal
a bc
    90,   120
* FCC  FCC is ABCABC…… type of structure.

Number of atoms per unit cell:

1 1 1
Corner atoms of layers A  12   part of 
6 3 2
2
1
Atoms present at faces  2   1
2
3 atoms of layer B will contribute full  3 1  3 .
So n  2 1 3  6  n6
{The atoms placed at the void will never coincide at the centre of others, so there contribution will be complete}.
* 1st nearest neighbour distance (2r) = a
a  lattice parameter or lattice constant
* 2nd nearest neighbour distance = C (height of unit cell)
1st nearest neighbours atoms (Co-ordination number) = 12
2nd nearest neighbours atoms = 2
1
* Volume of primitive unit cell will be of unit cell
3
n = 2  two atom basis

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c
  ratio:
a

a/2 
 3

cos 30  cos 30  
AD 
 2 

a
AD 
3

 AF    AD    FD 
2 2 2

2 2
 a  c
a 
2
  
 3 2
a2 c2
a2  
3 4
3a  a
2 2
c2

3 4
2a 2 c 2

3 4
c 2 2

a 3
c
  1.633
a
No. of atoms Volume of one atom
Packing fraction 
Volume of hcp unit cell

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4 4
6   r3 6   r3
P.F  3  3
3 area of base  height
 6  a 2  c
4  height

area of base

2r  a
4
6   r3
So P.F  3
3
 6   2r  1.633  2r
3

4
 P.F  74%
{Packing fraction of hcp and fcc is same}.

1 3 3 a 2c 3 2
* Volume of primitive =  rd part of hcp is primitive unit cell) of cell:   ac
3 2 3 2
No. of atoms in unit cell
Atomic density  n  
Volume of unit cell
6 4
 
3 3 2 3a 2 c
ac
2
Diamond Cubic Crystal: Diamond cubic crystal structure has fcc lattice with two atom basis.
1 1 1
If 1st atom occupies (0, 0, 0) position, then 2nd atom occupies  , ,  position.
4 4 4
Diamond cubic crystal structure can also be considered as inter penetration of two FCC unit cells. If 1 st unit cell is concerned
1 1 1
at (0, 0, 0), then 2nd unit cell must be concerned at  , , .
4 4 4
* C has 6-valence electrons, it is forming bonds with 4-atoms, so atoms are not free in diamond, this means, diamond is an
insulator
Diamond  two atom basis

1/ 4  3 / 4  1/ 4  3 / 4  distance

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1 1
Total number of atoms/unit cell  8  6  4  8
8 2
1 1 1
(1) 1st nearest neighbour distance   0, 0, 0  to  , , 
4 4 4
2 2 2
1 1 1
      
 4  4  4
3
 2r  a
4
* Number of 1st nearest neighbour atoms = 4.
a
* 2nd nearest neighbour distance 
2
2nd nearest neighbour atoms = 12
 a3
Volume of unit cell
8
Atomic density  3
a
No. of atoms Volume of one atom
Packing fraction 
Volume of unit cell
4
8  r3
P.F  3
a3
3 8r
we know that 2r  a  a
4 3
4
8  r3
 P.F  3  34%  loosely packing
3
 8r  
  Carbon carbon bonding
 3 strong

hard diamond
Example: Si, Ge, Sn etc.

ZnS blends structure (ZnS): This is similar to diamond cubic structure except two interpenetrating lattices have different
atoms of 1st lattice or unit cell is made from Zn atoms, then 2nd unit cell is made from sulphide atom.
If Zn  occupies the fcc position
S  Tetrahedral void occupies
Number of atoms per unit cell = 4Zn + 4S = 8
4 4
4   rZn3  4   rS3
Packing fraction  3 3
3
a
3
Here 1st nearest distance  rZn  rS  a
4
P.F  34%  exactly 
For example: GaAs, CdS, InSb etc.

NaCl structure: 2 atom basis [1Na + 1Cl] with FCC structure.

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1   1   1
If 1st atom occupies (0, 0, 0) position and 2nd atom occupies  , 0, 0  or  0, , 0  or  0, 0,  .
2   2   2
NaCl  Unit cells can also be considered interpenetration of two fcc unit cells.

1 1 1
Total number of atoms: 8   6   12   1  8
8
 2  4 
Cl Na
1 1
Number of Cl atoms   8   6  4
8 2
1
Number of Na atoms  12   1  4
4

a
(1) 1st nearest neighbour distance  rNa  rCl  
2
(2) Number of 1st nearest neighbour atoms = 6
a a
(3) 2nd nearest neighbour distance  2 
2 2
Number of 2nd nearest neighbour atoms = 12
Packing fraction  can’t be calculated exactly.

For example: KCl, NaBr, KBr, NaI, KI

Cesium Chloride (CsCl): 2  atom basis [1Cl + 1CS)

CsCl crystal can be considered as 2 interpenetrating simple cubic crystal one has the atoms of CS and other has the atoms of
1 1 1
Cl. The origin of one lattice is at (0, 0, 0) and other has origin at  , , .
2 2 2
1
Number of atoms per unit cell: Cs   8  1
8
Cs  1
n2

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3
(1) 1st nearest neighbour distance   rCS  rCl   a
2
(2) Number of 1st nearest neighbour atoms = 8
(3) 2nd nearest neighbour distance = a
(4) Number of 2nd nearest neighbour atoms = 6
(5) Volume of primitive unit cell a3
r
A packing fraction cannot find until CS ratio not known.
rCl
Graphene: Graphene has honey comb structure, carbon atoms are arranged in the honeycomb structure.

It consider lattice point on each atom position then it will not form a basis because surrounding of A and B are different. Only
A-A atoms or B-B atoms can form basis as they have same surrounding. So either connect nearly A-A atoms or B-B atoms.
This hexagon (non-primitive) is unit cell of graphene.
Number of atoms/per unit cell
1
corner atoms   6  2
3
atoms inside  1 4  4
 n6
Now to find 1st nearest neighbor distance:

sin120 sin 30


a a'
sin  90  30  sin 30

a a'
cos 30 sin 30

a a'

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3 1 a
  a' 
2a 2a ' 3

3 2 3 3 2
Area of the unit cell  6 a  a
4 2
a  3  a  a  3 2
Area of the primitive unit cell (having sides   6 4    2 a
3  3  3 

1
or area of primitive unit cell   Area of unit cell
3
a
(1) 1st nearest neighbour distance  a ' 
3
a
 2r 
3
Number of nearest neighbour atoms = 3
(2) 2nd nearest neighbour distance = a
2nd nearest neighbour atoms = 6
No. of atoms  area of unit cell
Atomic packing fraction 
area of unit cell in 2  D
6 r2
P.F 
3 3 2
a
2
 2r 3  a
6 r2
P.F 
3 3
 
2
  2r 3
 2 
 P.F  60%
Graphite: In 3-D
Made from carbon.
Number of atoms/unit cell = 4
Graphite is conductor  per C atom, 1e is free.

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Now for BaTiO3 structure

Ba Ti O3  Basis  5 ( no. of atoms / unit primitive cell )
    simple cubic 
edges body face no. of atoms 1  8 1 6  1
8 3
1 centered centered Lattice point 1
8
8 1 1
6
3
* Relation between lattice parameter and density 
given mass m
A   3
volume of unit cell a

 MA Molecular mass  gram / mol  
m   

 N A avogadro number  atoms / mol  

So
MA
A 
N Aa3
1/3
nM A  nM A 
And for crystal A   a 
 NAA 
3
N Aa
n  number of atoms per unit cell
a  lattice parameter.
If M A is given only in gram then
nM A
A 
a3
Interplanar spacing: Distance between two planes is interplanar spacing and it is represented by d hkl .
1
d hkl 
h2 k 2 l 2
 
a 2 b2 c2
h, k , l  miller indices
a, b, c  lattice parameters.
This formula is valid only cubic, tetrahedral and orthorhomic structure.
a
d hkl   for allowed plane
h  k2  l2
2

1 a 
d hkl   2  non  allowed plane
2  h  k2  l2 
(Non-allowed plane is checked by structure factor).
1 4  h2  hk  k 2  l 2
For hcp: 2    2
d hkl 3  a2  c
For Example: In BCC:

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a
Due to 1 extra plane, interplaner spacing  .
2
Miller indices: To find the orientation of planes in the crystal, miller indices are used. They are written as  hkl 
a b c
h:k :l  : :
OA OB OC
a, b, c  lattice parameter
OA, OB, OC  Intercept on x, y, z – axis
Another method, if
x  2a, y  3b, z  c
2a 3b x
: :  2 : 3:1
a b c
Take reciprocal
1 1 1
: :
2 3 1
Multiply by LCM  6
1 1 1
6  ,  6,  6   326   Miller indices
2 3 1
Cubic crystal:
(1) 1 0 0  h  1, k  0, l  0
OA  a, OB  , OC   (x-axis)
(Paint wall of room)
{infinite means  parallel to that axis}

(2)  0 1 0  h  0, k  1, l  0
OA  , OB  a, OC  

(3)  0 0 1  h  0, k  0, l  1
OA  , OB  , OC  a
(4) 1 1 0  h  1, k  1, l  0
OA  a, OB  a, OC  

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(5) 1 1 1  h  1, k  1, l  1
OA  a, OB  a, OC  a

(6)  2 0 0  h  2, k  0, l  0
1
OA  , OB   , OC  
2
* Parallel planes have same indices.
If h  1 then h  1 .

For example: 1 0 0 , h  1, k  0, l  0

OA   a, OA  , OC  

Planes in different crystals:

(1) (1 0 0) plane:

Planes {(0, 1, 0), (1, 0, 0), (0 0 1)}  same properties.

 internal angle 
 Sharing  
 360 
1
Number of atoms on (1 0 0)   4  1
4
Area of plane  a
2

Planar density = number of atoms per unit area

1

a2
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(2) (1 1 0) plane:

1
Number of atoms  4 1
4
Area a  
2a  2a 2

(3) (1 1 1) plane:

1 1
Number of atoms 3 
6 2
60 1
Sharing  
360 6

Area 
4
3
 2a  2a 
3
Area  a
2
* Larger planar density will be closely packed.
Reciprocal lattice: Every crystal has two lattice associated with it, the crystal lattice (direct space lattice) and the reciprocal
lattice. The concept of reciprocal lattice was introduced for the purpose of tabulating two important properties of crystal planes
their slopes and their interplanar spacing. Each set of parallel planes in a direct lattice can be represented by a normal to these
planes having length equal to the reciprocal of the interplanar spacing. The normal are drawn with reference to any arbitrary
origin and points are marked at their ends. These points form a regular arrangement which is called reciprocal lattice. Thus
each point in a reciprocal lattice is representative point of a particular set of parallel planes. It is easier to deal with such points
than to deal with set of planes. That’s why we use reciprocal lattice.

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 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

 1 
Thus reciprocal lattice vector is a vector whose magnitude is equal to the reciprocal to the interplanar spacing   and
 hkl 
d
direction is parallel to normal to ( hkl plane).
Volume  area  height
V  area  dhkl
1 1 1
 
V area d hkl
1 area

d hkl V
   b  c 
 bc 
a*  2    2     
 
Or
 V   a  bc 
 
 c  a 
b*  2     

 a bc 
  

 ab  
c*  2     

 a bc 
  
* Any point or position of any atom in direct lattice is represent by translational vector T

     
T  n1 a  n2 b  n3 c, a, b, c  lattice vectors in direct lattice
In reciprocal lattice, any point is represented by
   
G  ha * kb * lc *
  
a*, b*, c*  primitive lattice vector in reciprocal lattice.
{minimum distance between the atoms}.

(1) Reciprocal vectors of Simple-cubic structure:


a  aiˆ

b  ajˆ

c  akˆ
 abc
  
  
a  b  c  aiˆ  ajˆ  akˆ 
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 BANSAL ACADEMY CHANDIGARH
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V  a3
 
a* 

2 b  c   2  ajˆ  akˆ 
V a3
2 a 2iˆ
a* 
a3
2 ˆ
a*  i
a
 
b* 
2 c  a 
2   akˆ  aiˆ 
V a3
2 a 2 ˆj
b* 
a3
2 ˆ
b*  j
a
 
c* 
2 a  b 
2   aiˆ  ajˆ 
V a3
2 a 2 kˆ
c* 
a3
2 ˆ
c*  k
a
4
Reciprocal of simple cube is simple cube with edge length of .
a
(2) Reciprocal of BCC:

 a
2

a  i  ˆj  kˆ ,  First nearest neighbour distance
 a
 a a 111

b  i  j  kˆ
2
 2

 a
2

c  iˆ  ˆj  kˆ  
a 3
2

3a
2
 
 

 2 b  c atom present at
body centre
a*    
a bc 
    a2 
 a

V  a  b  c  i  j  kˆ
2
  
4
  
i  j  kˆ  i  j  kˆ 



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 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

i j k
  a2
bc  1 1 1  i 1  1  j  1  1  k 1  1
4
1 1 1
  a2
bc 
4

2iˆ  2 ˆj 
V
8

a3 ˆ ˆ ˆ

i  j  k   2i  2 j 

a3 a3
V   2  2 
8 2
a2
 2  2 i  2 j 
a*  4
 a3 
 
 2
 2 ˆ ˆ
 a* 
a
ij  
 
Now

b* 
2 c  a  
V
iˆ ˆj kˆ
  a2
ca  1 1 1
4
1 1 1

a2 
 i  0   j  1  1  kˆ 1  1 
4  
  a2
ca 
4

2 j  2kˆ 
 2 
a2
4

2 j  2kˆ 
b*  3
a2
 2 ˆ ˆ
 b* 
a
jk  
 
Similarly

c* 
2 a  b 
V
 2 ˆ ˆ
 c* 
a
k i  
4
Reciprocal of body centered cubic lattice is face centered cubic lattice with cube edge of .
a
(3) Reciprocal of face – centered cubic: (FCC)

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 BANSAL ACADEMY CHANDIGARH
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 a  a
2

a  iˆ  ˆj ,  a 
2
2
a
2

first nearest
distance in fcc
 a
b
2
 
ˆj  kˆ

 a

c  kˆ  iˆ
2

   a  
 
V  a  b  c  i  j   b  c
2
 
i j k
  a2
bc  0 1 1
4
1 0 1
  a2
bc 
4

i  j  kˆ 
 
3
a
V   i  j   i  j  kˆ
8
a3 a3
V  1  1 
8 4
  a2
 2  b c
4
2
 
a2
4
i  j  kˆ  
a*  
V a3
4
 2 ˆ ˆ ˆ
a* 
a

i  jk
 

b* 
2 c  a
 
 
 
Now
a bc

iˆ ˆj kˆ
  a2
ca  1 0 1
4
1 1 0

a2  ˆ ˆ ˆ
 i  j  k
4  

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 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

 2 
a2
4

i  j  kˆ 
b* 
a3
4
  a2
ca 
4

2 j  2kˆ 
 2 
a2
4

2 j  2kˆ 
b* 
a3
4
 2
b* 
a
 
i  j  kˆ
 

c* 
 
2 a  b
V
iˆ ˆj kˆ
  a2
ab  1 1 0
4
0 1 1

a2  ˆ
 i 1  ˆj  kˆ 
4  

 2 ˆ ˆ ˆ
Similarly c* 
a

i  jk 
4
Reciprocal of fcc is bcc with lattice side or cube eadge of .
a
(4) Reciprocal of square lattice:


a  aiˆ

b  ajˆ

Let c  akˆ
 
 2
a*  
b c 
a b  c 
  

a  bc   aiˆ   ajˆ  akˆ 
V  a3
 2 a 2  j  k 
a* 
a3
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 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

 2 iˆ
a* 
a
 

b* 

2 c  a

  
2 a 2 kˆ  iˆ
V a3
 2 ˆj
b* 
a
 

c* 

2 a  b

2 a 2  i  j 
V a3
 2 kˆ
c* 
a
 2 
The reciprocal of square lattice is square lattice with side  .
 a 
(5) Reciprocal of rectangular lattice:


a  aiˆ

b  bjˆ

Let c  ckˆ
  
  
V  a  b  c  aiˆ  bjˆ  ckˆ 
V  abc
 

a* 

2 b  c

2  bjˆ  ckˆ 
V abc
 2 iˆ
a* 
a
 

b* 

2 c  a

2   ckˆ  aiˆ 
V abc
 2 jˆ
b* 
b
 

c* 

2 a  b

2   aiˆ  bjˆ 
V abc
 2 kˆ
c* 
c
So reciprocal of rectangular lattice vector is rectangular lattice.

(6) Reciprocal of HCP:

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 BANSAL ACADEMY CHANDIGARH
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
a  a cos 60iˆ  a sin 60 ˆj
 a a 3ˆ
a  iˆ  j
2 2

b  a cos 60iˆ  a sin 60 j
 a a 3ˆ
b  iˆ  j
2 2

Let c  ckˆ
   a  
 
V  a  b  c  i  3 j   b  c
2
 
iˆ ˆj kˆ
  a 3a
bc  0
2 2
0 0 c

   3ac 
b  c  iˆ    ˆj  ac 
 2   2 
   
V
a
i  3 j  i  3ac   ˆj  ac  
2   2 
    2  
a2 
V 3c  3c 
4 
3a 2 c
V
2
 

a* 

2 b  c 
V
a 
2  i  3 ˆj   ckˆ 
 2 
2
3a c
2

a* 

2  ˆj  3iˆ 
3a
 2  ˆ ˆj 
a*  i  
a  3

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 BANSAL ACADEMY CHANDIGARH
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 
Now

b* 

2 c  a 
V
 2  ˆ 1
b*  i ˆj 
a  3


 
Directions of a * and b * are same to that of a and b, we can say that reciprocal of hcp is hcp.
(7) Reciprocal of Graphene:

  
a  a cos30iˆ  a sin 30 ˆj sin120 sin 30
 
a a
 3ˆ 1 sin  90  30  sin 30
a  3a  i  3a  ˆj  
2 2 a a
 3a 3a ˆ cos 30 sin 30
a  iˆ  j  
2 2 a a
 
b  b ˆj  3ajˆ 3 1
 
2 a 2a
 
Let c  ckˆ a  3a
    3a 3 ˆ
And
 
V  a  b  c   iˆ  j
2 
 3ajˆ  ckˆ 
 2

3 3 ˆ sin120 sin 30

V   aiˆ  aj 
2 
 3aciˆ  
b

a
2
3 3 2 3 1
V ac  
2 2 b 2a
  

a* 

2 b  c  b  3a
V
 

a* 

2 3ajˆ  ckˆ   a b
3 3a 2 c
2
 4 iˆ
a* 
3a

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 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

 

b* 

2 c  a 
V
3 3 ˆ
 
 2 ckˆ   aiˆ  aj 
2 
2

i j k
 
ca  0 0 1
3 3
a a 0
2 2
   3  3 
c  a  i   a   j a
 2  2 
 3 ˆ 3 ˆ
2   ai  aj 
  2 2 
b* 
3 3a 2 c
2
 2 
b*   3iˆ  3 ˆj 
3 3a 
So reciprocal of graphene is not same as graphene lattice.

X - Ray : EM radiations having wavelength of order 1A .


High energy

Production of X-rays: The X-rays are produced when a stream of high energy (inverse photoelectric effect) charged particle
is allowed to strike on metal target. Electrons loose some energy which is converted into electromagnetic radiations.
Production of EM radiation  accelerating charged particles emit radiations which is electromagnetic radiations.

Photo electric effect:

Intensity  no. of photons

Frequency  energy

* Greater the intensity, greater the number of e  or larger the current.

* Greater the frequency, greater the K.E.
I1  I 2  I 3  same when frequency  same

larger stopping potential
having large v

Stopping potential: Potential required to stop the e  to reach the anode plate.

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 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh


X-Ray diffraction: X-rays interact with the electrons cloud of the atom larger the e , larger is the diffraction. The X-rays are
scattered by adjacent atoms in crystal. The scattered X-rays interferes and give rise to diffraction phenomenon.
It gives information about internal arrangement of atoms.
Bragg’s law: Consider parallel lattice planes separated by distance d

In BGE
GE  d sin  , EC  d sin 
So path difference GE  EC  d sin   d sin 
 2d sin 
For constructive interference, the path-difference is an integral multiple of  . Thus the intensity will be maximum if
2d sin   n
n  1, 2,.......
This is bragg’s law
  2d , sin   1
The diffraction is occur at that point in crystal where bragg’s condition is satisfied.
2dhkl cos   n    angle measured from normal
Diffraction  bending of X-rays around the corners of an obstacle is called diffraction.

Condition: Size of the aperture and size of the obstacle should be comparable to the wavelength of wave for diffraction to
occur.

Diffraction angle  2 B , Bragg angle   B

  0, 2 , 4 .........
For constructive interference path difference
For destructive interference    , 3 , 5 .........
2
   path difference

Important point: As  B , sin  B , dhkl 
1
B  dhkl  interplanar spacing
dhkl
0   B  90
d  decreases  compression
d  increases  stretching

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 BANSAL ACADEMY CHANDIGARH
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Effect of temperature on XRD pattern:

Effect of temperature: (1) Peak is broaded

(2) Intensity decreases
(3) Peak position unchanged
(4) Line spacing (distance between two peaks) decreases.

Electron diffraction: In e  diffraction, X-ray beam would be replaced by e  beam

2dhkl sin  B  n
h h h
e   
pe 2mE 2m  eV 

1 150
e  or e  A
V EC  eV 

It used for surface study ( e beam do not penetrates deep inside the crystal).

Neutron diffraction: Neutron beam is used.

For atom having smaller number of electrons e  then we use neutron beam diffraction.
h h
n  
pn 2mn En
Intensity of XRD pattern: Intensity is depend upon two factors
I F
2

F  fs
F  amplitude of diffracted X-ray
f  atomic scattering factor
s  geometrical structure factor
amplitude of X  ray diffracted by an atom
f 
amplitude of X  ray diffracted by an e
* Higher the number of e  in an atom  higher f.
Geometrical structure factor (s): It is concerned with geometrical placing of atoms in the unit cell.
 
n
s  e
2 i u j h  v j k  w j l

j 1

j  number of atoms in unit cell, u j , v j , w j  position of i th atom

amplitude of X  ray diffracted by unit cell
s
amplitude of X  ray diffracted by e
(I) Structure factor for simple cubic: There is one atom at position (0, 0, 0)
2 i  000 
se 1
s 1
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 BANSAL ACADEMY CHANDIGARH
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So F  fs  f
 I f
2

Intensity does not depend upon h, k , l . Intensity does not depend on any particular type of plane i.e same for (all planes all
reflections are allowed) no restriction on h, k , l or all  h, k , l  are allowed.

(II) s for bcc:- n2

 u1, v1, w1    0, 0, 0
 u2 , v2 , w2   
1 1 1
, , 
2 2 2
i
2 i  0 0 0  2  h  k l 
se e 2

s  1 e  
 i h  k l

s is depending on h, k , l  particular type of plane.

(1) h  k  l  even
s0
(2) h  k  l  odd
s0
So reflections are allowed when  h  k  l  is even.

(III) s for FCC: n4

 u1, v1, w1    0, 0, 0
 u2 , v2 , w2   
1 1 
, , 0
2 2 
Position of atoms 
 u3 , v3 , w3    , 0, 
1 1
2 2

 u4 , v4 , w4    0,
1 1
, 
 2 2
h k h l  k l 
2 i    2 i    2 i   
2 i  0 0 0
se e 2 2
e  2 2
e  2 2

 i hk   i  h l   i  k l 
 s  1 e e e
* Reflections are allowed when all are even or all are odd. For e.g. (1 1 1), (2 2 2) ………………
* Reflections are not allowed when there is mixed combinations. For e.g. (1, 0, 2), (1, 0, 1)

(IV) Diamond Cubic:

Selection rule:  All odd, then reflections are allowed.
 All even, and  h  k  l   must be divisible by 4, those reflections will be allowed. For e.g. (2, 2, 0)
(1 1 1), (2 0 0), (2 2 0) ……………….  allowed

(V) NaCl: NaCl  follows the reflections of FCC.

(VI) KCl: Allowed reflections of KCl are 2  SC

In SC: (1 0 0), (1 1 0), (1 1 1) ………….
In KCl: (2 0 0), (2 2 0), (2 2 2) …………
(VII) HCP: {(n = 2) atoms per primitive unit cell}

29
 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

 u1, v1, w1    0, 0, 0
 u2 , v2 , w2   
1 2 1
, , 
3 3 2
 h 2k l 
2 i    
s  e e
0  3 3 2

(VIII) Base centered: (n = 2) orthorhombic structure

 u1, v1, w1    0, 0, 0
 u2 , v2 , w2   
1 1 
, , 0
2 2 
 i h k 
s  e0  e
Order of reflection: (1 0 0), (1 1 0), (1 1 1), (2 0 0), (2 1 0), (2 1 1) ……..
 decreasing d
(i) For S.C: All reflections are allowed
1 0 0 , 1 1 0  ...............
 
1st peak 2nd peak
(ii) For BCC: (h  k  l = even) are allowed
1 1 0 ,  2 0 0  ...............
 
1st peak 2nd peak
(iii) For FCC: h  k  l  all are even or odd are allowed
1 1 1 ,  2 0 0 ,  2 2 0  , 3 1 1 ,  2 2 2 
 
1st peak 2nd peak
(iv) NaCl: Same as FCC
(v) Diamond: All odd, even (h  k  l is divisible by 4) are allowed.
1 1 1 ,  2 2 0 ,  3 1 1 .......
 
1st peak 2nd peak
(vi) KCl: 2(SC)  allowed
 2 0 0 ,  2 2 0 ,  2 2 2  .......
 
1st peak 2nd peak
a
Important: d hkl  allowed reflection  
h2  k 2  l 2
a
d hkl  not allowed  
2 h2  k 2  l 2
Weigner sitze cell: Minimum volume cell also known as primitive cell or Weigner sitze cell.

30
 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

 
Bragg’s law in reciprocal lattice: If K be wave vector of incident wave (X-rays), K ' be the wave vector of diffracted X-
rays. G is the reciprocal lattice vector.
 2
Take K radius of sphere and draw the sphere. The points on which sphere cuts, bragg’s conditions satisfied


 2
K 

 2
K' 

 
K  K'
  
K G  K '
  2  2
   
K G  K '
 2  2   
K  G  2K  G  K '2
 
G 2  2K  G  0  Bragg’s law in reciprocal lattice
Brillouin zone: Brillouin zone are the boundaries where Bragg’s conditions will be satisfied in reciprocal lattice.
Weigner sitze cell in reciprocal lattice is called Brillouin zone.

(1) Brillouin zone in square lattice:


a  aiˆ

b  ajˆ

Let c  ckˆ
2 ˆ
a*  i
a
 2 ˆ
b*  j
a
Bragg condition in reciprocal lattice.
 2  
G  2K  G  0 1
  
where G  ha * kb *
31
 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

 2 ˆ 2 ˆ
Gh i k j
a a
 2
G  hiˆ  kjˆ 
a  

and K  K xiˆ  K y ˆj
So equation (1) becomes
4 2 2  2 
2 
h  k 2   2  hK x  KK y   0
a  a 

hK x  kK y  
a
h 2
 k2 


This is bragg’s condition in square lattice
h  0, k  0  both not zero at same point.

h  1, k  0 h  0, k  1
 
(i) Kx   Ky  
a a

 Kx  
 a  
1st brillouin zone
(ii) h  1, k  1
2
Kx  K y  
a
 2 
 Kx  K y   a 
 
 K  K   2 
 x y
a 
  2 Brillouin zone
nd

 K  K   2 
 x y
a 
 2 
 Kx  K y   
 a 

32
 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

(2) Brillouin zone for simple cubic:


a  aiˆ

b  ajˆ

c  akˆ
 2 ˆ
a*  i
a
 2 ˆ
b*  j
a
 2 ˆ
c*  k
a
   
G  ha * kb * lc *
 2
G  hiˆ  kjˆ  lkˆ 
a  

and K  K iˆ  K ˆj  K kˆ
x y z

Bragg’s law in reciprocal lattice is given by

 2  
G  2K  G  0
4 2 2  2 
 h  k 2  l 2   2    hK x  kK y  lK z   0
2 
a  a 


a
h 2
 k 2  l 2   hK x  kK y  lK z


 hK x  kK y  lK z  
a
h 2
 k2  l2 


Bragg’s condition for SC
h  1, k  0, l  0 
 
h  0, k  1, l  0   1 Brillouin zone
st

h  0, k  0, l  1
 
h  1, k  1, l  0 
 
h  0, k  1, l  1  Condition for 2 Brillouin zone
nd

h  1, k  0, l  1
 

33
 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

 2 
 K x  K y   a 
 
 2 
 K y  K z     2 Brillouin zone
nd

 a 
 2 
 K z  K x   a 
 

(1) Rectangular lattice  shape of B.Z is rectangular

(2) Hexagonal lattice  shape of 1st B.Z is hexagonal
(3) Cube lattice  shape of 1st B.Z is cube
(4) Square lattice  shape of 1st B.Z is square
(5) FCC lattice  shape of 1st B.Z is truncated octahedron
(6) BCC lattice  shape of 1st B.Z is rhombic dodecahedron.
 2 ˆ ˆ  2 ˆ ˆ  2 ˆ ˆ
Brillouin zone for BCC: a* 
a
 
i  j , b*  
a

j  k , c*  a
k i 
   
G  ha * kb * lc *
 2
G
a 
    
 h iˆ  ˆj  k ˆj  kˆ  l kˆ  iˆ   
 2
G iˆ  h  l   ˆj  h  k   kˆ  k  l  
a  
 2   4 2
G  G  G  2  h  l    h  k    k  l  
2 2 2

a  

k  k xiˆ  k y ˆj  k z kˆ
 2  
 G  2K  G  0
4 2  4
2 
h  l   h  k   k  l    k x  h  l   k y  h  k   k z  h  l   0
2 2 2

a  a 

  h  l    h  k    k  l    kx  h  l   k y  h  k   kz  h  l 
2 2 2

a 

For 1st B.Z: h  1, l  0, k  0

2 2
  kx  k y ,   k x  k y
a a
h  0, l  1, k  0
2 2
  kx  kz ,   k x  k z
a a
h  0, l  0, k  1
34
 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

2 2
  k y  kz ,   k y  k z
a a
 2   2   2 
So 1st B.Z of BCC is at  , 0, 0  ,  0, , 0  ,  0, 0, 
 a   a   a 
 2   2   2 
Similarly for FCC, 1st B.Z is at  , 0, 0  ,  0, , 0  ,  0, 0, 
 a   a   a 
Bonding in Solid

Primary Secondary

Ionic bonding Covalent Metallic bonding Vander Waals Hydrogen bonding

   bonding 
transfer of e

sharing of e 
sharing of e   when hydrogen atom
due to induced dipole bonded with some
(NaCl)
 H2  
e are not localised moment electromagnetic atom
Strongest
 H 2O 
(weakly directional)

e are localised Vander Waal’s forces Permanent dipole moment

Interatomic forces: There exists interatomic forces amongst the atoms of crystal that holds the atoms to form crystalline
structure.
(1) There must be an attractive forces between atoms or molecules in a solid which keeps them together.
(2) There must be a repulsive force acting between the atoms. That is why large external pressure is required to compress a
solid to any appreciable extent.
dU
F 
dr
* The attractive forces gives rise to negative potential and repulsive force gives rise to a positive potential.

U
At equilibrium point slope is zero, then F  0
r r  re

 2U
 0 minima
r 2 r  re

d 2U
 0 maxima
dr 2 r  re

35
 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

Cohesive energy: Energy of a solid is defined as the energy which will be given out in the process of the formation of a
crystal by bringing neutral atoms from infinity to the position of equilibrium separation.
The cohesive energy may also be defined as energy released when two atoms are brought close to each other at the equilibrium
distance r0 .
* Larger the energy released, more stable the bond formed and hence more stable in the crystal structure
U  U att .  U rep.
A B
U  
rm rn
dU
F 
dr
mA nB
 m1  n 1 0
r r r r0
mA nB

r0m1 r0n 1
A m
 r0mn  
B n
So potential energy at equilibrium separation r0 is given by

A B A  m
U  r0     n   m 1  
m
r0 rn r0  n
U  r0   binding energy or energy of cohesion or dissociation energy of molecule.

Binding or cohesive energy of ionic crystals:

Na Cl  Na Cl  Na Cl 


The coloumb energy of attraction between two ions separated by distance r is
e2
Ua  
4 0 r
In a crystal, each ion interacts with all its neighbouring ions of the same as well as of opposite sign. So net energy of attraction
per ion-pair may be written as
 e2
Ua  
4 0 r
  correction factor is called as Madelung constant.
B
(Repulsive potential energy between a pair of bond) is UR 
rn
U  Ua  U R
 e2 B
U   n
4 0 r r
dU
At minima: 0
dr
dU  e2  1  rB
   0
dr 4 0  r 2  r n 1

36
 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

 e2 r n 1
 B
n4 0
 e2  1 
U  1  
r  r0
4 0 r0  n 
Madelung constant: Madelung constant is the correction factor in the calculation of lattice energy of an ionic crystal when
only nearest neighbours is considered for the calculation of energy.
For 1-D chain of ionic crystals: For NaCl structure

e2
U1  
4 0 r
2e2
U1  U R  U L  
4 0 r
e2
U2 
4 0  2r 
2e2
U2 
4 0  2r 
2e2
U3  
4 0  3r 
Utotal  U1  U 2  U3  ...................
2e2 2e2 2e2
U total    
4 0 r 4 0  2r  4 0  3r 
2e2  1 1 
U total  1   ................
4 0 r  2 3 
x 2 x3
ln 1  x   x    ..............
2 3
At x 1
1 1
ln  2   1    ..............
2 3
2e2
U total   ln 2
4 0 r
e2
  2 ln 2 
4 0 r
  2ln 2  Madelung constant
 e2
U total  
4 0 r
  1.3862
37
 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

Madelung constant in 3-D: NaCl in 3-D, same structure for NaCl

e2  12 8 
U   6   ...........
4 0 r0 
 2 
3 
1.74 convergent series
e2 1.74 
U 
4 0 r0
 NaCl  1.747
Larger the value of madelung constant, more stable is the structure.
Lattice vibrations: For lattice vibrations, lattice can be considered as periodic arrangement of atoms connected through
elastic springs.

In lattice vibrations atoms are assumed to perform simple harmonic motion and vibrations of one atom are shared with all
connected atoms.
Each atoms = a harmonic oscillator
F  x '  Hooke ' s law
Lattice vibrations determine mechanical, thermal and electronic properties of solids.
 Energy of lattice vibrations in quantized and energy quanta of lattice wave (elastic wave) is phonon.
 Phonons follows Bose-einstein statistics and it is a boson.
* They are experienced force vibrations under some external forces. This force may be mechanical or electromagnetic. This
gives rise to Acoustical (mechanical) and optical properties of the solids.
In case of forced of vibrations 
(1) If we incident sound wave (longitudinal then atoms can vibrate along the direction of wave propagation, so sound wave
can have only one mode.
 Acoustical.
(2) If we incident electromagnetic wave (transverse) then atoms vibrate along the  direction of wave propagation. So EM
wave can have 2 mode of vibration.
 Optical.
(I) Vibration of 1-D Mono atomic solids:

38
 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

m  mass of each atom

md 2un
Equation of motion of nth atom: ma   C  un1  un   C  un 1  un 
dt 2
C  spring constant
un  u0eit kna 
By solving this, we get
4C ka
 sin
m 2
Frequency Relation between
of lattice  and k is
vibrations known as
or phonon dispersion relation

 2 
 : k 
 
Limiting case: (1) At low frequency and long

ka ka
sin 
2 2
ka 4C C
  ka 
2 m m
  k  linear relation.
 C
Phase velocity: VP  a
k m
d C
Group velocity: Vg  a
dk m
VP  Vg  For larger wavelength

Non-dispersive medium
* Dispersive medium: In which different waves travel with different velocities.
VP  Vg
* Non-dispersive medium: In which waves with different frequencies travel with same velocities.
VP  Vg

Case – II: Smaller wavelength limit: (for higher frequency)

39
 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

  small, k  large
4C ka
 sin
m 2
 1 4C ka
VP   sin
k k m 2
d a 4C ka
Vg   cos
dk 2 m 2
VP  Vg  dispersive medium
At what value of k, Vg  0

ka
cos 0
2
ka  
   k   Boundary of 1st B.Z
2 2 a
So at B.Z boundary, the group velocity is zero.

4C ka
max  sin
m 2
4C
max 
m
Frequency band  the allowed values of frequency for which wave propagates and beyond this frequency band  wave
will not propagate.
** Monoatomic lattice behave like low pass filter because frequency greater than max can not propagate i.e. only pass
through having frequency lower than max and stop the frequency more than max
  max  not propagate

Vibrations of one-dimensional Diatomic lattice: Two atom basis  2 atoms per unit primitive cell means 1 lattice point
contains 2 atoms.
Two atoms having masses m1 , m2
m2  m1

40
 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

Frequency of vibrations of diatomic lattice is

ka
   
2 4sin 2
1 1 1 1
2  C     C     2
 m1 m2   m1 m2  m1m2
Two values
2 , 2
* Higher frequency  corresponds to optical branch (optical phonons).

(1) Optical branch: Frequency 

2
 1 1   1 1  4 ka
  C  C    
2
 sin 2
 m1 m2   m1 m2  m1m2 2
(i) At low k, longer wavelength
ka
k  0 sin 2 0
2
 1 1   1 1 
2  C   C  
 m1 m2   m1 m2 
 1 1 
  2C    at k = 0
 m1 m2 

ka
(ii) At lower wavelength: k  high sin 2 1
2
2
 1 1   1 1  4
 C  C    
2

 m1 m2   m1 m2  m1m2
2C
2 
m1
2C
    Higher frequency behavior of optical branch depend upon lighter mass
m1
as k  high
ka  ka  
sin 2  1 or sin 2    
2  2  2
ka 

2 2

k   B-Z boundaries
a

 1 1 
  2C    at k = 0
 1
m m2 

41
 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

ka
 1
2 4sin 2
1   1 1 
(2) Acoustical branch: 2  C   C    
2
 m1 m2   m1 m2  m1m2
ka
(i) At k  0 sin 2 0
2
  0  Frequency of Acoustical branch will be zero but frequency of optical branch will not zero.
ka ka
(ii) At k low and high wavelength: sin  . So
2 2
  k  like mono-atomic
ka
(iii) At high value of k: k  high, sin 2 1
2
2
 1 1   1 1 
  C  C   
2

 m1 m2   m1 m2 
2C
    At zone boundary, frequency of acoustical branch depend upon the heaviour mass  m2  .
m2
So  of optical branch and  of acoustical branch at zone boundary are different. There is some gap between them known as
frequency gap.

2C 2C
Frequency gap  
m1 m2
Depends of masses
If m1  m2 , frequency gap = 0 (disappears)

m2
Frequency gap 
m1

42
 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

 If m1  , gap 
 If m2  , gap 
If m1  m2  gap = 0.

Allowed frequency range of propagation of wave is splitted into two parts:

(i) optical branch (ii) acoustical branches
Diatomic  two branches
Monoatomic  only acoustical branch
For optical branch  there must be 2 atom per permitive unit cell.

Optical branch: 2 atoms moves in opposite direction here centre of mass in optical branch remains fixed

Acoustical branch  move in same directions.

Important:
No. of branches in a solid: p  no. of atoms per primitive cell
Dimension Acoustical branch Optical branch Total branch
1 1 p–1 p
2 2 2p – 2 2p
3 3 3p – 3 3p

(Branch) N = Modes
Dimension Acoustical modes Optical modes Total modes
1 1N (p – 1)N pN
2 2N (2p – 2)N 2pN
3 3N (3p – 3)N 3pN
* If N is not given in question, take it one (N = 1).

Specific heat: Amount of heat required to raise the temperature of 1g of solid by 1C .
Specific heat of solid

+ve ion core motion of Free e  Ce 

+ve core
 Lattice vibration (Thermal motion)

(phonons)  CP 
Theory of lattice specific heat

(1) Classical theory (2) Quantum Theory

(Dulong-Petit Law)
(i) Einstein theory (ii) Debye theory

(1) Classical theory: Dulong Petit law:

Assumption: (i) Each vibrating atom is equivalent to a classical harmonic oscillator.
(ii) All atoms/harmonic oscillators are vibrating with same fundamental frequency and their motions are independent to each
other.
(iii) Each atom is equivalent to 3 dimensional classical harmonic oscillator.
43
 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

Let there are ‘N’ atoms per mole in solids.

1 atom = 3D harmonic oscillator
1 atom = 3 modes of vibrations
Total no. of modes for solid = 3N
1 2 P2
H kx 
2 2m
According to equipartition theorem
1
E  k BT
2
So internal energy of solid
U  3NkBT , NkB  R
U  3RT

 dU 
C p phonon
   3R
 dT V
 At constant volume
Clattice  3R  at all temperature
Failure: This theory remains valid at high temperature, but fails at low temperature.

(2) Quantum theory (Einstein theory of lattice):

Assumptions: (i) Each vibrating atom is equivalent to quantum harmonic oscillator.
(ii) All atoms/oscillators are vibrating with same fundamental frequency and their motions are still independent to each other
 1
E   n   
 2
(iii)   constant
 e  i
 i

average energy  U  i

e  i
 i

 
 
1  
So U  3N     
2  kT 
  e  1 
B

 
  
dU
Clattice 
dT


3N   
2
e k BT k
Clattice     B
k B  T    2
 kB
 e B  1
k T
 
 

44
 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh


Einstein temperature  E 
kB
E
 
2
eT
So Clattice  3R  E 
 T   E
2

 e  1
T

 
* At high temperature: T   E
E
 1
T
ex  1  x
So Clattice  3R

* At low temperature: T   E
E
E
 1, e T  1
T

   E
2

So Clattice  3R  E  e T
T 
E

Clattice  e T
at low temperature

Conclusion: Einstein theory remains valid at high temperature but fails at low temperature because experiments show that
specific heat should behave as Clattice  T in low temperature range.
3

(3) Quantum theory (Debye theory):

Assumptions: (i) Each vibrating atom is equivalent to a quantum harmonic oscillator.
(ii) All the oscillators are move dependly and propagate a large no. of frequencies from low frequency to high frequency.
(iii) K
3 D
   e x x 4 dx
 D  D , CV  3R  D  
T  e  1
2
kB 0
x

* At low temperature: T   D
3
12 T 
Clattice   3R  
5  D 
Clattice  T 3
* At high temperature: T   D
Clattice  3R
The theory is valid at low as well as at high temperature.
* For debye theory: (Acoustical phonons)

45
 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

 1  D  Clattice  T 
 
s  1, 2  D  Clattice  T 2 
3  D  C 3
 lattice  T 

[Debye’s assumptions are good for acoustical branch and Einstein’s assumptions are good for optical branch].
Debye theory is valid only for K  0 (longer wavelength) and they assume that   K

3
T 
3  D  Cp   
 D 
2
T 
2  D  Cp   
 D 
1
T 
1 D  Cp   
 D 
T
Ce   for 1D, 2D, 3D
EF

* Specific heat of a boson in low temperature range: Cboson  T

d /s

where d  dimension
 s  1 For massless boson 
 
 s  2 For massive boson 
  k s  s can be find out by this relation.
1.   k , s  1 (massless bosons) e in photon, acoustical phonon, graphene (move relativiscally)


* magnon (anti-ferromagnetism).
s  2,   k 2
For optical phonon, Magnon (ferromagnetism)

* Graphite is treated as 2-D for lattice vibrations

 Clattice For graphite  T 2  at low temperature

46
 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

d
1
Density of modes (density of states): D     s
d
1
DE  E s

For acoustical phonons (s = 1)

1  D  D     0
2  D  D    1
3  D  D     2
Internal energy of lattice vibrations (phonon energy)
 at high temperature  U  T 
 at low temperature  U  T 4 
 
Density of states and debye cut off frequency: Polarization = 1 in 1 – D
Polarization = 2 in 2 – D
Polarization = 3 in 3 – D
3 – D: Consider N no. of atoms in a lattice
4 3
 k  Volume in momentum space
No. of modes 3  3
2 
3
Polarization 

 
 L 
4 k 3 L3
N' 1
8 3
  kC   kV
 
Velocity
Velocity of phonons
of light
( Phonons are moving in a medium)
In debye theory
k
  kV

k
V
So equation (1) becomes
4 L3 3 L3 3
N'  3 3
8 3V 3 2 V
dN '
Density of states  D   
d
3L3 2
D    2 3
2 V
In 3-Dimensional, there are 3N oscillators, so
N '  3N (total oscillator)
L3D3
 3N
2 2V 3
6 N 2V 3
D3 
L3
47
 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

1
D   6n 2V 3  3
N
 n  no. density
L3
  1
 D  D   6n 2V 3  3
kB kB
V 1
D 
kB
 
6 n 2 3

k2
2 – D: No. of modes 2 
Polarization  2 
2

 
 L 
2   k 2 L2
N'
4 2
k 2 L2
N'
2
  kV

k
V
 2 L2
N'
2 V 2
dN ' 2 L2  L2
Density of states  D     
d 2 V 2  V 2
In 2-Dimensional, there are 2N oscillators, so
N '  2N
D2 L2
 2N
2 V 2
4 NV 2
D2 
L2
1
 4 NV 2  2
D   2 
 L 
1
   2V   N 2
D  D   2 
kB kB  L 
2V 1
D   n  2
kB
N N
n   no. density
L2 A
1-D: Consider N atoms in lattice

48
 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

1 2k 
No. of modes  N'
 2 
 
 L 
Lk
N'


  kV , k 
L
L
N'
V
dN '
Density of states  D   
d
L
D   
V
In 1-D, there N oscillators, so
N' N

k
L
LD
N
V
 VN
D 
L
  VN  Vn
D  D  
kB kB L kB
N
n  density
L
Free electron theory:
1. Classical (Lorentz-Drude theory) 2. Quantum (Summerfield theory)

1. Classical (Lorentz-Drude theory):

Assumption: (i) e  are assumed completely free.
 
(ii) In this theory it is assumed that, when a e free moves in solid then its P.E is zero i.e. e can move freely throughout the
crystal
P.E = 0

In this +ve ions and other free e do not apply only force on moving free e
E=0
Potential energy of insidee  is less than outside e  because inside P.E is –ve.

This is an  barrier so no e can cross this barrier
e  obey M-B statistics

In classical theory motion of e  is compared to gas molecules. So it is called free e  gas and e  will follow M-B statistics.

Features of classical free e  theory:

49
 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

(i) It explains Ohm’s law


(ii) These free e s can move freely so metals have high electrical and thermal conductivity
(iii) Ratio of thermal conductivity to electrical conductivity is constant
K
 constant  Widemann Franz law
T
K
 constant  Lorentz no.

Failure:
(i) Not explain temperature dependence of electrical resistivity.
(ii) It fails to explain electronic heat capacity and paramagnetic susceptibility of free e s
Paramagnetic susceptibility of free e  , experimentally
X  Independent of temperature T
1
By this theory X
T
(iii) It not explain positive value of Hall coefficient.
(iv) It not differentiate between semiconductor, conductors and insulators.

2. Quantum (Sommerfield theory): In this all the assumptions of Quantum e  theory are same as Classical free e  theory
 
except now e s follows the Fermi-dirac statistics (Pauli-exclusion principle)  No two e can be have same quantum state.
* Due to attraction of all +ve ion core, cannot leave the surface but free to move in solid.
 Sommerfield replace 1-D solid by 1-D potential box to determine the energy states.

The wave function is given by

2 n x
 sin
L L
And energy is given by
n2 2 2
E
2mL2
as n increases, energy increases.

At T = 0K:
Fermi energy: It is defined as energy below which all levels are filled and above which all levels are empty at 0K.
Energy of Fermi level is Fermi energy.
* If total e  s in solid are N, each can accumate 2e . So
N  2nF
nF2  2  2
EF 
2mL2
N
nF 
2
N 2 2  2
EF 
8mL2

50
 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

P2
e  are free so E 
2m
 2 K F2
EF 
2m
N  
2 2 2
 2 K F2
So 
8mL2 2m
N 2 2
N
 2
 K F2  K F 
4L 2L
P
Fermi velocity VF  F
m
Fermi temperature  EF  kBTF
EF
TF 
kB
4
2 V   p 3
In 3-D: No. of states      3
h3
degeneracy
V  volume of Cartesian co-ordinates
4 3
 p  volume of momentum space
3
Also find from this
 

 d /2 d 
V p 
  p  
d  d 
, E  Ap 
s

   !h

 2 

For fermions p  2mE
3
4
2V   2mE  2
 3
h3
d
Density of states g E 
dE
3
8 V  2m  2 3 12
g E   E
3h3 2
3
4 V  2m  2 12
g E  3
E
h

A
d
1
 g E  E s
d  3, s  2
1 1
g  E   E 2  AE 2

51
 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

1
Fermi distribution function: Probability of occupancy of states f E  E  EF

e k BT
1

T  0K
1; 0  E  EF 
f E    1
0; E  EF 
Case-I: At T  0K and E  EF
E  EF

e  e  
k BT

1
f E   0

It is 100% sure that no state above EF is filled (completely empty).
Case-II: At T  0K and E  EF
E  EF

e  e  0
k BT

1
f E  1
1 0
Probability of state to be filled is 1 i.e. state is 100% filled.
Case-III: At T  0K and E  EF
E  EF

e  e0  1
k BT

1
f E   0.5
11

Now to find density of states: E  Ap

s

d
 E s
d
d
V   2
V p 2 d
 A
No. of states   
d  d 
hd  ! hd  !
2 2
d
Density of states g  E  
dE

52
 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

d
 1 s 1  d 
d d
V    E  s  
2

g E   A s
d 
hd  !
2
d
1
g E  E s

d
1
g  E   BVE s
d
 1 s  d 
d
    
2

where B  A  s 
d 
hd  !
2
 1 
A  for massive particles, s  2 
 2m 

 A  c for massless particles , s  1 

EF

Total number of particles: N  f  E  g  E  dE

0
EF EF d

using equation 1

1
N  g  E  dE  BV  E
0 0
s
dE

d
Es
N  BV F
d
s
VBs ds
Average no. of particles N  EF
d

Internal energy or Average energy  U   Ef  E  g  E  dE
0
EF d
1
or ground energy U  VB  EE s
dE
0
d
1
Es
U  VB F
d
1
s
 s 
d
1
U V   F
BE s

sd 
Average energy per particle is given by
U  d 
  EF
N d s
 d 
U  N  EF
d s

53
 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

For fermions in 3-D: {d = 3, s = 2}

3
U  N   EF  zero point energy or ground state
5
2 1
In 2-D: U  N   EF  N   EF d  2, s  2
4 2
1
In 1-D: U  N   EF d  1, s  2
3
we know that EF  kBTF
So
d
s
N  VB TF  s
d
 s 
d
1
U V   BTF
s

sd 
d
dU
CV  , CV  T s
dT
Relation between no. density (n) and fermi energy EF :
At T = 0k
8
3 
n 2mEF 
3/2
In 3-D:
3h
3h3n
E 3/2

8  2m 
F 3/2

h2 4 2
2/3
 3n 
EF     {divided and multiply by 4 2 }
 8  2m 4 2
2/3
 3n  2 3  2
EF   
 8  2m
 
2
EF   3n 2 
2/3

2m
 2 k F2
But EF 
2m
 kF   3 2 n 
1/3

Important Ques: E  k 2 (given)  find dependency of CV with T for bosons

S=2
3
1
g E  E2
1
g E  E2

U   Eg  E  f  E  dE
0

At T  0k

54
 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

1
f E   E  EF 
e k BT
1
1 3
 2 
EE dE E 2 dE
U   E  EF 
  E  EF 
1 1
0 k BT 0 k BT
e e
E
Let x
kT
E  xTkB
dE  kBTdx
3

So U 

 kTx  2  kTdx 
0
ex 1
3
5 2
x dx
U  k 2T 2
e x
1
5
 U T2
 dU 
CV   
 dT V
3
CV  T 2

3
* Specific heat of e  : Classical  E  RT {only K.E}
2
3
Ce  R
2
kT
Quantum mechanical theory: Ce 
EF
Ce  T  For 3-D, 2-D, 1-D
Ctotal  Celectronic  C phonon

3  D Ctotal  T  T 3
2  D Ctotal  T  T 2 at low temperature

1  D Ctotal  T  T 1
Ctotal  3R  T   at high temperature

(1) At low temperature: Electronic specific heat is dominating

55
 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

Ctotal  T
(2) At ordinary temperature: C T3
C phonon is dominating
Ce  BT  is present at all temperature but dominate only at low temperature.

For insulators: Ctotal  T  C phonon .

3

Pauli Paramagnetism (For fee e  system)

Paramagnetic susceptibility of free e
K

EF
1
or 
EF
1
It is now independent of temperature T but classically  .
T
 Quantum free e  theory successfully defines the temperature dependence of electrical resistivity, electronic specific

heat and paramagnetic susceptibility of free e s .
 But it is failed to explain the +ve value of Hall’s coefficient for same metals and distinction between metal and
insulators, semiconductors.
Drude’s conductivity (classical theory): If we have a solid and connect it with battery than free e  start moving. Due to this
electric field, e  will drift and e  do motion by +ve ion core

F dv F eE
a ,  
m dt m m

 dv  eE
 dt   dt
0 dt 0 m
e
  relaxation time
m
eE
vd 
m

drift velocity
Relaxation time: Average time between two successive collisions.
I
I  nevd A, current density J 
A
J  nevd

56
 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

eE
J  ne 
m
ne E
2
J
m
or J   E  Ohm ' s law
ne2
where 
m

electrical conductivity of metal
 
If we apply a ac voltage, then conductivity is not constant
ne2
   frequency of applied voltage
m 1  i 
Mean free path
   v  velocity  time


v
Temperature dependency of electrical resistivity: In a lattice there are 2 types of scattering
(1) e  e scattering e  phonon scattering
(2)
  
Case-I: At low temperature: Both e  e , e  phonon scattering are responsible for temperature dependence of
conductivity.
At low temperature, e  e scattering will dominate but since there are some phonons present there will be both e  e
and e  phonon scattering.
1
Due to e  phonon,   3
,  T3
T
1
Due to e  e ,   ,  T2
T2
1
Total  5
,  T5
T

Case-II: At high temperature: e  phonon will dominate because no. of phonons increases as temperature increases
1
  ,  T
T
Total resistivity
 
i  
T
due to temperature
impurity dependance
resistivity

i  independent of T but depend on impurity concentration and defects.

* If impurities in metal , i 

57
 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

* If impurities in metal , i 
* T is independent on impurity, depend on temperature T

Question:

which one is more pure among A and B?

 B is more pure than A because its impurity factor is less in graph.
* Important points:
 Conductivity of metal  with  temperature
 Conductivity of semi conductors  with  temperature.
Thermal conductivity: Thermal conductivity is a process in which heat is transformed from one part of the body to the
another as a result of temperature gradient
KT  Ke  K phonon
For metals: KT  Ke  no. of e  are more in case of metal}
1
K  C v
3
 mean free path
C  specific heat per unit volume
v  average velocity
1
So Ke  C v F
3
ve  v F  is independent of temperature
1
K e  Ce e v F
3

Case-I: At very low temperature: T   D

58
 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

Ce  T
1
 Ke  T , K e  Ce v F e
3
 e  Independent of temperature

Case-II: At low temperature: T  D

Ce  T
 Ke  T 2
 e  T 3

Case-III: At high temperature: T   D

Ce  T
 Ke  Independent of temperature
 e  T 1

Thermal conductivity of insulators: KT  K p Ke  0

1
KT   p C p v p
3
* Velocity of phonon is equal to velocity of sound. It does not depend upon temperature v p  vs 
  same for e  and phonons.

Case-I: At low temperature: T   D

1
C p  T 3 , K p  v pC p  p
3
v p  independent upon T
e  independent of T

Kp  T3

Case-II: T   D
C p  3R  independent of T
v p  independent of upon T
1
e 
T
1
 Kp 
T

Band theory of solids: Free e  theory was failed for some reasons
59
 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

(i) Like not able to classify insulators, semiconductors and metals.

(ii) RH  ve (Hall’s coefficients)
These failures were arised mainly due to over simplified assumptions that electrons moving in zero potential (v = 0) of +ve
ions. In real solids, motion of electrons is not completely free due to non-zero potential of ion core (lattice potential) i.e.
v  0 ion core (lattice potential). The form of lattice potential is complicated but for reasonable approximation it can be
assumed potential (periodic) with the period equal to lattice constant
1 e2
P.E  
4 0 r
If r  0, U  

Bloch theorem: According to this theorem, potential inside the solid is periodically varying with period equal to lattice
constant
U  x  U  x  a
Hence solution of electron wave is not   eikx . This is the solution of plane wave i.e. solution of e  wave is not plane wave.

If e is completely free then its solution will be plane wave. But if e  is not completely free, then solution of e  wave is
given by
  x   eikxU k  x 
U k  x   Bloch function
So Uk  x  a   Uk  x 

Function repeats itself after a period of time
Hence   x  a   U k  x  a  eikx  eika
  x  a     x  eika
Kronig Penny modal: Kronig Penny simplified this as now potential barrier is not infinite and potential inside the well = 0.
There is a finite probability that e  can penetrate the barrier. Kronig-Penny solve this rectangular potential to solve the wave
function of e  wave.

V  x  V  x  a  b Periodicity  a  b
2 d 2
  V  x   x   E  x 
2m dx 2

60
 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

d 2 2m
or 
dx 2 2
 E  V  x    x   0
In region II: V 0 0 xa
d 2 2m
 E  x   0
dx 2  2

2
d 2
  2  x   0
dx 2
2mE
where 2  2

In region I: E  V0 b  x  0
d 2 2m
  E  V0   x   0
dx 2 2
d 2 2m
 V0  E   x   0
dx 2 2
2m
where  2  2 V0  E 

d 2
 2
  2  x   0
dx
Now   x   U k eikx
P sin  a
Result :  cos  a  cos ka (1)
a
mV0 ab
P
2

 sin  a 
Case-I: P  cos  a  cos ka
 a 
||
0
As V0  , P  
sin  a  0
 a  n

61
 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

or  2 a2  n2 2
2mE 2
a  n2 2
2
n 2 2 2
E
2ma 2
when V0   , the energy band changes to discrete energy levels.

Case-II: When V0  0, P  0
So using equation (1)
cos  a  cos ka
  a  ka
 k
or 2  k2
2mE
 k2
 2

2 k 2
 E
2m

Energy of the free particle
As

as V  0 , the energy levels changes to continuous energy levels.

2 k 2
For free e ' s : E 
2m
E  k2

Parabola
E-k diagram:

62
 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

Band theory (weak potential) V0 

* k  0 (centre of Brillouin zone)  bottom of band


*k  (Brillouin zone boundary)  top of the band.
a
d 1 d   
Group velocity: Vg  
dk  dk
 E  
1 dE
So Vg 
 dk

Effective mass: Effective mass of e  is different from its free e  . In the solids, motion of e  is not completely free rather
e  moves under the influence of lattice potential. Lattice potential may vary from one solid to other solid. Thus to count the

effect of lattice potential in band theory, free e mass is replaced by effective mass. The concept of effective mass remains
 
valid only inside the solid or effective mass of e is the mass of e , when it is experiencing some force within the structure.
2 k 2 2
E m*  2
2m d E
dE  2k 2
dk 2

dk 2m 
Effective mass
d E 
2 2

dk 2 m

63
 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

1
m* 
slope of Vg Vs k 
* Effective mass of e  is negative, if due to its behavior as a hole.
Total no. of wave functions in a band: Total no. of possible states in any energy band is equal to no. of primitive unit cells N
e  s in a band because each state can accumulate 2e 
in the crystal. Hence there are 2N total no. of
 N  states 
 
 2 N  electrons 
Distinction between metals, insulators and semiconductors:
Insulator: A crystal can be insulator only if no. of valence e  s in the primitive unit cell of crystal is even integer
Eg  7eV or more
 If A crystal has even no. of valence e  in the primitive unit cell, it is necessary to consider whether top most filled level
and empty level are overlapped or not.
If bands are not overlapped and no. of valence e  s are even in the primitive unit cell then it is insulator.

Semi-metal or metal: For even e s if energy levels overlap, then it behaves as metal.
(the insulators which turns into metals by overlapping are called semi-metals and are bad conductors).

Metals: If no. of e  are odd per primitive cell, it will necessarily a metal.
Semi-conductors: If Eg  2eV , then it is a semi-conductor.

Si  Eg  1.1eV
Ge  Eg  0.7eV
At T = 0K, it is an insulator and T = room temperature, it is a metal

64
 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

* No. of electrons in primitive cell = no. of atoms in primitive cell  valency of each atom.
For example:
(1) Cu (copper)
p = 1, Valency = 1

N = no. of e in primitive cell
 p  valency
N  11
N = 1(odd)  Half filled (metal)
(2) Be  hcp
p = 2, valency = 2
N  2  2  4  even no.  fully filled

Diamond: Valency of C is 4 and 2-atoms/primitive cell

N  4 2
N  8  diamond is an insulator
* If valency is even and the band is overlapped, then it will be a semi-metal.
There is 1 atom per primitive unit cell in BCC structure and valency of atom is 1, find the nature of solid?
Valency = 1
Atoms/unit primitive cell = 1
(BCC)
N  1 odd 

metal

Tightly binding theory: When e  is tightly bind to nucleus, then this model is applicable.
 
For example: Valence e of Cu = free e model

Valence e of diamond = tightly bound model
 
Because of e s of Cu are totally free and e s of diamond are tightely bound.

Tightly bind energy expression expression: E  k       eik r n
n

where  ,  are constants


r n  position vector of nth atom in the lattice

k  wave – vector
** This expression is taken only in nearest neighbor.
65
 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

(1) Tightly binding energy of simple cubic solid: We have 6 nearest neighbours and these positions are
 a, 0, 0 ,  0,  a, 0 ,  0, 0,  a 

k  k xiˆ  k y ˆj  k z kˆ

r  xiˆ  yjˆ  zkˆ

E  k      eikx a  eikx a  e  eikz a  eikz a 

ik y a
e
ik y a

 eikx a  eikx a eik y a  eik y a eikz a  eikz a 

E  k     2    
 2 2 2 
 E  k     2 cos k x a  cos k y a  cos k z a 
If ka  1
 ka 
2

cos ka  1   ..............
2!

    kya  
 kz a  
2 2 2
 k a
So E  k     2 1  x 
 ........   1  
 ........  1   ........  
 2!   2!   2! 
     
 a2 
 E  k     2 3   k x2  k y2  k z2  
 2 
 a2k 2 
E  k     2  3 
 a 
where k 2  k x2  k y2  k z2
2
m* 
d 2E
dk 2
dE
 2 a 2 k
dk
d 2E
 2 a 2
dk 2
2
m* 
2 a 2

(i) Centre of Brillouin zone (bottom of the band):  k , k , k    0, 0, 0 .

x y z

66
 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

(ii) 1st B.Z boundary (top of the band):  k , k , k    a , a , a 

x y z

Band width of lowest band (1st B.Z): E  Etop  Ebottom

E     6      6 
E  12
* If position of top band is not mentioned then let is at corner (1st B.Z boundary)
 
 If band width is given i.e. along (1 0 0) direction, then top   , 0, 0 
a 
e B
Frequency of cyclotron  C 
m*
3
a  2r .
(2) T.B energy expression for BCC: Nearest neighbor atom = 8 at
2
a a a a a a  a a a  a a a a a a
Atomic positions:  , , ,  ,  , ,   ,  , ,   ,  , ,  , ,  ,
2 2 2 2 2 2  2 2 2  2 2 2 2 2 2
a a a  a a a  a a a
 ,  ,  ,   ,  ,  ,   , ,  
2 2 2  2 2 2  2 2 2

E  k      eik r n
 k a  kya   kz a 
E  k     8 cos  x   cos    cos  
  2   2   2 
 2   2   2 
Top (boundary of 1st B.Z)   , 0, 0  ,  0, , 0  ,  0, 0, 
 a   a   a 
Bottom (centre of B.Z) = (0, 0, 0)
Band width  E  16 .

a
(3) T.B energy expression for fcc: No. of nearest atom = 12 at 2r  .
2
a a  a a  a a  a a  a a  a a
Atomic positions:  , , 0  ,  , 0,  ,  0, ,  ,   , , 0  ,  ,  , 0  ,  , 0,   ,
2 2  2 2  2 2  2 2  2 2  2 2
 a a  a a   a a  a a  a a  a a
  , 0,  ,   ,  , 0  ,   , 0,   ,  0,  ,   ,  0, ,   ,  0,  , 
 2 2  2 2   2 2  2 2  2 2  2 2
 k a k a k a k a k a  k a 
 E  k     4 cos  x  cos  y   cos  y  cos  z   cos  z  cos  x  
  2   2   2   2   2   2 
 2   2   2 
Top (boundary of 1st B.Z)  , 0, 0  ,  0, , 0  ,  0, 0, 
 a   a   a 
Bottom (centre of B.Z) = (0, 0, 0)
Band width  E  24 .

Generalization: Band width E  2Z 

where Z = no. of nearest neighbor atoms
For SCC: Z 6
 E  12
67
 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

For BCC: Z 8
 E  16
For FCC: Z  12
 E  24
n
 L  dk
Density of state: D  E   2  
 2  dE

due to spin degeneracy
n = 1, for 1 – D
n = 2, for 2 – D
n = 3, for 3 – D

k  k x2  k y2  k z2
For 3 – D n=3
3
 L  dk
D E  2 
 2  dE

 m*xx m*xy m*xz 

 
Effective mass tensor:
*
meff   m*yx m*yy m*yz 
 m*zx m*zy m*zz 

2 2
where m*xx  , m*
xy 
d 2E d 2E
dk x2 k x k y
2 2
m*yx  , m*
yy 
d 2E d 2E
k y k x dk y2
2 2
m*yz  , m*
zx 
d 2E d 2E
k y k z k z k x
2 2
m*zy  , m*
zz 
d 2E d 2E
k z k y dk z2

*
*
mtop  mbottom
*


 
 Find 
*
 mbottom 
Semiconductors: Semiconductors are those materials whose conductivity lies between metals and insulators. These are
important because their conductivity can be controlled through the introduction of impurity.
The introduction of impurity in a controlled manner is known as doping.
Low doping – low conductivity
High doping – high conductivity.
E.g: Ge, Si, GaAs etc.

Classification of semi-conductors:
(1) Intrinsic (pure) semi-conductors (2) Extrinsic (doped) semi-conductors

68
 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

(1) Intrinsic semiconductors: E.g.: Ge, Si

Crystal structure of Ge and Si = diamond cubic
E.g.: diamond > Ge > Si
* Band gap measures the lattice potential
* More the band gap, more the lattice potential.
 Every semiconductor at 0K behaves as an insulator

 On raising the temperature above 0K, some of the bands of e  will break

 In semi-conductor holes are free in valence band and e  s are free in conduction band.
In intrinsic semiconductors

n = concentration of e = no. of free e  /volume
p = concentration of holes
ni  pi  intrinsic carrier concentration

at T  0K , ni  pi  0
as T , ni and pi 
 EC  EF 

n  NC e k BT


density of C.B edge
(means no. of
states in a range)
Concentration of holes
 EF  EV 

p  NV e k BT

3/2
 2 me*k BT 
where NC  2  
 h2 
3/2
 2 mh* k BT 
NV  2  
 h2 
69
 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

* Law of mass action  ni pi  np

Intrinsic carrier concentration  ni  n  p
2

 EC  EF   EF  EV 
 
n  NC NV e
2
i
k BT
e k BT

 EC  EV 

n  NC NV e
2
i
k BT

EC  EV  Eg (energy band gap)

Eg

n  NC NV e
2
i
k BT

Eg

ni  NC NV e 2 k BT

3/2 3/2
 2 me*k BT   2 mh* k BT 
NC NV  2   2 
 h2   h2 

 2 kBT 
3/2

NC NV  4 
 h 
2  m m  *
e
* 3/2
h

 2 kBT 
3/2

NC NV  2 
 h 
2  m m  *
e
* 3/4
h

Eg
 2 kBT 
3/2

 ni  2 
 h 
2  m m 
*
e
* 3/4
h e 2 k BT
1
In general mh  me  Lattice potential will act more on holes of
* *
VB then that of e s of CB
T , ni increase exponentially  in intrinsic semiconductors 
 
T , n  independent of temperature  in metals 
T , conductivity of metal decreases 
 

From equation (1)

Eg

ni  AT e3/2 2 k BT

3 E
ln ni  ln A  ln T  g
2 2k BT

if T is inside log value then it
has very small constant value
E
ln ni  
2kBT

70
 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

The equation is of the form y  mc


slope

Eg
slope  
2k BT
Eg
 ln ni  constant 
2kBT
* Eg  slope  2kB

 more slope  more Eg (band gap)

** Relation between effective mass and Fermi energy levels: In intrinsic semiconductors
n p
 EC  EF   EF  EV 
 
NC e k BT
 NV e k BT

 EC  EF  EF  EV 
 NV
e k BT

NC
 EC  EV  2 EF 
 NV
 e k BT

NC
 EC  EV  2 EF 
 N 
ln e k BT
 ln  V 
 NC 
2 EF EC  EV N 
  ln  V 
kBT k BT  NC 
EC  EV kBT  NV 
 EF   ln  
2 2  NC 
3/2
E  EV k BT  mh* 
EF  C  ln  * 
2 2  me 
EC  EV kBT  3   mh* 
 EF     ln  
2 2  2   me* 
* at T = 0k
EC  EV
EF 
2

71
 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

* At room temperature, Fermi level  EF  is at middle of band gap in intrinsic semiconductor. Fermi level does not depend
* * * *
upon me and mh but at Fermi temperature it depend on me and mh . If temperature  , then Fermi level is slightly moves
in upward direction but this movement is negligible. It can be neglected at room temperature.

 E  EC  kBT  N d 
N-type SC: EF   d  ln  
 2  2  NC 
Ed  donor level energy
N d  donor concentration

As temperature  , intrinsic carrier concentration ni increases exponentially.

As ni  , Fermi level moves in down-word directions.

Ea  EV kBT  N a 
P-type semiconductor: EF   ln  
2 2  NV 
Electrical conductivity:   ene e  epe h

  e  ne  p p  1
Minimum value of conductivity in semiconductors 
ni2  np
ni2
p
n
 ni2 
  e  n e  h 
 n 
d
For minimum value 0
dn
 ni2 
 e  e  2  h   0
 n 
ni2
 e  h
n2
h
n 2  ni2
e

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 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

h
 n  ni
e
ni2
Similarly n
p
  e  ne  ph 
 ni2 
  e e  p  h 
 p 
d  n2 
 e   i2 e  h   0
dp  p 
ni2 e
 h
p2
e
ni  p
h
e
 p  ni
h
So equation (1) becomes
   
  e  ni h e  ni e h 
 e h 


  e ni h e  ni h e 
  2eni h e
e e e
where h  *
, h  *h
me mn
e   h
Temperature variation of mobility:

As T   lattice vibrations  , scattering of e  with phonons ,   .

* Scattering of e  with Si  lattice scattering

* Scattering of e with impurity  impurity scattering
e

m
    relaxation time 
As T ,  ,  
Now from equation (1)
73
 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

Eg

  ce 2 k BT

On temperature ,  (electrical conductivity increases exponentially)

Hall effect in semiconductors: Consider a semiconducting slab which is having length L, width W and thickness t (smallest


current is carried by both holes e s ). When a n-type semiconductor is placed in a magnetic field B (along z-direction) and
a current density (along x-direction) passed through it. The current flow consists almost entirely of electrons moving from
right to left just opposite to the convectional flow of current. If v is the velocity of electrons at right angle to the magnetic field

there is downward force on each e of magnitude BeV. This cause the electron to the defected in a downward direction and
causes a negative charge to accumulate on the bottom face of the slab. A potential difference is therefore established from top
to bottom of the specimen with bottom face negative. This potential difference causes a field EH in the negative of y-
direction and so there is a force of eEH acting in the upward direction on the electron. Equilibrium occurs when
Fe  FB  eE  e  v  B    90
eEH  eBv
EH  Bv (1)

If J x is current density in the x-direction,

J x  nev
Jx
v
ne
So equation (1) becomes
BJ x
EH 
ne

74
 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

EH 1
  RH  hall coefficient
BJ x ne
1
RH  
ne
{-ve sign used because E is developed in negative y-direction)
In p-type semi-conductor
1
RH 
pe
In intrinsic semiconductors, hall effect is observed because e   h (mobility of e  is higher tan mobility of holes) and
me*  mH* .

Hall coefficient: RH 
 p 2
h  ne2 
e  p  h  n e 
2

n  e concentration
p  hole concentration
 Sign of Hall coefficient gives information about majority charge carriers usually when majority charge carriers are
e ' s, RH is negative if holes then RH is +ve.
Limiting case:
(1) Intrinsic semiconductor: n  p  ni
ni  h2  e2 
RH 
eni2  h  e 
2

ni  h  e  h  e 
RH 
eni2  h  e 
2

 h  e
 RH 
eni  h  e 
In general e   n
RH  ve  small  ve 

(2) n-type semiconductors: VH  n  type   VH  intrinsic 

e  are majority, lower at surface has more –ve charge. Hence more hall voltage will be observed.
Hall effect will be strongly observed in n-type.
 Higher is majority carrier concentration, stronger would be hall effect
ne2 1
RH    n  p
e  n e 
2
ne

RH  n  type   RH  intrinsic 
More hall effect, lesser RH .
 By measuring hall effect, it can be measured that how much doping is done.
(3) p-type semiconductors: p  n

75
 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

1
RH  
pe
RH  0 is pH2  ne2
* In a very lightly doped p-type semi-conductors RH  0 .
(4) Metals: At lower surface =-ve charge accumulated
At upper surface = +ve charge accumulated
e  concentration in metals  nmetal
e  concentration in n-type  nntype
1
nmetal  nntype , RH    metals
ne
Hall effect should be stronger in metals.
* Order of hall effect: Metals > doped semiconductors > intrinsic
 Lesser the value of RH , more the hall effect
* n  atomic density valency

EH 1
 n-type: RH  
J x Bz ne
Ix Ix
Jx  
A t
EH  t 1

I x Bz ne
V V
EH   H
distance W
VH t 1
So 
I x   Bz ne
I x Bz
VH  
net
I
J
A
Iy  Jy  A
I y  J y   t 
I y   Ey t 
I y   E yt
V V
or Iy   t Ey 
 
  p  peh ,  n  nee

I x Bz
 p-type: VH  .
pet
Applications of hall effect:
(1) To find majority carrier concentration.
76
 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

(2) To find type of semiconductor

(3) To find magnetic field (B)
(4) To find mobility of majority carriers.

Direct band gap Indirect band gap

* Top of valence band and bottom of conduction band lies at * For indirect band gap top of V.B and bottom of C.B lie at
same value of K then e can make a transition from EV to different values of K. Hence when e  jumps from EV to


EC without involvement of phonon. EC momentum conservation takes place with the help of
phonon because momentum of incident photon is not enough
to make transition.
* It means momentum is not transferred to lattice (phonons).
* If e  jumps back from EC to EV entire energy is * If e  jumps back from EC to EV , energy is not only
librated in the form of photon only then these type of semi- emitted in the form of photon but some of the energies also
conductors are used in upto electronics e.g. GaAs, CdS. carried by phonon. Hence these semiconductors are not
suitable for opto-electronic devices e.g. Si, Ge.
Dielectric properties of solids: Dielectric are perfect insulator width the additional properties of polarization and a charge is
induced when placed in an electric field.
Dielectric
Polar Non-Polar
(whose molecules have permanent electric dipole moment) (which do not have permanent electric dipole moment) e.g.
e.g. H 2O, NaCl , KCl , KBr (depend upon temperature) solid CO2 (independent of temperature
Classius Mossotti Relation: If we apply external electric field on non-polar dielectric then it will be polarized and this
polarization is called induced polarization
 
pin  E
 
pin   E 1
  polarisability of atoms/molecule
Polarization = dipole moment per unit volume
 
p 0 e E mac  2
For Non-polar molecule: If we have a large parallel plate capacitor and we filled a non-polar dielectric between the plates.
Suppose external applied field is E0 . Due to this E0 , non-polar dielectric will be polarized then plates acquire some bound
charge and electric field develop is E1 which is less than E0 .

77
 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

 
Emac  Eresultant E field  E 0  E1
Local electric field is microscopic field acting on individual dipoles.
Macroscopic field  at the level of solid
Microscopic field  at the level of (local field) dipole (single dipole)
Elocal  E0  E1  E2  E3  due to atoms inside cavity
 
Next field Lorentz
acting on field due
atom to cavity

E0  E1  macroscopic field  Emac

E3  0 (net electric field of +ve and –ve charges cancel out due to symmetry)
 p 1 
E2   factor for spherical cavity 
3 0  3 
P
So Elocal  Emac   3
3 0
pin  Eloc  for one atom
pin   Eloc  for one atom

atomic polarizability

Polarization  P  Npin
P  N  Eloc
 P 
P  N  Emac  
 3 0 
N P
P  N Emac
3 0
 N 
P 1    N Emac
 3 0 
N Emac
P
N
 4
1
3 0
but D  0E  P
E m   0 E  P
E r 0   0 E  P
E 0  r  1  P
  r  1  e
and P   0 e Elocal
P   0  r  1 Elocal  5
e  tells us the degree of polarization of a material in response to applied electric field
r  dielectric constant
Comparing equation (4) and (5),

78
 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

N Elocal
 0   r  1 Elocal 
N
1
3 0
 N  N
 r  1 1  
 3 0   0
 N  N
 r  1   r  1  
 3 0   0
 N  N
 r  1   r  1  
 3 0   0
N   r  1 
 r  1  1
 0  3 


 r 1 N

3   r 1 0
3
 r  1 N
 Classius-Mossotic
 r  2 3 0
equation

Valid for non-polar This gives relation between
molecules microscopic and macroscopic
quantities

  microscopic quantity
 r  macroscopic quantity.
Types of polarization:
(1) Electronic polarizability
   e  i   D
  
electronic ionic dipolar

(i) e (in non-polar molecules): Electronic polarizability arises due to displacement of electron cloud of an atom relative to
its nucleus in the presence of applied electric field.
The electronic polarisability is given by
e  4 0 R2 , R  radius of atom

* This polarizability is independent of temperature but depends upon the frequency of applied electric field.
(2) Ionic polarizability: This type of polarizability arises due to change in separation in ions on the application of electric
field.

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Distance between them changes on continuous change of electric field which cause vibration in them. This polarizability
depends on frequency of applied field but remains independent of temperature.
e
i 
10
(3) Dipolar polarizability: This type of polarizability arises due to the permanent dipole moment of the molecule. This is
arises due to rotational motion of molecules in the presence of electric (external) field.

p 2p
d 
3k BT
p p  permanent dipole moment of the molecule.
*  d  depend upon both temperature and frequency of the field.
p 2p
 total   e   i  
3kBT
p 2p
 total   0 
3k BT

This is Langevin-debye equation. This is valid only for polar molecules.
 e , i  arises in non-polar molecules
d  arises in polar molecules.

Frequency response of polarizability: Mass of electrons is less than ions and dipolar, so it response to the external frequency
quickly. So its relaxation time is less. Due to larger mass of dipolar molecule so its relaxation time is more so
{   relaxation time}
d  i  e lesser the  , faster the response
1
f 

f e  fi  f d
In visible region, total polarization is electronic polarization    e  .

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mass of  e  i   d

{ e can easily match the frequency because its mass is less}
fe  fi  fd
    
e i d

 r  1 N
 
 r  2 3 0
In optical region or visible region
  e
 r  n2 , n  refractive index

n 2  1 N e
  Lorentz – Lorentz Relation
n 2  2 3 0

p 2p
*  total   0 
2k BT

More slope  more polar

More intercept  more electronic or ionic polarizability.

Magnetism: Magnetism in solids arise from magnetic moment of individual atoms.


Diamagnetism: Diamagnetism is universal effect and it is present in every metal. The e revolving in the orbital will produce
a current in opposite direction to its motion and the magnetic moment produce by the current will oppose/cancel out the
externally applied magnetic field   IA

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Diamagnetism is a very weak effect (paired electrons).

Diamagnetic susceptibility   dia  is –ve and independent of temperature
m  susceptibility tells us the degree of magnetization of a material in response to an applied magnetic field
 m  ve and independent of T

dia  0 and  1  dia  0

 m  r  1  r  1   m
r  relative permability (is the measure of resistance of a material against the formation of a magnetic field).

M
Magnetism:  dia 
H
M  dia H  ve
 M  ve

Example: Cu, Au, Si etc.

Diamagnetic susceptibility of a solid according to Quantum Mechanics is given by
0 NZ
 dia   e2 r 2
6me
N  no. of atoms per unit volume
Z  atomic number
me  mass of e 
r 2  average value of r 2 over the particular orbit.

1. Paramagnetic materials: Paramagnetism in solids arises mainly due to unpaired e  spins in atoms.

Paramagnetic occur in those solids which have permanent magnetic moment due to spins of unpaired e s on the application
of magnetic field. These magnetic moment aligned in the direction of applied magnetic field. Hence effect is attractive type.
This is strong effect as compare to diamagnetic effect.
O2  exception  paramagnetism.
(i) Curie paramagnetism: It is followed by atoms or ions

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C
 curie 
T
C  curie constant
curie  ve

(ii) Pauli paramagnetism: Pauli paramagnetism is followed by free or conduction e s

 Pauli  ve and independent of T

1
Important: {The paramagnetic susceptibility depends on Fermi energy as 
F 

In Curie’s paramagnetism:
M
 Para   ve 
H 
H  0, M  0

 H  strong

After removing H, it will return to ‘0’ through same path.
 Para  0, M  0
r  1
Ms  N ,
N = atomic density,  magnetic moment of each atom.
Example: Li, Mg, Mo etc.

 B
Magnetisation: M  N  B tanh  B 
 k BT 
B B  kBT
(i) At high temperature

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B B B B
tanh 
kBT k BT
 B
M  N B  B 
 k BT 
N  B2 B
M
k BT
But B  0 H
M 0 N  B2
 
H k BT
1

T
(ii) At low temperature or strong magnetic field
B B  kBT
B B
tan 1
k BT
So M s  N B  this is called saturation magnetization when all spins are aligned in the direction of applied magnetic
field.
M s N B
S  
H H
 is independent of temperature when temperature is low or B is strong.

(2) Ferromagnetic materials:


(i) Like paramagnetism, ferromagnetism is also associated with unpaired e s spins in the atoms.
(ii) Ferromagnetic solids contains permanent magnetic moment in their atoms.
(iii) Unlike paramagnetism, ferromagnetism exhibits spontaneous magnetization (magnetization remains present in the
absence of applied magnetic field is known as spontaneous magnetization). This spontaneous magnetization arises from strong
interaction between adjacent spin magnetic moment of ferromagnetic materials

The region in which magnetization is saturated is known as domain.

* Domain formation is key reason behind spontaneous magnetization.
(3) In absence of magnetic field, magnetization is zero
H 0M 0

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 On the application of applied magnetic field or external magnetic filled, magnetization first increases due to domain wall
expansion.
On the application of strong magnetic field domains start flipping their direction along external magnetic field. This saturates
the magnetization.
M
* Ferromagnetic material is non linear 
H
* Diamagnetic and paramagnetic materials are linear M  H
 If magnetic field is removed, then magnetisation remain non-zero
at H = 0
B = spontaneous or remanent magnetisation.
 If magnetic field is increased in reverse direction, then magnetisation drops to zero. Hence the magnetic field required to
destroy remanent magnetization is coercivity.
coercivity  HC  at C point
 If magnetic field (H) is increased further in reverse direction, the curve again saturates and a process repeats.
The curve ABCDEFA is known as hysteresis curve
 * On the basis of hysteresis curve, we can differentiate soft and hard magnetic materials.
 If H C is small, then soft materials.
 If H C is large, then we require large amount of magnetic field to magnetise and demagnetize the material.
H C large  hard materials
Soft  less coercivity
Hard  large coercivity

Total magnetic field inside the ferromagnetic material can be expressed as

  
Btotal  Bext  Bexchange

Bexchange  Weiss field or exchange field
 
Bexchange   M
  Weiss constant, M  spontaneous magnetisation

In paramagnetic Bexch  0
Every ferromagnetic material has two states:
(i) Ferromagnetic state for T  TC
(ii) Paramagnetic state for T  TC
TC  curie temperature
 fer  0 (large positive),

r  1
M  0
C
For T  TC ,    curie weiss law
T  TC
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For T  TC ,   complex
Curie weiss law is valid in paramagnetic region of ferromagnetic state
TC  C ;   Weiss’s constant

T  TC ,   
At T  TC , discontinuous
Any ferromagnetic material converts into paramagnetic matrial at T  TC

1 T
 

 C
1 T TC
 
 C C
at T 0
1 T
 C
 C
Temperature depends of spontaneous magnetisation:

At T  TC  , M s  0
Material become paramagnetic.
(4) Anti-Ferromagnetism: This is arises when adajcent-spin magnetic moments are anti-parallely coupled
Ms  0 

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complex; T  TN  anti  ferromagnetic


 anti  f   C
 T  T ; T  TN  paramagnetic state
 N

TN  Neel temperature

TN  C
  mean field constant
 has two components   and 
(i) B is applied  to spin

 B  x (independent of temperature)
(ii) B is applied  to spin
  B  x (linearly with temperature)

(5) Ferri-magnetism: These are same as anti-ferromagnetic materials except now magnetic moment of a site is not equal to
magnetic moment of B site.
        (spontaneous magnetisation  0 )
{due to unequal strength of dipoles}
Magnons: It is energy quanta of spin wave or energy quanta of critical magnetic fluctuations.
* Magnon is a boson.
It follows   k 2 dispersion relation in ferromagnetic field.
It follows   k in anti-ferromagnetic solid.

At low temperature: Cmagnon  T 3/2  FM

Cmagnon  T 3  AFM
 For Fe  e , phonon, magnon
Ctotal  AT  BT 3  CT 3/2
  
Ce C phonon Cmagnon
T  TC  ve (small)
  T  TC   M
1

T  TC  ve (small)
  TC  T   M
1/2

Superconductivity: When certain material below a certain temperature, their electrical resistivity drops to zero. These
material are known as superconductors. This phenomenon is known as superconductivity.

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TC  critical temperature of superconductor.

Critical temperature  the temperature at which resistivity drops to zero.

Ideal conductor:  0

Superconductor has two properties:

(1) Zero electrical resistivity (2) Perfect diamagnetism
Perfect diamagnetism or Meissner effect: When called superconductors is placed in an external magnetic field, it expels
magnetic flux from its interior and acts as a perfect diamagnetic material

  

Bin  0 H  M  0 
M  H
M
  1
H
r  1   m
r  1  1  0
r  0
So   0,   1 but for diamagnetic material 1  e  0 .

superconductor

2. Critical Magnetic field  H C  : It is minimum amount of magnetic field required to destroy superconductivity below TC .
(After crossing this minimum amount of magnetic field lines will start penetrating the material).

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  T 2 
H C T   H C  0  1    
  TC  
at T  0, H C T   H C  0 

at T  TC , H C T   0

 T  TC 
   superconductor
H  HC 
 T  TC 
   normal conductor
H  HC 

3. Critical current density  J C  : It is maximum amount of current density that can pass through superconductor with
destroying superconductivity

 T  TC 
 
 H  H C   S .C
JJ 
 C 

Types of superconductors: (1) Type – I (2) Type – II

(1) Type – I: Superconductors follow meissner effect strictly means transition from superconductivity state to normal state is
sharp at H  HC

Type – I  are soft { H C is small}

e.g.  Hg, Pb, Sn, ……. etc.

(2) Type – II: Superconductor do not follow meissner effect strictly means transition from super-conductivity state to normal
state is not sharp

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 H  H C  superconducting state

 H C1  H  H C2  vortex state

 H  H C2  N .C
Type – II  hard { H C is large}
For practical applications type – II superconductor usually works in mixed state. In this state resistivity is very small. Hence it
can offer large amount of current.
Example: Liquid He (at 4K), N2 , YBa2Cu3O7
London theory of superconductivity: This theory assumed that superconductors has two types of electrons.
n  nn  ns
nn  normal e  concentration
ns  super e  concentration
* Normal e  follow J   E (ohm’s law) but super e  are not follow (ohm’s law)
as T , ns , nn 
At T = 0K
n  ns
Equation of motion for superconductors e s

F  qE  eE
dv
F  ma  m
dt
 dv  
 m s   eE 1
 dt 
vs  velocity of super e 
 
 J s  ns ev s

 Js
vs  
ns e
So equation (1) becomes

m dJs 
  eE
ns e dt


 
d Js


ns e2 E
(1)
dt m
First London equation will replace Ohm’s law.

  B
Farraday’s law:  E    2
t
Taking curl of equation (1) both sides
d   n e2  
dt
 
 J s  s  E
m
 
Using equation (2)

d   ns e2  B
dt
 J s   m t
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  n e2  n e2  H
  J s   s B   s 0 , B  0 H
m m
  n e2  H
 J s   s 0  2nd London equation
m
 
B   A
A  magnetic vector potential
 
 
 J s  
ns e2   A  
m
  n e  
 
2
 J s  s  A  0
m
   n e2  
   J s  s A  0
 m 
 n e2 
 Js  s A 0
m
 n e 
2
Js   s A (3)
m

  ns e2 B
London’s penetration depth  L  :   J s  
m
  
From ampere law  B  0 J s
  
  B  0 J s
    

  B  0  J s  

    0 ns e2 B
 
  B  B   2

m
 
  B  0

  n e2 B  1 
So  B 0 s
2
 0  2 B  2 B  0
m 
 x/  x/
B  B0e , J  J 0e
1 0 ns e2

2 m
 1 
  J s  2 H 
  
m

0 ns e2
1
  {if superconducting e  s are large, then penetration depth would be less}
ns
at x
B
B 0
e
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1
London penetration depth is the distance at which magnetic field drops to value of surface magnetic field.
e
B  B0e x /   this equation tells us that some magnetic field gets inside the superconductor and decreases exponentially.
Dynamics of magnetic field or current in a super-conductors can be explained by London equations.
Meissner effect is super-conductor can not be described by Maxwell’s equation along. This effect can be explained by ‘Two
fluid Modal’. Acoording to this modal superconductor consist of 2 types of e s

(1) Normal e s (2) Super e s
Macroscopic Ohm’s law
J E
J
E

For superconductors  0
 
J
E

 E 0

  B
Also  E  
t

B
0
t

 B  constant B  0

 
So Meissner effect fails according to which no B can pass through superconductor.

That is why London’s equations are introduced.

* Fluxoid: 0 
h
0 
2e
nh
Magnetic flux 
2e
  n0
when magnetic flux passes through a superconduction ring, it passes in discrete form (in the form of packets) therefore this
type of flux is know as fluxoid.
# Barden, Cooper, Schrieffer theory (BCS Theory): BCS theory is most successful theory of super-conductivity. This is
mainly based on cooper pair inside the superconductivity material.
* e 1 is interacting with lattice and it gives some momentum to lattice which comes to excited state after taking some
energy from it.

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when e  2  is interacted with excited lattice, then the energy gained by it from e 1 is given to e  2  . So energy is
exchanged between two e  s by a lattice.
These two e  s from a bound pair (energy of bound pair is always attractive).

Bound e s  Cooper pair. {These form bound pair if exchanged energy overcomes columbic repulsive energy). For
superconductor, there is no role of single e  . There is cooper pair.
* Cooper pair is zero-spin particle spin  0    
* Cooper pair is a boson.
* Cooper pair lies in BCS ground state.
* The gap between BCS ground state and lower most Fermi state is called superconducting band gap E g

Eg  1meV {microwave region}

ch arg e  2e , spin  0    
This B-E is break by
(1) By increasing temperature (2) By incident of photon

Coherence length   : (Is the length upto which cooper pair remains connected)
2vF

 Eg
vF  fermi velocity
Type  I    
Type  II    
 
H C1  0 2 , H C2  0 2 , H C  H C1 H C2
L 
This theory s valid only for low temperature superconductors.
It fails for high temperature superconductors.
at T  0 K , all particles will follow B  E distribution function 
   
0  T  TC  some e will follow B.E and some e will follow F  D 
  
T  TC  All e s will follow F  D 
Thermodynamics:
(1) Free energy of super conducting state is small as compare to normal state. This shows the super-conducting state is more
stable as compare to normal state
FN  0   FS  0 
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(2) Entropy: Entropy of SC state < entropy of N.C {because SC state is more ordered.
(3) Specific heat:
For normal metals: CV  AT  BT 3
 
for free for lattice
e  phonon 
Eg

For superconductors CV  Ae 2 k BT
 BT 3
 
for free phonon
e
Eg  band gap
1/2
Isotope effect: TC  m

TC m1/2  constant 1

* Debye temperature of solid D also depends on isotopic mass by some relation i.e.

 D  m1/2  2
TC
 constant
D
 This signifies e  -phonon interaction is deeply involved in superconductivity.
Josepheson effect: If an insulating thin layer in sandwiched between two superconductors, then this forms a SIS junction or
weak link or Josephson junction.

Josephson effect
(1) DC Josephson effect (2) AC Josephson effect

If there is no bias is applied to the junction then a DC

current flows through the junction due to phase difference of When a DC voltage is applied to the junction and AC current
cooper pair on both sides. This is DC Josephson effect. flows across the junction. Frequency of AC current can be
calculated as
hv  2eV

This factor is due to pair of e s

The value of AC  I  I 0 sin t   

 phase difference
  2eV
2eV


 2eVt 
So I  I 0 sin   
  
Crystal defects: There are some defects in crystals
(1) Point defect: Vacancies, interstitial impurity, substitutional impurity (O-D defect).
* Comes when temperature increases and atom moves out of its place, creating vacancy.

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 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

(A) Vacancy: If some of the atoms are missing from their lattice ‘side’, vacancies in the real crystal minimize the free energy
of the crystal. Hence vacancies are necessary in the real crystal
EV

n  Ne k BT

n  no. of vacancies per unit volume

N  total no. of atoms per unit volume
EV  energy required to create the vacancy
kBT  thermal energy
(B) Impurity: Two types
(1) Substitutional impurity: If impurity occurs lattice site.
(2) Interstitial impurity: If impurity occurs interstitial site.
Point defects: (For ionic crystals)
(1) Schottky defect: (For ionic crystals)
Complete molecule (pair) comes out so that crystal structure remains electrically neutral
Na Cl   pair is removed together
EP

n  Ne 2 k BT
{2 factor is due to 2 atoms}
n  no. of vacancies
N  no. of atoms
EP  energy of pair formation .
(2) Frankel defect: Frankel defect can happen to both simple and ionic crystals.
  
For Na Cl crystal, Na will occupy the interstitial site because its size is smaller than Cl  .
{atoms comes at interstitial site}
Ee

n  NN 'e 2 k BT

n  no. of vacancies
N  no. of lattice sites
N '  no. of interstitial sites
Ee  energy to create a vacancy and to put an atom at interstitial site.
Colour centres: Pure alkali metal halides are transparent to visible light. But due to presence of a lattice defect these crystals
absorb visible light. This defect is colour defect.
(1) F-centre: -ve ion (anion) vacancy.
(2) V-centre: +ve ion (cation) vacancy.

Rotational symmetry: After rotating by an angle  , crystal is transforming into itself

2
n

n  fold rotation
n  1, 2, 3, 4, 6
2  
   2 ,  , , ,
3 2 3
{Five-fold symmetry does not exist}
2
  is not possible
3
Quasi crystal: It has 5-fold symmetry.
Example: A 6 Mn .
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 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

Fermi surface: Fermi surface is a constant energy surface in K-space. It has following properties:-
1. Fermi surface is a characteristic property of metals only.
2. In 3-D Fermi-surface would be a sphere of radius KF
2
 3 2 n  1
2/3
F 
2m
2 K F2
Also F   2
2m
By comparing (1) and (2)

K F   3 2 n 
1/3

N
where n
V

In this sphere, free e  s are filled.

In 2-D: Fermi disk

 2 N 
1/2

KF   
 A 
In 1-D: It is a line
N
KF 
2L
Volume occupied by Fermi surface in 3-D
4 4  3 2 N 
VFS   K F   
3

3 3  V 
4 3 N
VFS 
V
N
VFS  depend upon n  , not depend upon lattice potential.
V
Shape: (1) If lattice potential = 0
Then Fermi surface  spherical
(2) If lattice potential  0
Then Fermi surface  derivate from spherical shape.

 L 
Density of modes and total no. of modes: N   K 
1  D
 2 
K
or N 2 
  L 
electrons  
due to

 2 
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 BANSAL ACADEMY CHANDIGARH
SCF-19, Sector 16-D, Chandigarh

2 K 2
N 
2  D
 2 
2

 
 L 
4
2  K3
N 3 
3  D
 2 
3

 
 L 

97