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Conductivity

Superconductivity

Electronic Properties

Robert M Rose, Lawrence A Shepart, John Wulff

Wiley Eastern Limited, New Delhi (1987)

Mechanisms of conduction and origin of resistance

Conduction by electrons and ions (including protons).

Any impediment to motion gives rise to resistance. The relevant material property is

resistivity.

Scattering of the moving electron under a potential gradient from various sources (atoms,

phonons, etc.) lead to resistance in electronic conductors.

Spin dependent electron scattering is also possible (e.g. in the GMR effect). Repeated

scattering can lead to phenomena like Anderson localization.

For conduction: (i) driving field is required and (ii) energy levels should be available for

electrons to be promoted to. The issue of cross coupling terms.

In conductors the field leads to current. In dielectrics (insulators) it may cause polarization.

Conductivity depends on the number of charge carries and their mobility.

Field and current are vectors and hence resistivity (ij) and conductivity (ij) are second

order tensors.

Resistivity range in Ohm m 25 orders of magnitude L

R

A

Metallic materials Semi-conductors

Ag

Ni Sb Bi Ge

Cu Al Ge Si

Pb Graphite (doped)

Au

- Solid electrolytes -

Insulators

Window Porcelain

glass Diamond Lucite SiO2

Bakelite PVC

Ionic Rubber Mica (pure)

conductivity Polyethylene

Metals

Classification Semi-metals

based on Semi-conductors

Band structure

Semi-insulator

Insulators

Semi-insulators are: (i) doped semi-

conductors with dopant level near band

edge or (ii) large band-gap semi-

conductors are referred to as semi-

insulators.

Semi-metals have an (i) overlap of valence

and conduction bands across ‘k’ values or

(ii) valence band just touches the

conduction band.

Metals Cu, Ag, Au High Small negative Electrons

Semi-conductors Ge, Si Intermediate Large positive Electrons (+holes)

Semi-insulators GaAs, ZrO2 “ Large positive Ions/Electrons

Insulators Al2O3 Low Very large, positive Ions /+ electrons

Semi-insulators are: (i) doped semi-

conductors with dopant level near band

edge or (ii) large band-gap semi-

conductors are referred to as semi-

insulators.

Semi-metals have an (i) overlap of valence

and conduction bands across ‘k’ values or

(ii) valence band just touches the

conduction band.

Graphene is not a semiconductor, not an

insulator, and not a metal,

Free Electron Theory

Outermost electrons of the atoms take part in conduction.

These electrons are assumed to be free to move through the whole solid

Free electron cloud / gas, Fermi gas.

Potential field due to ion-cores is assumed constant potential energy of electrons is not a

function of the position (constant negative potential).

The kinetic energy of the electron is much lower than that of bound electrons in an isolated

atom.

Wave particle duality of electrons

→ de Broglie wavelength

h 6.62 x 1034 J s 7.27 x104

31

m v → velocity of the electrons

mv (9.109 x 10 kg ) v v h → Planck’s constant

k 2 v

2 1 h2 2 h 2 m

k E mv 2 E 2 k

2 8 m 2

1 kh h2k 2

E m

k is a vector in 2D/3D and is represented as a scalar in 1D 2 2 m 8 2 m

h2 2

E 2 k

8 m

↑→ k↓→E↓

E →

Free electrons (Pauli’s exclusion principle)

k →

Confined Electron L

Electron in an 1D box

n=1

n=3

n=2

If the length of the box is L (e.g. a crystal) Number of electrons moving from left to right

equals the number in the opposite direction

n

nx L k x

2 L h2

Enx n

2

x 2

Quantization of Energy levels

8mL

nx L

2

h 2 nx

2

nx2 h 2

1 2 n x En x 2

nx L k 8 m L 8mL2

2 k L

1

8mL 2

2 1

L

2 2 n 2 2 Enx 8mEnx

2

k

k nx h nx h

In 3D h2k 2

2 x z 2

2 2 2

h h 8mL E

En n 2

n 2

y n 2

n 2

n 2

2

En 8 2 m

8mL 8mL h

Each combination of the quantum numbers nx , ny , nz corresponds to a distinct quantum

energy state.

Many such quantum states have the same energy and said to be degenerate.

S(E), the number of quantum states with energy equal to or less than En is proportional to

the volume of the sphere (1/8 of the total volume as the quantum numbers are positive).

The probability of finding an electron at any point in box is proportional to the square of the

amplitude there are peaks and valleys within L.

If the electron wave is considered as a travelling wave the amplitude will be constant.

3/2

1 4 3 8mL 2

S(E ) n 2 E

3/2

8 3 6 h

Discrete ‘n’

The density of states

The number of energy states per unit energy is called the density of states (DOS, (E)).

DOS is obtained by differentiating S(E) w.r.t to E.

The density of states increases with E.

The highest filled energy level is called the Fermi level (EF).

3/2

1 4 3 8mL2

S(E ) n 2 E

3/2

8 3 6 h

3/2

dS 8mL2

(E ) 2 E

1/2

dE 4 h

Energy Bands in Conductors

The energy levels in conductors are continuous.

In conductors reciprocal lattice points in ‘k’ space can be defined (/a, 2/a, 3/a, etc.), but

these have no real significance.

The information spread across reciprocal lattice points can be reduced within /a the reduced

zone scheme).

zones shown (e.g. the

first BZ extends from

/a to +/a)

2

k

2D: Brillouin zones

The first three Brillouin zones are shown in the figures below. The region enclosed between

the perpendicular bisectors of the reciprocal lattice vectors are the zones. For zones of the

higher order, the extended limiting lines of the lower order zones provide the inner boundary.

All zones have the same area.

Fermi level

At zero K the highest filled energy level (EF) is called the Fermi level.

If EF is independent of temperature (valid for usual temperatures)

► Fermi level is that level which has 50% probability of occupation by an electron.

EF is typically in the range of 2-12 eV.

The kinetic energy of an electron gas is given by the Fermi-Dirac statistics. The probability

that a certain energy level is occupied by electrons is given by the Fermi function (F(E)).

The energy range over which the function is smeared out (at a given T) is E. E is about

1% EF.

At high energies (E >> EF) the upper end of the Fermi function can be approximated to the

Boltzmann distribution.

E T>0K 1

P( E )

1 0K E EF

1 exp

kT

P(E) →

E EF

E>>EF P( E ) exp

kT

0

E → EF

Population density

The number of electrons per unit energy (N(E), the electron population density) is calculated

as a product of number of possible energy levels and the probability for their occupation.

Further, each state can be occupied by 2 electrons (up and down spin).

At zero Kelvin, N(E)=2(E).

The area below the curve is the number of electrons (N*), which have energy less than or

equal to En.

N ( E ) 2 ( E ) P( E )

3/2

8mL2 1

N (E ) 2 E

1/2

4 h2 E EF

1 exp

kT

dN * N ( E ) dE

EF EF 8mL2 3/2

EF

N * (0K ) N ( E ) dE ( E ) dE 2 E dE

1/2

0

0 0

4 h

2/3

3N * h2

3/2

8mL2

N (0 K ) 2 EF EF

3/2

2

*

3 h 8mL

Fermi surface (2D)

In 2D the Fermi surfaces are curves. At low energies these are circles, but close to the BZ

boundary their shape changes (figure below).

Conduction by free electrons

If there are empty energy states above the Fermi level then in the presence of an electric

field there is a redistribution of the electron occupation of the energy levels.

Field

EF Electric EF

E →

Field

k → k →

m → mass of an electron

F ma Ee E → applied electric field

In the presence of the field the electron velocity increases by an amount (above its usual

velocity) by an amount called the drift velocity.

The velocity is lost on collision with obstacles.

Collisions vd

F m Ee

vd

vd → Drift velocity

→ Average collision time

Velocity →

Ee

vd

m

time →

The flux due to flow of electrons → Current density (Je) [charge/area/time]

number charge 1 m

Je drift velocity 3

Coulomb

volume electron m s

ne E

2

Ee n → number of free electrons

J e n e vd vd

m m

Flux (J e )

Conductivity ( ) Je E ~ Ohm’s law

Unit potential gradient (E)

n e2

Amp 1 V

m m 2 Ohm m m

Actually n has to be

V

V IR Ohm Amp

replaced by n* and

m by m*.

n * e2

m* Amp V 1

m 2 Ohm m 2

n* is the number of electrons

at the Fermi level

Mean free path (MFP) (l) of an electron

The mean distance travelled by an electron between successive collisions is called the mean

free path (MFP, l). l = vd .

For an ideal crystal with no imperfections (or impurities) the MFP at 0 K is .

Ideal crystal there are no collisions and the conductivity is .

Scattering centres → MFP↓ , ↓ ↓ , ↑.

Scattering centres

Sources of

Solute / impurity atoms

Electron Scattering

Defects

Dislocations

Grain boundaries

Etc.

Thermal scattering

At T > 0K → atomic vibration scatters electrons → Phonon scattering

T↑→↓→↑

Low T

MFP 1 / T3

1 / T3

High T

MFP 1 / T

1 / T

Impurity scattering

Resistivity of the alloy is higher than that of the pure metal at all T

The increase in resistivity is the amount of alloying element added!

Cu, Cu-Ni alloy Increased phonon scattering

5

Cu-3%Ni

4

Cu-2%Ni

3

2

Impurity scattering (r) With low density of

1 imperfections

Pure Cu

→ 0 as T→ 0K

100 200 300

T (K) →

Mattheissen rule = T + r

Conductors

Power transmission lines → low I2R loss → large cross sectional area

Al used for long distance distribution lines

(Elastic ModulusAl increased by steel reinforcement)

OFHC (Oxygen Free High Conductivity) Cu (more expensive) is used for

distribution lines and busbars.

► Fe, P, As in Cu degrade conductivity drastically

Electrical contacts

Properties:

► High electrical conductivity

► High thermal conductivity → heat dissipation

►High melting point → accidental overheating

► Good oxidation resistance

Cu and Ag used

Ag strengthened by dispersion strengthening by CdO

■ CdO

► Strengthens Ag

► Improves wear resistance

► If arcing occurs → decomposes (At MP of Ag) to

absorb the heat

Resistor

Properties:

► Uniform resistivity → homogenous alloy

► Stable resistance → Avoid aging / stress relaxation / phase change

► Small T coefficient of resistance (R) → minimizes error in measurement

► Low thermoelectric potential wrt Cu 1 dR

► Good corrosion resistance R

R dT

Manganin (87% Cu, 13% Mn, R = 20 x 106 / K) and

Constantan (60% Cu, 40% Ni) are good as resistor materials

[R (Cu) = 4000 x 106 / K]

Low thermoelectric potential wrt to contact material (usually Cu) reduces error due to

temperature difference between junctions. For high precision dissimilar junctions should

be maintained at same temperature

Ballast resistors are used in maintaining constant current →

I↑→T↑→R↑ I↓

Requirement: high R (71% Fe, 29% Ni → R = 4500 x 106 / K)

Heating elements

Properties:

► High melting point

► High resistivity

► Good oxidation resistance

► Good creep strength

► Resistance to thermal fatigue

low elastic modulus

low coefficient of thermal expansion

■ Upto 1300oC

Nichrome (80% Ni, 20% Cr), Kanthal (69% Fe, 23% Cr, 6% Al, 2% Co)

■ Upto 1700oC: SiC & MoSi2

■ Upto 1800oC: Graphite

Mo and Ta need protective atmosphere at high T

W (MP = 3410oC) is used is used as filament in light bulbs → creep

resistance above 1500oC improved by dispersion hardening with ThO2

Resistance thermometers: ► High temperature coefficient of resistivity

► Pure Pt

SUPERCONDUCTIVITY

Superconducting transition

Resistivity () [x 10-11 Ohm m] →

10 Ag 20 Sn

5 10

0 10 20 0 Tc 5 10

T (K) → T (K) →

Current carrying capacity

The maximum current a superconductor can carry is limited by the magnetic field that it

produces at the surface of the superconductor

Hc / Jc

Normal

Jc [Amp / m2] →

0 Hc [Wb / m2] →

Superconducting

T (K) → Tc

Meissner effect

Flux lines of the magnetic field are excluded out of the superconductor Meissner effect

Normal Superconducting

Theory of low temperature superconductivity-

Bardeen-Cooper-Schreiffer (BCS) theory

Phonon scattering due to lattice vibrations felt by one electron in the Cooper pair is

nullified by the other electron in the pair

the electron pair moves through the lattice without getting scattered by the lattice

vibrations

The force of attraction between the electrons in the Cooper pair is stronger than the

repulsive force between the electrons when T < Tc

Type I and Type II superconductors

Type I (Ideal) superconductors

Type I SC placed in a magnetic field totally repels the flux lines till the magnetic field attains

the critical value Hc

Type I

H H H c

M

0 H H c

M →

Normal

Superconducting

H → Hc

Type II (Hard) superconductors

H H H c1

Type II SC has three regions

M H H (H c1 , H c2 )

0 H H c2

Type I

Vortex Region

Gradual penetration of the

magnetic flux lines

M →

Super

Vortex

conducting Normal

H → Hc1 Hc Hc2

As type II SC can carry high current densities (Jc) they are of great practical importance

The penetration characteristics of the magnetic flux lines (between Hc1 and Hc2) is a function

of the microstructure of the material presence of pinning centres in the material

Pinning centres:

Cell walls of high dislocation density

(cold worked/recovery annealed)

Grain boundaries

(Fine grained material)

Precipitates

(Dispersion of very fine precipitates with interparticle spacing ~ 300 Å)

Jc ↑ as Hc2 ↑

Nb – 40%Ti alloy, T = 4.2 K, Magnetic field strength = 0.9 Hc2

Microsctructure Jc (A / m2)

Recrystallized 105

Cold worked and recovery annealed 107

Cold worked and precipitation hardened 108

Potential Applications

(without heating, without large power input)

Logic and storage functions in computers

Josephson junction → fast switching times (~ 10 ps)

Magnetic levitation (arising from Meissner effect)

Power transmission

High Tc superconductivity

Compound Tc Comments

Nb3Ge 23 K Till 1986

La-Ba-Cu-O 34 K Bednorz and Mueller (1986)

YBa2Cu3O7-x 90 K > Boiling point of Liquid N2

Tl (Bi)-Ba(Sr)-Ca-Cu-O 125 K

Manufacture of YBa2Cu3O7-x

Crystal structure of YBa2Cu3O7x

Cu

Ba

Electron in a periodic potential

Let us consider a periodic potential with lattice spacing of ‘a’.

h2

Enx n

2

x 2

8 ma

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