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Lecture notes by
Michael Hilke
McGill University
(v. 10/25/2006)
Contents
Introduction
H2 O - An example
Binding
Van der Waals attraction
Derivation of Van der Waals
Repulsion
Crystals
Ionic crystals
Quantum mechanics as a bonder
Hydrogen-like bonding
Covalent bonding
Metals
Binding summary
3
3
3
3
3
4
4
4
5
5
5
Structure
Illustrations
Summary
6
6
6
Scattering
Scattering theory of everything
1D scattering pattern
Point-like scatterers on a Bravais lattice in 3D
General case of a Bravais lattice with basis
Example: the structure factor of a BCC lattice
Braggs law
Summary of scattering
6
7
7
7
8
8
9
9
17
17
18
18
19
19
21
21
21
22
22
23
Semiconductors
Band Structure
Electron and hole densities in intrinsic (undoped)
semiconductors
Doped Semiconductors
Carrier Densities in Doped semiconductor
Metal-Insulator transition
In practice
p-n junction
24
24
25
26
27
27
28
28
29
29
30
superconductivity
BCS theory
30
31
2
INTRODUCTION
Crystal
Crystal
Supraconductivity
Opto-effects
Metals
Insulators
Magnetism
Semiconductors
properties
3
THE THEORY OF EVERYTHING
The Van der Waals force arises simply from the change
in energy due to the cross Coulomb interactions between
atom a and b, which is simply a dipole-dipole interaction.
H = (H0 ) + (Hint )
with
~2 2
e2
e2
1
1
1
1
2
2
H=
1 + 2
+e
+
2m
r1a
r2b
rab
r12
r1b
r2a
a b
,
6
rab
(3)
(1)
6
12
,
(r) = 4
r6
r12
(2)
(4)
which is usually referred to as the Lennard-Jones potential. The choice of the repulsive term is somewhat
arbitrary but it reflects the short range nature of the
interaction and represents a good approximation to the
full problem. The parameters and depend on the
molecule.
Problem 1
Repulsion
~2
1
1
A
(5)
2
' 3.8eV for the potential in a 1
A quantum box
(6)
4
In comparison to room temperature (300K' 25meV)
these energies are huge. Hence ionic Crystals like NaCl
are extremely stable, with binding energies of the order
of 1eV.
Ionic crystals
(10)
e2
e2
r
|r R|
+
b(r)
V(r)
a(r)
Energy
e2 C
14.4eV C
+
= + n =
with 6 < n 12,
R
Nionpair
d d
[d/
A] dn
(7)
where is the Madelung constant and can be calcur
0
lated from the crystal structure. C can be extracted experimentally from the minimum in the potential energy
and typically n = 12 is often used to model the effect
of the Pauli principle. Hence, from the derivative of the
FIG. 3: The potential for two protons with the bonding and
anti-binding wave function of the electron
potential we obtain:
1/11
12C
d0 =
(8)
The average energy (or expectation value of Eb ) is
e2
Eb = hb Hb i/hb b i
(12)
so that
A+B
with
(13)
= E0
Energy
11e2
1+
=
(9)
Z
Nionpair
12d0
(14)
A = e2 dr 2 (r)/|r R|
How good is this model? See table below:
Z
(15)
B = e2 dr(r)(|r R|)/r
Z
Quantum mechanics as a bonder
=
dr(r)(|r R|),
(16)
Hydrogen-like bonding
where hi
dr and similarly,
Ea = E 0
AB
1
(17)
5
Hence, the total energy for state b is now
Ebtotal = Eb + e2 /R
(18)
-8
Covalent bonding
E [eV]
tot
Ea
Antibonding
-12
Ea
-13.6 eV
tot
Eb
-16
Eb
R0
Bonding
Metals
Z
Eel =
drn(r)
X
R
In metals bonding is a combination of the effects discussed above. The idea is to consider a cloud of electrons
only weakly bound to the atomic lattice. The total electrostatic energy can then be written as
Z
X
e2 n(r1 )n(r2 )
e2
e2
+
+
1/2
dr1 dr2
0
rR
RR
|r1 r2 |
0
(19)
R>R
1/3
e2
3
Eel =
where rs =
(20)
2rs
4n
and is the Madelung constant. Deriving this requires
quite a bit of effort. On top of this one has to add the
kinetic energy of the electrons, which is of the form:
2/3
9
3~2
Ekin =
(21)
4
10mrs2
And finally we have to add the exchange energy, with is
a consequence of the Pauli principle. The expression for
this term is given by
1/3
9
3
Eex =
(22)
4
4rs
Putting all this together we obtain in units of the Bohr
radius:
30.1a20
24.35a0
12.5a0
+
eV/atom (23)
E=
rS
rS2
rs
6
Coulomb
Quantum mechanics (Pauli)
Miller indices can be obtained through the construction illustrated in the figure below:
STRUCTURE
Illustrations
FIG. 6: Plane intercepts the axes at (3a1 , 2a2 , 2a3 ). The inverse 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 indices are (233). For a negative intercept the convention is
1.
(Picture from Ashcroft and Mermin)
SCATTERING
7
Physics is hidden in n(r), which contains the information on the position of scatterers and their individual
scattering distribution and probability. In the following
we discuss the most important implications.
dV
Incident
beam
crystal
1D scattering pattern
k Outgoing
beam
e ikr
ik 'r
A(q ) dr 3 n (r ) e [iqr ]
V
q = k - k'
A(q) =
n(x, y, z) =
N 1
C X
(y an)(x)(z),
N n=0
N 1
C X iqan
C 1 eiaqN
C when q = 2m/a
=
= Cq,G
e
=
N
~
0 when q 6= 2m/a
N n=0
N 1 eiaq
(26)
and
N 1
~
C X i~qR~n
C when ~q G
e
=N
= Cq~,G
~
~
N n=0
0 when ~q
/G
(28)
In this case the Bravais lattice (or Real-Space) is
A(~q) =
(29)
(25)
(27)
(30)
where
2 a~2 a~3
2 a~3 a~1
2 a~1 a~2
b~1 =
, b~2 =
and b~3 =
|a~1 a~2 a~3 |
|a~1 a~2 a~3 |
|a~1 a~2 a~3 |
(31)
8
As a simplification we suppose that f1 = f2 = f , then
S(~q) = (1 + e(ia/2)~q(x+y+z) )fe(~q),
2q~,G
~ if q1 + q2 + q3 is even
e
A(~q) = S(~q) q~,G
=
f
(~
q
)
~
0 if q1 + q2 + q3 is odd
(38)
The most general form for n(~r), when the atoms sits
on the basis {u~j } along the Bravais lattice R~n is
C
n(~r) =
N
M,N
X1
(32)
j=1,n=0
C
N
C
=
N
M,N
X1
Z
fj (~r R~n u~j )ei~q~r d3 r
j=1,n=0
M,N
X1
j=1,n=0
(33)
M Z
X
fj (~r)ei~q~r d3 r ei~qu~j
(34)
j=1
This is the most general form. It is interesting to remark that in most case, experiments measure the intensity I(~q) = |A(~q)|2 , rather than the amplitude.
Example: the structure factor of a BCC lattice
(35)
where ~u1 = 0(
x + y + z) and ~u2 = (a/2)(
x + y + z).
The structure factor then becomes:
X Z
S(~q) =
fj (~r)ei~q~r ei~qu~j d3 r.
(36)
j=1,2
(37)
9
Braggs law
Point-like Bragg
(1,0,0)
(0,1,0) Miller index
in
out
q2=k -k2
k1out
q1=kin-k1out
a
kin
y z
x
Powder diffraction:
(39)
hence,
n
2
= 2 sin() |k~in | = |q~1 |,
a
(40)
Liquid diffraction:
(41)
hence,
n
2
= 2 cos() |k~in | = |q~2 |,
b
(42)
~
or q~2 = y2/b G.
Summary of scattering
10
where the pre-factor 2 comes from the spin degeneracy.
Hence,
The single electron approximation can be used to derive the energy and density of the electrons. This simplest model will always serve as a reference and in some
cases the result is very close to the experimental value.
Alkali metals (Li, Na, K,..) are reasonably well described
by this model, when we suppose that the outer shell electron/atom (there is 1 for Li, Na, K) is free to move inside
the metal. This picture leads to the simple example of N
electrons in a box. This box can be viewed as a uniform
and positively charge background due to the atomic ions.
We suppose that this box with size LLL has periodic
boundary conditions, i.e.,
H=
N
X
~2 2n
with (0) = (L)
2me
n=1
(44)
2
L
kF3
4 3
in D = 3 since VkDF =
k
3 2
3 F
k2
= F in D = 2 since VkDF = kF2
2
2kF
=
in D = 1 since VkDF = 2kF ,
n3D
=
e
(48)
n2D
e
(49)
n1D
e
EF =
~2 kF2
the Fermi energy
2me
(51)
(2mEF )3/2
.
3 2 ~3
(52)
n(EF )
D(E)dE = D(E) =
n(E), (53)
E
0
which leads to
m 2mE
D(E) =
in 3D
~3 2
m
D(E) = 2 in 2D
~
r
2m
D(E) =
in 1D
~2 2 E
and illustrated below.
3D
2D
1D
(46)
(50)
D(E)
(54)
(55)
(56)
11
hEi
n
2
5 nEF ,
P
V
Compressibility 1 = V
= 35 EF
1 hEi
CV =
V T
where hEiV is
= 23 nEF
Hence,
CV
T
=
,V
2 2
k T D(EF )
3
(64)
fF D =
1
e(E)/kT + 1
(57)
X
~2 2
V
(x na)
2m
n
(65)
EF
2
(kT )2 D(EF ) + ...
(61)
6
0
hni = n(T = 0)
(62)
2
0
D (EF )
(T ) ' EF
(kT )2
+ ...
(63)
6
D(EF )
'
ED(E)dE +
(1)
(2)
R na+
na
The solutions for na < x < na+a are simply plane waves
and can be written as
(x) = An eikx + Bn eikx .
(66)
~
( 0 (na
2m
(67)
+ ) (na )) = V (na).
(69)
ika
(70)
and
ik
2m
(68)
An eikan
| {z }
n+1 eika n
2i sin(ka)
eika n n1
2i sin(ka)
eika n n1
2i sin(ka)
(71)
12
hence,
~
k
ika
eika eika eika ) = V n
2n+1 + 2n1 + n (e
|
{z
}
2m 2 sin(ka)
(72)
4 cos(ka)
and finally,
n+1 + n1
2m sin(ka)
V
+
2
cos(ka)
=
n , (73)
~2 k
|
{z
}
(74)
(75)
2 W 2
(77)
-2
<W
<2
E(k)
W
<2
Let us consider the general potential due to the arrangement of the atoms on a lattice:
H=
~2 2 X
+
V0 (~r R~n )
2m
n
{z
}
|
This is a very general form for a periodic potential assuming that we only have one type of atoms. The periodicity
is given by the lattice index R~n . For a general periodic
potential Blochs theorem (see A& M for proof) tells us
that a solution to this Hamiltonian can be written as
~
/a
(78)
V (~
r)
-2
W<
(76)
(79)
~ ~
k (~r + R~n ) = eikRn k (~r)
(80)
13
hl (r Rm )|H|l (r Rn )i = tl
+ l m,~
m,~
~ n
~ n+~i + m,~
~ n~i
(81)
~i=
x,
y ,
z
c~ln l (r R~n )
(82)
~
n
l
= El (k)clm
cm+
~
~ ~i
(83)
~i=
x,
y ,
z
~
n
whenever ~n and m
~ are related by a linear combination of
Bravais vectors. Moreover, the tight binding equation in
~
(83) is the same but with c~ln replaced by c~ln eikR~n
E
a
1
-1.0
/a
-0.5
0.0
0.5
1.0
/a
14
where c~n takes on only to possible values due to Blochs
theorem: cA or cB . This leads to the following simplified
tight binding equations (assuming hl (r Rn )|H|l (r
Rn )i = A or B and t = hl (r Rn )|H|l (r Rm )i
when n and m are nearest neighbors):
cA A t
cB B t
P
~
Pi=x,y
~i=
x,
y
~~
cB eiaki = E(~k)cA
~~
cA eiaki = E(~k)cB
A
t g
cA
cA
~
= E(k)
,
t g B
cB
cB
ia~
k
x
ia~
k
x
ia~
k
y
In this case we consider the effect of the periodic potential V (~r) as a perturbation on the plane wave solution
2 2
0
(~r) = k0 (~r) + k+K
(~r),
(85)
ia~
k
y
with g = e
+e
+e
+e
. The dispersion relation or band structure is then simply given by
obtaining the eigenvalues of HBT B , where
A
t g
HBT B =
.
t g B
k
and
k0 (~r) = eik~r , with corresponding energies 0k = ~2m
0
0 0
Hamiltonian H0 , i.e., H0 k (~r) = k k (~r). Since the origin of this energy dispersion relation can be chosen from
any site of the reciprocal lattice, we have 0k+K = 0k ,
hence these energies are degenerate. This implies that
we have to use a degenerate perturbation theory. The
mathematical procedure is very similar to the tight binding approximation, but we now expand the solution (~r)
of the full Hamiltonian H = H0 + V (~r) in terms of a sum
of plane waves k0 (~r). Since 0k+K = 0k we will only use
0
two plane waves in this expansion: k0 (~r) and k+K
(~r).
Hence,
(86)
R
R
0
d3 r(k0 ) (~r)(H E)k0 (~r) +R d3 r(k0 ) (~r)(H E)k+K
(~r) = 0
,
3
0
0
3
0
0
d r(k+K ) (~r)(H E)k (~r) + d r(k+K ) (~r)(H E)k+K
(~r) = 0
(87)
3
0
0
E)k+K
(~r) = d3 reikr (H0 + V (r) E)ei(k+K)r = d3 reiKr (0k+K + V (r) E) = VK
R d3 r(k0 ) (~r)(H
0
d
r(
)
(~
r
)(H
E)
r) = 0k+K E
k+K
k+K (~
R 3
0
d r(k+K
) (~r)(H E)k0 (~r) = VK ,
(88)
R 3 iK~
R
R
~
and VK
d re r V (~r) (the Fourier transform), d3 reiKr = 0 (for K 6= 0), and d3 rV (~r) = 0. With coefficients
~ =
(88), equation (87) leads to the following couple of equations:
0
q 0 0
0
0
E
2
(0k E) + VK = 0
VK
k
= 0 E = k +k+K (k k+K ) + VK VK .
(89)
0
0
2
4
VK + (k+K E) = 0
VK k+K E
Localization
15
Bloch wave solutions but localization of the wave functions occur. This is particularly important in low dimensional systems and tends to suppress transport.
2
~
(k i)2 + V E(k) uk = 0.
(93)
2m
|
{z
}
Hk E(k)
In order to calculate hvi we use first a first order perturbation 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
1
n E(k)
|{z}
2 |{z}
2
=
k k
P
spin
k
1
1 N E(k)
=
4
L k k
1
2 E(k)
D(E) =
,
k
D(E) =
=
=
(90)
=
=
~2
E(k) + heikr | q(k i))|eikr i
m
~
E(k) + h|q~ (i)|i
m
E(k) + q~h|v|i
E(k) + qk E(k) (Taylor expansion)
1
hvi = k E(k).
~
(94)
D(E) =
(91)
P
2
where we used E = (k E(k)) k,
E(k)=E (k)
R
2
3
3
d k, and n/(k) = 1/(2) . This result shows
E(k)=E
that the density of state in the presence of a periodic
potential, i.e., for a crystal depends only on the slope of
the dispersion relation or the band structure.
The idea is to describe the average motion of an electron in the presence of an external field (electric, Eel , or
magnetic, B) in a semiclassical way. Hence, we want
m
(95)
Average velocity
The average velocity of an electron in a periodic potential is given by the expectation value of the velocity,
i.e.,
hvi = h|v|i,
d
hvi = F = (qEel or qhvi B),
dt
(92)
2 E
m =~ 2 .
k
2
(96)
(97)
16
of an electron is q = e but if kE2 < 0 then q is positive
(+e). In this case we describe the particles as holes.
They represent missing electrons. With these definitions
of q and m , which is also called the band mass, the
semiclassical equations of motion of single electrons in a
periodic potential are simply given by eqs. (95) and (96).
In general, the effective mass is given by a tensor defined as
2
1
2 E
m = ~
,
(98)
k k
(104)
Bloch oscillations
In the presence of an electric field and a periodic potential we can use the equation of motion (96), i.e.,
eEel
~k = eEel k =
t,
(99)
~
but in a periodic potential and in the tight binding approximation the energy is given by E(k) = 2t0 cos(ka),
where a is the lattice constant and t0 the nearest neighbor
overlap integral. Hence, since v = r and hvi = ~1 E/k
we have
2t0
aeEel t
hri =
cos(
).
(100)
eEel
~
This means that the average position of the electrons
oscillates in time (Bloch oscillations). In artificial structures these Bloch oscillations are typically of the order of
1THz.
Semiclassical motion in a magnetic field
(101)
t = t2 t1 =
dt =
dk /|k|.
(102)
t1
k1 =k(t1 )
~2
t =
qB
2
k2
k1
~ d
qB dE
dk
E/kk
k2
k1
kk dk .
(103)
mx 0 0
m = 0 my 0
(105)
0 0 mz
and that the energy dispersion is harmonic (which is usually true at a band extremum, i.e.,
E(k) =
~2 ky2
~2 kx2
~2 kz2
+
+
.
2mx
2my
2mz
(106)
2
~2 kk2
~2 k
+
,
2m
2mk
(107)
2
where k
= kx2 +ky2 . Using (104) and (107 we then obtain
2
S = k
= (2m E/~2 ) kk2 m /mk
dS
2m
=
dE
~2
2
qB
c =
=
,
T
m
(108)
17
500
450
400
1
1
H=
Pk2 +
(P + qA)2 ,
2mk
2m
(109)
Rxx []
350
300
Rxx []
200
100
0
300
250
1/B [T ]
200
150
where B = A A = By
x in the Landau Gauge if
B is along z. In analogy to the harmonic oscillator, the
eigenvalues of (109) are then given by
En,kk =
~2 kk2
2mk
+ (n + 1/2)~
qB
.
m
|{z}
100
50
0
0.0
0.5
1.0
B [T]
(110)
FIG. 15: Magneto-resistance oscillations in a GaAs/AlGaAs
quantum well.
2 2
2
2
~ kk
Py
qB
1
(y y0 )2 n (y y0 ).
2mk + 2m + 2 m m
In the y direction this is simply the harmonic oscillator
with eigenvalues (n + 1/2)~c and in the direction
parallel to the field we have a plane wave so that the
total energy is given by (110). The quantized levels
(n + 1/2)~c due to the magnetic field are called the
Landau levels.
Magneto-oscillations
=~
( EF )1 (n2 n1 )
B1
B2
m |{z}
In general:
Mu
l =
lm um ,
(112)
us
u s +1 u
s+2
1
B
~2
2m
F 2
~2 (kx
)
2m
(111)
u s +1 u s + 2
us+3
2q 1
S ,
~
u s 1 u s
kk dk = (kxF )2 =
~ S
= 2m
. Hence, the Magneto(kyF )2 and EF =
s 1
s +1
us+4
K
FIG. 16: Two types of lattice displacement waves in 2D, transverse and longitudinal modes
18
1. Acoustic mode:
s
PIn 1D equ. 112 for nearest neighbors and using
m lm = 0 simply reduces to
Mu
l = K(ul+1 2ul + ul1 )
(113)
'
C
ka
2(M1 + M2 )
(117)
2. Optical mode:
s
'
2C(M1 + M2 )
M1 M2
(118)
(114)
K
M | sin(ka/2)|
(K
Mono-atomic dispersion
M)
0.8
0.6
0.4
0.2
0
-/a
/a
k
2/a
The situation is quite different when there is an addition symmetry breaking in the problem. In the 1D case
this occurs when there is a second species with a different
mass, for example, or when there are two different elastic
constants. Let us discuss the case where there are two
different masses but only one elastic constant C:
M1 u
l = C(ul+1 2ul + ul1 )
M2 vl = C(vl+1 2vl + vl1 )
(115)
M1 + M2
19
0
~
~in (~k) ~out
(k~0 ) = ~(K)
|
{z
} | {z }
phonon
in/out particle
(119)
(120)
Hions =
NX
ions
i
NX
ions
~2 2i
qi qj
+
2mi
|r
rj |
i
i<j
(121)
X
(r1 , . . . , rn ) = (r10 , . . . , rn0 ) +
{z
}
|
ri
i
Cohesive energy
|
Equilibrium pos.
! displacment
z}|{
1 X 2
ui
+
ui uj +
2 i,j ri rj
ri0
0
ri
{z
} |
{z
}
0
~ ~
(123)
i,j
{z
(124)
(k)
u~l = ~ eikRl it ,
(122)
where (k)
is a 3 3 matrix, since lm too. This leads
to an eigenvalue equation for 2 with three eigenvalues:
2
L
(for ~k k ~) and T2 (1,2) (for ~k ~). Hence, we have
on longitudinal mode and two transverse modes and all
phonon modes can be described by a superposition of
these.
If we have two different masses, we have two addi-
20
tional equations of the form (124). This leads to the
general case, where one has two branches the optical one
and the acoustic one and each is divided in longitudinal
and transverse modes. The acoustic branch has always
a dispersion going to zero at k = 0, whereas for the optical mode at k = 0 the energy is non-zero. The acoustic phonons have a gapless excitation spectrum and can
therefore be created at very low energy as opposed to
optical phonons which require a miniumum energy to be
excited.
1
D() =
(2)3
DL,T () =
(125)
D()d =
1
(2)3
2
2 2 c3L,T
(128)
1
2
+ 3
c3
c
| L {z T }
(129)
1
c3
(130)
E() =
k2
2 2 cL,T
2
Dtot () =
2 2
(126)
(127)
or
+d
dk
=const
dS
|k |
Quantum case
While many of the properties, like the dispersion relation, can be explained in classical terms, which are simply
vibrations of the crystal ions, others, such as statistical
properties need a quantum mechanical treatment.
Phonons can simply be seen as harmonic oscillators
which carry no spin (or spin 0). They can, therefore, be
accurately described by bosons with energy
X
n
En Pn = (1 e~/kB T )~
(n + 1/2)(e~/kB T )n
n=0
= ~ + ~/k T
B
2 e
1
|
{z
}
(131)
hni
zero energy state is totally degenerate (this does suppose that there are no interactions between bosons, with
interactions the delta function will be a little broader).
The total average energy can then be calculated from the
density of states as:
Z
hEi =
dD()E()
(133)
21
d
dT
If
the
electrons
flow
without
collisions,
(137)=g(r, k, t) = fF D .
The situation changes if
collisions (f. ex. between electrons, impurities, or
phonons) are included. In this case
CV =
1
c3
L
1
3
d 3(kB T )4
=
dT 2 2 (c~)3
2 2 kB
=
5
Z
|
kB T
~c
2
c3
T
d exx1
t dt) = gcoll.
g(r, k, t) g(r rdt,
k kdt,
(kB T )4
~3
g
g
g
dg
r
+ k
+
=
r
k
t
dt
{z
}
|
x3
d x
e 1
{z
}
(134)
3
kD
and
6 2
= ~D = ~ckD (D : Debye temperature)
3
12 4 kB
T
=
n
(135)
5
D
T + T 3
|{z}
|{z}
electrons
(139)
coll.
n =
= CV
dg
dt
4 /15
k B D
(138)
dg
dt
1
= (g fF D )
coll.
1
dg
= (g fF D )
=
dt
(140)
It is quite intuitive to see from where this approximation comes from, since a kick at t = 0 would lead to
solution of the form
g(t) =
(136)
et/
+ fF D fF D (when t = )
(141)
This is the basic framework, which allows us to evaluate the effect of external fields on the system and to
estimate the linear response to them.
phonons
(137)
~ = eE
~
Case 1: F
d3 k
v g(r, k, t). (142)
(2)3
22
~k = eE, Boltzmanns equation (139) in the relaxation
time approximation becomes
g
k
k
|{z}
1
= (g fF D )
~ g
eE
~
~
k
~
eE
~
g =
+fF D
~k
|{z} |{z}
'
fF D
(143)
j = 2e
In the case where the scattering of electrons is dominated by inelastic diffusion, we can write a very simple
form for the conductivity or resistivity tensor. Indeed, in
a diffusive regime the average velocity is directly proportional to the external force and to the inverse effective
mass. The proportionality coefficient is then simply the
scattering probability 1/ . Hence,
~~
v
m
~ e~v B
~
~v = F~ = eE
~ = m ~v e~v B
~
eE
|{z}
} | {z }
|
{z
eEx
'jy B/n
Z
d3 k
fF D
~
v e E ~v
+ ( v fF D ), (144)
(2)3
|
{z
}
jx
' m en
=0
Ex =
which leads to
=
j
= 2e2
E
d3 k
fF D
v v
()
3
(2)
(145)
d3 k
fF D
v
(2)3 ~k
Z
3
d k
fF D
= e2
v
(2)3
~k
Z
Z
3
d k
v
2
= e
fF D /~
f F D v
(2)3 k
k
|{z}
|
{z
}
Z
(148)
m
B
jx +
jy
2
ne
ne
(149)
m
ne2
B
ne
B
ne
m
ne2
0
0
= 1
(150)
m
ne2
= 2e2
e
=
m
~ /m
=0
d k
2
fF D
(2)3
|
{z
}
(146)
e2 n
(147)
g
k
k
|{z}
1
= (g fF D ),
(151)
~ v f
'eE~
fF D =
1
e((r))/kT (r)
+1
r T
r ( )
T
f
r T
~
g = ~v
eG + ( )
+ fF D ,(152)
f
f
=
23
~ = eE+
~ (r)
~
where we defined the generalized field eG
~ (r)
~
~ (r),
and the external forces are now eE,
and T
corresponding to an external electrical field, a gradient
in the chemical potential (f.ex. a density gradient), and
a temperature gradient. The electrical current density is
the same as before but is now expressed (in the linear
response) in terms of the additional external fields:
Z
j~e = 2e
d3 k
~ + L12
~v g ' L11 G
(2)3
~
T
T
j~Q = 2e
d3 k
~ + L22
( )~v g ' L21 G
(2)3
j
= 2e2
E
(153)
~
T
T
!
.
d3 k
v v (x)( x), (155)
(2)3
jQ
~
T
T
d k
f
= 2e2
v v ( )2 ()
(2)3
Z
f
=
dx ( )2 ().
(156)
L22
=
21
L12
= L
L11
L22
T
T
2 k2 T
=
3 e2
(154)
Here L are the linear transport coefficients and =
L11 . We now want to evaluate these expressions in the
low temperature limit, where we can use fF D / '
( F ), hence the expression for in (145) can be
written as
(x) =
O(T 4 )'0
An expression for the thermal current can be deduced from the following thermodynamical relation dQ =
T dS = dU dN , hence
Z
~
T
11 ~
12
0, hence at low temperatures, L G+L
T =
0 and
!
~
T
jQ = (L12 (L11 )1 L12 L22 )
|
{z
}
T
Physical quantities
(158)
L12
2 k2 T 0
=
L11 T
3 e
(159)
24
metal
semiconductor
insulator
Band Structure
SEMICONDUCTORS
FIG. 22:
Band structure of
ioffe.rssi.ru/SVA/NSM/Semicond)
Si.
(Figures
from
mij
~ ki kj
(160)
hence
E(~k) = Ec + ~
kx2 + ky2
k2
+ x
2mt
2ml
!
(161)
25
2
~2~klp
~2~kh2
~2~k 2
' Ev
E(~k) = Ev
2mh
2mlp
2mp
(162)
for the valence band, where there are typically two bands,
the heavy holes and the light holes. These dispersion relations are generally good approximations to the real system. In addition, the valence band has another band due
to spin-orbit interaction. However, at zero wavenumber
(~k = 0) this band is not degenerate with the other two
light and heavy hole bands.
mn
Si
0.36
Ge
0.22
GaAs 0.063
mp
0.81
0.34
0.53
mt
0.19
0.0815
0.063
ml
0.98
1.59
0.063
mh
0.49
0.33
0.51
mlp
0.16
0.043
0.082
gap [eV]
1.12
0.661
1.424
conduction
h Eg
phonon
photon
valence
vs k
ck E g/ h
no electrons in the conduction band (n = 0). At nonzero temperatures, the situation is very different and the
carrier concentrations are highly T -dependent since all of
the carriers in an intrinsic (undoped) semiconductor are
thermally induced.
In this case, the Fermi-Dirac distribution defines the
temperature dependent density
Z Etop
Z
n=
DC (E)fF D (E)dE '
DC (E)fF D (E)dE
Ec
Ec
(163)
Ev
p=
DV (E)(1 fF D (E))dE
(164)
material exciton
GaAs 1ns(109 s)
Si
19s(105 s)
Ge
1ms(103 s)
TABLE II:
26
wk = v 2
T=0
clearly kinetic
energy increases
e(E)/kB T
h k
k = -E +
F
2m
that D(E) =
(2m ) 2
2 2 ~3
E. Thus,
3
(2mn ) 2 p
DC (E) =
E EC
2 2 ~3
(165)
23
2mp p
DV (E) =
EV E
2 2 ~3
(166)
f(E)D (E)
EC
EF
EV
(1 - f(E))D (E)
f(E)
DV
FIG. 27: The density of states of the electron and hole bands
1
e(E)/kB T
= e(E)/kB T
(168)
+1
1
e(E)/kB T
+1
' e(E)/kB T
(169)
since e(E)/kB T is small. Thus, the concentration of
electrons n
3
Z
(2mn ) 2 /kB T p
n '
E EC eE/kB T dE
e
2 2 ~3
EC
3
Z
3
1
(2mn ) 2
(EC )/kB T
2
x 2 ex dx
=
(k
T
)
e
B
2
3
2 ~
|0
{z
}
/2
= 2
2mn kB T
h2
3
2
e(EC )/kB T
C
(EC )/kB T
= Nef
fe
(170)
Similarly
p=2
2mp kB T
h2
23
V
(EV )/kB T
e(EV )/kB T = Nef
fe
(171)
C
V
where Nef
and
N
are
the
partition
functions
for a
f
ef f
classical gas in 3-d and can be regarded as effective
densities of states which are temperature-dependent.
Within this interpretation, we can regard the holes and
electrons statistics as classical. This holds so long as n
and p are small, so that the Pauli principle may be ignored - the so called nondegenerate limit.
In general, in the nondegenerate limit,
3
23 Eg /kB T
kB T
np = 4
mn mp e
(172)
2
2~
this, the law of mass action, holds for both doped and intrinsic semiconductor so long as we remain in the nondegenerate limit. However, for an intrinsic semiconductor,
where n = p, it gives us further information.
ni = pi = 2
kB T
2~2
23
mn mp
43
eEg /2kB T
(173)
1eV
' 10000 K 300 K
kB
e(E)/kB T
kB T
2 2
'
+1
Eg
2
(167)
C
(EC )/kB T
V
(EV )/kB T
n = p = Nef
= Nef
(174)
fe
fe
e2 /kB T =
V
Nef
f
C
Nef
f
(175)
27
or
1
1
(EV + EC ) + kB T ln
2
2
3
1
(EV + EC ) + kB T ln
2
4
V
Nef
f
!
(176)
C
Nef
f
mp
mn
(177)
# ionized
EC
ED
mp
mn ,
Thus if
6=
the chemical potential in a semiconductor is temperature dependent.
ND = N D + ND
EF
# un-ionized
+
EA
NA = NA + NA
EV
Doped Semiconductors
FIG. 30: Ionization of the dopants
(178)
at T ' 300 K
Si
Si
Si
Si
Si
e+
Si
Si
Si
Si
Si
Si
Si
Si
Si
Si
Si
Si
Si
Si
Si
Si
Si
Si
Si
Si
Si
Si
P
Si
e-
r
Si
(179)
2
Si 3s 3p
2
P 3s 3p
B 3s2 3p
2
r = h 2 big!
m* e
n - SeC
EF
EC
EC
ED
occupied at T= 0
EV
unoccupied at T= 0
(occupied by holes at T = 0)
EA
EV
EF
FIG. 29: Left, the density of states of a n-doped semiconductor with the Fermi level close to the conduction band and,
right, the equivalent for a p-doped semiconductor.
(180)
(181)
hence,
n = ni e(i )/kB T and p = ni e(i )/kB T
C
V
Eg
np = Nef
= n2i = p2i ,
f Nef f e
(182)
28
Metal-Insulator transition
In n-type semiconductors, when EF < EC , carriers experience a gap = EC EF . Hence at low temperatures
the system is insulating. Indeed,
n = NC e
|{z}
EC
kB T
(184)
T 3/2
ne2
0 when T 0.
m
where the constants (0 , A and B) depend on the material. In most metals and heavily doped semiconductors
the temperature dependence of the resistivity is dominated by these three mechanisms, which means that the
importance of impurities, electron-phonon and phononphonon interactions can be extracted from the temperature dependence of the resistivity.
A special case is the magnetic impurity case (Kondo),
which gives rise to an additional term in 1/K
(T /TK )2 .
(185)
= ne
m > 0 even for T 0, since the density does
no vanish. In general, also depends on temperature.
Indeed, in the metallic phase the most important temperature dependence comes from . To evaluate the contributions from different scattering mechanism we can
consider 1/ as the scattering probability. This follows
directly from Boltzmanns equation, where
X
dg
=
((k 0 k) (kk 0 )),
(186)
dt coll
0
In practice
p-n junction
where
(See also pn junction supplement)
0
g(k)
(1 g(k ))
(kk ) = W (kk )
|{z}
| {z }
| {z }
prob. kk0 # of states in k # of empty states in k 0
(187)
is the transition rate from state k to k 0 . Local equilibrium
implies kk0 = k0 k , hence g = fF D .
The most important scattering cases are the following:
Impurity scattering (for a density of impurities nI ):
1
eimp
nI
(188)
Electron-electron scattering:
1
(T /TF )2
ee
(189)
Electron-phonon scattering:
1
eph
(T /TD )
(190)
1
eimp
m
' 0 + A
e2 n
ee
eph
2
5
T
T
+B
(191)
TF
TD
29
distribution can then be obtained by solving Poissons
equation
e
2 V (x)
= (x)
2
x
0
(192)
Z
I = env = e
L
kF
~(kFL )2 (kFR )2
2m
2e
= ( R L )
h |{z} |{z}
eVR
no holes
charge density
+
+
+
+
+
+
eVL
=
-
z}|{
dk ~k
2
2 m
= e
p type
R
kF
2e
(VR VL )
h
(193)
n type
no electrons
in depletion region
potential
electric field
Vo=(n-p)/e
FIG. 32: Sketch of the charge density, the electric field and
the internal potential distribution due the transfer of charges
in a pn junction
Suppose that we have a perfect one-dimensional conductor (quantum wire) connected by two large electron
reservoirs. In real life they would be electrical contacts.
The left reservoir is fixed at chemical potential L and
the right one at R . The current is then given as usual
by
The previous result is specific to the purely onedimensional case. In general the system can be extended
to a system of finite width, W . In this case the electron
energy is given by
=
~2 (n/W )2
~2 kx2
+
2m
2m
(194)
30
FIG. 34: Conductance quantization of a quantum point contact in units of 2e2/h. As the gate voltage defining the constriction is made less negative, the width of the point contact
increases continuously, but the number of propagating modes
at the Fermi level increases stepwise. The resulting conductance steps are smeared out when the thermal energy becomes
comparable to the energy separation of the modes.
FIG. 35: Imaging of the channels using an AFM (1 to 3 channels from left to right). The images were obtained by applying
a small negative potential on the AFM tip and then measuring the conductance as a function of the tip scan and then
reconstruct the 2D image from the observed change in conductance. (From R.M. Westervelt).
-M (magnetization)
~2 (/W )2
~2 (2/W )2
<
E
<
(195)
F
2m
2m
then we recover the ideal case of a one-dimensional quantum wire, or single channel. If, however,
~2 (N /W )2
~2 ((N + 1)/W )2
<
E
<
(196)
F
2m
2m
we can have n channels, where each channel contributes
equally to the total conductance. Hence in this case G =
N 2e2 /h, where N is the number of channels. This
implies that a system, where we reduce the width of the
conductor will exhibit jumps in the conductance of step
2e2 /n. Indeed, this is what is seen experimentally.
QUANTUM HALL EFFECT
Type
Type
HC1
HC2
B (internal field)
B=O (Meissner)
HC1
HC2
(Abrikosov
vortex crystal)
TC
HC1
HC2
Superconductivity can be destroyed by an external magnetic field Hc which is also called the critical field (Kammerlingh-Onnes, 1914). Empirically,
Hc (T ) = Hc (0)(1 (T /Tc )2 )
The Meissner-Ochsenfeld effect (1933). The magnetic field does not penetrate the sample, the magnetic induction is zero, B = 0. This effect distinguishes two types of superconductors, type I and
type II. In Type I, no field penetrates the sample,
whereas in type II the field penetrates in the form
of vortices.
Superconductors have a gap in the excitation spectrum.
31
Due to retardation, the electron-electron Coulomb repulsion may be neglected!
The net effect of the phonons is then to create an
attractive interaction which tends to pair time-reversed
quasiparticle states. They form an antisymmetric spin
k
e
1000
Vanadium
e
- k
ions
e-
+
8
vF 10 cm/s
+
+
e-
+
+
region of
positive charge
attracts a second
electron
FIG. 38: Origin of the retarded attractive potential. Electrons at the Fermi surface travel with a high velocity vF . As
they pass through the lattice (left), the positive ions respond
slowly. By the time they have reached their maximum excursion, the first electron is far away, leaving behind a region of
positive charge which attracts a second electron.
When an electron flies through the lattice, the lattice deforms slowly with respect to the time scale of
the electron. It reaches its maximum deformation at
a time ' 2D ' 1013 s after the electron has passed.
In this time the first electron has travelled ' vF '
13
108 cm
s 10 s ' 1000A. The positive charge of the lattice deformation can then attract another electron without feeling the Coulomb repulsion of the first electron.
(~q )2
((k) (k q))2 (~(q))2
(197)
p2
H1p (x) = E(x)
2m
(198)
Lets define
c+
1 (x)
(199)
vacuum
32
to one electron in state (x) which we call 1. c+ is also
called the creation operator, since it creates one electron from vacuum. c is then the anhilation operator, i.e.,
c1 c+
1 |0i = |0i, which corresponds to creating one electron
from vacuum then anhilating it again. Other properties
include
+
c1 |0i = 0 and c+
1 c1 |0i = 0
(200)
(201)
.
j
j
i,j
i
i
Finally we can write down the two particle hamiltonian
as
H2p =
t1 c+
1 c1
t2 c+
2 c2
+
gc+
1 c1 c2 c2
(202)
We used the mean field approximation, which replaces c1 c2 by its expectation value ha|c1 c2 |ai = a
+
ha|c+
1 c2 |ai = a, where |ai is the ground state of the
Hamiltonian. The idea now is to
Pdiagonalize HM F , i.e.
a Hamiltonian in the form H = i c+
i ci . The trick here
is to use the Boguliubov transformation:
(
(
c1 = A1 cos() + A+
2 sin()
c+
=
A
sin()
+
A+
1
2
2 cos()
A1 = c1 cos() c+
2 sin()
+
A2 = c1 sin() + c+
2 cos()
(204)
+
It is quite straightforward to see that A+
i Aj +Aj Ai = ij ,
+ +
+ +
Ai Aj + Aj Ai = 0, and Ai Aj + Aj Ai = 0 using the
properties of ci . We can now rewrite HM F in terms of
our new operators Ai :
HM F =
=
=
+
+
+
+ +
2
t(c+
1 c1 + c2 c2 ) ga(c1 c2 c1 c2 ) + ga
+
t(A1 cos() + A2 sin())(cos()A1 + sin()A+
2 ) +
+
+
(A1 A1 + A2 A2 )(t cos(2) ga sin(2))
t(1 cos(2)) + ga sin(2) + ga2
+
(A+
(205)
1 A2 A1 A2 ) (t sin(2) + ga cos(2))
|
{z
}
=0 to diagonalize HM F
ga
ga
sin(2) = p
2
t
t + (ga)2
(206)
E2 = + ga
E1 = ga2
E0 = + ga2
(209)
a = sin(2)/2
(210)
33
Combining (206) and (210) we obtain
2a = p
ga
(211)
t2 + (ga)2
g /4t
'=ga
(216)
~ =
~ A
~ as usual. This is
The magnetic induction is B
in fact Londons equation for superconductivity. We can
now take the rotational on both sides of (216), hence
Normal
~j
|{z}
Superconductor
ne2 ~
~
A
mc
~ B=
~ 4 ~j
c
2
~
~ B
~ = 4ne B
~
mc2
Bx ex/L
g/2
(213)
q
with L =
length.
mc2
4ne2
|ai = (1 +
(214)
X
k,
tk c+
k, ck,
|{z}
spin
+
Vq c+
k+q, ck+q, ck, ck,
(215)
Here Vq is positive and represents the effective phonon
induced attraction between electrons at the Fermi level.
Its maximum for q = 0. The second term describes the
process of one electron with momentum k and another
electron with momentum k which are anhilated in order to create one electron with momentum k + q and
e -x/
Vacuum
(217)
Inside the
superconductor
FIG. 41: The decay of the magnetic field inside the superconductor. The decay is characterized by the London penetration
length L .
t
t mc2
(218)
c t
34
A remarkable aspect of superconductivity is that one
of the most fundamental symmetries is broken. Indeed,
~ What hapGauge invariance is broken because ~j A.
pens is that below Tc we have a symmetry breaking,
which leads to new particles, the Cooper pairs. Mathematically, we have
U (2)
| {z }
= SU (2)
| {z }
U (1)
| {z }
N ormal state
SC state
Gauge invariance
(219)