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CONDUCTIVITY

 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

109 10 7 105 103 101 101 103


Ag
Ni Sb Bi Ge
Cu Al Ge Si
Pb Graphite (doped)
Au
- Solid electrolytes -

Insulators

105 107 109 1011 1013 1015 1017

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.

Material E.g. Conductivity d/dT Carrier Type


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 1034 J s 7.27 x104
  31
 m  v → velocity of the electrons
mv (9.109 x 10 kg ) v v  h → Planck’s constant

Wave number vector (k) Non relativistic mv kh


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 →

Discrete energy levels


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 → integer (quantum number)


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 

Energy state in quantum number space

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).

Only one half of the


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).

Brillouin zone boundary


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 →

Force experienced by an electron


  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

Thermal vibration → Phonons


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

Resistivity () [x 10-8 Ohm m] →


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

Net resistivity (approx.) = Thermal resistivity + Resistivity due to impurity scattering


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

 Electrical contacts in switches, brushes and relays


 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 106 / K) and
Constantan (60% Cu, 40% Ni) are good as resistor materials
[R (Cu) = 4000 x 106 / 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 106 / 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] →


Resistivity () [x 10-11 Ohm m] →

10 Ag 20 Sn

5 10

0 10 20 0 Tc 5 10
T (K) → T (K) →

Superconducting transition temperature


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

 A superconductor is a perfect diamagnet (magnetic suceptibility  = 1)


 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

 Three way interaction between an two electron and a phonon


 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

 Strong magnetic fields → 50 Tesla


(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

Please read from text book


Crystal structure of YBa2Cu3O7x

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 