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Solids PDF
ke2 12 8 6 20 ke2
U Coulomb = 6 + + ... =
r 2 3 2 5 r
The constant alpha is called the Madelung constant of the crystal structure.
Alpha is positive and the Coulomb energy is negative.
As we saw for ionic molecules, the potential energy of the crystal compared to the
constituent ions has a term from the exclusion principle repulsion.
ke2 A
U (r ) = U Coulomb + Eex = + n
r r
dU ke2 nA
F= = 2 n+ 1
dr r r
At equilibrium,
ke2 nA
F = 0 = 2 n+ 1
ke2
2 = n+1
nA ke2r0n 1
A=
r0 r0 r0 r0 n
r r / 2 a0
20 = C20 2 e
a0
I
j=
A
Units: A/m2.
nAev d
j= = nev d
A
E = J
V V = I = IR
= J A
V I R= =
= A A
A
8kT
< v >=
me
Free Electron Gas in Metals
We must treat electrons as fermions, not classical particles.
So we have zero-point energy and exclusion principle in effect.
3 N /2 2
2 E1 n 2 E 1 ( N / 2) 3 E 1 N
< E >= = =
N 3 0
N 3 3 2
EF
< E >=
3
n( E ) = ( E 1 E )
1/ 2
at T = 0 K , for E < EF and
n( E ) = 0 for E > EF .
Three-Dimensional Electron Gas
We can extend this to a three-dimensional electron
gas using results from chapter 8.
3/ 2 3/ 2
E 2mL2 E
n= = 2 2 .
6 E0 6
From this we calculated the density of states in equation 8-64 (with the extra 2 for fermions):
dn 2(2m) 3/ 2 L3 1/ 2 2(2m) 3/ 2 V 1/ 2
g( E ) = 2 = E = E .
dE 4
2 3
4
2 3
The number of electrons can be used to normalize, but this is a difficult integral.
2(2m) 3/ 2 VE 1/ 2 1
N= g( E ) f
0 FD ( E )dE =
0 4 2 3
e ( E E F )/ kT
+1
dE
Since the Fermi-Dirac distribution function takes a simple form at T = 0 K, we can evaluate it:
EF EF 2(2m) 3/ 2 V 1/ 2 2(2m) 3/ 2 V 2 3/ 2
N= 0
g ( E )dE = 0 4
2 3 E dE =
4
2 3
3
EF
2/3
3 N 2 3
2 2 N
2/3
EF = = 3 .
3/ 2
(2m) V 2m V
EF
TF =
k
We can express the density of states in terms of the Fermi energy as
2(2m) 3/ 2 V 1/ 2 3 NE 1/ 2
g( E ) = E = .
4 2 3 2 E F3/ 2
Remember that at T = 0 K, n(E)=g(E) for E<EF and n(E)=0 for E>EF.
So the average energy at T = 0 K is
1 1 EF 3N
< E >=
N 0 En ( E ) dE =
N 0
E 3
2E F / 2 E 1/ 2 dE
3 EF 3 2 5/ 2 3
< E >=
2 E F3/ 2
0
E 3/ 2
dE = E = EF
2 E F3/ 2 5 F 5
2(2m) 3/ 2 V 1/ 2 3 NE 1/ 2
The density of states is given by g( E ) = E = .
4 2 3
2 E F3/ 2
The number of states within an energy of kT of the Fermi energy is about
3 NE F1/ 2 3 NkT
g( E F ) E = kT = .
2 E F3/ 2 2E F
So the fraction of free electrons that are affected by changes in temperature is of the order kT/EF.
Since these electrons are changing their energy by an amount of the order of kT,
the increase in kinetic energy per electron is of the order (kT)2/EF or kT2/TF.
The increase in energy per mole of ions is then of the order of RT2/TF
and the molar heat capacity associated with this energy is of the order 2RT/TF.
Since T/TF is very small, this contribution is small compared with the lattice heat capacity.
Magnetism in Solids
0 M ( + + )
2
2
For high temperatures where B < < kT , = = = .
B kT kT
This is Curies law.
Curies law applies to electrons bound to atoms in a solid but not to the free electrons in a metal.
The free electrons are almost all in doubly occupied states and the energy cost of increasing the
population of spin down is quite large.
Diamagnetism
Free electrons will spiral or circle in a magnetic field.
Second Iteration: Add effect of ion cores localized at particular locations, i.e.
electrons are moving in a periodic potential
Need to determine potential and solve Schrodinger Equation.
Well start with a simplified potential energy function in one-dimension.
Felix Bloch showed that solutions to Schrodingers equation for a one-dimensional periodic
potential, U(x),
2 d 2 ( x )
2 + U ( x ) ( x ) = E ( x )
2m dx
must have the form
( x ) = uk ( x )e ikx
where uk ( x ) = uk ( x + L) = uk ( x + nL)
and k = 2 / .
This form (called Bloch states) is the wave function for a free electron, eikx,
times a periodic modulation, uk(x).
( x + nL) = uk ( x + nL)e ik ( x + nL )
( x + nL) = uk ( x )e ikx e iknL
( x + nL) = ( x )e iknL
Well look at the solutions for the simplest periodic potential, the Kronig-Penney potential.
U ( x) = 0
for 0 < x < a
U ( x) = U 0
for a< x< a+b= L
We can solve for the constants A1, A2, B1, and B2 as we did in chapter 6.
There are only solutions for some values of E, but instead of discrete values, there are ranges of
allowed energies (called bands) and ranges of forbidden energies (called energy gaps).
Within each band there are N states, where N is the number of atoms in our one-dimensional chain.
For large values of N, we can take the energy states to be continuous.
The energy gaps occur at kL = n .
At these values of k only standing waves occur.
The ranges of k-values, 0 < k < / L , / L < k < 2 / L , and 2 / L < k < 3 / L ,
are called the first, second, and third Brillouin zones.
Filled or empty bands do not conduct. Electrons have no place to go.
If an allowed band is partially filled, an electric field can easily excite an electron to an unfilled
part of the band where conduction can occur.
We will have the same number of holes created in the valence band.
Both the electrons and the holes contribute to the conduction.
The electrons at the bottom of the conduction band can be characterized by an effective mass.
For a free electron E = 2 k 2 / 2me or d 2 E / dk 2 = 2 / me .
Because the band is not parabolic at the edge of the Brillouin zone, but has a larger curvature,
the effective mass of the electrons in the conduction band is lower, d 2 E / dk 2 = 2 / m * .
Impurity Semiconductors
The energy of the donor state relative to the bottom of the conduction band is
2
1 ke m * 2
En = 2 2
2 n
me
< rn > = a 0 n 2
m*
Hall Effect
qE = qv d B
VH = Ew = v d Bw
j iB
VH = v d Bw = Bw =
ne ent
Quantum Hall Effect
VH RK h / e 2 25,813
RH = = = =
i n n n
N e e e (V Vb )/ kT = N e e eV / kT e eVb / kT
I = I 0 e eVb / kT
I net = I 0 (e eVb / kT
1)
Solid-State Lighting
2
BC (T ) T
= 1
BC (0) TC
Theory: At low temperatures electrons pair up. The attractive interaction comes from the fact that
an electron moving through the lattice attracts the positive ions and so produces a traveling
distortion of the lattice, a phonon. This traveling local increase in the positive charge density is
attractive to another electron. So there is an attraction between two electrons mediated by the
vibrations of the lattice, phonons. At low enough temperatures, this attractive force is larger than
the Coulomb repulsion and a bound state is formed, a Cooper pair.
The electrons that form a pair have opposite spins and opposite linear momenta!
Together the pair forms a boson and so all pairs can be in the same energy state.
The energy to break up the pair is called the
superconducting energy gap, Eg.
As the temperature is increased, more and more
pairs get broken up. The unpaired electrons
decrease the binding energy of the remaining pairs,
i.e. they decrease the energy gap.
High TC Superconductors
Type II superconductors with high critical temperatures
and high critical fields.
All have copper and oxygen and are in the perovskite structure.
I = I max sin(2 1 )
ac Josephson effect
If a voltage is applied to the junction, the
current oscillates with frequency
f = 2eV / h