AUTONOMOUS

FREE ELECTRON THEORY OF METALS

CLASSIFICATION OF SOLIDS
ELECTRICAL PROPERTIES

Some solids conduct current at all temperatures and, generally, the resistivity of such solids increases with temperature. These are METALS Other solids stop conducting at low temperatures and their resistivity falls with increasing temperature. These INSULATORS and SEMICONDUCTORS

Free Electron Theory

The common physical properties of metals; Great physical strength High density Good electrical and thermal conductivity, etc. This chapter will calculate these common properties of metals using the assumption that conduction electrons exist and consist of all valence electrons from all the metals; thus metallic Na, Mg and Al will be assumed to have 1, 2 and 3 mobile electrons per atom respectively. A simple theory of free electron model which works remarkably well will be described to explain these properties of metals.

FREE ELECTRON THEORY

According to free electron model (FEM), the valance electrons are responsible for the conduction of electricity, and for this reason these electrons are termed conduction electrons. Na11 1s2 2s2 2p6 3s1
Core electrons Valance electron (loosely bound)

This valance electron, which occupies the third atomic shell, is the electron which is responsible chemical properties of Na.

When we bring Na atoms together to form a Na metal,

Na metal

Na has a BCC structure and the distance between nearest neighbours is 3.7 A
y

The radius of the third shell in Na is 1.9 A

Solid state of Na atoms overlap slightly. From this observation it follows that a valance electron is no longer attached to a particular ion, but belongs to both neighbouring ions at the same time.

A valance electron really belongs to the whole crystal, since it can move readily from one ion to its neighbour, and then the neighbours neighbour, and so on. This mobile electron becomes a conduction electron in a solid.
y
+ + +

The removal of the valance electrons leaves a positively charged ion.

FREE ELECTRON THEORY

Classical

and Quantum Free Electron Models of Electrical Conductivity

THE CLASSICAL FREE ELECTRON THEORY OF METALS(DRUNDE-LORENTZ)

Postulates of CFEM

In an atom electrons revolve around the nucleus and a metal is composed of such atoms

The valence electrons of atoms are free to move about the whole volume of the metals like the molecule of a perfect gas in container . The collection of valence electrons from all the atoms in a given piece of metal forms electron gas .it is free to move throughout the volume of the metal.

+ + +

These free electrons move in random directions and collide with either positive ions fixed to the lattice or other free electrons. All collisions are elastic.

During every collision both the direction And the magnitude of velocity change.

The movements of free electrons obey the laws of the classical kinetic theory of gases .

CFET

The electron velocities in a metal obey the M-B distribution of velocities . The free electron move in a completely uniform potential field due to ions fixed in the lattice . When an electric field is applied to the metal ,the free electrons are accelerated in the direction of opposite applied electric field.

12

Applied Electric field E Electron cloud + -- -- - ----Atom Nucleus

ELECTRICAL CONDUCTIVITY

According to the Ohms Law I=V/R R resistance of the wire

** The current is due to the motion of the conduction electrons under the influence of the electric field. ** The field E exerts a force eE on the electron

When an external field applied the electrons accelerated. Here we consider the frictional force acting on the electron due to the collision. If Yis the velocity of the electron and is the time between two consective collisions The frictional force can be written as Y

X useNewton ' sLaw dY Y ! eE  m dt X underSteadyStateCondition m

F ! m

This is the steady-state velocity

dY !0 dt  eX Y! E m

DRIFT VELOCITY AND MEAN FREE PATH

In the absence of the field the electrons have random motion ,just as gas molecules move randomly in a gas container ,the randomly moving electrons undergo scattering and the change the direction. This random motion contributes zero current and the corresponding velocity is called the random velocity

DRIFT VELOCITY AND MEAN FREE PATH

In the presence of a field, in addition to random velocity ,there is an additional net velocity associated with electrons called drift velocity due to applied electric field . Due to drift velocity (vd )electrons with negative charge move opposite to the field direction

DRIFT VELOCITY AND MEAN FREE PATH

In the presence of a field, in addition to random velocity ,there is an additional net velocity associated with electrons called drift velocity due to applied electric field . Due to drift velocity (vd )electrons with negative charge move opposite to the field direction

DRIFT VELOCITY AND MEAN FREE PATH

If n is the number of conduction per unit volume ,then the charge per unit volume is (ne).The amount of charge crossing a unit area per unit time is given by the current density J
 eX J ! ( ne)Y d ! ne( E) m ne 2X E ! m J ! WE ne 2X W! m

DRIFT VELOCITY AND MEAN FREE PATH

Mean Free Path: The average distance traveled by an electron between two successive collision in the presence of applied field is known as Mean Free Path

RELAXATION TIME

Relaxation Time can be defined as the time taken for the drift velocity to decay to 1/e of its initial value.

Let assume that the applied field is cut off after the drift velocity of the electron has reached its steady value.Drift velocity after this instant is governed by
dY d Y ! m m dt X dY d dt ! Yd X Y d (t ) ! Y d (0) exp(t / X )

Vd(0)is the stedy state drift velocity

RELAXATION TIME

Vd(0)

Let t=T Vd(t)=vd(0)/e

vd

MOBILITY

Mobility of the electron is defined as the steady state drift velocity<vd> per unit electric field.

Yd eX Q! ! E m ne 2X eX W! ! ne. m m W ! neQ m m 1 V! ! ! 2 W neQ ne X Where( V )resistivity

The electrical conductivity depends on two factors ,the charge density n and their mobility . These two quantities depend on temperature. In metals n is constant and decreases slightly with temperature and hence with increase of temperature ,the conductivity decreases.

In semiconductors the exponential increase of n with temperature is responsible for increase of conductivity with temperature In insulator n remains constant and above certain temperature increase exponentially resulting in dielectric breakdown

SUCCESS OF CLASSICAL FREE

ELECTRON THEORY
** It verifies Ohms Law ** It explains the electrical and thermal conductivities of metals ** It derives Wiedemann-Franz Law ** It explains Optical Properties of metals.

DRAWBACKS OF CLASSICAL FREE ELECTRON THEORY

The phenomena such as photoelectric Effect, Compton Effect and the Black Body Radiation couldnt be explained by free electron theory. According to CFET the value of specific heat of metals is given by 4.5Ru.Where as the experimental value nearly equal to 3Ru. Electrical conductivity of Semiconductor or Insulators Couldnt be explained using this model

QUANTUM THEORY OF FREE ELECTRONS

This theory is proposed by Sommerfeld in 1928,with help of quantum of statistics (Fermi-Dirac) explained QFET. The difficulty of classical FET arises M-B it permits all the free electrons to gain energy. But in Quantum Statistics turn out that only about one percent of the free electron to gain a energy

Free electron moving in uniform potential within in a metal .potential field inside the metal not uniform. But instead ,the field experienced by a moving free electrons varies periodically with the periodicity of the crystal. To determine the restriction imposed by quantum mechanics the energies that free electron can have inside the metal

It is assumed that valence electrons are traped in constant potential well

V(x)

2 Jk 2 n 2 h 2 E ( n) ! ! 2 2m 8mL

X=0

X=L

QUANTUM THEORY OF FREE ELECTRONS

When an external electric field E is applied the force exerted on the electron is eE. Since force is also rate of change of momentum

dp  eE ! dt h h 2T v !J p! ! k P 2T P d dk (  eE ! (J) ! J ) k dt dt eE dk !  dt J

QUANTUM THEORY OF FREE ELECTRONS

This Means that origin of the k space moves through a distance dk in time dt on application of external field. Because of collision with imperfection, displacement of k space becomes steady k and dt is then the average collision time

QUANTUM THEORY OF FREE ELECTRONS

(k !  eEX J p ! mY ! J, incrementalVelocity(Y k

(Y !

J J eEX (k ! ( )( ) m m J eEX (Y !  m No.of e-s per unit volume is n,then J is J ! n(e)(Y ne 2 EX J! m J ! WE

ne 2X W! m
This treatment tell us that current carried out by very few electrons

FREE ELECTRON MODELS

Classical Model: Quantum Model: Metal is an array of positive ions Electrons are in a potential with electrons that are free to well with infinite barriers: roam through the ionic array They do not leave metal, but free to roam inside y Electrons are treated as an ideal

neutral gas, and their total energy depends on the temperature and applied field In the absence of an electrical field, electrons move with randomly distributed thermal velocities When an electric field is applied, electrons acquire a net drift velocity in the direction opposite to the field

Electron energy levels are discrete (quantized) and well defined, so average energy of electron is not equal to (3/2)kBT Electrons occupy energy levels according to Paulis exclusion principle Electrons acquire additional energy when electric field is applied

FERMI-DIRAC DISTRIBUTION
. The Fermi function f(E) specifies how many of the existing states at the energy E will be filled with electrons. The function f(E) specifies, under equilibrium conditions, the probability that an available state at an energy E will be occupied by an electron. It is a probability distribution function.

EF = Fermi energy or Fermi level k = Boltzmann constant = 1.38v 1023 J/K = 8.6 v 105 eV/K T = absolute temperature in K

FERMI-DIRAC DISTRIBUTION FUNCTION

At a temperature T the probability of occupation of an electron state of energy E is given by the Fermi distribution function

f FD !

1 1  e ( E  EF ) / k B T

Fermi distribution function determines the probability of finding an electron at the energy E.

FERMI-DIRAC DISTRIBUTION FUNCTION

At a temperature T the probability of occupation of an electron state of energy E is given by the Fermi distribution function

f FD !

1 1  e ( E  EF ) / k B T

Fermi distribution function determines the probability of finding an electron at the energy E.

Fermi-Dirac distribution: Consider T p 0 K

1 f ( E " EF ) ! ! 0 1  exp (g) f (E 1 EF ) ! ! 1 1  exp (g)

For E > EF :

For E < EF : E

EF

f(E)

Temperature dependence of FermiDirac distribution

FERMI FUNCTION AT T=0

AND AT A FINITE TEMPERATURE
f FD ! 1 1  e ( E  EF ) / k B T

fFD=? At 0K

fFD(E,T)

i. E<EF
f FD ! 1 e

1
( E  EF ) / k BT

!1

0.5

ii. E>EF
f FD !
E E<EF EF E>EF

1
( E  EF ) / k B T

1 e

!0

FERMI-DIRAC DISTRIBUTION
FUNCTION AT VARIOUS TEMPERATURES,

FERMI-DIRAC DISTRIBUTION FUNCTION

At any temperature other than 0k,if E=Ef F(E)=1/2 Fermi level is that state at which the probability of electron occupation is at any temperature above 0k and also it is the highest level of the filled energy state at 0k