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Solid State Physics: H O - An Example F e E
Solid State Physics: H O - An Example F e E
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properties
3
H2 O - AN EXAMPLE
BINDING
The Van der Waals force arises simply from the change H = (H0 ) + (Hint ) (1)
in energy due to the cross Coulomb interactions between
atom a and b, which is simply a dipole-dipole interaction. with
µ ¶ µ ¶
~2 ¡ 2 2
¢ e2 e2 2 1 1 1 1
H= − ∇1 + ∇2 − − +e + − − (2)
2m r1a r2b rab r12 r1b r2a
Using standard perturbation theory it is then possible which leads to a total potential of the form
to evaluate the gain in energy due to Hint . This is left µ 6 ¶
as an exercise. The result is σ σ 12
φ(r) = −4² − , (4)
r6 r12
−αa αb
∆E ' 6 , (3) which is usually referred to as the Lennard-Jones po-
rab
tential. The choice of the repulsive term is somewhat
arbitrary but it reflects the short range nature of the
where αx are the atomic polarizabilities.
interaction and represents a good approximation to the
full problem. The parameters ² and σ depend on the
molecule.
Derivation of Van der Waals
Crystals
Problem 1
What about crystals? Let’s first think about what kind
of energy scales are involved in the problem. If we assume
Repulsion that the typical distance between atoms is of the order
of 1Å we have
We just saw that there is an attractive potential of
e2 /1Å ' 14.4eV for the Coulomb energy and (5)
the form −1/r6 . If there were only a Coulomb repul-
sion of strength 1/r this would lead to the collapse of our µ ¶2
molecule. In fact there is a very strong repulsion, which 1
~2 ' 3.8eV for the potential in a 1Å quantum box
comes from the Pauli principle. For the general pur- 1Å
pose this repulsive potential is often taken to be ∼ 1/r12 , (6)
4
In comparison to room temperature (300K' 25meV) the ground state energy is then given by E 0 =-13.6 eV.
these energies are huge. Hence ionic Crystals like NaCl What happens if we add one proton or H + to the system
are extremely stable, with binding energies of the order which is R away. The potential energy for the electron is
of 1eV. then
e2 e2
U (r) = − − (10)
Ionic crystals r |r − R|
The lowest eigenfunction with eigenvalue -13.6eV is
Some solids or crystals are mainly held together by the µ ¶3/2
electrostatic potential and they include the alkali-halides 1 1
ξ(r) = √ e−r/a0 , (11)
like (N aCl −→ N a+ Cl− ). π a0
where a0 is the Bohr radius. But now we have two
d protons. If the protons were infinitely apart then the
general solution to potential 10 is a linear superposi-
tion ,i.e., ψ(r) = αξ(r) + βξ(r − R) with a degener-
ate lowest eigenvalue of E 0 = E 0 =-13.6 eV. When R
is not infinite, the two eigenfunctions corresponding to
the lowest eigenvalues Eb and Ea can be approximated
by ψb = ξ(r) + ξ(r − R) and ψa = ξ(r) − ξ(r − R). See
figure 3.
- +
Ψb(r)
-8 Covalent bonding
tot
Covalent bonds are very similar to Hydrogen bonds,
Ea only that we have to extend the problem to a linear com-
Antibonding
E [eV]
-16 Eb Bonding
R0
Metals
R [distance between protons]
In metals bonding is a combination of the effects dis-
FIG. 4: The energies as a function of the distance between cussed above. The idea is to consider a cloud of electrons
them for the bonding and anti-binding wave functions of the only weakly bound to the atomic lattice. The total elec-
electron trostatic energy can then be written as
Z X X Z
e2 e2 e2 n(r1 )n(r2 )
Eel = − drn(r) + 0
+ 1/2 · dr1 dr2 (19)
r−R 0
R−R |r1 − r2 |
R R>R
which corresponds to an ionic contribution of the form This last expressions leads to a minimum at rs /a0 = 1.6.
µ ¶1/3 We can now compare this with experimental values and
αe2 3 the result is off by a factor between 2 and 6. What went
Eel = − where rs = (20)
2rs 4πn wrong. Well, we treated the problem on a semiclassi-
cal level, without incorporating all the electron-electron
and α is the Madelung constant. Deriving this requires
interactions in a quantum theory. This is very very diffi-
quite a bit of effort. On top of this one has to add the
cult, but in the large density case this can be estimated
kinetic energy of the electrons, which is of the form:
and a better agreement with experiments is obtained.
µ ¶2/3
9π 3~2
Ekin = (21)
4 10mrs2
Binding summary
And finally we have to add the exchange energy, with is
a consequence of the Pauli principle. The expression for There are essentially three effects which contribute to
this term is given by the binding of solids:
µ ¶1/3
9π 3 • Van der Waals (a dipole-dipole like interaction)
Eex = − (22)
4 4πrs
• ionic (Coulomb attraction between ions)
Putting all this together we obtain in units of the Bohr
radius: • Quantum mechanics (overlap of the wave-function)
µ ¶
24.35a0 30.1a20 12.5a0 In addition we have two effects which prevent the collapse
E= − + − eV/atom (23)
rS rS2 rs of the solids:
6
STRUCTURE
FIG. 6: Plane intercepts the axes at (3aˆ1 , 2aˆ2 , 2aˆ3 ). The in-
verse of these numbers are (1/3, 1/2, 1/2), hence the smallest
integers having the same ratio are 2,3,3, i.e., the Miller in-
dices are (233). For a negative intercept the convention is 1̄.
FIG. 5: Pyrite, F eS2 crystal with cubic symmetry.
(Picture from Ashcroft and Mermin)
Illustrations SCATTERING
Scattering theory of everything Physics is hidden in n(r), which contains the informa-
tion on the position of scatterers and their individual
scattering distribution and probability. In the following
we discuss the most important implications.
dV
← crystal
k r 1D scattering pattern
Incident
k’ Outgoing
beam ϕ
beam
This formulation can describe any scattering process where C is simply a constant. Hence, by inserting 25
in terms of the scattering amplitude A(~q). The entire into 24, and defining ~q = (0, q, 0) we have
N −1 ½
C X iqan C 1 − eiaqN C when q = 2πm/a
A(q) = e = =N →∞ = Cδq,G
~ (26)
N n=0 N 1 − eiaq 0 when q 6= 2πm/a
We start again with the general form of A(~q) from 24 G~m = m1 b~1 + m2 b~2 + m3 b~3 , (30)
and assume that our 3D crystal is formed by point-like
~ Hence,
scatterers on a Bravais lattice R.
where
The most general form for n(~r), when the atoms sits
on the basis {u~j } along the Bravais lattice R~n is
M,N
X−1
C
n(~r) = fj (~r − R~n − u~j ), (32)
N j=1,n=0
Bragg’s law nuclear sites. The scattered wave amplitude with wave
number ~k is then
Equivalence between Bragg’s law for Miller planes and Z
~ ~
the reciprocal lattice. A(~k − k~in ) ∼ d3 rn(~r)ei(k−kin )·~r (43)
V
q1=kin-k1out θ
a
kin
FIG. 8: Point-like Bragg peaks from a single crystal. (Ref:
lassp.cornell.edu/lifshitz)
y z
x
• Powder diffraction:
nλ = 2a sin(θ). (39)
hence,
2π
n = 2 sin(θ) · |k~in | = |q~1 |, (40)
a
since k = 2π/λ and we supposed that k~in is perpendicular FIG. 9: Circle-like Bragg peaks from a powder with different
~
to ẑ. This condition is equivalent to q~1 = x̂2π/a ∈ G. grain sizes
The same relation applies for the scattering of the plane
perpendicular to ŷ or Miller index (0,1,0) the following
diffraction condition applies: • Liquid diffraction:
nλ = 2b cos(θ). (41)
hence,
2π
n = 2 cos(θ) · |k~in | = |q~2 |, (42)
b
~
or q~2 = ŷ2π/b ∈ G.
~
We have an incoming wave eikin ·~r diffracting on some
sample with volume V and with a scattering probability The liquid diffraction is essentially the limiting case
n(~r) inside V . For X-ray n is typically given by the elec- of the powder diffraction when the grain size be-
tron distribution whereas for neutrons it is typically the comes comparable to the size of an atom.
10
PROPERTIES OF SOLIDS AND LIQUIDS where the pre-factor 2 comes from the spin degeneracy.
Hence,
The Theory of everything discussed in the first section
kF3 4π 3
can serve as a guideline to illustrate which part of the n3D
e = in D = 3 since VkDF = k (48)
Hamiltonian is important for a given property. For in- 3π 2 3 F
stance, when interested in the mechanical properties, the k2
n2D
e = F in D = 2 since VkDF = πkF2 (49)
terms containing the electrons can be seen as a pertur- 2π
bation. However, when considering thermal conductivity, 2kF
n1D
e = in D = 1 since VkDF = 2kF , (50)
for example, the kinetic terms of the ions and the elec- π
trons are important. where the maximum energy of the electrons is
In the following we will start by considering a few cases
and we will start with the single electron approximation. ~2 kF2
EF = the Fermi energy (51)
2me
µ ¶D E
2π
(46)
L
of volume in k-space, if D is the dimension of the space. FIG. 11: Density of states in 1D, 2D and 3D
If we now want to compute the electron density (number
of electrons per unit volume ne = N/LD ) in the ground
state, which have k < kF (Fermi sphere with radius kF ),
we obtain:
Properties of the free electron model
µ ¶D
D L
ne = 2 · VkF · /LD , (47)
2π Physical quantities at T=0:
11
hEi
• Average energy per electron: n = 35 EF
¶
• Pressure: P = − ∂(hEiV )
= 2 1 ∂hEi π2 2
∂V 5 nEF , where hEiV is CV = = k T D(EF ) (64)
the total energy. V ∂T µ,V 3
∂P
• Compressibility κ−1 = −V ∂V = 23 nEF Hence, CV
= γ, which is the Sommerfeld parameter.
T
Case 2: T6= 0: In equilibrium
Periodic potentials
1
fF D = , (57)
e(E−µ)/kT + 1 The periodicity of the underlying lattice has important
consequences for many of the properties. We will walk
where the chemical potential is the energy to add one
through a few of them by starting with the simplest case
electron µ = FN +1 − FN . µ = EF at T=0 and F is the
in 1D.
free energy.
The Sommerfeld expansion is valid for kT << µ and
Z ∞ Kronig-Penney model
hHi = dEH(E)FF D (E) (58)
0
Z µ Let us first consider the following simple periodic po-
π2
' H(E)dE + (kT )2 H 0 (µ) + ... (59) tential in 1D.
0 6
Z ∞ X
~2 ∇2
hEi = dEED(E)FF D (E) (60) H=− −V δ(x − na) (65)
0 2m n
Z EF
π2
' ED(E)dE +(kT )2 D(EF ) + ...
(61) The solutions for na < x < na+a are simply plane waves
0 6
and can be written as
hni = n(T = 0) (62)
π 2 0
D (EF ) ψ(x) = An eikx + Bn e−ikx . (66)
⇒ µ(T ) ' EF − (kT )2 + ... (63)
6 D(EF )
Now the task is to use the boundary conditions in order
Physical quantities at T6=0: Specific heat to determine An and Bn . We have two conditions:
½
An−1 eikna + Bn−1 e−ikna = An eikna + Bn e−ikna = ψ(na) = ψn
(68)
An−1 eikna e−ika + Bn−1 e−ikna eika = ψn−1
½ ¡ −ika ¢
e−ika ψn − ψn−1 = Bn−1 e−ikan
¡ e − e¢ika
=⇒ (69)
eika ψn − ψn−1 = An−1 eikan eika − e−ika
½ ¡ −ika ¢
e−ika ψn+1 − ψn = Bn e−ikan e−ika
¡ e −¢eika
and (70)
eika ψn+1 − ψn = An eikan eika eika − e−ika
~
− ik An eikan −ik Bn e−ikan −ik An−1 eikan +ik Bn−1 e−ikan = V ψn , (71)
2m | {z } | {z } | {z } | {z }
ψn+1 −e−ika ψn ψn+1 −eika ψn eika ψn −ψn−1 e−ika ψn −ψn−1
2i sin(ka) −2i sin(ka) 2i sin(ka) −2i sin(ka)
12
hence,
2
~ k −ika
− 2ψn+1 + 2ψn−1 + ψn (−e − eika − eika − e−ika ) = V ψn (72)
2m 2 sin(ka) | {z }
−4 cos(ka)
and finally, This equation is often called the tight binding equation
µ ¶ as we will see in the next section. Finding a solution for
2m sin(ka) this equation is trivial since
ψn+1 + ψn−1 = − V + 2 cos(ka) ψn , (73)
~2 k
| {z }
W ψn = eipan (75)
Which can be rewritten as
is a solution. This is easily verified by plugging (75) into
ψn+1 + ψn−1 = W ψn (74) (74), which yields
−2 ≤ W ≤ 2 (77)
Let us consider the general potential due to the ar-
We now recall that the Eigenstate of the original Hamil- rangement of the atoms on a lattice:
2 2
tonian is given by E(k) = ~2m k
, where eikx is the plane
~2 ∇2 X
wave between two δ functions, hence the dispersion re- H=− + V0 (~r − R~n ) (78)
2 2 2m
lation is equal to E(k) = ~2mk
as long as −2 ≤ W ≤ 2. |
n
{z }
This condition will create gaps inside the spectrum as V (~
r)
illustrated in the graph below:
This is a very general form for a periodic potential assum-
ing that we only have one type of atoms. The periodicity
is given by the lattice index R~n . For a general periodic
2
<2
<W
-2
~
-2
ψk (~r) = eik·~r uk (~r), (79)
W<
0 1 2 3
~ ~
FIG. 12: Dispersion curve for the Kronig-Penney model ψk (~r + R~n ) = eik·Rn ψk (~r) (80)
X
hφl (r − Rm )|H|φl (r − Rn )i = −tl δm,~
~ n+~i + δm,~
~ n−~i
+ ²l δm,~
~ n (81)
~i=x̂,ŷ,ẑ
Hence, only the nearest neighbor in every direction is Combining Bloch’s theorem with the tight binding
taken to be non-zero. Further, we assume that there is no approximation
overlap between levels of the one atom potential, which
allows us to look for a general solution of the following The tight binding approximation is very general and
form for each energy level ²l . can be applied to almost any system, including non-
periodic ones, where the tight binding elements can be
X
ψl (r) = c~ln φl (r − R~n ) (82) assembled in an infinite matrix. For the periodic case,
~
n
on the other hand, it is possible to describe the system
with a finite matrix in order to obtain the full disper-
with eigenvalue El (k). To calculate El (k) we plug-in
sion relation. This is obtained by combining the Bloch
this Ansatz into eq. (82) and obtain an equation for
theorem for periodic potentials, where the wave-function
the coefficients c~ln , which leads to the following equation
from (79) is again:
when using the tight binding approximation given in eq.
(81). ~
ψk (~r) = eik·~r uk (~r)
X
clm
~ ²l − tl
l
cm+
~ ~i
= El (k)clm
~ (83) Instead of writing (82) we write the Bloch-tight-
~i=±x̂,ŷ,ẑ binding solution as
The solution of this equation are plane waves, which X ~
i~
k·R~m ψlk (r) = eik·R~n c~ln φl (r − R~n ),
can be verified readily by taking clm
~ = e and plug-
~
n
ging it into the equation to obtain
which now depends explicitly on the wavevector ~k. Using
El (k) = ²l − tl (2 cos(kx ax ) + 2 cos(ky ay ) + 2cos(kz az ), Bloch’s theorem this implies that
(84)
where ~a is the lattice constant in all 3 space directions: c~ln = cm
l
~,
~a = Rm+â
~ − Rm ~ . The energy diagram is illustrated in
fig. . The degeneracy of each original single atomic en- whenever ~n and m~ are related by a linear combination of
ergy level ²l is lifted by the coupling to the neighboring Bravais vectors. Moreover, the tight binding equation in
~
atoms and leads to a dispersion curve or electronic band (83) is the same but with c~ln replaced by c~ln eik·R~n
structure.
E
a
ε3 B
ε2
ε1
-1.0 -0.5 0.0 0.5 1.0
FIG. 13: Dispersion curve for the tight binding model We apply this to the simple example of a diatomic
square lattice of lattice constant a with alternating atoms
A and B shown in figure . We will further assume that
This tight binding approximation is very successful we have only one band l. Hence, the Bloch-tight-binding
in describing the electrons which are strongly bound to solution is written as
the atoms. In the opposite limit where the electrons or
X ~
more plane-wave like, the weak potential approximation ψ k (r) = eik·R~n c~n φ(r − R~n ),
is more accurate: ~
n
14
~ 2 2
where c~n takes on only to possible values due to Bloch’s ψk0 (~r) = eik·~r , with corresponding energies ²0k = ~2mk
and
theorem: cA or cB . This leads to the following simplified 0 0 0
Hamiltonian H0 , i.e., H0 ψk (~r) = ²k ψk (~r). Since the ori-
tight binding equations (assuming hφl (r − Rn )|H|φl (r − gin of this energy dispersion relation can be chosen from
Rn )i = ²A or ²B and t = −hφl (r − Rn )|H|φl (r − Rm )i any site of the reciprocal lattice, we have ²0k+K = ²0k ,
when n and m are nearest neighbors): hence these energies are degenerate. This implies that
P we have to use a degenerate perturbation theory. The
~~
cA ²A − t ~ cB eiak·i = E(~k)cA mathematical procedure is very similar to the tight bind-
Pi=±x̂,ŷ ~~
cB ²B − t ~i=±x̂,ŷ cA eiak·i = E(~k)cB ing approximation, but we now expand the solution ψ(~r)
of the full Hamiltonian H = H0 + V (~r) in terms of a sum
It is now quite straightforward to rewrite these equa- of plane waves ψk0 (~r). Since ²0k+K = ²0k we will only use
tions in matrix form: two plane waves in this expansion: ψk0 (~r) and ψk+K 0
(~r).
µ ¶µ ¶ µ ¶ Hence,
²A −t · g cA ~ cA
= E(k) ,
−t · g ∗ ²B cB cB
ψ(~r) = αψk0 (~r) + βψk+K
0
(~r), (85)
ia~
k·x̂ −ia~
k·x̂ ia~
k·ŷ −ia~
k·ŷ
with g = e +e +e +e . The disper-
sion relation or band structure is then simply given by where the coefficients α and β have to be determined in
obtaining the eigenvalues of HBT B , where order to solve Schrödinger’s equation:
µ ¶
²A −t · g
HBT B = . (H − E)ψ(~r) = 0. (86)
−t · g ∗ ²B
½ R R
R α d3 r(ψk0 )∗ (~r)(H − E)ψk0 (~r) +R β d3 r(ψk0 )∗ (~r)(H − E)ψk+K
0
(~r) = 0
3 0 ∗ 0 3 0 ∗ 0 , (87)
α d r(ψk+K ) (~r)(H − E)ψk (~r) + β d r(ψk+K ) (~r)(H − E)ψk+K (~r) = 0
Finally if ²0k = ²0k+K , we have E = ²0k ± |VK |, which the wavevector which corresponds to the two dispersion
leads to a splitting 2|VK | of the energy levels at these curves which led to the degenerate energy level.
degenerate energies. For the example in figure , this
weak potential approximation would give us a splitting of
2|VK=2π/a | at k = −π/a and k = K − π/a = π/a. This Localization
implies that the first order calculation of the energy split-
ting due to the weak periodic potential V (r) is equal to
When, instead of having a purely periodic potential
twice the fourier transform of this potential evaluated at
disorder is included into the system, we no more have
15
Bloch wave solutions but localization of the wave func- equation Hψ = E(k)ψ it follows that uk is a solution of
tions occur. This is particularly important in low dimen- µ 2 ¶
sional systems and tends to suppress transport. ~
(k − i∇)2 + V − E(k) uk = 0. (93)
2m
| {z }
Hk −E(k)
Electronic properties due to periodic potential
In order to calculate hvi we use first a first order pertur-
Density of states bation in k + q, where q is very small. Therefore, the
eigenvalue corresponding to Hk+q is E(k + q), which is
to first order
Density of states in 1D:
E(k + q) = E(k) + huk |Hk+q − Hk |uk i
∂n δn ~2
D(E) = ' = E(k) + hψeikr | ( q 2 +2q(k − i∇))|e−ikr ψi
∂E δE 2m |{z}
¯ ¯−1 →0
δn ¯¯ ∂E(k) ¯¯
= × |{z}
2 × |{z}
2 ~2
δk ¯ ∂k ¯ P = E(k) + hψeikr | q(k − i∇))|e−ikr ψi
spin ±k
m
¯ ¯−1 ~
1 δN ¯¯ ∂E(k) ¯¯ = E(k) + hψ|q~ (−i∇)|ψi
= ×4 m
L δk ¯ ∂k ¯ = E(k) + q~hψ|v|ψi
¯ ¯−1
2 ¯¯ ∂E(k) ¯¯ = E(k) + q∇k E(k) (Taylor expansion)
D(E) = , (90)
π ¯ ∂k ¯ 1
⇒ hvi = ∇k E(k). (94)
~
where we used that δE = (∂E/∂k)δk and δk = 2π/L for
one electron, i.e., δN = 1. Hence, the expectation value of the velocity is determined
In three dimensions (D=3) we have: by the slope of the dispersion relation. This also implies
that the sign of the average velocity depends on the sign
of ∂E/∂k.
∂n δn
D(E) = '
∂E δE
X δn −1
Response to an external field and existence of holes and
= |∇k E(k)| × |{z}2 electrons
δk
E(k)=E spin
Z The idea is to describe the average motion of an elec-
2 −1
= d2 k |∇k E(k)| , (91) tron in the presence of an external field (electric, Eel , or
(2π)3 E(k)=E
magnetic, B) in a semiclassical way. Hence, we want
P 2
where we used δE = (∇k E(k)) · δk, E(k)=E (δk) → d
R 2 3 3 m∗ hvi = F = (qEel or qhvi × B), (95)
E(k)=E
d k, and δn/(δk) = 1/(2π) . This result shows dt
that the density of state in the presence of a periodic
potential, i.e., for a crystal depends only on the slope of where m∗ is an affective mass and q the charge. Using
the dispersion relation or the band structure. (95) and (94) we have
∂hvi
m∗ k̇ = qEel
Average velocity ∂k
1 ∗ ∂2E
m k̇ = qEel
The average velocity of an electron in a periodic po- ~ ∂k 2
tential is given by the expectation value of the velocity, ⇒ ~k̇ = qEel = F, (96)
i.e.,
Where we defined the effective mass m∗ as
hvi = hψ|v|ψi, (92) ¯ 2 ¯−1
∗
¯ ¯
2 ¯∂ E ¯
m =~ ¯ 2¯ . (97)
where ψ is the wavefunction from the Hamiltonian with ∂k
2 2
periodic potential V , i.e., H = ~2m
∇
+ V . From Bloch’s 2
theorem (79) we can write ψ(r) = eikr uk (r), where uk (r) If ∂∂kE2 is negative we need to change the sign of q in order
2
has the same periodicity as V (r). From the Schrödinger to remain consistent. Hence, when ∂∂kE2 > 0, the charge
16
2
of an electron is q = −e but if ∂∂kE2 < 0 then q is positive Using (101) and (94) and since k̇ is perpendicular to hvi
(+e). In this case we describe the particles as holes. ˙ ∼ ∂E/∂kk we obtain
and B, (k)
They represent missing electrons. With these definitions
Z k2
of q and m∗ , which is also called the band mass, the ~2 dk⊥
semiclassical equations of motion of single electrons in a δt =
qB k1 ∂E/∂kk
periodic potential are simply given by eqs. (95) and (96). 2 Z k2
~ d
In general, the effective mass is given by a tensor de- = kk dk⊥ . (103)
fined as qB dE k1
¯ 2 ¯−1
∗
¯
2¯ ∂ E ¯
¯ For a complete turn this leads to
mαβ = ~ ¯ , (98)
∂kα ∂kβ ¯ I
~2 d
where α and β are the spatial directions. An important T = kk dk⊥ . (104)
qB dE
consequence of this semiclassical description of the mo- | {z }
S
tion of electrons is the dependence of the effective mass
on the energy and the band structure. In some cases the Here S is the area enclosed by an orbit in k-space. This
2
effective mass can even diverge (when ∂∂kE2 = 0). Sim- orbit corresponds to an equipotential line perpendicular
ilarly the sign of the carriers also depends on the band to the magnetic field.
structure and the energy of the carriers. By definition we Let’s suppose for simplicity that the effective mass ten-
call the bottom of an energy band and electronic band sor m∗ is diagonal and given by
2
when ∂∂kE2 > 0 and a hole band when at the top of the
2 mx 0 0
energy band ∂∂kE2 < 0.
m∗ = 0 my 0 (105)
0 0 mz
Bloch oscillations
and that the energy dispersion is harmonic (which is usu-
ally true at a band extremum, i.e.,
In the presence of an electric field and a periodic po-
tential we can use the equation of motion (96), i.e., ~2 kx2 ~2 ky2 ~2 kz2
E(k) = + + . (106)
eEel 2mx 2my 2mz
~k̇ = −eEel ⇒ k = − t, (99)
~
If we assume that the magnetic field is along z and that
but in a periodic potential and in the tight binding ap- the average effective mass perpendicular to B is given by
proximation the energy is given by E(k) = −2t0 cos(ka), m⊥ , we can rewrite (106) as
where a is the lattice constant and t0 the nearest neighbor
overlap integral. Hence, since v = ṙ and hvi = ~−1 ∂E/∂k ~2 k⊥
2 ~2 kk2
we have E(k) = + , (107)
2m⊥ 2mk
2t0 aeEel t
hri = cos( ). (100) 2
eEel ~ where k⊥ = kx2 +ky2 . Using (104) and (107 we then obtain
This means that the average position of the electrons 2
S = πk⊥ = π(2m⊥ E/~2 ) − πkk2 m⊥ /mk
oscillates in time (Bloch oscillations). In artificial struc-
tures these Bloch oscillations are typically of the order of dS π2m⊥
⇒ =
1THz. dE ~2
2π qB
⇒ ωc = = , (108)
T m⊥
Semiclassical motion in a magnetic field
which is the cyclotron frequency. Hence, the cyclotron
In the presence of a magnetic field (B), we can describe frequency depends on the average effective mass perpen-
the semiclassical trajectories in k-space using (96), i.e., dicular to the magnetic field. This allows us to measure
the effective mass along different directions, simply by
~k̇ = qhvi × B. (101) changing the direction of the magnetic field and by mea-
Hence, only the values of k perpendicular to the magnetic suring the cyclotron frequency.
field will change, which we denote by k⊥ . The component
parallel to the field, kk is not affected by B. During a Quantization of the cyclotron orbit: Landau levels
small time difference
Z t2 Z k2 =k(t2 )
In quantum mechanics the energies of these cyclotron
δt = t2 − t1 = dt = dk⊥ /|k̇|. (102)
t1 k1 =k(t1 ) orbits become quantized. To see this we can write the
17
500
Hamiltonian of an electron in a magnetic field in the har- 450 300
Rxx [Ω]
200
monic approximation (107) as 400
100
350
0
300
Rxx [Ω]
1 1
1.1 1.3 1.5 1.8 2.0 2.2 2.4 2.6 2.8
qB1 qB2
~ (n1 + 1/2) = EF⊥ = ~ (n2 + 1/2)
m⊥ m⊥
1 1 q
⇒ − =~ ( EF⊥ )−1 (n2 − n1 ) us+4
B1 B2 m⊥ |{z} u s −1 u s u s +1 u s + 2 us+3
~2 K
2πm⊥ ·S
µ ¶
1 2πq −1
⇒ ∆ = S , (111) s −1 s s +1 s+2 s+3 s+4
B ~
H
where the maximum S is S = kk dk⊥ = π(kxF )2 = FIG. 16: Two types of lattice displacement waves in 2D, trans-
~2 (kx
F 2
)
~ S 2
π(kyF )2 and EF⊥ = = 2πm
2m⊥ ⊥
. Hence, the Magneto- verse and longitudinal modes
oscillations are periodic in 1/B and the period depends
on S. An example of these oscillations in resistance is
shown in figure 15 as a function of B and 1/B.
18
ul = eikla−iωt
2
=⇒ M ω 2 =q2K(1 − cos(ka)) = 4K sin (ka/2) (114)
K
=⇒ ω = 2 M | sin(ka/2)|
1.2
ω Mono-atomic dispersion
1.0
2 (K M)
0.8
0.6
0.4
0.2
0 k
-π/a 0 π/a 2π/a
Optical branch
NX NX
ions
~2 ∇2i ions
qi qj
Hions = − + (121)
i
2mi i<j
|ri − rj |
! displacment
X ∂φ z}|{ 1 X ∂2φ
φ(r1 , . . . , rn ) = φ(r10 , . . . , rn0 ) + ui + ui uj + · · · (122)
| {z } ∂ri 2 i,j ∂ri ∂rj
i ri0 0
ri
Cohesive energy | {z } | {z }
Equilibrium pos. 0 φi,j
The linear term has to be zero for stability reasons (no trated in fig. 18. From 123 we have
minimum in energy otherwise). The classical equation X ~ ~ ~
of motion is then simply given by equ. 112, because mω 2~² = φl,m eik·(Rl −Rm ) ·~² (124)
F~ = −∇φ.
~ To solve this equation in general, one can |
m
{z }
write a solution of the form φ̂(k)
,
where φ̂(k) is a 3 × 3 matrix, since φlm too. This leads
i~ ~l −iωt
k·R
to an eigenvalue equation for ω 2 with three eigenvalues:
u~l = ~² · e , (123) ωL2
(for ~k k ~²) and ωT2 (1,2) (for ~k ⊥ ~²). Hence, we have
on longitudinal mode and two transverse modes and all
phonon modes can be described by a superposition of
where R ~ l are the lattice sites. One then has to solve these.
for the dispersion relation ω(~k) in all directions, as illus- If we have two different masses, we have two addi-
20
Quantum case k2 ω2
DL,T (ω) = = (128)
2π 2 cL,T 2π 2 c3L,T
While many of the properties, like the dispersion rela-
or
tion, can be explained in classical terms, which are simply
vibrations of the crystal ions, others, such as statistical
properties need a quantum mechanical treatment. µ ¶
ω2 1 2
Phonons can simply be seen as harmonic oscillators Dtot (ω) = + 3 (129)
2π 2 c3 c
which carry no spin (or spin 0). They can, therefore, be | L {z T }
accurately described by bosons with energy 1
c3
X ∞
X
E(ω) = En Pn = (1 − e−~ω/kB T )~ω (n + 1/2)(e−~ω/kB T )n
n n=0
1 1
= ~ω + ~ω/k T (131)
2 e B − 1
| {z }
hni
here hni is the expectation value of quantum number n zero energy state is totally degenerate (this does sup-
at T , which is nothing else but the Bose Einstein distri- pose that there are no interactions between bosons, with
bution. As is well known, Bosons obey the Bose-Einstein interactions the delta function will be a little broader).
statistics, where he Bose-Einstein distribution function is The total average energy can then be calculated from the
given by density of states as:
1 Z
fBE = (132)
eE/kB T − 1 hEi = dωD(ω)E(ω) (133)
Important: at T = 0, fBE is simply a delta function
δ(E). This is the Bose-Einstein condensation, where the This also allows us to calculate the specific heat CV =
21
d
dThEi in the isotropic case and in the linear dispersion If the electrons flow without collisions,
approximation D(ω) ∼ ω 2 /c3 , hence (137)=g(r, k, t) = fF D . The situation changes if
collisions (f. ex. between electrons, impurities, or
Z ∞ phonons) are included. In this case
d
CV = dωD(ω)E(ω)
dT 0
Z ∞
d ~ω g(r, k, t) − g(r − ṙdt, k − k̇dt, t − dt) = δgcoll. (138)
= dωD(ω) ~ω/k T
dT 0 e B −1
Z ∞ where gcoll. describes the collisions. gcoll. = 0 without
d 3 1 ~ω 3
= 2 3
dω ~ω/k T collisions. Expanding (137) to first order and using (138)
dT 2π c
|{z} 0 e B −1 we obtain
µ ¶| {z }
1 1 2 R∞ 3 (kB T )4
3 c3
+
c3 0
dω exx−1 ~3
L
Z
T
¶
d 3(kB T )4 ∞
x3 ∂g ∂g ∂g dg
= dω x ṙ + k̇ + = (139)
dT 2π 2 (c~)3 e −1 | ∂r {z∂k ∂t
} dt coll.
0
| {z } dg
π 4 /15 dt
µ ¶3
2π 2 kB kB T This is Boltzmann’s equation.
= (134)
5 ~c
where we had defined the variable x = ~ω/kB T and Relaxation time approximation
where 1/c3 is the average over the 3 acoustic modes.
The Debye model assumes a linear dispersion (ω = ck) Solving Boltzmann’s equation is not easy in general
and uses the analogy to electrons where (n = kF3 /3π 2 ) to and therefore approximations are used. The simplest one
define kD . Since phonons have no spins one obtains: is the relaxation time (τ ) approximation. In this approx-
imation:
3
kD
n = and ¶
6π 2 dg 1
= − (g − fF D )
k B ΘD = ~ωD = ~ckD (ΘD : Debye temperature) dt coll. τ
µ ¶3
12π 4 kB T dg 1
=⇒ CV = ·n (135) =⇒ = − (g − fF D ) (140)
5 ΘD dt τ
The typical Debye temperature is of the order of 100K. It is quite intuitive to see from where this approxima-
Finally, combining this result with the contributions from tion comes from, since a kick at t = 0 would lead to
electrons (64), we obtain the expression valid for low tem- solution of the form
peratures:
e−t/τ
g(t) = + fF D → fF D (when t = ∞) (141)
CV = γT + βT 3 (136) τ
|{z} |{z}
electrons phonons This is the basic framework, which allows us to eval-
uate the effect of external fields on the system and to
estimate the linear response to them.
TRANSPORT (BOLTZMANN THEORY)
~ = −eE
Case 1: F ~
Transport allows us to calculate transport coefficients
such as resistances and thermal conductivities. While
several transport theories exist, Boltzmann’s approach In this case we look for a response in current density
is the most powerful and applies to most situations in and define the conductivity tensor in linear response as
condensed matter. The main idea in Boltzmann theory
is to describe the electrons by a distribution function g.
In equilibrium g is simply the Fermi-Dirac distribution ~
~j = σ E
Z
function fF D . In general, g(r, k, t) and at t − dt it can be d3 k
⇒ jα = σαβ Eβ = −2e vα g(r, k, t). (142)
written as: (2π)3
~k̇ = −eE, Boltzmann’s equation (139) in the relaxation Diffusion model of transport (Drude)
time approximation becomes
In the case where the scattering of electrons is domi-
∂g 1 nated by inelastic diffusion, we can write a very simple
k̇ = − (g − fF D )
∂k τ form for the conductivity or resistivity tensor. Indeed, in
|{z}
−eE~ ∂g ∂² a diffusive regime the average velocity is directly propor-
∂² · ∂~
~ k tional to the external force and to the inverse effective
~
eEτ ∂g ∂² mass. The proportionality coefficient is then simply the
⇒g = · +fF D (143) scattering probability 1/τ . Hence,
~ ∂² ∂~k
|{z} |{z}
∂fF D
'− ∂µ
~~
v
m∗
Here we used the first order approximation ∂g/∂² ' ~v = F~ = −eE
~ − e~v × B
~ (148)
τ
−∂fF D /∂µ, which is justified if the correction g − fF D is
smoother than ∂fF D /∂µ, which is close to a delta func- If we suppose that the magnetic field is small and in
tion when kT << EF . Hence, using (143) to evaluate ~ along x̂, then eq. (148) becomes
the ẑ direction and E
the current (142), we obtain
∗
Z Z ~ = − m ~v −e~v × B
eE ~
d3 k ~ ∂fF D |{z} τ } | {z }
jα = 2e vα eτ E · ~v + ∼ ( vα fF D ), (144) eEx | {z
(2π)3 ∂µ 'jy B/n∗
| {z } ' mτ en
jx
=0
m∗ B
which leads to Ex = 2
jx + jy (149)
ne τ ne
Z
∂jα d3 k ∂fF D
σαβ = = 2e2 3
vα vβ τ (²) (145) Since in general E ~ = ρ~j and because the resistivity
∂Eβ (2π) ∂µ ~
along B is not affected by the magnetic field we can write
This is one of the most important expressions for the ~ in the ẑ direction,
for B
conductivity. Since ∂fF D /∂µ is almost a delta function
for kT << EF this expression shows that only electrons
m∗ B
close to the chemical potential µ will significantly con- ne2 τ ne 0
m∗
tribute to transport. It is possible to evaluate (145) in ρ= B
− ne ne2 τ 0 = σ −1 (150)
∗
m
simple cases. 0 0 ne2 τ
Let’s assume that τ does not depend on the energy,
then we can rewrite (145) as This is the famous Drude formula in a magnetic field.
This formula is in fact equivalent to the relaxation time
Z µ ¶ approximation in the Boltzmann theory (147).
d3 k ∂² ∂fF D
σαβ = 2e2 τ v α −
(2π)3 ~∂kβ ∂²
Z 3
µ ¶
d k ∂fF D Case 2: Thermal inequilibrium
= e2 τ vα −
(2π)3 ~∂kβ
Z 3 Z We now consider the case, where we also have a spacial
2 d k ∂vα
= e τ fF D /~ − f F D vα gradient. Hence (139) and (140) become
(2π)3 ∂kβ k⊥β
|{z} | {z }
~δαβ /m∗ =0 ∂g ∂g 1
Z ṙ + k̇ = − (g − fF D ), (151)
e τ 2
d k 3 ∂r
|{z} ∂k
|{z} τ
= 2 fF D δαβ (146) ~ v ∂f
m∗ (2π)3 v · ∂f
'~ ∂~
r '−eE·~ ∂²
| {z }
n
here we used again that g − f is smooth so that ∂(g −
• If τ (²) = τ we therefore obtain the most important f )/∂² << ∂f /∂². Moreover, since
formula of conductivity (the Drude formula)
e2 τ n 1
σαβ = δαβ (147) fF D =
m∗ e(²−µ(r))/kT (r)
+1
µ ¶
Using the same approach but in the presence of a mag- ∂f ∂f ∇r T
⇒ = −∇r µ − (² − µ)
netic field, F~ = −eE−e~
~ v × B, ~ we can derive an equivalent ∂r ∂² T
µ ¶
expression for σαβ , but in this case the off-diagonal com- ∂f ~ ∇r T
⇒ g = ~v · τ eG + (² − µ) + fF D ,(152)
ponent is not zero anymore. (See assignment). ∂² T
23
~ = eE+
where we defined the generalized field eG ~ ∇µ(r)
~ Is obtained from eqs. (153,154,157), by setting j´e =
³
and the external forces are now −eE,~ ∇µ(r)
~ ~ (r),
and ∇T 11 ~
0, hence at low temperatures, L G+L 12 ~
∇T
− T =
corresponding to an external electrical field, a gradient 0 and
in the chemical potential (f.ex. a density gradient), and à !
a temperature gradient. The electrical current density is ~
∇T
the same as before but is now expressed (in the linear jQ = (L12 (L11 )−1 L12 −L22 ) −
| {z } T
response) in terms of the additional external fields: ∼O(T 4 )'0
L22
Z Ã ! = − ∇T
d3 k ~
−∇T T
j~e = −2e ~ + L12
~v g ' L11 G . (153)
(2π)3 T π2 k2 T
⇒ καβ = σαβ (158)
3 e2
An expression for the thermal current can be de- This is the well known Wiedemann-Franz law
duced from the following thermodynamical relation dQ =
T dS = dU − µdN , hence ~ = Q∇T with je = 0. In
• Thermopower (Q): E
this case
Z Ã !
d3 k ~
−∇T L12 π2 k2 T σ0
j~Q = 2e ~ + L22
(² − µ)~v g ' L21 G . Q= = (159)
(2π)3 T L11 T 3 e σ
(154)
Here Lαβ are the linear transport coefficients and σ = • Peltier effect (∇T = 0): jQ = Πje ⇒ Π =
L11 . We now want to evaluate these expressions in the L21 /L11 = T Q
low temperature limit, where we can use ∂fF D /∂µ '
δ(² − ²F ), hence the expression for σ in (145) can be Historical note:
The Seebeck effect: The discovery of thermoelectricity
written as
dates back to Seebeck [1] (1770-1831). Thomas Johann See-
beck was born in Revel (now Tallinn), the capital of Estonia
Z which at that time was part of East Prussia. Seebeck was a
∂jα d3 k
σαβ (x) = = 2e2 vα vβ τ (x)δ(² − x), (155) member of a prominent merchant family with ancestral roots
∂Eβ (2π)3 in Sweden. He studied medicine in Germany and qualified
as a doctor in 1802. Seebeck spent most of his life involved
where σαβ = σαβ (²F ). We will use this new function σ(x) in scientific research. In 1821 he discovered that a compass
to express the other transport coefficients. For instance needle deflected when placed in the vicinity of a closed loop
in linear response, formed from two dissimilar metal conductors if the junctions
were maintained at different temperatures. He also observed
that the magnitude of the deflection was proportional to the
∂jQ temperature difference and depended on the type of conduct-
e2 L22
αβ = ³ ´
∂
~
−∇T ing material, and does not depend on the temperature distri-
T bution along the conductors. Seebeck tested a wide range of
β
Z 3 materials, including the naturally found semiconductors ZnSb
d k ∂f
= 2e2 vα vβ (² − µ)2 τ (²) and PbS. It is interesting to note that if these materials had
(2π)3 ∂µ been used at that time to construct a thermoelectric genera-
Z
∂f tor, it could have had an efficiency of around 3% - similar to
= dx (² − µ)2 σαβ (²). (156) that of contemporary steam engines.
∂µ
The Seebeck coefficient is defined as the open circuit volt-
2
Using that (²F − µ) ' π6 (kT )2 D0 (²F )/D(²F ), we ob- age produced between two points on a conductor, where a
uniform temperature difference of 1K exists between those
tain (derivation in assignment).
points.
The Peltier effect: It was later in 1834 that Peltier[2] de-
π2 scribed thermal effects at the junctions of dissimilar conduc-
L22
αβ = (kT )2 σαβ (²F ) and similarly tors when an electrical current flows between the materials.
3e2 Peltier failed however to understand the full implications of
π2 his findings and it wasn’t until four years later that Lenz[3]
L12 21
αβ = Lαβ = − (kT )2 σαβ 0
(²F )
3e concluded that there is heat adsorption or generation at the
L11 = σαβ (²F ) (157) junctions depending on the direction of current flow.
αβ
The Thomson effect: In 1851, Thomson[4] (later Lord
Kelvin) predicted and subsequently observed experimentally
the cooling or heating of a homogeneous conductor resulting
Physical quantities
from the flow of an electrical current in the presence of a
temperature gradient. This is know as the Thomson effect
• Thermal conductivity (κ): jQ = κ(−∇T ) and is defined as the rate of heat generated or absorbed in a
24
Band Structure
FIG. 20: Thermoelectric cooling (left): If an electric current
is applied to the thermocouple as shown, heat is pumped from
the cold junction to the hot junction. The cold junction will Clearly the band structure of the semiconductors is
rapidly drop below ambient temperature provided heat is re- crucial for the understanding of their properties and their
moved from the hot side. The temperature gradient will vary device applications. Semiconductors fall into several cat-
according to the magnitude of current applied. Thermoelec- egories, depending upon their composition, the simplest,
tric generation (right): The simplest thermoelectric generator
consists of a thermocouple, comprising a p-type and n-type
type IV include silicon and germanium. The type refers
thermoelement connected electrically in series and thermally to their valence.
in parallel. Heat is pumped into one side of the couple and The band structure is quite rich and shown in figure
rejected from the opposite side. An electrical current is pro- (22) for silicon. Germanium is very similar to Si and does
duced, proportional to the temperature gradient between the
hot and cold junctions.
the heavy holes and the light holes. These dispersion re- valence
photon ck ≅ ω ≅ E g/ h
material τexciton
Electron and hole densities in intrinsic (undoped) GaAs 1ns(10−9 s)
semiconductors Si 19µs(10−5 s)
Ge 1ms(10−3 s)
At zero temperature, the Fermi energy lies in the gap,
hence there are no holes (p = 0) in the valence band and TABLE II:
26
Eg
wk = v 2
k T=0 clearly kinetic
Thus, assuming that E − µ & 2 À kB T
energy increases
1
1 1
' = e−(E−µ)/kB T (168)
e(E−µ)/kB T +1 e(E−µ)/kB T
ie., Boltzmann statistics. A similar relationship holds for
E
0 ξ k = -E +
h k
2 2
holes where −(E − µ) & 2g À kB T
F 2m
1 1
FIG. 26: Partially filled conduction band and hole band at 1− = ' e(E−µ)/kB T
e(E−µ)/kB T +1 e−(E−µ)/kB T +1
non-zero temperature (169)
since e(E−µ)/kB T is small. Thus, the concentration of
3 √ electrons n
(2m∗ ) 2
that D(E) = 2π 2 ~3 E. Thus, 3 Z
(2m∗n ) 2 µ/kB T ∞ p
3 n ' e E − EC e−E/kB T dE
(2m∗n ) 2 p 2π 2 ~3 EC
DC (E) = E − EC (165) Z ∞
2π 2 ~3 3
(2m∗n ) 2 3 1
−(EC −µ)/kB T
= 2 3
(kB T ) 2
e x 2 e−x dx
2π ~
¡ ∗ ¢ 23 |0 {z }
√
2mp p π/2
DV (E) = EV − E (166) µ ¶ 3
2π 2 ~3 2πm∗n kB T 2
= 2 e−(EC −µ)/kB T
for E > EC and E < EV respectively, and zero otherwise h2
EV < E < EC . C −(EC −µ)/kB T
= Nef fe (170)
In an intrinsic (undoped) semiconductor n = p, and so
EF must lie in the band gap. Physically, this also means Similarly
that we have two types of carriers at non-zero temper- µ ¶ 23
atures. Both contribute actively to physical properties 2πm∗p kB T
p=2 e(EV −µ)/kB T = Nef
V
fe
(EV −µ)/kB T
such as transport. h2
(171)
C V
DC
where Nef f and N ef f are the partition functions for a
classical gas in 3-d and can be regarded as ”effective
f(E)D (E)
densities of states” which are temperature-dependent.
EC C
EF Within this interpretation, we can regard the holes and
EV
f(E)
(1 - f(E))D (E)
V electrons statistics as classical. This holds so long as n
and p are small, so that the Pauli principle may be ig-
DV
nored - the so called nondegenerate limit.
In general, in the nondegenerate limit,
FIG. 27: The density of states of the electron and hole bands µ ¶3
kB T ¡ ∗ ∗ ¢ 23 −Eg /kB T
np = 4 2
mn mp e (172)
If m∗n 6= m∗p (ie. DC 6= DV ), then the chemical 2π~
potential, EF , must be adjusted up or down from the this, the law of mass action, holds for both doped and in-
center of the gap so that n = p. trinsic semiconductor so long as we remain in the nonde-
Furthermore, the carriers which are induced across the generate limit. However, for an intrinsic semiconductor,
gap are relatively (to kB T ) high in energy since typically where n = p, it gives us further information.
Eg = EC − EV À kB T .
µ ¶ 23
kB T ¡ ¢ 43
Eg (eV ) ni (cm−3 )(300◦ K) ni = pi = 2 m∗n m∗p e−Eg /2kB T (173)
2π~2
Ge 0.67 2.4 × 1013
Si 1.1 1.5 × 1010 (See table (II)). However, we already have relationships
GaAs 1.43 5 × 107 for n and p involving EC and EV
C −(EC −µ)/kB T V (EV −µ)/kB T
TABLE III: Intrinsic carrier densities at room temperature n = p = Nef fe = Nef fe (174)
V
1eV Nef f
' 10000◦ K À 300◦ K (167) e2µ /kB T = C
e(EV +EC )/kB T (175)
kB Nef f
27
Thus if m∗p
6= m∗n ,
the chemical potential µ in a semicon- EF
# un-ionized
ductor is temperature dependent. EA
+ 0
NA = NA + NA
EV
Doped Semiconductors
FIG. 30: Ionization of the dopants
Since, σ ∼ nτ , so the conductivity depends linearly
upon the doping (it may also effect µ in some materials, C
np = Nef V
f Nef f e
−βEg
= n2i = p2i , (180)
leading to a non-linear doping dependence). A typical
metal has where β = 1/kB T . Using (177) we can define
µ ∗¶
1 3 mp
nmetal ' 1023 /(cm)3 (178) µi = (EV + EC ) + kB T ln , (181)
2 4 m∗n
whereas we have seen that a typical semiconductor has hence,
n = ni e(−µi −µ)/kB T and p = ni e(µi −µ)/kB T (182)
1010 ◦
ni ' at T ' 300 K (179)
cm3 To a good approximation we can assume that all
donors and all acceptors are ionized. Therefore,
Thus the conductivity of an intrinsic semiconductor is
quite small! n − p = ND − NA and np = n2i
To increase n (or p) to ∼ 1018 or more, dopants are n2
used. For example, in Si the elements used as dopants ⇒ n = ND − NA + i
n
p
are typically in the third or fifth column. Thus P or B ND − NA (ND − NA )2 + 4n2i
= +
2
Si 3s 3p
2 2 2
⇒ n ' ND and p ' n2i /ND for ND À NA
Si Si Si Si Si Si Si Si
e+ 2 3
P 3s 3p
Metal-Insulator transition where the constants (ρ0 , A and B) depend on the mate-
rial. In most metals and heavily doped semiconductors
In n-type semiconductors, when EF < EC , carriers ex- the temperature dependence of the resistivity is domi-
perience a gap ∆ = EC −EF . Hence at low temperatures nated by these three mechanisms, which means that the
the system is insulating. Indeed, importance of impurities, electron-phonon and phonon-
µ−EC
phonon interactions can be extracted from the tempera-
n = NC e kB T
(184) ture dependence of the resistivity.
|{z}
∼T 3/2
A special case is the magnetic impurity case (Kondo),
which gives rise to an additional term in 1/τK ∼
Since from Drude −(T /TK )2 .
ne2 τ
σ= → 0 when T → 0. (185)
m∗
In practice
When EF > EC , the semiconductor behaves like a
metal. In this case we obtain again from Drude that
2 To determine the density (n-p) the Hall resistance can
σ = ne τ
m∗ > 0 even for T → 0, since the density does be used. The ration τ /m∗ can then be obtained from
no vanish. In general, τ also depends on temperature.
the Drude conductivity and m∗ can be obtained from
Indeed, in the metallic phase the most important tem-
magneto-oscillations due to the Landau levels. This can
perature dependence comes from τ . To evaluate the con-
in principle be done for all temperatures, hence it is possi-
tributions from different scattering mechanism we can
ble to extract m∗ , n(T ), and τ (T ) simply by using trans-
consider 1/τ as the scattering probability. This follows
port and to deduce the dominant scattering mechanisms
directly from Boltzmann’s equation, where
¶ in the systems under study.
dg X
= (Γ(k 0 k) − Γ(kk 0 )), (186)
dt coll 0 k
p-n junction
where
(See also pn junction supplement)
0 0 0
Γ(kk ) = W (kk ) · g(k) · (1 − g(k ))
| {z } |{z} | {z }
prob. k→k0 # of states in k # of empty states in k 0
(187)
is the transition rate from state k to k 0 . Local equilibrium
implies Γkk0 = Γk0 k , hence g = fF D .
The most important scattering cases are the following:
• Impurity scattering (for a density of impurities nI ):
1
∼ nI (188)
τe−imp
• Electron-electron scattering:
1
∼ (T /TF )2 (189)
τe−e
• Electron-phonon scattering:
FIG. 31: Formation of a pn junction, with the transfer of
1 5 charges from the n region to the p region and the alignment
∼ (T /TD ) (190) ~ r) = 0. The depletion
of the chemical potential so that ∇µ(~
τe−ph
and accumulation regions are delimited by xn and −xp , re-
spectively.
In general, the total scattering probability is the sum
of all possible scattering probabilities, hence
When two differently doped semiconductors are
brought together they form a pn junction. In general,
1 1 1 1
= + + electrons form the more n-type doped region will trans-
τtot τe−imp τe−e τe−ph fer to the less doped or p-type region. This leaves a
∗
µ ¶2 µ ¶5
m T T positively charged region on the n side and and accumu-
⇒ρ= ' ρ0 + A +B (191)
e2 nτ TF TD lation of negative charges on the p side. The potential
29
- +
- +
- +
p type - + n type
- +
- +
no holes no electrons
charge density in depletion region
electric field
potential
Vo=(n-p)/e
FIG. 34: Conductance quantization of a quantum point con- FIG. 35: Imaging of the channels using an AFM (1 to 3 chan-
tact in units of 2e2/h. As the gate voltage defining the con- nels from left to right). The images were obtained by applying
striction is made less negative, the width of the point contact a small negative potential on the AFM tip and then measur-
increases continuously, but the number of propagating modes ing the conductance as a function of the tip scan and then
at the Fermi level increases stepwise. The resulting conduc- reconstruct the 2D image from the observed change in con-
tance steps are smeared out when the thermal energy becomes ductance. (From R.M. Westervelt).
comparable to the energy separation of the modes.
-M (magnetization)
at the boundary (like for an electron in a box of width
W ). In general, if
Vanadium ξ ∼ 1000Α°
e
- k↓
8
region of + +
+ + + +
vF ∼ 10 cm/s positive charge
attracts a second
+
electron BCS theory
p2
When an electron flies through the lattice, the lat- H1particle = ⇒ H1p ψ(x) = Eψ(x) (198)
2m
tice deforms slowly with respect to the time scale of
the electron. It reaches its maximum deformation at Let’s define
a time τ ' ω2πD ' 10−13 s after the electron has passed. c+ |0i = ψ(x) and h0|c1 (x) = ψ ∗ (x)
1 (x) (199)
In this time the first electron has travelled ' vF τ ' |{z}
108 cm −13
s · 10 s ' 1000Å. The positive charge of the lat-
vacuum
tice deformation can then attract another electron with- With these definitions, |0i is the vacuum (or ground
out feeling the Coulomb repulsion of the first electron. state), i.e., state without electrons. c+
1 (x)|0i corresponds
32
Combining (206) and (210) we obtain another one with momentum −k − q, hence momentum
is conserved in this scattering process and a phonon with
ga momentum q is exchanged.
2a = p (211) How can we relate BCS theory to the observed Meiss-
t2 + (ga)2 ~ into the
ner effect? By including the vector potential A
which is the famous BCS gap (∆) equation. Indeed, it BCS Hamiltonian it is possible to show that the current
has two solutions, density is then given by
2
a = 0 ⇒ ha|c1 c2 |ai = 0 ⇒ Normal ~j = ne A~ (216)
a 6= 0 ⇒ t2 + (ga)2 = g 2 /4 ⇒ Superconductor(212) mc
| {z }
√ 2
∆=ga= 2
g /4−t The magnetic induction is B ~ =∇~ ×A ~ as usual. This is
in fact London’s equation for superconductivity. We can
'=ga now take the rotational on both sides of (216), hence
Normal
~ × ~j ne2 ~ ~
∇ = ∇×A
Superconductor |{z} mc
~ B=
∇× ~ 4π ~j
c
t 2
g/2
FIG. 40: The gap of a BCS superconductor as function of the
~ ×∇
⇒∇ ~ = − 4πne B
~ ×B ~
mc2
kinetic energy.
⇒ Bx ∼ e−x/λL (217)
This gives us the condition for superconductivity g ≥ q
mc2
2t. Hence the attraction between our two electrons has with λL = 4πne2 which is the London penetration
to be strong enough in order to form the superconducting length.
gap ∆. Typically, t is directly related to the temperature,
hence there is a superconducting transition as a function
of temperature.
We now want to find the expression for our supercon- B
ducting wavefunction |ai. The most general possible form
is e -x/ L
Vacuum
|ai = α|0i + β1 c+ + + +
1 |0i + β2 c2 |0i + γc1 c2 |0i (213) Inside the
superconductor
A remarkable aspect of superconductivity is that one where U (1) ⇔ c → ceiα (Gauge invariance), U (2) ⇔ c →
of the most fundamental symmetries is broken. Indeed, Ac (A = eiφ/2 a) and a+ a = 1, SU (2) ⇔ φ = 0.
~ What hap-
Gauge invariance is broken because ~j ∼ A.
pens is that below Tc we have a symmetry breaking,
which leads to new particles, the Cooper pairs. Math-
ematically, we have