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Chemistry 754 Solid State Chemistry Lecture #20 May 14, 2003
References Conductivity
There are many references that describe electronic conductivity in metals and semiconductors. I used primarily the following texts to develop this lecture. The Electronic Structure and Chemistry of Solids
P.A. Cox, Oxford University Press, Oxford (1987).
C.M. Wolfe, N. Holonyak, Holonyak, Jr., G.E. Stillman, Stillman, Prentice Hall, Englewood Cliffs, NJ (1989).
Ca Ti Mn Zn Cu Ag Pb
3.9 10-6 42 10-6 185 10-6 5.9 10-6 1.7 10-6 1.6 10-6 21 10-6
Most semiconductors in their pure form are not good conductors, they need to be doped to become conducting. Not all so called ionic materials like oxides are insulators.
Microscopic Conductivity
We can relate the conductivity, , of a material to microscopic parameters that describe the motion of the electrons (or other charge carrying particles such as holes or ions).
where
EF
EF
Valence Band
DOS Metal
DOS Semimetal
In a metal the Fermi level cuts through a band to produce a partially filled band. In a semiconductor/insulator there is an energy gap between the filled bands and the empty bands. The distinction between a semiconductor and an insulator is artificial, but as the gap becomes large the material usually becomes a poor conductor of electricity. A semimetal results when the band gap goes to zero.
Generally this means that EF should cut a band to achieve appreciable carrier concentration. Alternatively impurities/defects are introduced to partially populate a band.
Fermi-Dirac Function
The FermiFermi-Dirac function gives the fraction of allowed states, f(E), at an energy level E, that are populated at a given temperature.
Carrier Mobility
Recall the expression for carrier mobility: where, e = electronic charge m* = the effective mass = the relaxation time between scattering events What factors determine the effective mass? m* depends upon the band width, which in turn depends upon orbital overlap. What entities scatter the carriers and reduce the mobility? A defect or impurity ( increases as purity increases) Lattice vibrations, phonons ( decreases as temp. increases) = e/m*
Crystal Momentum
To better understand the meaning of k, consider an electron at the outer edge of the Brillouin zone, where k = /a. The phase of the electronic wavefunction changes sign every unit cell (similar to a p-orbital changing phase at its nodal plane)
a = 2a a = /2 k = /a a = /k
/2 = /k k = 2/ = 2/k
Crystal Momentum
Now consider the DeBroglie relationship (wave-particle duality of matter)
From the ideas on the previous 2 slides one can derive the following relationships to describe the properties of a conduction electron:
Velocity v = hk/2 /dk) hk/2m = (2 (2/h)(dE /h)(dE/ dk) 2 * Energy E = (h/2 (h/2)(k /2m ) * Effective Mass m = (2 (2/h)2 (1/{d2E/dk2})
dE/ dE/dk The first derivative of the E vs. k curve. d2E/dk2 The second derivative of the E vs. k curve. Quantity dE/ dE/dk Velocity m* Wide Band Large High Fast Light Narrow Band Small Low Slow Heavy
EF cuts the very wide (disperse) s band, giving rise to a large carrier concentration, along with high mobility. This combination gives rise to high conductivity.
Temperature Dependence-Metals
Recall that In Metals The carrier concentration, n, changes very slowly with temperature. is inversely proportional to temperature ( 1/T), due to scattering by lattice vibrations (phonons). Therefore, a plot of vs. 1/T (or vs. T) is essentially linear. Conductivity goes down as temperature increases. = ne2/m*
Bandstructure for Ge
CB minimum VB maximum
Figure taken from Fundamentals of Semiconductor Theory and Device Physics, by S. Wang
Direct Gap Semiconductor: Maximum of the valence band and minimum of the conduction band fall at the same place in k-space. (h-Eg)1/2 Indirect Gap Semiconductor: Maximum of the valence band and minimum of the conduction band fall different points in k-space. A lattice vibration (phonon) is involved in electronic excitations, this decreases the absorption (h-Eg)2 efficiency.
Doping Semiconductors
The FermiFermi-Dirac function shows that a pure semiconductor with a band gap of more than a few tenths of an eV would have a very small concentration of carriers. Therefore, impurities are added to introduce carriers. n-doping Replacing a lattice atom with an impurity (donor) atom that contains 1 additional valence electron (i.e. P in Si). Si). This e- can easily be donated to the conduction band. p-doping Replacing a lattice atom with an impurity (acceptor) atom that contains 1 less valence electron (i.e. Al in Si). Si). This atom can easily accept an e- from the VB creating a hole.
Conduction Band
e-
Conduction Band EF
e-
EF
Valence Band
Valence Band
Properties of Semiconductors
Compound Si Ge AlP GaAs InSb AlAs GaN Structure Diamond Diamond Sphalerite Sphalerite Sphalerite Sphalerite Wurtzite Bandgap (eV) eV) 1.11 (I) 0.67 (I) 2.43 (I) 1.43 (D) 0.18 (D) 2.16 (I) 3.4 (D) e- mobility (cm2/V-s) 1,350 3,900 80 8,500 100,000 1,000 300 h+ mobility (cm2/V-s) 480 1,900 --400 1,700 180 ---
Temperature Dependence-Semiconductors
Recall that In Semiconductors The carrier concentration increases as temperature goes up, due to excitations across the band gap, Eg. n is proportional to exp{-E exp{-Eg/2kT}. is inversely proportional to temperature The exponential dependence of n dominates, therefore, a plot of ln vs. 1/T is essentially linear. Conductivity increases as temperature increases. = ne2/m*
p-n Junctions
In the middle of the junction EF falls midway between the VB & CB as it would in an intrinsic semiconductor.
When a p-type and an n-type semiconductor are brought into contact electrons flow from the n-doped semiconductor into the p-doped semiconductor until the Fermi levels equalize (like two reservoirs of water coming into equilibrium). This causes the conduction and valence bands to bend as shown above.
MOSFET Transistor
Photovoltaic Cell