Solid Stae PDF

Solid State Physics
Solid State Physics

Ananta Charan Pradhan
NIT Rourkela
February 11, 2016
Ananta Charan Pradhan (NIT Rourkela)Solid State Physics
February 11, 2016
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Solid State Physics
OUTLINE
Solid State Physics

Introduction to Crystals
Band theory of Solids
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Solid State Physics
Amorphous and crystalline solids

Solid consists of atoms, ions, or molecules packed closely together
with strong forces of attraction.
Solid maintains both a well-defined volume and shape.
Classified as crystaline and amorphous depending upon the
arrangement of atoms or molecules.
Amorphous
1. Short range
2. No sharp melting point
3. Irregular Shape
4. Isotropic
5. Less rigid
e.g., glass, rubber, plastics,
cement
Crystaline
1. Long range
2. Sharp melting point
3. Regular shape
4. Anisotropic
5. More rigid
e.g., Copper, quartz, mica,
sugar, diamond
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Solid State Physics
Amorphous and Crystalline solids
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Solid State Physics
Crystal Defects
Actual crystals are never perfect.

Defects: missing of atoms, atoms out of place, irregularities in
the spacing of rows of atom and the presence of impurities in the
crystal are defects.
Nature and concentration of defects highly influence the properties
of the crystal.
Simplest types:
1
2
Point defects (Vacancies & Interstitials)

Line defects (Dislocation)
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Solid State Physics
Types of Crystal Defects

Point defects
a. Vacancy b. Interstitial
c. Substitutional impurity
d.Interstitial Impurity
Line defect or Dislocation

a. Dislocation line
b. Dislocation force
c. edge & d. screw dislocation
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Solid State Physics
Forces in Crystals
Electrical forces are responsible in binding the atoms and molecules
giving different solid structures.
Forces are two types : attractive (to keep the atoms together) and
repulsive (comes into play when the atom is compressed).
Cohesive enegry: It is the energy that must be supplied to the solid to
separate its constituents into neutral free atoms at rest.
Classification of solids based on bonding or cohesion:
1. Ionic crystals (e.g. NaCl)
2. Covalent crystals (e.g. Diamond and other corresponding
structures).
3. Metallic crystals (e.g. Na).
4. Van der Waals crystals (e.g. Argon and other noble elements).
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Solid State Physics
Ionic Crystals
Need atleast two atoms; one with low ionization and other with high
electron affinity.
In an ionic crystal the ions (+ve and -ve) assemble themselves in an
equilibrium configuration in which the attractive forces between positive
and negative ions balance the repulsive forces between the ions.
In an ionic crystal each ion is surrounded by as many ions of the
opposite sign as can fit closely, which leads to maximum stability.
Ionic crystals thus can be described as an ensemble of hard spheres
which try to occupy a minimum volume while minimizing electrostatic
energy at the same time.
Ionic crystals are insulators and has no directionality.
e.g., NaCl and CsCl.
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Solid State Physics
Ionic crystals
The number of nearest neighbors for a constituent particle is defined as
coordination number. In other words the number of spheres which are
touching a particular sphere is known as its coordination number.
Unit Cell:A unit cell is the smallest unit of volume that contains all of the
structural and symmetry information to build-up the macroscopic structure of
the lattice by translation.
NaCl : fcc, lattice points=(1/8)8+(1/2)6=4, Coordination # 6
CsCl : bcc, lattice points = (1/8)8+1=2, Coordination # 8
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Solid State Physics
Cohesive Energy of Ionic Crystals
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Solid State Physics
Consider a Na+ in NaCl.

Each Na+ ion in NaCl has 6 nearest Cl+ neighbors and at a distance r.
6e2
The PE of the Na+ ion due to these 6 Cl ions is U1 = 4
0r
The next nearest neighbors are 12 Na+ ions, each one the distance 2r away
2
and the PE of a Na+ ion due to 12 Na+ ions is U2 = + 412e2r
0
When the the summation is continued over all the + and - ions in a crystal of
infinite size, the result is
12
e2
e2
e2
(6
+ ...) = 1.748 4
= 4
Ucoulomb = 4
0r
0r
0r
2
This result holds good for Cl as well.
The quantity is called the Madelung constant of the crystal. It has the
same value for all crystals of the same structure.
Simple crystal structures have between 1.6 and 1.8.
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Solid State Physics
Cohesive Energy continue ....

Repulsive energy Urepulsive = + rBn
rn implies a short range force that increases as the interionic distance
decreases.
e2
Utotal = Ucoulomb + Urepulsive = 4
+ rBn
0r
At the equillibrium separation r0 of the ions, U is a minimum and dU/dr = 0
when r = r0 . Hence
e2
nB
( dU
dr )r=r0 = 40 r 2 r n+1 = 0
0
e
rn1
B = 4
0n 0
The total potential energy at equillibrium separation is given by
e2
U0 = 4
(1 n1 )
0 r0
We must add this amount of energy per ion pair to separate an ionic crystal
into individual ions.
The average value of the exponent is n 9 which can be found from the
observed compressibility of the crystal. The repulsive force varies sharply
with r.
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Solid State Physics
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Solid State Physics
Covalent crystals
Covalent crystals arise from the sharing of electrons by adjacent atoms.

Each atom in the covalent bond contribute an electron to the bond.
Because there are no delocalized electrons, covalent solids do not conduct
electricity.
The rearranging or breaking of covalent bonds requires large amounts of
energy; therefore, covalent solids have high melting points.
e.g., allotropes of C (Diamond, graphite).
Cohesive energies are greater in covalent crystals than in ionic crystals.
As a result covalent crystals are harder. (diamond, boric nitride (2nd
hardest))
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Solid State Physics
Covalent crystals: Graphite

Graphite and diamond are identical chemically but are different physically.
1
Opaque and metallic
Hexagonal structure, coordination

number = 3
Layers of C atoms in a hexagonal

Sheet like structure in which each
atom is joined to three others by
weak cavalent bonds. One
electron per carbon atom is free
to circulate through the network.
Weak van der Waals forces bond
the layers together.
Conductor of electricity.
Graphite is very soft.
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Solid State Physics
Covalent crystals: Diamond
diamonds are transparent and

brilliant (refractive index = 2.41,
internal reflection).
Tetrahedron structure and

coordination number 4.
Each carbon atom is strongly

bonded to four adjacent carbon
atoms.
Bad conductor of electricity.
Diamonds are the hardest.
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Solid State Physics
van der Waals Bond

All atoms and molecules (even inert gas atoms) exhibit weak, short range
(r7 ) attraction for one another due to van der Waals (molecular) forces.
Arose to explain departures of real gases from ideal gas law.
Van der Waals (molecular) bonding originates from the fluctuation of
electron distribution between two distorted inert gas atoms.
Van der Waals force responsible for the condensation of gases into liquids
and the freezing of liquids into solids in the absence of ionic, covalent,
metalic bond.
friction, surface tension, viscosity, adhesion, cohesion and so on are arise
from these forces.
Polar molecule can attract non-polar molecule due to this force as shown
in the figure below.
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Solid State Physics
van der Waals Bond continue .....
The van der Waals attraction between two molecules the distance r apart is
proportional to r7 , so that it is significant only for molecules very close
together.
Alignment of polar molecules with ends of opposite sign adjacent and
attractive force between a polar and a non-polar molecule is due to the van
der Waals.
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Solid State Physics
van der Waals Bond continue .....

The electric field E a distance r from a dipole of moment p is given by
E=
3(p.r)
1 p
r]
[
40 r3
r5
(1)
The field E induces an electric dipole moment p in non-polar molecule which

is proportional to E in magnitude. Induced dipole moment p=E, where is
called the polarizability of the molecule.The energy of the induced dipole in
the electric field E is
U = p .E = E.E =
p2 3p2
3p2
9p2
( 6 6 cos2 6 cos2 + 6 cos2 ) (2)
2
(40 ) r
r
r
r
So the interaction energy,

U =
p2
(1 + 3cos2 ) 6
2
(40 )
r
(3)
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Solid State Physics
van der Waals Bond continue.....

The potential energy of the two molecules that arise from their
interaction is negative i.e., force between them is attractive.
U r6 , hence F = dU/dr r7
On the average, nonpolar molecules have symmetrical charge

distribution, but at any instant the distributions are asymmetric. The
fluctuation in the charge distributions of nearby molecules are
coordinated which leads to an attractive force between them.
van der Waal forces are much weaker than forces in ionic and covalent
Molecular bonds. Molecular solids are soft, often volatile, have low
melting temperatures, and are electrical insulators.
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Solid State Physics
Hydrogen Bond
Strong type of van der Waals bond is called a hydrogen bond occurs
between certain molecules containing hydrogen atoms.
Hydrogen bonds occurs between H containing molecules due to
permanent dipole moments (e.g. H2O, NH3, HCl).
H2 O is non-symmetric, tetraheron
structure and prone to H-bond.
Each H2 O can form H-bond with
four other H2 O, central molecule
provides bridging proton for two
bonds and the attached molcules
provides the other two.
The open bridge like structure of
ice is due to H-bonding. Hence
low density.
H-bonding in biological matterials
Hydrogen bond of water and Ice

structure.
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Solid State Physics
Metalic bond
Atoms in metals lose weakly bound electrons to form cations. Sea of

delocalized electron gas surrounds the ions. Metallic bonds (electrostatic
interactions between the ions and the electron cloud) hold the metallic
solid together.
Because outer electrons of metal atoms are delocalized and highly
mobile, metals have electrical and thermal conductivity.
The total energy of atoms is lower when they bound together than when
they are separate atoms.(Explaination: Linear combination of atomic
orbitals)
PE of free electrons reduced and the KE is increased.
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Solid State Physics
Summary of crystal bondings
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Solid State Physics
Ohms law
Ohms law : I = VR
Where V is the potential difference across the ends of a metal conductor
and I is the resulting current, R is the resistance.
Ohms law follows from the free electron model of a metal. Free electrons
in metal move randomly and undergo frequent collisions and these
collisions represent the scattering of electrons waves by the crystal
irregularities.
Collision time: = vF
where vF is the electron velocity corresponding to the Fermi energy F ,
since only electrons at the top of their energy distribution can be
accelerated and = mean free path.
q
vF = ( 2mF ) and it is extremely high compared to the drift velocity (vd )
produced by electric field.(e.g., for Cu vF = 1.57 107 m/s and vd < 1
mm/s).
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Solid State Physics
Drift Velocity
n = number of free electrons per unit volume

Q = neAL = total charge in length L of the conductor
t = vLd = time for this charge to pass through the cross section
= neAvd
Current, I = Qt = neAL
L
vd
The drift velocity of the electron is, vd =
I
nAe
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Solid State Physics
Drift Velocity
Example 10.2 Find the drift velocity vd of the free electrons in a copper
wire whose cross-sectional area is A=1.0 mm2 when the wire carries a current
of 1.0 A. Assume that each copper atom contributes one electron to the
electron gas.
Answer
we know that, in Cu, n = N/V
8.94103 kg/m3
mass/m3
= (63.5u)(1.6610
=atoms/m3 = mass/atom
27 kg/u)
=8.48 1028 atoms/m3 = 8.5 1028 electrons/m3 , and here I = 1.0 A and A
= 1.0 mm2 = 1.0 106 m2 .
I
Hence vd = nAe
= 7.4 104 m/s
But if the free electrons have so small a drift velocity, why does an
electric appliance go on as soon as its switch is closed and not
minutes or hours later?
The answer is that applying a potential difference across a circuit very rapidly
creates an electric field in the circuit, and as a result all the free electrons
begin their drift almost simultaneously.
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Solid State Physics
Resistivity
Electric field E produced due to potential difference V across the ends of a
conductor of length L is E = V /L and the force, F = eE on the free electrons
F
= eE
whoes acceleration is a = m
m
Drift velocity
eE
eE
vd = a = (
)( ) =
(4)
m vF
mvF
I
But we also know
= nAe
. Substituting this in the above equation, we get
2vd
2
A
E
= ne
I = nAe
mvF
mvF
L V
Resistance of metal conductor
mv L
F
(5)
nAe2 A
The quantity in parentheses is known as the resistivity of the metal and is
mvF
a constant for a given sample at a given temperature and = nAe
2
R=
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Solid State Physics
Resistivity
The scattering of free electron waves in a metal that leads to its electric
resistance.
Again the scattering of free electron waves depends on crystal
imperfections as well as temperature.
Thus resistivity of a metal = i + t , where t ) depends on
temperature and i depends on the concentration of crystal impurity.
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Solid State Physics
Band theory of Solids

Why band theory?
The energy band structure of a solid determines whether it is a
conductor, an insulator, or a semiconductor.
Resistivity of Cu (conductor), = 1.7 108 .m
Resistivity of qartz (insulator), = 7.5 1017 .m

A huge span in resistivity (order of 25).
Origin of band structure

When the individual atoms brought together to form the solid, their
velency electron wave function overlaps giving a band structure (1cc Cu
= 1023 atoms).
Closely spaced energy levels form an energy band that consists of a
virtually continuous spread of permitted energies.
The energy bands, the gaps between them, and the extent they are filled
by electrons determine the electrical behaviour of solids.
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Solid State Physics
Formation of band structure
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Solid State Physics
Formation of band structure: Na

Na: 1s2 2s2 2p6 3s1 and r0 = 0.367 nm.
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Solid State Physics
Distribution of electron energies
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Solid State Physics
Conductor
Sodium solid:
Na: 1s2 2s2 2p6 3s1 . 3s can hold 2(2l+1) = 2
electrons. 3s band formed by N atoms can hold
2N es.
3s band is half filled and fermi energy (F ) lies in
the middle of the band.
Supply of energy drifts the electron to the
partially filled energy band making it a good
conductor.
Magnesium solid:
Mg: 1s2 2s2 2p6 3s2 , filled 3s shell. 3s and 3p
bands overlap as Mg atoms come close together.
N Mg atoms can hold 8N electrons (3s+3p).
With only 2N electrons in the band, it is only
one-quarter filled and so Mg is a conductor.
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Solid State Physics
Insulator
Carbon:
C: 1s2 2s2 2p2 and Si: 1s2 2s2 2p6 3s2 3p2
The 2s and 2p bands overlap at first and
then at smaller distance the combined
bands split into two bands each
containing 4N electron.
The lower valency band is completely
filled 4N electrons and the conduction
band is empty and the two bands are 6
eV wide (band gap).
Fermi energy (F ) is at the top of the
valency band.
At room temperature diamond has not
enoogh energy (0.025 eV) to jump the 6
eV gap.
8 (NIT Rourkela)Solid State Physics
Ananta Charan Pradhan
A field of 10 V/m needed to gain 8 eV
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Solid State Physics
Semiconductor
Si: 1s2 2s2 2p6 3s2 3p2 .
Eg = 1.1 eV in Si. Better than diamond at room temperature.
At low temperatures a small number of its valence electrons have enough
thermal energy to jump the forbidden band and enter the conduction
band. Allow a small amount of current to flow when an electric field is
applied.
Thus silicon has a resistivity intermediate between those of conductors
and those of insulators (0.1-60 ohm m).
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Solid State Physics
Impurity Semiconductors
N-type Semiconductor
Small amount of impurity can drastically change the conductivity of a
semiconductor (e.g., As atoms in a Si crystal).
Si: 1s2 2s2 2p6 3s2 3p2 & As: 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p3
As has 5 valency es and Si has 4. The fifth electron needs very little
energy - only about 0.05 eV in Si and about 0.01 eV in Ge to be
detached and move about freely in the crystal.
Fermi level lies in the middle of the gap for intrinsic semiconductor but
addition impurity (N-type) shifts it towards conduction band due to the
donor levels below the conduction band.
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Solid State Physics
Impurity Semiconductors
P-type Semiconductor
Si: 1s2 2s2 2p6 3s2 3p2 & Ga: 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p1
As has 5 valency es and Si has 3. Presence of Ga leaves holes in the
crystal structure and an electron needs little energy to enter into the hole
and as it does leaves another hole in the crystal. Electron moves towards
anode filling succesive holes.
Fermi level lies in the middle of the gap for intrinsic semiconductor but
addition impurity (P-type) shifts it towards valency band due to the
acceptor levels below the conduction band.
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Solid State Physics
ENERGY BANDS: ALTERNATIVE ANALYSIS
Discussed: Bringing together isolated atoms to form a solid has the effect of
broadening their energy levels into bands of allowed electron energies.
Electrons in the Solid:
1
Free Electrons
Nearly free Electrons ENERGY BANDS
Tightly bound Electrons
Reciprocal lattice : Fourier transform of direct lattice (k-space).

2
( K = 2
and a a )
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Solid State Physics
ENERGY BANDS: ALTERNATIVE ANALYSIS

Alternative Approach: An electron in a crystal moves in a region of
periodically varying potential that cause diffraction.
Difraction limits the electron to specific allowed energy bands.
de Broglie Wavelength of a free electron =
h
p
Low energy electrons : > a (lattice spacing)

High energy electrons (F ): a (lattice spacing) = diffraction of
electrons.
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Solid State Physics
Bragg reflection
Bragg reflection of electron from the atomic planes of crystal:
n = 2a sin n=1,2,3,....
General Approach : Electron waves in a crystal is explained in terms
p
n
of k = 2
= ~ and the Braggs formula in terms of k is k = a sin
Bragg reflection in 2D square lattice

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Solid State Physics
Bragg reflection in crystal

1
Reflection occurs when component of k in x-direction, kx =

component of k in y-direction ky = n
a .
k<
n
a
and
= electron moves freely through the lattice in any direction.
When k = a = electron prevented from moving in the x or y direction

by reflection.
The more k exceeds a , the more limited the possible directions of
motion, until when k = a sin 45 = 2 a the electrons are reflected, even

when they move diagonally through the lattice.
Bragg plane: Perpendicular bisector to the line joining to the origin of
the reciprocal space to any reciprocal lattice point. Loci of k-values that
are bragg reflected and hence may be considered as the reflecting planes.
2
p
The energy of a free electron is related to its momentum p by E= 2m
and to
2 2
~ k
its wave number k by E = 2m
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Solid State Physics
Brillouin Zones in 2D
First Brilouin zone : The region in k-space that low k-electrons can occupy
without being diffracted or Region which does not cross any Bragg plane
( a < kx (&ky ) < a ).
Second Brilouin zone : The region which crosses the 1st Bragg plane but
not the 2nd Bragg plane.
Third Brilouin zone : The region which crosses the 2nd Bragg plane but
not the 3rd Bragg plane.
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Solid State Physics
Energy Contour of Brillouin Zones

Energy and wave number in the 1st BZ: E =
~2 k2
2m
Reflection ocurs from the boundary of a BZ in k-space by virtue of the

interaction of the electron with the periodic array of positive ions that occupy
the lattice point.
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Solid State Physics
Origin of band gaps

At k = a , E has two values, the lower belonging to the 1st brillouin zone and
the higher to the 2nd BZ.
The gap between the possible energies in the first and 2nd BZ corresponds to
the forbidden band. The same pattern continues succesively higher BZs.
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Solid State Physics
Origin of band gaps
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Solid State Physics
Standing waves at BZ boundary

only electrons which have k = /a feel the periodic potential, and they
form standing wave patterns.
Possible solution of Schrodingers eqn which gives standing waves are
2
= A sin( x
a ) and charge density = e| |
+ 2
+ = A cos( x
a ) and charge density = e| |
Potential energy of an electron is greatest at midway between the ions

and least at the ions themselves.
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Solid State Physics
Energy discontinuity by standing waves

Two solutions at k= a gives rise to band gap i.e., the difference between the
expectation values of these 2 energy levels at BZ boundary.
R
Eg = U(x)[| + |2 | |2 ]dx
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Solid State Physics
Electron energy distributions in BZ

An Example: The distribution of electron energies at the Brillouin zones.
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Solid State Physics
Forbidden Band for different k

There is possibility of crystals having no forbidden band depending on values
of k.
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Solid State Physics
Electron energy contours and fermi levels

Electrical behaviour of solid depends on the degree of occupancy of its energy
bands as well as on its band structure.
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Solid State Physics

Solid State Physics

February 11, 2016

Ananta Charan Pradhan (NIT Rourkela)Solid State Physics

February 11, 2016

Solid State Physics

Solid State Physics

Ananta Charan Pradhan (NIT Rourkela)Solid State Physics

February 11, 2016

Solid State Physics

Amorphous and crystalline solids

Ananta Charan Pradhan (NIT Rourkela)Solid State Physics

February 11, 2016

Solid State Physics

Amorphous and Crystalline solids

Ananta Charan Pradhan (NIT Rourkela)Solid State Physics

February 11, 2016

Solid State Physics

Actual crystals are never perfect.

Point defects (Vacancies & Interstitials)

Ananta Charan Pradhan (NIT Rourkela)Solid State Physics

February 11, 2016

Solid State Physics

Types of Crystal Defects

Line defect or Dislocation

c. edge & d. screw dislocation

Ananta Charan Pradhan (NIT Rourkela)Solid State Physics

February 11, 2016

Solid State Physics

Ananta Charan Pradhan (NIT Rourkela)Solid State Physics

February 11, 2016

Solid State Physics

Ananta Charan Pradhan (NIT Rourkela)Solid State Physics

February 11, 2016

Solid State Physics

Ananta Charan Pradhan (NIT Rourkela)Solid State Physics

February 11, 2016

Solid State Physics

Cohesive Energy of Ionic Crystals

Ananta Charan Pradhan (NIT Rourkela)Solid State Physics

February 11, 2016

Solid State Physics

Cohesive Energy of Ionic Crystals

Consider a Na+ in NaCl.

Ananta Charan Pradhan (NIT Rourkela)Solid State Physics

February 11, 2016

Solid State Physics

Cohesive Energy continue ....

Ananta Charan Pradhan (NIT Rourkela)Solid State Physics

February 11, 2016

Solid State Physics

Cohesive Energy of Ionic Crystals

Ananta Charan Pradhan (NIT Rourkela)Solid State Physics

February 11, 2016

Solid State Physics

Covalent crystals arise from the sharing of electrons by adjacent atoms.

Ananta Charan Pradhan (NIT Rourkela)Solid State Physics

February 11, 2016

Solid State Physics

Covalent crystals: Graphite

Opaque and metallic

Hexagonal structure, coordination

Layers of C atoms in a hexagonal