Semiconductor and Superconductor Physics %28korjattu%29 PDF

Semiconductor and Superconductor
Physics
Erkki Lähderanta
Lectures follow the books:

Puolijohdeteknologian perusteet (Sinkkonen) and
A. L. Rose-Innes and E. H. Rhoderick: Introduction to Superconductivity
Contents
1 Classical conductor 3
1.1 Electrical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.1.1 Conductivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.1.2 Hall effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.1.3 Frequency dependence of conductivity . . . . . . . . . . . . . . 8
1.2 Optical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2 Quantum mechanics 15
2.1 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
2.2 Schrödinger equation (1926) . . . . . . . . . . . . . . . . . . . . . . . . 20
2.3 Classical limit (macroscopic particles) . . . . . . . . . . . . . . . . . . . 21
2.4 Solution of Schrödinger Equation . . . . . . . . . . . . . . . . . . . . . 25
3 Structure of material 29
3.1 Atom . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
3.2 Atomic bonds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
3.3 Solid material and crystal structure . . . . . . . . . . . . . . . . . . . . 31
3.4 Lattice vibrations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
4 Free-electron model of metals 34

4.1 Free electron gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
4.2 Thermal emission current . . . . . . . . . . . . . . . . . . . . . . . . . 40
4.3 Field emission current . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
5 Energy bands 45
5.1 Formation of bands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
5.1.1 Periodical potential . . . . . . . . . . . . . . . . . . . . . . . . . 48
5.2 Models for free energy bands . . . . . . . . . . . . . . . . . . . . . . . . 52
5.2.1 Free electron model . . . . . . . . . . . . . . . . . . . . . . . . . 52
5.2.2 Kronig-Penney-model (1930) . . . . . . . . . . . . . . . . . . . . 54
5.3 Electrons movement in the energy band . . . . . . . . . . . . . . . . . . 57
1
5.3.1 Semiclassical equation of motion . . . . . . . . . . . . . . . . . . 57
5.3.2 Electrical conductivity . . . . . . . . . . . . . . . . . . . . . . . 63
5.3.3 Charge carriers in semiconductor: Holes . . . . . . . . . . . . . 64
5.4 Energy bands for various materials . . . . . . . . . . . . . . . . . . . . 66
5.4.1 Metal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
5.4.2 Semiconductors and insulators . . . . . . . . . . . . . . . . . . . 67
5.5 Interaction between electron and wave . . . . . . . . . . . . . . . . . . 68
5.5.1 Disturbation theory . . . . . . . . . . . . . . . . . . . . . . . . . 68
5.5.2 Optical properties of semiconductor . . . . . . . . . . . . . . . . 71
6 Semiconductor physics 74
6.1 Density of charge carriers . . . . . . . . . . . . . . . . . . . . . . . . . . 74
6.1.1 Density of states in energy band . . . . . . . . . . . . . . . . . . 74
6.1.2 Electron and hole densities . . . . . . . . . . . . . . . . . . . . . 76
6.1.3 Doped semiconductor . . . . . . . . . . . . . . . . . . . . . . . . 78
6.1.4 Charge carrier density of doped semiconductor . . . . . . . . . . 80
6.2 Mobility, µ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
6.3 Generation and recombination of charge carriers . . . . . . . . . . . . . 85
6.4 Diffusion current . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
6.5 Current caused by temperature gradient . . . . . . . . . . . . . . . . . 90
6.5.1 Current density . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
6.5.2 Density of heat flow rate (lämpövirrantiheys) . . . . . . . . . . . 91
7 Preparation of semiconducting materials 93

7.1 Crystal growing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
7.2 Selective doping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
7.3 Diffusion and ion-implantation . . . . . . . . . . . . . . . . . . . . . . . 95
7.4 Oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
7.5 CVD-growing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
7.6 Metal growing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
7.7 MBE-method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
8 Spintronics 102
8.1 Magnetic semiconductors . . . . . . . . . . . . . . . . . . . . . . . . . . 102
8.2 CMR and GMR phenomenon . . . . . . . . . . . . . . . . . . . . . . . 103
8.3 Multilayer structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
8.4 Spintronics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
2
Chapter 1
Classical conductor
Electrons in metal. Free electron gas and positive metal ions.

Current carrier react on electromagnetic field ⇒ ELECTRICAL and OPTICAL proper-
ties.
Density of atoms ≈ 5 · 1022 atoms/cm3 ⇒ dense medium.
Medium ⇒ Crystal lattice ⇒ periodic potential ⇒ modify properties of current carriers
and gives energy bands.
Temperature ⇒ Thermal vibrations.
1.1 Electrical properties

1.1.1 Conductivity
Figure 1.1
E = 0 ⇒ motion + collision + motion + collision + . . .

Short motion is linear and to arbitrary direction Brownian motion.
Thermodynamic stability ⇒ statistical methods, specially AVERAGE.
Velocity distribution of a classic particle: Maxwell-Boltzmann distribution
− 12 m(vx2 + vy2 + vz2 )

−Ekin
f (vx , vy , vz ) = N exp = N exp (1.1)
kT kB T
3
N = normalization constant;
vx , vy , vz = velocity in x, y and z direction;
m = mass of particle;
kB = Boltzmann constant = 1.380 622 · 10−23 J K−1 = 8.6173 · 10−5 eV K−1 .
If T = 300 K ⇒ kB T = 0.0258 eV (small).

(1.1) is symmetric ⇒ velocity average = 0 ⇒ particle drift and electric current = 0.
Thermodynamics and statistical physics ⇒
Average kinetic energy per direction 12 mv 2 always positive

x y z 1
= hEkin i = hEkin i = hEkin i= kB T
2
3 dimension hEkin i = 32 kB T
⇒ “most common”speed = thermal speed ≡ vT .
r
1 3 3 kB T
mvT2 = kB T ⇐⇒ vT = (1.2)
2 2 m
)
Numerical values m = 9.1 · 10−31 kg cm m km
⇒ vT ≈ 107 = 105 = 100 (1 mm in 10 ns)
T = 293 K s s s
Electric field E 6= 0 ⇒ F = −qE ⇒ Equation of motion
dv
F = ma ⇐⇒ m = −qE (1.3)
dt
q
E = constant ⇒ v(t) = v(t0 ) − E(t − t0 ) (1.4)
m
t0 = initial moment and v(t0 ) = initial velocity.
Speed depends linearly on E and on (t − t0 ).
If t0 = previous collision, then (1.4) is working up to next collision. For every electron

we have own (1.4) and own t0 . Average of (1.4) over collision times t gives v

(1.4) q
q
v = − E t − t0 = − τ E ≡ vD (1.5)
m m

τ = t − t0 = average time between collision = “relaxation time”.

In (1.5) is taken into account v(t0 ) = random ⇒ v(t0 ) = 0.
Average velocity vD , proportional to electrical field E
vD = drift velocity.
4
ELECTRIC CURRENT
Figure 1.2
We investigate time period τ ⇒ electrons move distance ∆x = vD τ

Electron density ≡ n ⇒ across the area A is moving amount of electric charge
∆Q = qn∆xA ⇒ Electric current density J
I ∆Q/τ qn∆xA qnvD τ (1.5) q 2 τ n

J= = = = = · E ≡ σE (1.6)
A A τA τ m
Here is definition of conductivity
q2τ
σ≡ ·n (1.7)
m
This gives resistivity

ρ ≡ σ −1 (1.8)
Ohmic law (1.6): Electric current density is directly proportional to electric field
strength
Proportionality constant σ depends on
∧
n = density of current carriers and τ = relaxation time (= collision frequency)
Numerical values. Metal n ≈ amount of atoms ≈ 5 · 1022 electrons/cm3

σ ≈ 106 Ω−1 cm−1
(1.7)
⇒ τ ≈ 10−13 s.
Free path, l = free distance = how long is average distance between the collisions.
Thermal speed = vT = 105 m s−1 ⇒ l = vT · τ = 105 m s−1 · 10−13 s = 10 nm (293 K).
Much less than size of component.
MOBILITY, µ
Average velocity (1.5) vD can be written
|vD | = µE (1.9)
5
(1.5) gives
qτ
µ= (1.10)
m
which is MOBILITY of current carrier.
Numerical values: τ ≈ 10−13 s ⇒ mobility µ ≈ 200 cm2 V−1 s−1 .
Average velocity, vD , is much less than thermal velocity, vT .
If E = 10 V cm−1 = 1 kV m−1 ⇒ vD = 20 m s−1 , but vT ≈ 105 m s−1 .
Now we try to take vD from equation of motion.
ma = F , i.e. m dv
dt
= −qE could give vD , but collisions??
⇒ Drude model: we take collision into account with additional friction term.
Drude model. Collision (i.e. scattering) is limiting F = −qE to times with t < τ
Similar result if we add a term which is similar to friction, i.e. term proportional to
velocity, vD ⇒
dvD
ma = F − Ff riction ⇐⇒ m = −qE − γvD (1.11)
dt
Friction-term taken from physics of fluid dynamics (viscosity). In steady state (t →
big) ⇒
dvD (1.5) m
= 0 ⇐⇒ γ = (1.12)
dt τ
Solution of Eq. (1.11) if E is switched ON when t = 0 ⇒

−qEτ −t
vD (t) = 1 − exp (1.13)
m τ
Figure 1.3
Now we see why τ is called as “relaxation time”:

After a change (e.g. field ON or OFF), the velocity vD becomes stable after one collision,
that is after t ≈ τ .
Equation (1.11) is called Hydrodynamic model, or Drude model. Charges behave like
particles in liquid ⇒ result is obtained from average and viscosity.
6
1.1.2 Hall effect
σ = σ(n, µ), meaning σ depends on mobility, µ, and electron density, n.
How to measure n? Answer: B.
Lorentz-force

F = −qv × B F ⊥v and F ⊥B (1.14)

Total force ΣF = −qE + −qv × B

⇒ In material appears small voltage perpendicular (⊥) to direction of current F ⊥v

and magnetic field F ⊥B .
Figure 1.4
This voltage is called Hall-voltage.

Drude model ⇒
dv D (1.11)−(1.14) m
m = − v D − q(E + v D × B) (1.15)
dt τ
dv D (1.6)
Steady state situation ⇒ dt
= 0 and current density J = −qv D n ⇒
1
E= J − RH J × B (1.16)
σ
where
1
RH = − = Hall-constant (1.17)
nq
Eq. (1.16) has 2 parts
1. Usual ohmic voltage parallel to current
1 vD
EL = J= (1.18)
σ µ
2. E H = field perpendicular to current:
E H = −RH J × B = −v D × B (1.19)
7
In steady state this E H compensates the Lorentz-Force ⇒ Hall-voltage=
1 I ·B
UH = EH · H = · (1.20)
qn W
In measurements longitudinal voltage gives σ
L I
UL = EL · L = · (1.21)
σ WH
In measurements perpendicular voltage, Hall-voltage, gives n, density of current carries.
These together gives mobility, µ.
Ratio of EH and EL (1.18) and (1.19) ⇒
EH
= µB (1.22)
EL
EH
Numerical values. If B = 1 T = 1 V s m−2 and µ = 600 cm2 V−1 s−1 ⇒ EL
≈ 0.06.
1.1.3 Frequency dependence of conductivity

Electron collision to positive atoms ⇒ different time windows give different results.
Apply electric field
E = E0 exp(−iωt) (1.23)
E0 = amplitude
ω = angular frequency (2πυ = ω)
⇒ this gives average velocity, drift velocity, from (1.4) and conductivity

−qτ 1
vD = E (1.24)
m 1 − iωτ
σDC
σ(ω) = (1.25)
1 − iωτ
where σDC is given in (1.7).

τ
AC-behaviour by replacing τ → 1−iωτ
in DC-behaviour
8
(1.25) in 2 parts
Re[σ(ω)] = σDC /(1 + ω 2 τ 2 )

(1.26)
Im[σ(ω)] = ωτ σDC /(1 + ω 2 τ 2 )
Figure 1.5
Low frequency < τ1 ⇒ σ = σDC

High frequency (ωτ 1) ⇒ Re → 0 like ω12 .

Im-part grows linearily with ω, when ω τ1 , maximum at ω = τ1 .
Im > Re when ω > τ1
wire behaves like impedance. Maxwell-equation
∂E
J tot = J + ε (1.27)
∂t
J = usual current density with J = σ(ω) · E

∂E
ε = dieletric displacement current (siirrosvirta)
∂t
(1.25) means that resistance and inductance are in series
Λ
R= (1.28)
σDC · A
τΛ m Λ
L= = 2 (1.29)
σDC · A q nA
A = cross-section; Λ = length.
Second term in Maxwell equation (1.27) is connected to capacitance, so called “geomet-
rical capacitance”in parallel
εA
C= (1.30)
Λ
Conductor, wire, is LC-circuit with losses
9
Figure 1.6
Geometrical capacitance is charged when voltage is applied.

Electrons behave in inductive way. Resistance from collision (t → τ ).
Resonance frequency of LC-circuit =
r
1 q2n
ωp = √ = (1.31)
LC εm
Name: PLASMA FREQUENCY
1.2 Optical properties

Real part of conductivity means losses and damping of the wave σ = σ(ω) ⇒ Different
frequencies give different reflection and propagation
∂B
Maxwell ∇ × E = − (1.32)
∂t
1 ∂E
∇×B =J +ε (1.33)
µ ∂t
ε = permittivity;
µ = permeability.
Ohm law
J = σE (1.34)
If additional charge ⇒ Electric field

ρ
∇E = (1.35)
ε
where ρ = charge density.
4 equations ⇒ Electromagnetic fields.
Wave equation. Start with neutral and homogenous conductor (ρ = 0)
Calculation ⇒
∂E ∂ 2E
∇2 E = µσ + µε 2 (1.38)
∂t ∂t
Solution is
E = E 0 exp[i(k · r − ωt)], which is a wave (1.39)
10
k · r − ωt = phase angle ≡ φ(r, t), E 0 = amplitude, k = wave vector.
Phase angle φ is constant if r⊥k, meaning in direction perpendicular to propagation of
the wave.
In direction of wave propagation (r k) phase angle ϕ = const if
ω
r= · t − r0 (t = time)
k
Interpretation: In direction of propagation the phase moves with velocity, so called
phase velocity (vaihenopeus) vp .
Figure 1.7
∆r ω
vp = = (1.40)
∆t k
During distance of wave length λ, phase angle ϕ change by 2π ⇒ ∆φ = 2π ⇐⇒
∆r · k + ∆(ωt) = 2π ⇐⇒ λ · k = 2π ⇐⇒
| {z }
=0
2π
k= (1.41)
λ
i.e. lenght of wave vector is connected to λ

Question: When (1.39) is solution of Maxwell equations?
(1.32) ⇒ B = B 0 exp[i(k · r − ωt)] (1.42)

1
with amplitude B 0 = k × E 0 (1.43)
ω
In other words: Magnetic field component in plane wave is perpendicular to E and k.

(1.35)
Moreover, because charge density ρ = 0 ⇒ ∇ · E = 0 and therefore also
k·E =0 (1.44)
⇒ In electromagnetic wave B and E are ⊥ in comparison to propagation

Exist 2 directions of polarization.
Wave equation (1.38) requires (calculations)
k 2 = iωµ(σ − iωε) (1.45)
11
Figure 1.8
This is called dispersion relation and it gives k = k(ω).

Dispersion = wave beam splits to wave components.
Tangential components(direction of surface) is continuous ⇒
0
incident angle = angle of reflection; θ = θ
00 00
snell law k sin θ = k sin θ (1.46)
00 00
if k = k (ω) ⇒ wave beam will split to components.
Figure 1.9
INSULATOR. σ = 0, µ and ε are real constants (non-imaginary) ⇒
√ 1
(1.45) gives k = εµ · ω ≡ ω (1.47)
v
1
where v ≡ √ = velocity (1.48)
εµ
v usually is written as
c
v= (1.49)
n
with c = velocity in vacuum; n = index of refraction (“how thick optically”).
r
εµ c
n= = (1.50)
ε0 µ 0 v
12
(1.47) can be written also in the form
ω
k=n (1.51)
c
Snell law (1.46) can be written in the form
00 00
n sin θ = n sin θ (1.52)
CONDUCTOR. σ = const, real number ⇒

1/2
1
(1.45) iσ
k = ω 1+ (1.53)
v ωε
Wave number k: Imaginary part gives attenuation, damping (k 2 = εµω 2 + iσµω).

Low frequency σ ωε ⇒
r
1 1
Imk = µσω ≡ (1.54)
2 δ
where δ is called skin depth (Finnish language ≈ penetration depth)

High frequency ⇒ σ is complex, similar to (1.25)
Figure 1.10
If ωτ 1 ⇒ Eq. (1.53) (τ is the time between collision).

If ωτ 1 ⇒ Imσ Reσ ⇒ Conductor behave like insulator and wave number
becomes 2 1/2
1 ωp
k = ω 1− (1.55)
v ω
where ωp is plasma frequency (1.31).
If ω > ωp ⇒ k is real (non-imaginary) and NO DAMPING of the wave.
Interpretation: Free electrons cannot follow the electromagnetic fields ⇒ X-rays
penetrate the material.
13
In metals ωp ≈ 1015 s−1 (2000 nm?).
Reflectance. From air to material with index of refraction = n electric field components
E0 = incoming, E1 = reflected, E2 = refracted. Tangential components continuous ⇒
E0 + E1 = E2 (1.56)
Figure 1.11
Magnetic field components in similar way B0 + B1 = B2


1
(1.43) B 0 = k × E 0 

(1.56)
ω ⇒ B0 proportional to n · E0 =⇒
ω
(1.50) k = n 

c
E0 − E1 = nE2 (1.57)
calculations E1 1−n E2 2
=⇒ E0 = 1+n
and E0
= n+1
Coefficient of reflection =
2
v0 |E1 |2

intensity of reflecting wave 1−n
R= = =
intensity of incoming wave v0 |E0 |2 1+n
(1.58)
Coefficient of trasmission =
v0 2
intensity of trasmission n
n |E2 |2 4n
T = = 2
=
intensity of incoming wave v0 |E0 | (1 + n)2
(1.59)
(v0 = velocity of incoming wave, in vacuum).

More high frequency ⇒ X-rays (λ ≈ 0.1 nm) ⇒ Macroscopic quantities, such as
dielectricity constant, not enough.
Reflection from atoms, not from surface ⇒ Bragg law
2d sin θ = λ · integer (1.60)
14
Chapter 2
Quantum mechanics
First experimental results, which were not possible to explain classical physics.
Figure 2.1
2.1 History
A. Black body radiation Classical model: Energy densisty of radiation E ∝ ω 2 .
Experimentally ω 2 dependence only with small ω, with high frequency intensity
→ 0, when ω increases
Classical model: Radiation energy E is continuous. In temperature T average
15
energy for waveform=
R∞
dE · E · exp(−E/kt)
hEi = 0 R ∞ = kB T = const (2.1)
0
dE exp(−E/kt)
Density of waveform ∝ ω 2 ⇒ Energy density ∝ ω 2 .

PLANCK (1901): Energy exchange between electromagnetic wave and material
happens as portions, quantas, not continuous and size of energy quanta ∝ ω.
Meaning, energy of generated irradiation has form
E = n}ω (2.2)
with n = integer and } = constant.

R∞ P
In this case average will be discrete ( 0
→ )⇒
P∞
n=0 n}ω exp(−n}ω/kt) }ω

E = P ∞ = (2.3)
n=0 exp(−n}ω/kt) exp k}ω −1
BT
h
Energy quantization explained spectrum of radiation. } = Planck constant = 2π .
Irradiation contain photons and each photon has energy = }ω ⇒ Amount of
photons in a wave =
1
hni = (2.4)
exp k}ω
BT
− 1
This has a name Bose-Einstein distribution and it describe behaviour of Bosons

(spin is integer number. Spin half ⇒ Fermion).
Figure 2.2: Experimental arrangement and explanation
16
B. Photoelectric effect No current until ω > ω0 = threshold frequency. Light
intensity influence only on size of current.
Threshold frequency not possible to understand with classical model.
Planck idea about quantization of energy in light ⇒ Einstein explained threshold
frequency (1905):
When frequency is enough, only then energy }ω is able to lift electron to height
of W0
ω0 = workfunction.
} turned out to be the same constant as in black body radiation. Energy that
remain after ω0 , will be kinetic energy
1
}ω − W0 = mv 2 (2.5)
2
C. Specific heat of solid state materials (phonon) Classical physics: Atom vi-
brating around equilibrium position ⇒ Energy of Harmonic oscillator
1 1
E = M vx2 + αx2 (2.6)
2 2
M = mass, α = string constant.
If classical ⇒ Maxwell-Boltzmann distribution gives energy average
hEi = kB T (2.7)

This is x−direction. 3-dimensional ⇒ E = 3 kB T and final result ⇒
∂ hEi
Specific heat = cv = = 3 kB per particle (2.8)
∂T
In high temperatures OK, in low temperatures experiments show that cv → 0
Einstein explained (1906) low temperature behaviour: Energy for vibrating atom
is also quantized:
E = n}ω (2.9)
Quantum is called PHONON
D. Bohr model (1913) Classical mechanics: Particle energy is continuous, therefore

infinite amount of orbits.
Experiments: Emission and absorption spectrum not continuous, sharp lines.
17
Figure 2.3
Bohr (1913): Angular momentum is quantized
L = n} (2.11)
⇒ Only fixed orbits are accepted.

Circular motion: v = ωr ⇒ p = mv = mωr ⇒ L = pr = mωr2 ⇒
mωr2 = n} (2.12)
Additionally F = ma ⇒
1 q2
2
= mω 2 r (2.13)
4πE0 r
⇒ Possible orbits
e4 m 1
En = 2 2
· 2 (2.14)
2(4πE0 } ) n
4πE0 }2 2
rn = ·n (2.15)
e2 m
Valid for atoms with one electron (hydrogen-like). n = quantum number.
E. Compton scattering (Phys. Rev. 22, 409 (1923))

Experiment: X-rays into electrons.
Interaction between photon and electron is like collision of two particles. Also
conservation of momentum.
Classical physics: light has energy (but no particles and therefore no momentum)
Quantum mechanics: light consists of photons and photons have momentum.
18
For photon, with m0 = 0 and velocity = c, we have E = pc and E = }ω ⇒
}ω h
p= = with h = 2π} (2.16)
c λ
Photoelectric effect: All photon energy to electron, photon disappears.

Compton scattering: Part of the photon energy to electron, amount of photons
remain constant.
F. Wave nature of electron (de Broglie, PhD-thesis 1924)

Photon has wave nature and also particle behaviour.
de Broglie: Also particle have both behaviours, including wave nature. Photon
p = λh , de Broglie: this is valid also for particles ⇒
h h
λ= = (2.17)
p mv
Also energy similar to photon E = }ω ⇒
E
ω= (2.18)
}
Additional result: Simple interpretation of Bohr quantization rule: (2.17) and

(2.18) ⇒ Length of the orbit must be
2πr = nλ (2.19)
Figure 2.4
Question: de Broglie is theoretical idea. What about experiments?

Answer: 1927 Yes, Electron beam to crystal gave scattering according to Bragg
law
2d sin θ = nλ (2.20)
19
2.2 Schrödinger equation (1926)
On atomic level the measuring accuracy is not enough for “usual”measuring.
Tunneling microscope: ∆r is ok, but ∆t is not ok.
Fast lasers (“attolaser”, < 10−15 s): ∆t is ok but ∆r is not ok.
Electromagnetic radiation (λ ≈ 10−11 m): ∆r ok and ∆t ok, but energy too big
⇒ Must not think about orbit or equation of motion.
Instead, statistical ideas, like photon, average behaviour should be taken from wave
nature.
Question: Wave equation for particle wave?
We take ready result:
}2 d2 U(x)
− + V (x)U = EU(x) (2.26)
2m dx2
Time independent Schrödinger equation. Here U(x) is “amplitude”function of wave
function
Ψ(x, t) = U(x) exp(−iωt) (2.22)
Time dependence ⇒
}2 ∂ 2 Ψ(x, t) ∂Ψ(x, t)
− 2
+ V (x)Ψ(x, t) = i} (2.27)
2m ∂x ∂t
New physics, not possible to derive from something old. Experimentally: it is working.
More general case: Charged particles in alternating electromagnetic field ⇒ One more
term in Schrödinger equation (more complicated).
General features
1. Linear combinations of Ψ are also solutions of Schrödinger. ⇒ Superposition and

interference of electron diffration.
2. Solution is called: WAVEFUNCTION. Complex.
3. |Ψ|2 = Square of wavefunction magnitude = probability distribution.

Probability dP to have particle in volume d3 r is
dP = Ψ∗ Ψ d3 r (2.31)
4. Ψ must be single-valued and finite. Ψ and ∇Ψ continuous.
20
2.3 Classical limit (macroscopic particles)
Quantum mechanics is for atom-size objects. For macroscopic particles the results must
be similar to classical mechanics. We describe macroscopic particles with wavefunction:
First we think about free microscopic particle. 1D Schrödinger gives wavefunction with
normalization:
1 E(k)t
Ψ(x, t) = √ exp i kx − (2.33)
L }
where k = wavenumber, L = size of volume (1D) and ω has been replaced by E(k)
}
,
where
}2 k 2
E(k) = energy = (2.34)
2m
Example:
Probability distribution = |Ψ|2 = Ψ∗ Ψ = L1 = const.
Linear combination of (2.33)

E(k)t
Z
Ψ(x, t) = dk a(k) exp i kx − (2.35)
}
is also solution of Schrödinger. We call this wave packet.

What is a(k)?
It is simply multiplication function. Wave packet (2.35) is solution of Schrödinger and
it describes a particle with all a(k)−functions.
We can describe classical particle by choosing

1, when k − ∆k < k < k + ∆k
0 2 0 2
a(k) = (2.36)
0, elsewhere
Figure 2.5
Calculation easier if we put ∆k small ⇒

dE
E(k) = E(k0 ) + k − k0 ) (2.37)
dk k=k0
21
⇒ Possible to calculate wavefunction (2.35). Final result as probability distribution
( ∆k )2
sin (x − v g t)
|Ψ(x, t)|2 = ∆k 2 ∆k
2
(2.38)
2
(x − vg t)
where
1 dE(k)
vg = (2.39)
} dk k=k0
⇒ Highest probability to find the particles is when
x = vg t (2.40)
and width of the distribution in x−space =
2π
∆x ∼
= (2.41)
∆k
CLASSICAL PARTICLE
∆k
Figure 2.6: Horizontal axis = α = 2 (x − vg t). Wave packet in real-space (x−space).
We take derivate of (2.34) and group velocity (2.39) will be
}k0
vg = (2.42)
m
Classical particle has scattering of position ∆x in real space and scattering in wavenumber-
space ∆k.
(2.41)
Momentum for particle = p = }k ⇒ ∆p = }∆k ⇒
∆x · ∆p = 2π} (2.43)
22
Looks like Heinsenberg uncertainty principle.
Heinsenberg was also building theory of quantum mechanics.
Heinsenberg was using matrices, matrix mechanics.
Question: When wavepacket (2.35) is good presentation of a particle?
Answer: If it is possible to allow uncertainty ∆x · ∆p = 2π}.
Uncertainty in time
(2.42) (2.40) ∆x (2.41) 2π (2.31) }2 k2
vg = = } km0 , ∆(t) = vg
, ∆(x) = ∆k
, E(k) = 2m
⇒
∆E · ∆t = 2π} (2.46)
Numerical values: ∆E < kB T ⇒ in roomtemperature ∆t > 10−13 s.
Example. Particle in circular motion ⇒ p = mωr. Small r and small p ⇒ Uncertainty

becomes relatively large. Limit for “small r”≈ radius in Bohr model.
Figure 2.7
Example 2. In superconductors the Cooper pairs. Interaction between electrons is

mediated by phonon, virtual process. Phonon energy is “virtual”∆E · ∆t ≈ },
with ∆t = lifetime of phonon.
Wavepacket, particle, with potential V (x)

Also in this case quantum mechanics gives a result, which is in agreement with classical
mechanics.
Quantum mechanics gives
dvg
m = −qE (2.50)
dt
23
or in more general case with B, Schrödinger equation gives for a localized particle
dv g
m = −q(E + v g × B) (2.51)
dt
These are similar results as one obtains from classical mechanics F = ma.
24
2.4 Solution of Schrödinger Equation
Pratical examples, situations with different energy barriers.
Introduction: Wavepacket in two parts

Et
Ψ(r, t) = Ψ(r) exp(−iωt) = Ψ(r) exp −i (2.52)
}
where dependence on time and on place are separate functions. Function which is
depending on place, fulfills time independent Schrödinger equation:
}2 ∇2

+ V (r) Ψ(r) = EΨ(r) (2.53)
2m
A. Potential step Solution of (2.53) separately for both sides
Figure 2.8
Ψ1 = A exp(ikx) + B exp(−ikx) (2.54)

Ψ2 = C exp(ikx) + D exp(−ikx) (2.56)
where wavenumber has form (E = electron kinetic energy)

r
E
k= 2m 2 (2.55)
r }
(E − V0 )
k 0 = 2m (2.57)
}2
Mathematics: Adjust these two parts (2.54) and (2.56) together in such a way
that boundary conditions are fullfilled. This means to find correct A, B, C and D.
Final result: Electron penetrate inside the potential step in depth
1 }
σ= =p (2.62)
η 2m(V0 − E)
25
where V0 = height of the potential step, E0 = energy of the particle and k 0 = iη.
Also one obtains:
0 2
B 2 1− kk
Reflection R = A = k0
1+ k
Trasmission (How big part of the particles penetrate the step)

0
k 0 |C|2 4 kk
T = = 0 2
k|D|2 1 + kk
Compare with (1.59) and (1.60). Naturally R + T = 1
Figure 2.9: Penetration of particles to other side. In quantum mechanics T goes to 100%
more slowly.
Figure 2.10
B. Potential barrier, energy barrier Mathematics more complicated. Both poten-

tial steps are calculated separately. If potential barrier is symmetric (V2 = V0 ) ⇒
Mathematics gives trasmission.
1
T = V 2 sinh2 ηL
(2.78)
1+ 4E(V1 −E)
where r
2m
η= (V1 − E) (2.77)
}2
V = V1 − V0 = heigth of the barrier, E = energy of the particle. If ηL 1
26
calculations
(Energy difference (V1 − E) big or barrier thickness L big) =⇒
T ≈ exp(−2ηL) 1 (2.79)
In the other textbook (Young-Freedman)
T = G exp(−2ηL)
q
where G = 16 VE1 1 − E
V1
and η = 2m
}2
(V1 − E).
Example: Quantum mechanical tunneling
Figure 2.11: Trasmission T vs. barrier height E
C. Time dependent tunneling Tunneling velocity complicated. In lecture some

graphs from computer simulations. One proposal (1982) for tunneling velocity
r
V1 − E
V = 2 (2.80)
}
D. Potential well (compare: standing wave)
Figure 2.12
27
Important, because this shows electron behaviour inside the material. Mathematics
similar to potential barrier (V1 > V0 , now V1 < V0 ).
Intermediate result
kL
η = k tan (2.81)
2
or
kL
η = k cot (2.82)
2
q q
where definitions k = 2m
}2
E and η = 2m }2
(V0 − E) (see (2.77)).
kL nπ
V0 big ⇒ 2
= 2
(“standing wave”), meaning
nπ
k= (n ∈ N) (2.83)
L
Final result: Energy levels
} 2 π 2 n2
En = (n ∈ N) (2.84)
2mL2
These are “deep well” energy levels (V0 very high)

If V0 < ∞ ⇒ Energy levels little below (2.84).
28
Chapter 3
Structure of material
3.1 Atom
Bohr model is rather simple. More detailed with Schrödinger equation. Hydrogen like
atom possible to describe. Schrödinger equation
}2 2 e2

− ∇ − Ψ(r) = EΨ(r) (3.1)
2m 4πε0 r
gives solution
Ψ(r) = Ψnlml (r) = Rnl (r)Ylml (θ, ϕ) (3.2)
In spherical coordinates Ψ(r) separates in two parts: one part depending on distance
and one part depending on direction. Variables for spherical coordinates r, θ and ϕ.
Figure 3.1
Electron energy in hydrogen atom in state n:
e2 m 1 13.6 eV
En = − 2
· 2 =− (3.3)
2(4πE0 }) n n2
29
In solution (3.2) indices n, l, ml are called quantum numbers, they characterize different
solutions.
For hydrogen the energy depends only on main quantum number n. In more complicated
atoms the electron energy depends also on l and ml
l = orbital quantum number = 0, 1, 2, . . . , n − 1 (3.4)
describes angular momentum of electron.
ml = magnetic quantum number = 0, ±1, ±2, . . . , ±l (3.5)
describes z−component of angular momentum of electron.

Angular momentum L = p×r act as operator and spherical harmonic function Ylml (θ, ϕ)
fulfill:
L2 Ylml = }l(l + 1)Ylml (3.6)

Lz Ylml = }ml Ylml (3.7)
Here is more clearly seen that l is connected to magnitude of L and ml is connected to

z−component of L.
Question:Where is z−axis of an atom?
Answer: Need external interaction, meaning a magnetic field ⇒ z−axis is definited in
direction of B ⇒ Name for ml = magnetic quantum number.
More heavy atoms ⇒ Many particle problem and correction terms. Energy depends
also on l ⇒ E = Enl
Correction terms: In Schrödinger equation is second derivate. Not exact solution, only
approximations. In magnetic field energy depends also on ml (Zeeman spliting).
Names and spectroscopic notations
Occupation of electron shell nlx
x = amount of electrons in subshell nl

n = main quantum number, n = 1, 2, 3...
Orbital quantum number notation with letter



 l = 0 ⇒ s-state

 l = 1 ⇒ p-state


 l = 2 ⇒ d-state
l = 3 ⇒ f-state

30
Example 1.
1s2 describes electron shell of He
Example 2.
Every shell with own notation. Larger atom ⇒ more shells 1s2 2s2 2p6 is spectroscopic
notation of electron shell for Ne.
3.2 Atomic bonds

A. Ionic bond. Coulomb interaction.
B. Covalent bond. Neighbouring atoms have common electrons.
C. Metallic bond. Electron gas, electron sea, about 1 electron from each atom.
8-N-rule.
3.3 Solid material and crystal structure

Lattice points are similar: Each of them have similar environment. Lattice vector:
R = n 1 a1 + n 2 a2 + n 3 a3 (3.8)
ai = basis of lattice (i = 1, 2, 3) and ni are integers.

Exist 14 different lattice structures, for example 3 different cubic structures
Miller indices. Macroscopically crystal looks like planes. Mathematical name for
different planes = Miller indices. Described in lectures.
Direction corresponding to plane: Similar numerical values for Miller indices, but
different kind of brackets; (nkl) = b plane and [nkl] direction ⊥ (nkl).
31
3.4 Lattice vibrations
Figure 3.2
Average total energy per atom = 3kB T (3 dimensions). Vibration of atoms is connected
to each other, modelling with ideas from springs, collective behaviour. Nearest neighbour
interaction ⇒ equation of motion for atom i (ma = F )
d2 ui
M = γ[(ui+1 − ui ) − (ui − ui−1 )] = γ[ui+1 + ui−1 − 2ui ] (3.9)
dt2
M = mass of atom i
ui = deviation from stable position
γ = “elastic”constant = “string”constant
Figure 3.3
Differential equation (3.9) has solution as plane wave
un = A exp[i(kna − ωt)] (3.10)
Inserting (3.10) into (3.9) ⇒ It is required

r
γ ka
ω= 2 sin (3.11)
M 2
This has a name dispersion relation, frequency as function of k. With long wave lengths
32
Figure 3.4
(3.10) is elastic wave, meaning sound wave. λ long ⇒ k small. When k → 0 we have
(3.11) in form r r
γ ka ka<<1 γ
ω= 2 sin ≈ · ka = vk (3.12)
M 2 M
This is linear dependence, where r
γ
v=a (3.13)
M
is velocity of wave = velocity of sound.
Numerical values v ≈ 104 m s−1 . Lattice constant = a ≈ 0.5 nm ⇒
ωmax = maximum angular frequency = 2v a
≈ 4 · 1013 s−1 .
Quantum mechanics: Energy has values=
E = n}ω (n ∈ N) (3.14)
Here phonon energy is }ω.

Maximum energy for phonon = Emax = }ωmax ≈ 0.02 eV ≈ kB T , meaning size of
thermal energy. Lattice vibration appear with temperature.
Brillouin zone. Enough to have information with wave vector values − πa < k < πa . For
longer k−value the information can be reduced to 1st Brillouin zone.
33
Chapter 4
Free-electron model of metals
In this chapter will be combined Fermi-Dirac distribution with Schrödinger equation.

Results will support earlier results of classical conductor.
Figure 4.1
4.1 Free electron gas

Electrons are completely free inside the metal. No interactions. Infinite potential-energy
barriers in edge of the metal.
Schrödinger equation has solution as plane wave
1
Ψ = √ exp(i · k · r) (4.1)
V
where V = volume of the metal. Putting (4.1) to Schrödinger equation will give equation
between E and k:
}2 k 2
E(h) = (4.2)
2m
Here E is kinetic energy.
34
Figure 4.2
Figure 4.3
Size of the metal L × L × L, with L macroscopic. Periodic boundary condition: wave

function Ψ similar in opposite edges:
Ψ(x = 0, y, z) = Ψ(x = L, y, z) ⇒ kx L = 2π · n (n ∈ N)
(In reality Ψ = 0 in the edges because infinite energy barrier in the edge. This is difficult
to calculate and it is enough to have periodic boundary condition).
Periodic boundary condition in 3D ⇒
2π
k= nx î + ny ĵ + nz k̂ (4.3)
L
2π
Difference between neighbouring k-values = L
⇒ one k-vector, meaning one STATE,
occupies in k-space a volume
3
(2π)3

2π
δVk = = (4.4)
L V
⇒ Density of states is constant in k−space.

Density of state g(E) (“How many places for electrons?”) Amount of states, dN ,
35
Figure 4.4
between energy values E → E + dE per unit volume:

3/2
√

2 ∆Vk (4.4) 1 2 (4.2) 1 2m
dN = g(E) dE = = 2 k dk = E dE (4.5)
V δVk π 2π 2 h2
In calculations in more details.

∆Vk = volume in k-space between E and E + dE.
Numerical values ⇒ g(E) ≈ 1022 states/(eVcm3 ).
3/2 √
(4.5) ⇒ g(E) = 2π1 2 2m
}2 E (density of states for free electron)
Figure 4.5
Fermi-Dirac distribution
Maxwell-Boltzmann distribution: Classical, particle density small, individual particle
possible to indentify.
)
Pauli exclusion principle
⇒
Electrons are identical (not possible to identify)
36
In state with energy = E, the amount of electrons is on average
1
f (E) E−EF
(4.6)
exp kB T
+1
This is the possibility that state, with energy = E, is occupied by an electron.

Fermi-energy EF
1. Parameter. Strong connection with particle density. Depends on temperature.
2. In zero temperature electron exist up to EF . Electrons take lowest energy.
3. New electron appearing in the system ⇒ It has energy ≈ EF .
Analysing the distribution

A. States with low energy are all occupied
E EF ⇒ EF − E >> kB T ⇒ f (E) = 1 = 100 %
B. States with high energy are occupied according to Maxwell-Boltzmann

E EF ⇒ E−EI ∼
= E
⇒ f (E) = exp(E/kT ) | exp(. . .) 1 ⇒ exp(. . .) + 1 ≈
kT kT
exp(. . .).
Fermi-Dirac distribution changes strongly only near EF :
Practical estimation for width is ≈ 4kB T .
In metal n ≈ 1022 el/cm3 and density of states ≈ 1022 states/(eVcm3 ) ⇒ EF few eV but
kT ≈ 0.02 ⇒ Also in room temperature approximation

1, when E < E
F
f (E) = (4.7)
0, when E > EF
Figure 4.6
Approximation (4.7) ⇒ possible to calculate density of electrons, n, as a function of

energy E
3/2 Z ∞
∞ √
Z
1 2m
(4.5) (4.7)
n= g(E)f (E) dE = 2 2
Ef (E) dE =
0 2π } 0
3/2 Z EF 3/2 (4.8)
√

1 2m integrate 1 2m
= 2 E dE = EF
2π }2 0 3π 2 h2
37
⇒ Information about where is Fermi-level, meaning we get Fermi-energy EF dependence
on electron density n
}2
EF = (3π 2 n)2/3 (4.9)
2m
States are occupied up to EF .
EF in “other unit”:
- Fermi wave vector, meaning radius os Fermi-sphere
kF = (3π 2 n)1/3 (4.10)
- Electron wave length on the Fermi-surface
2π π 1/3
λF = =2 (4.11)
kF 3n
- Fermi velocity, meaning electron velocity on Fermi-surface
}kF
vF = (4.12)
m
Numerical values:
vF ≈ 10×classical thermal velocity and λF ≈ 2×distance between electrons.

Example: Specific heat
∂U
C= (4.13)
∂T
3 3
Classical U = kB T and Cclassical = kB per electron (4.14)
2 2
Experimentally electron contribution smaller.
Explanation: Fermi-Dirac distribution ⇒ Only those electrons that are near EF can
absorb energy. Specific heat due to these electrons only. Width of the area where
changes ≈ 4kB T ⇒ Classical result must be scaled by ≈ 4kEBF T ⇒
3 4kB T
Cel ≈ · kB (4.15)
2 EF
38
kB T EF ⇒ Cel Cclassical , meaning specific heat much less than classical prediction.
Figure 4.7
39
4.2 Thermal emission current
Figure 4.8
Electrons in potential well. Zero level for potential energy: Electrons free from the well.
Photoelectric effect: Fermi level distance from zero level is = qΦ = W = Workfunction.
Distribution of electron velocity
Electron has state Ψ(k) and momentum p = hk, meaning velocity =
p }k
v= (4.16)
mm
(2π)3
One state occupy in k-space a volume (Eq. (4.4)) δVk = V
⇒ Amount of states dN
per unit volume with wave vector in k-volume d3 k
d3 k d3 k 1
dN = 2 · /V = 2 3
/V = 3 d3 k (4.17)
δVk (2π) /V 4π
Multiplication 2 from spin.

Fermi-Dirac distribution f (E) ⇒ density dn of electrons with wave vector in k-volume
d3 k
(4.17) 1 1
dn = f (E) dN = 3 E−EF
d3 k (4.18)
4π exp kT + 1
3 2 k2
v = m} k ⇒ d3 v = m} d3 k and kinetic energy E = }2m = 12 mv 2 ⇒
1 m 3 d3 v
dn = 1
(4.19)
4π 3 } mv 2 −E
exp 2 kB T F ) + 1
This is so called thermal emission = current of electrons from metal to vacuum = out
from the potential well.
40
Electrons need E = 21 mv 2 > EF + qΦ ⇒ Calculation of current density
Z Z
J= dn = [Eq. (4.19)] dvx dvy dvz
q
Integral from 1
2
mvx2= EF + qΦ, meaning integral from = vx = 2(EFm+qΦ) .
Additionally approximation qΦ kT ⇒ Maxwell-Boltzmann ⇒ Final result for current
density (thermal)
2 −qΦ
J = CT exp (4.24)
kB T
with
2
qmkB
C = Richardson constant = 2 3
= 120 A cm−2 K−2 (4.25)
2π }
More clear presentation for current density (4.24) with n = density of electrons

−qΦ
J = −qveff n exp (4.26)
kB T.
This equation hasmoreclear interpretation:

Probability is exp k−qΦ
BT
that electron has enough big energy, qΦ. These electrons move
with effective velocity 2
3 kB T
veff = vF (4.27)
8 EF
2
where Fermi velocity is decreased by a factor kEBFT . Probability exp k−qΦ BT
is very
small in room temperature ⇒ To have current it is needed heating.
Extreme example wolfram qΦ = 4.5 eV ⇒ Needs very high temperature ⇒ On the other
hand it can stand high temperature (light bulb).
Numerical values for wolfram: T = 2500 K ⇒ J = 3 mA cm−2 .
Quantum mechanical correction
Part of electrons are reflected even if enough energy. Current density even more small.
41
Figure 4.9
4.3 Field emission current

TEMPERATURE ⇒ Electric field instead.
(a) (b)
Figure 4.10
In chapter 4.2 electrons go out from metal with help of temperature. Now we see how
electrons go out form metal with help of electric field.
Electric field E > 0 to −x direction ⇒ Electron has potential energy
V = −qEx (4.29)
⇒ Potential barrier with height EF + qΦ.

In quantum mechanics barrier replaced by but mathematics is similar ⇒ Tunneling
42
probability (2.79), meaning current, meaning field emission current
" 1/2 #
3/2
2m (EF + qΦ − E)
T (E) ∼
= exp(−2ηL) = exp −2 (4.30)
}2 qE
where E = kinetic energy.

Remarks:
1 Tunneling probability increases when E increases.
2 Tunneling only from those states that are occupied ⇒
2a Occupied states exist up to EF

−E
2b Above EF states are occupied with probability exp kB T
= small ⇒
Tunneling mainly form Fermi-level ⇒ E = EF ⇒ Current is

" 1/2 #
(qΦ)3/2

2m
J ∝ T (E) ∝ exp −2 (4.20)
}2 qE
Does not depend on temperature.

Question: When current flows?

−qΦ
Answer: Compare Eq. (4.20) to Eq. (4.26) where probability is exp kB T
⇒ Tunneling
current if " 1/2 #
(qΦ)3/2

2m −qΦ
−2 > ⇐⇒ (4.21)
}2 qE kB T
Need electric field 1/2
kB T 2mqΦ
E> ·2· (4.22)
q }2
Numerical values: If qΦ = 4.0 eV and T = 300 K ⇒ E > 5 · 106 V cm−1 (Comparable
with electric break down 3 MV m−1 = 0.03 · 106 V cm−1 )
Practical example: Tunneling microscope. G. Binning and H. Rohrer (1982, Nobel
1986).
(4.30) ⇒ J ∝ exp(L)
(
Vertical direction ≈ 0.1 Å
Resolution
Horizontal direction ≈ 1 Å
Tunneling, feed back circuit, scanning the sample surface. STM and AFM. Feedback
voltage is the measuring result.
43
Figure 4.11
44
Chapter 5
Energy bands
Up to now two extreme cases
A. Electrons inside the atom. Localized. Sharp energy levels and line spectrum.
Describes behaviour of insulators.
2 2
k
B. Free electrons in metal, chapter 4. Delocalized. Energy E = }2m , energy is
continuos meaning all energy values are permitted (if the metal piece is macroscopic.
See calculations).
Between these two extreme cases is SEMICONDUCTOR: The energy is continuos

only with some energy values =
b ENERGY BANDS. Between energy bands exist
FORBIDDEN BAND, energy gap, with no allowed states for electron.
Roughly:
• Electric properties of semiconductor ⇐⇒ Free-electron behaviour.
• Optical properties of semiconductor ⇐⇒ Behaviour inside energy gap.
5.1 Formation of bands
Figure 5.1
45
Start with metal. One atom, for example Na. Then many Na atoms and crystal ⇒
Potential is sum of individual atoms. When atoms come near, potential barrier between
the atoms is less than energy of 3s-electrons ⇒ 3s electron is FREE ⇒ METAL.
Figure 5.2
In energy-axis appear band widening of sharp line. In this picture 5 atoms and 5
electrons with 3s energy. In reality approximately 1023 electrons (about 1 mol).
Spin ⇒ every electron has 2 possibilities, meaning 2 allowed states.
⇒ Band has double amount of states and band is half filled.
⇒ Fermi energy EF in the middle of the band, INSIDE THE BAND.
}2 π 2
No 3s-electron in potential well ⇒ Standing wave with λ0 = 2a and E0 = 2ma 2 . Two
atoms ⇒ Two electrons and two potential wells.
Figure 5.3
If these two atoms are near each other ⇒ one energy well, standing wave
2(2a) = nλ (5.1)
meaning λ1 = 4a and λ2 = 2a. Also two energy levels En nE02 , meaning E1 = E0 and
E2 = 14 E0 .
Finally, many Na atoms and many potential wells: N wells near to each other.
46
Figure 5.4
Standing wave N (2a) = nλ (n = 1, 2, ..., N ) (5.2)

1
Energy levels En = 2 E0 (n = 1, 2, ..., N ) (5.3)
n
Formation of bands in covalent material
Previous analysis was metal. Now we take covalent material. For example silicon
(1s2 2s2 2p6 )3s2 3p2 .
Outermost electrons are 3s and 3p states. Totally 4 electrons ⇒ 4 wavefunctions.
A. First we think that Si-atoms are far from each other (but with correct crystal
structure, DIA) ⇒ Atoms are separated and energy levels are sharp
Figure 5.5
1. B. Atoms closer, lattice constant smaller. Potential barrier between the atoms
reduces (compare with metal) ⇒ electrons will spread to neighbouring atoms and
appears covalent bond, valence bond. Sharp energy levels widen to be bands.
C. Atoms more closer ⇒ 3s2 and 3p2 bands overlap giving one wide band similar to
2 ×(|{z}
metal. Total amount of states = 8 = |{z} 1 + |{z}3 ) per atom.
spin 3s 3p
D. Atoms more and more closer ⇒ One wide band deviates to two parts. These
parts have equal amount of states. Lower band is VALENCE BAND. Upper band
47
Figure 5.6
is CONDUCTION BAND. In between NO ALLOWED STATES. Width = energy

gap = Eg ⇒ FORBIDDEN GAP. In reality the lattice constant gives situation D.
Figure 5.7
In valence band the total amount of states (with N = amount of atoms) = 12 × (total)
= 12 × [2 × (1 + 3) × N ] = 4N ⇒ 4N electrons and 4N states ⇒ valence band is full
and conduction band is empty.
For silicon Eg = 1.1 eV.
Eg kB T at room temperature ⇒ no electrons in conduction band.
Interesting electrons (for example possible current carriers) are near the edges, meaning
near to valence band maximum and conduction band minimum. This is correct
regardeless the bands are several eV wide.
5.1.1 Periodical potential

Lattice symmetry: Periodicity
V (r + R) = V (r) (5.4)
with R = n1 a1 +n2 a2 +n3 a3 = lattice vector. a1 , a2 , a3 = unit vector, ni ∈ Z. Quantum
48
Figure 5.8
number in the case of atom n, l, ml . Now in the case of periodical potential new “quantum
number”k. Very useful when talking about energy bands. In physics sense k is wave
number of electron.
Symmetry. Solution of Schrödinger equation, wavefunction Ψ(x), describes electron
and is connected to a specific energy value E. We move the coordinate system by one
step (a): x0 = x + a and results should remain similar because V (x + a) = V (x) ⇒
dΨ(x0 ) dΨ(x + a) d2 Ψ(x0 ) d2 Ψ(x + a)

= and = (5.6)
dx0 dx dx02 dx2
⇒ Also wave function Ψ(x0 ) is solution of Schrödinger equation ⇒ Ψ(x0 ) and Ψ(x) are
linearily dependent:
Ψ(x + a) = Ψ(x0 ) = cΨ(x) (5.7)
Normalization
Z ∞
|Ψ|2 = 1 ⇐⇒ |c|2 = 1 ⇐⇒ c = exp(iα) = eiα (5.8)
−∞
Nonreal wave equation can be given in two parts
Ψ(x) = eiϕ(x) R(x) (5.9)
where Phase function, ϕ(x), Amplitude function, R(x), are real.

Periodical potential (symmetry) ⇒ Physical properties are periodic
2 calculation
|Ψ(x)|2 = eiφ(x) R(x) = |R(x)|2 ⇒ R is periodic. Periodicity and (5.9)

=⇒
Ψ(x + a) = ei[ϕ(x+a)−ϕ(x)] Ψ(x) (5.10)
Comparing this with (5.7) and (5.8) ⇒ c has phase angle
α = ϕ(x + a) − ϕ(x) (5.11)
49
This was result of moving one step. Then we move 2 steps: x0 = x + 2a ⇒ result will be
2α = ϕ(x + 2a) − ϕ(x) (5.12)
And general case with n steps ⇒
nα = ϕ(x + na) − ϕ(x) (5.13)
⇒ LINEARITY. Phase and phase function are linear vs. position
ϕ(x) = k · x (k = const.) (5.14)
And finally, we write wave function (5.9) in general form
Ψ(x) = eikx R(x) (5.15)
This is Bloch theorem (1928). Wave function (5.15) has name Bloch function. Felix
Bloch, PhD 1928 about quantum theory of solids. Nobel 1952 about developing the
nuclear magnetic resonance method.
We put Bloch function (5.15) into Schrödinger equation ⇒ we get wave equation for
R(x), for the periodic amplitude function
}2 d2 R(x) ik}2 dR
2 2
}k
− − + + V (x) R(x) = ER(x) (5.16)
2m dx2 m dx 2m
Wave function depends on k ⇒ solution R(x) depends on k ⇒ energy E depends on k
Ψ(x) = Ψnk = eikx Rnk (x) (5.17)

E = En (k) (5.18)
k appears in a same way like quantum number of atom.

k = wave number. Very near to each other. Solution Ψ (or R) can be understood
analyzed as a function of k.
n is index for energy band. Energies with one n−value form energy band curve as a
function of k, meaning an energy band.
Next: in 3 dimensions.
3 dimensional analysis. Bloch function (5.15) will be in form
Ψ(r) = Ψnk (r) = eik·r Unk (r) (5.19)
k = wave vector.
Unk = function with periodicity of the lattice: Unk (r + R) = Unk (r) with R = lattice
50
vector.
Again move the coordinate system with a step of lattice vector ⇒ Final result in 3D
for Bloch function
Ψnk (r + R) = eik·R Ψnk (r) (5.20)
and energy values becomes k-dependent
E = Eη (k) (5.21)
This was traslation symmetry, when moving the coordinate system. Similar way would
be obtained result when using lattice rotation symmetry or inversion symmetry:

En k En −k (5.22)
Possible k-values
First 1 dimension. Boundary conditions, size of the crystal = L = N a and wave function
must fulfill Ψ(x + N a) = Ψ(x) ⇒ We get
2π
k · n (n = 0, 1, 2, . . . , N − 1) (5.24)
Na
k is wave number and (5.24) is similar to Bohr quantization for free electron.
Figure 5.9
If n in (5.24) gets values n = 0, 1, 2, . . . , N − 1 ⇒ All possible phase angles in (5.20).

All possible phase angles ⇒ All possible Ψ possibilities ⇒ amount of k-values = N =
amount of “atoms”. kmax = 2π a
and distance between neighbouring k−values = 2π L
= N2πa .
Usually N = 0, 1, 2, . . . , N − 1 is replaced by n = 0, ±1, ±2, . . . , ± N2 ⇒ − πa ≤ k ≤ πa .
3−dimensional
First usual cubic structure (SC). All coordinate axis in the same way ⇒ In k-space
possible k−values form cubic lattice with length of crystal face = 2π L
. Full length of the
2π
crystal = a . k-vector has totally N different values. This has a name First Brillouin
zone, 1st BZ. If original crystal is not simple cubic ⇒ 1st BZ will be different. Also in
these cases k-vector has N values. k-vector takes in k-space a volume
(2π)3
δVk = (5.25)
V
51
Figure 5.10: 1st BZ of SC-crystal
Similar to (4.4) for free electron.
Figure 5.11: 1st BZ of FCC-crystal. Symmetry points and lines are noted in standard way
5.2 Models for free energy bands

5.2.1 Free electron model
Old information: wave function
1
Ψ(x) = √ eiqx (5.26)
L
Energy
}2 k 2
E= (5.27)
2m
52
For wave number we use symbol q. Divide in 2 parts:
q =k+K (5.28)
where k = wave number inside 1st BZ and

2π
K = integer × (5.29)
a
⇒
1
Ψ(x) = eikx · √ · eiKx = Ψnk (5.30)
L
Meaning periodic amplitude function R(x) is described by eikx and index n, that labels
the bands, is in form of k ⇒ Energy bands
}2
E = En (q) = (k + K)2 (5.31)
2m
Original En (k) values are moved by value of K ⇒ Energies are inside 1st BZ. Physical
results remains unchanged.
Figure 5.12
53
Figure 5.13
5.2.2 Kronig-Penney-model (1930)

We describe lattice by rectangle potential, name Kronig-penney-potential. Calculate
Ψ(x) in different parts. Result:
Ψ0 = A exp(ik0 x) + B exp(−ik0 x); 0 ≤ x ≤ a

Ψ1 = C exp(ik1 x) + D exp(−ik1 x); a ≤ x ≤ a + b (5.32)
Ψ2 = E exp(ik2 x) + F exp(−ik2 x); a + b ≤ x ≤ 2a + b
r r
2mE (E − V0 )
k0 = k2 = and k1 = 2m (5.33)
}2 }2
It is possible to calculate coefficients A, B, C, . . . and to obtain condition for Ψ existence.
We will not calculate here, but we make simplification ⇒
Barrier height V0 → ∞ and width b → 0 in such way that area remains: meaning
delta-functions, δ-function ⇒
X
V (x) = V0 bδ(x − na) (5.41)
n
⇒ Coefficient A, B, C, D, . . . will have solution only if
Figure 5.14
sin αa
P + cos αa = cos ka (5.42)
αa
54
where
ma
P = V0 b (5.43)
}2
and r
2mE
α=
}2
Right-hand side of (5.42) only cos ⇒ this is between [−1, +1] ⇒ also left-hand side
Figure 5.15: Left-hand side of (5.42)
must be between [−1, +1].

Exist forbidden values for α and therefore for energy E, values where A, B, C, . . . not
exist and Ψ not exist ⇒ ENERGY GAPS.
Maximum of each band in place αa = nπ ⇐⇒
}2 π 2 n2
En = (5.44)
2ma2
These maxima in same level as free electron energies. Large potential: Area σ−function
= V0 b → ∞. Eq (5.42) has solution sin α = 0 and final result will be sharp energy levels
like isolated atoms.
Area of δ-function = V0 b large, but < ∞ ⇒ Final result will be
}2 π 2 n2

W n
En (k) = 1− [1 − (−1) cos ka] (5.47)
2ma2 nπ
where width of the belt, W , should not be large.
55
Figure 5.16
This shows that sharp energy levels start to develop to be wide, to be belt. This
approximation has name “tight binding approximation”.
Weak potential. Other extreme case, electrons almost free. V0 b small. Approximations
and series expansion and mathematics ⇒
(5.43) }2 α2 }2 2
En (k) = = (α + 2α0 δ) (5.50)
2m 2m 0

where α0 = k + n 2π a
, meaning k when 1st BZ and n · 2π addition for other Brillouin
a
zone. In Eq. (5.50) δ is small correction because of the potential. Without potential ⇒
}2 α2 2 k2
no δ and En = 2m0 = }2m . Values for δ in extremes of energy band (edge or center of
1st BZ) 
0
δ= (5.51)
 2P 2
α0 a
Two values in edge of 1st BZ and two values in center of 1st BZ. These give corrections
to energy 
0
∆E = (5.52)
 }2 ·2P2 (5.43)
= 2V b
0a
ma
⇒ In extremes of energy band, appears a gap 2V0 ab , meaning forbidden gap = Eg = 2V0 ab .
Expanded description of band: wave number can change by multiple of 2π a
⇒ similar
result.
56
Figure 5.17
Inversion symmetry: E(k) = E(−k) because cos is symmetric.

Derivative antisymmetric:
dE(k) dE(−k)
=− (5.54)
dk dk
Derivative = b velocity ⇒ Full energy band has antysimmetric velocity distribution (later
in details).
5.3 Electrons movement in the energy band

5.3.1 Semiclassical equation of motion
Bloch-function and quantum mechanics is difficult ⇒ Better to build semiclassical.
Particle is decribed by wave packet. Electron stay inside one energy band. Wave packet:
- One energy band.
- From Bloch function.

E(k 0 )t
Z
0 0 0
Ψ(x, t) = Uk (x) dk a(k ) exp i k x − (5.55)
}
General case for electron in energy band.
Simplifications
57
Figure 5.18
A. Multiplication function a(k 0 ) thin in k-space. Upper graph.
2π
δk , meaning δ width of BZ (5.56)
a
B. In the area of δk, the amplitude function Uk0 , amplitude of Ψ
Uk0 ≈ Uk = const. (5.57)
⇒ wave packet
E(k 0 )t
Z
0 0 0
Ψ(x, t) = Uk (x) dk a(k ) exp i k x − (5.58)
}
Important result ⇒
1. Wave packet is superposition of plane waves.

2. Same form as for free electron (Eq. (2.35))
58
3. BUT. Wave packet must be multiplied with periodic amplitude function from
Bloch-function ⇒ menaning envelope of plane wave superposition modulates
the periodic part Uk (x). Lower graph.
Width of the wave packet (compare with chapter 2) =
2π
δx = (5.59)
δk
and δx lattice spacing. δx a, but small in the sense that it describes point like
particle.
Energy in wave packet is energy of energy band. Periodic potential changes dynamics
of particle ⇒ E(k) no longer quadratic.
Velocity will be similar to Eq. (2.39)
1 dE(k)
v= (5.60)
} dk
and in vector form in 3D
1
v=∇k E(k) (5.61)
}
For equation of motion, F = ma, compare the equation of motion in electromagnetic
field
dk
} = −q(E + v × B) (5.62)
dt
Take derivative of (5.61)

dv (5.61) 1 dk (5.62) 1
a= = ∇k ∇k E(k) = ∇k ∇k E(k) · (−q)[E + v × B] (5.63)
dt } dt }2
1
· F gives idea about mass, effective mass m∗ (reciprocal tensor)

F = ma a = m
1 1 d2
= E(k) (5.64)
m∗ }2 dk 2
2
in 1D: m1∗ = }12 dk
d
2 E(k) ⇒
“Mass”, i.e. effective mass, depends on shape (curvature) of energy band ⇒ Effective
mass depends on material.
Eq. (5.61) and (5.63) give path of current carriers, if shape of E(k) is known ⇒
Semiclassical equation of motion.
Not need to know periodical potential, nor Bloch function, E(k) is enough. Usually
E(k) can be modelled using a few parameters.
59
Example. Kronig-Penney tight binding approximation (compare (5.47))
E(k) =W (1 − cos ka) (5.65)

(5.61) W a
⇒ v(k) = sin ka (5.66)
}
○
1 For small k ⇒ v(k) is linear like in the case of free electron (see Fig. 5.20).
○
2 There exist maximum in v(k) (see Fig. 5.20).
○
3 v(k) = 0 in the border of 1st BZ.

Reason: v(k) = 0 antisymmetric
π π ⇒ v(k) = 0 in BZ border
v k= =v k=− 
a a
Figure 5.19: a)Energy band b)Velocity v(k) c)Effective mass m∗ (k) for tight binding ap-
proximation
Effective mass (5.64) ⇒

∗ }2 }2
m = d2 E 2 = (5.67)
/ dk W a2 cos ka
60
(See Fig 5.20)
2
with small k-values m∗ = W}a2
m∗ can be different from m, depends on width W of the energy band.
k increases ⇒ m∗ increases. m∗ → ∞ when k → 2a π
. m∗ negative when k > 2a
π
(See Fig
5.20) (mass < 0??).
Eq (5.63) for acceleration ⇒ Negative m∗ has similar meaning like q changing the sign.
∴ m∗ < 0 can be described by positive charge (hole).
Add ELECTRIC FIELD
dk
(5.62) ⇒ } − qE (5.68)
dt
If E constant ⇒ wave vector
1
k(t) = k0 − qEt (5.69)
}
If E negative ⇒ k increases with time and in the border of 1st BZ electron reflects
(heijastuu) to equivalent state − πa ⇒ Electron oscillates in k-space inside 1st BZ
Figure 5.20: Electron wave vector if E 6= 0. Semiclassical equation of motion
2π}
Period = T = (5.70)
q|E|a
Numerical values:
)
a = 0.5 nm
5 −1
T = 10−12 s (THz frequency)
E = 10 V cm
This happens inside one energy band (See Fig 5.21) For free electron the wavevector
would be
1
q = q0 − qEt (5.71)
k
61
Figure 5.21: Electron moving in electric field inside one energy band. Dashed and dotted
line describes free electron
and kinetic energy

}2 q(t)2
Ekin = (5.72)
2m
W
Tight binding belt ⇒ velocity (5.66) v(k) = }
sin ka ⇒ Integral gives location. k(t) is
taken from (5.69) ⇒
Z t
0 0 (5.66) W 1
x(t) = v[k(t )] dt = ... = 1 − cos q|E|at (5.73)
0 q|E| }
cos ⇒ oscillates also in x-space
1 2π
Frequency = ω =
q|E|a = (5.74)
} T
W
Amplitude of oscillations = A = (5.75)
q|E|
These are called Bloch oscillations:

)
E = 105 V cm−1
⇒ Amplitude ≈ 0.1 µm
W = 1 eV
Electric field causes (aiheuttaa) oscillating current. (Strange). This is because of

periodic potential, which makes electrons to behave atomic-like.
Bloch oscillations never observed experimentally.
62
Scattering cut electron movement before electron goes through all 1st BZ.
Scattering has relaxation time τ ≈ 10−14 . . 10−13 s 10−12 s.
Extreme experiment: Artificial superlattice with a ≈ 5 nm ⇒ Even in this case no clear
observation.
5.3.2 Electrical conductivity

Scattering ⇒ Drude model ((1.11), electrons flow like viscous liquid)
Now we insert friction force to equation of motion of wave vector
dk }k
(5.62) ⇒ } =− − q[E + v × B] (5.76)
dt τ
τ = relaxation time of scattering.
If only electric field (B = 0) ⇒ solution (with k = k0 when t 6= 0)

t 1 t
k(t) = k0 exp − − qEτ 1 − exp − (5.77)
τ } τ
t < τ ⇒ No scattering and behaviour similar to Eq. (5.69) that is k ≈ k0
1
t > τ ⇒ k(t τ ) ≈ qEτ (5.78)
}
All electrons in the energy band feel change of k by an amount
1
∆k > q|E|τ
}
Total velocity and current = 0 (J = 0) in a full energy band.
Reason: Energy band inversion symmetric in k-space (E(−k) = E(k)) ⇒ Popula-
tion probability (miehitystodennäköisyys) inversion symmetric. Additionally velocity
antisymmetric (v(−k) = −v(k)) ⇒ Total velocity, of all electron, is = 0.
If E 6= 0 ⇒ electrons move by ∆k = 1h̄ qEτ . If energy band full ⇒ Population probability
does not change ⇒ J = 0
∴ Electrical conductivity exist only if there is energy band with incomplete occupation.
Only in this case inversion symmetry is lost and J 6= 0. J ∝ dissymmetry of velocity
distribution.
dE(k0 )
∆k small ⇒ J ≈ q · 2∆kv(k0 ) = 2q 2 Eτ (5.79)
dk0
Based on energy band structure, it is possible to distinguish between conductor and
insulator.
63
Figure 5.22: Electric field and scattering ⇒ Population becomes dissymetric. Must have
partly filled energy band (metal)
5.3.3 Charge carriers in semiconductor: Holes

Maximum of valence band and minimum of conduction band are important: The charge
carriers are here.
In Fig 5.23 is direct energy gap: Maximum of valence band and the minimum of
conduction band in the same place in k-space. Other possibility: indirect energy gap.
Figure 5.23
Not big influence in electrical properties but optically important.

In the minimum of conduction band the amount of electrons . 1020 cm2 ⇒ non dense
(harva) charge carrier gas ⇒ Maxwell-Boltzmann distribution. Taylor series for energy
64
band-curve ⇒
∂ 2 E(k)

∼ 1
E(k) = E(k 0 ) + }(k − k 0 ) 2 · h̄(k − k 0 ) (5.80)
2 } ∂k∂k k=k0
k 0 = location of energy minimum.

Electron motion with semiclassical equation of motion. For example effective mass m∗
with Eq. (5.64). Valence band negative curvature ⇒ m∗ negative. But it is enough to
change the sign of the charge ⇒ motion of hole.
∴ New particle: Positive charge ⇒ Positive mass m∗ (not need m∗ negative).
Hole. Properties opposite to electron, but moves like an electron.
E(k) graph for hole by changing → −E and k → −k.
Ehole = Ea = −Eelectron = −Ee (5.81)

khole = ka = −kelectron = −ke (5.82)
For example velocity of hole =
Figure 5.24
1 ∂Ea 1 −∂Ee
va = = = ve (5.83)
} ∂ka } −∂ke
⇒ velocities are similar.

Wave vector for hole (5.62) ⇒
dk a dk e
} = −} = − −|q|[E + V × B] = |q|[E + V × B] (5.84)
dt dt
65
This shows that hole has positive charge. Moreover: (5.81) and (5.82) ⇒ hole has
positive m∗ .
Electric current in valence band
X
I = −|q| V (k i ) (5.85)
i∈ occupied
i ∈ occupied states ⇒
X
I = −|q| V (k i ) (5.87)
holes
Conclusion
1. For electric current it is enough to analyze empty state and to forget other states,
namely in valence band to forget states that are full.
Holes in thin energy layer ⇒ enough to know m∗ .
2. Exist electrons and holes. Both form non-dense (harva) charge carrier gas. Charge
carriers behave like free particles, but m → m∗
3. Classical free particle model (Returning back to simple ideas after long and
difficult discussion)
5.4 Energy bands for various materials

5.4.1 Metal
1D ⇒ simple parabola (Fig 5.25) usually FCC. 1D ⇒ More complicated energy band
structure (Fig 5.26). Scaling with
}2 k02 (2π})2
E0 = = (5.88)
2m 2ma2
which is energy for electron having wave number k0 = 2π a

.
Numerical value: a ≈ 0.5 nm ⇒ E ≈ 6.0 eV. In Fig 5.26 the horizontal lines show
Fermi-energy (EF ) for different amount of electrons per unit cell (=
b valence-number)
Analyze of Fig 5.26
Valence z = 1 ⇒ lowest energy band half empty ⇒ charge carriers are usual electrons.
For example earth metals Li, Na, Ka,. . . and noble metals Cu, Ag, Au.
Valence z = 2 (Cd, Zn) ⇒ EF in places where degeneracy and system is sensitive to

the influence of periodical potential. In k−place the lowest energy band is empty.
66
Figure 5.25
In L-place next energy band is filled up ⇒ Charge carriers are holes near k-place
of 1st BZ and charge carriers electrons near L-place of 1st BZ.
Earlier in lectures were described meaning of k and L: Places in 3- dimensional
Brillouin zone, in 3-dimensional reciprocal space.
Valence z = 3 (Al) ⇒ Lowest energy band is full. Second and third partly occupied.
One example. Energy bands fo Cu. Electron structure (Ar)3d10 4s0 . Colour
comes from optical transition from 3d-belts to EF . Difference ≈ 2 . . 3 eV which is
red-yellow wavelength.
5.4.2 Semiconductors and insulators

Ge, Si, GaAs. Most important semiconductors. Valence band similar: each has
maximum in the center of 1st BZ.
Two valence bands, different curvature (m∗ ) meaning heavy and light band.
GaAs direct energy gap. (Place of conduction band minimum)
)
Si has conduction band minimum near BZ border
indirect
Ge has conduction band minimum in BZ border
Rotation symmetry. Energy bands have similar rotational symmetry like the crystal
lattice.
⇒ Si has 6 minima (minimum in [100] direction) and Ge has 8 minima (minimum
in [111] direction). Equal-energy surface: GaAs sphere but Si and Ge spheroid ⇒
Curvature different ⇒ m∗ has 2 components: Longitudinal and transversal.
67
Figure 5.26
Insulator. Similar to semiconductor, but Eg wide.

SiO2 is most important in technical applications. Amorphic (non crystalline).
5.5 Interaction between electron and wave

5.5.1 Disturbation theory
Earlier electromagnetic field, E constant, ω optical and }ω kB T ⇒ Semiclassical
equations of motion.
Now we investigate }ω ≈ eV (Semiconductor) ⇒ }ω kB T .
Schrödinger equation ((2.27)) H0 Ψ = i} ∂Ψ
∂t
.
}2 ∂ 2
Here H0 is “operator”, H0 = − 2m ∂x2 + V (x)
Giving for free electron

Ei t
Ψ(r, t) = exp i k i · r − (5.91)
}
Interaction with wave means that now we have in Schrödinger-equation one additional
68
Figure 5.27
INTERACTION-term ⇒
∂Ψ
(H0 + H 0 )Ψ = i} (5.90)
∂t
This additional interaction term
H 0 = A ei(q·r−ωt) + e−i(q·r−ωt)

(5.89)
is like an disturbation for electron movement (Ψ(r, t)).

Eventually mathematics shows that disturbation H 0 gives additional, new plane wave
components with
Ef = Ei ± }ω (5.93)
kf = ki ± q (5.94)
where Ef and k f are final energy and wave vector and Ei and k i are initial, before
interaction. q is the wave vector of the wave (for example photon).
Disturbation makes electron to have transition from initial state i to final state f . Eq.
(5.93) and (5.94) are clearly the conservation laws for energy and momentum. Eq.
(5.94) gives momentum if multiplied by }.
± means disappearance (+) and appearance (-) of an energy quanta. These can be
called absorption/annihilation (+) and emission/creation (-).
For electromagnetic wave }ω is photon. v = λf ⇒ Energy and momentum are con-
nected
}ω = v}k (5.95)
69
Figure 5.28
This can be understood as photon energy band curve v = 3 · 108 m s−1 ⇒ }ω = 1 eV

when λ = 1.24 µm and q = 5.1 · 104 cm−1
Comparison to wave vector of an electron:
2π 2π a a
q = · =k· k (5.96)
λ a λ
|{z} λ
=k
⇒ Photon wave vector q ≈ 0 in comparison to electron wave vector k, because

a
λ
≈ 5 · 10−4 .
∴ Electron wave vector remain unchanged in optical transition.
PHONON. v ≈ vsound ≈ 1000 m s−1 ≈ 105 times less than light velocity.
(5.95) ⇒ Phonon energy very small (< 10−2 eV) for those k-values which are important
(1st BZ).
∴ In interaction with phonon, the charge of electron energy is small but change of
electron wave vector (momentum) is big.
70
Figure 5.29
5.5.2 Optical properties of semiconductor

Energy structure gives clear and easy explanation.
Direct energy gap (For example GaAs).
}ω > Eg gives allways transition. One electron jump from valence band to conduction
band and one photon disappears. Limit for optical absorption clearly from Eg .
Inirect energy gap (Si, Ge, etc.)
For transition is needed also a phonon (∆k 6= 0) ⇒ Transition probability smaller
(because more complicated).
In practical situation light with }ω ≈ Eg is absorbed to GaAs about 100 times stronger
than to Si. Many applications in components.
71
Figure 5.30
72
Figure 5.31: Energy-wave vector diagram for photon and phonon
Figure 5.32
73
Chapter 6
Semiconductor physics
- Amount of charge carriers.
- How to influence to the amount of charge carriers.
- How well they move.
6.1 Density of charge carriers

6.1.1 Density of states in energy band
Charge carriers are near the max of valence band and min of conduction band. Equal
energy-surface is ellipsoid. Energy in conduction band
3
X }2 (ki − koi )2
E(k) = Ec + (6.1)
i=1
2m∗ii
Ec = Energy of the minimum in conduction band

koi = location of Ec in k−axis
m∗ii = effective mass in i−axis direction
If m∗ii scalar ⇒ Eq. (6.1) looks like free electron energy.

Density of states for free electron Eq. (4.5) ⇒ Now density of states =
3/2 p
2m∗

1
gc (E) = 2 · E − Ec (6.2)
2π }2
Here m is replaced by m∗ and E is replaced by (E − Ec ).
74
Figure 6.1: Near to the min of conduction band
If m∗ii values are different ⇒ m∗ is average. One can get:
m∗ = (m∗11 m∗22 m∗33 )1/3 (6.3)
If more than one energy minimum ⇒ (6.2) must be multiplied by the amount of minima.
For valence band in similar way
3/2 p
2m∗

1
gv (E) = 2 Ev − E (6.4)
2π }2
Ev = Energy of the maximum in valence band

m∗h = average effective mass for the hole
75
Figure 6.2: Near to the max of valence band.
6.1.2 Electron and hole densities

√
Density of states increases as E ⇒ Fermi energy EF defines how big amount of charge
carriers fit into the energy band. Usually EF inside forbidden band and usually
Ec − EF kB T (6.5)
EF − Ev kB T (6.6)
This kind of semiconductor is called non-degenerated semiconductor (degeneroitumaton)

In this case charge carriers form non-dense (harva) “gas”⇒ Fermi-Dirac → Maxwell-
Figure 6.3: Density of states for valence band and conduction band
76
Boltzmann distribution
1 calculations 1 −
(E−EF )
f (E) = eE−EF
−→ fe (E) = eE−EF
=e kB T
(6.8)
kB T
+1 kB T
(EF −E)
−
Similar approximation in valence band fh (E) = e kB T .
Now we can calculate current carrier density with integral
Z ∞ (Ec −EF )
(6.2)−(6.8) −
n= g(E)f (E) dE = ... = Nc e kB T
(6.12)
Ec
3/2
m∗e kB T

Nc = 2 = effective density of states in conduction band (6.13)
2π}2
R ∞ √ −x √
In integral is used 0 xe dx = 2π
Nc ≈ Amount of states
volume
within thin energy layer of kB T above Ec .
Numerical values: )
m∗ = m
Nc = 1019 cm−3
T = 300 K
For holes in similar way:
Z Ev (EF −Ev )
−
p= gv (E)fh (E) dE = Nv e kB T
(6.14)
−∞
where Nv is similar to Nc but with m∗h (i.e. effective density of states in valence band).
(6.12) and (6.14) are basic equations for charge carrier densities for non-degenerated
semiconductors.
Multiply (6.12) × (6.14) ⇒ “np”- rule (EF disappear, supistuu).

−Eg
np = Nc Nv exp = n2i (6.15)
2kB T
For pure clean semiconductor (without doping): electrons are from valence band ⇒
n=p (6.16)

p −Eg
⇒ n = p = ni = Nc Nv exp (6.17)
2kB T
For example Si: ni ≈ 1010 cm−3 . Depends exponentially on T . Very small.
)
(6.12) m∗e

1 3 1
⇒ E F = EF i = (Ec + Ev ) − kB T ln ≈ (Ec + Ev ) (6.18)
(6.14) 2 | {z } 4 |{z} m∗h 2
few eV 0.02 eV
77
Meaning EF approximately in the middle of forbidden band.
6.1.3 Doped semiconductor

Changing of charge carrier concentration by doping. Basis for semiconductor technology.
Enough 10−6 doping, every 1 000 000th atom.
DONOR: Impurity that has one electron more than host atoms (other atoms) in crystal.
This electron becomes free, rise to conduction band.
ACCEPTOR: Impurity that has one electron less than host atoms. Takes one electron
(“accepts electron”) from enviroment and the result is a hole in valence band.
∴ Donor increases density of electrons and acceptor increases density of holes.
For Si donor impurities are V-group atoms (P, As, Sb) and acceptor impurities are
III-group atoms (B, In, Ga, Al). For compound semiconductor (yhdistepuolijohde), e.g.
GaAs, situation is more complex: Donor impurities are VI-group atoms and acceptor
impurities are II-group atoms. IV-group atoms can be donor or acceptor, depending on
if impurity replaces Ga or As. This depends on concentration.
Energy of electron of donor-atom Take one donor-atom. Donor will result in one elec-
tron plus positive im . Weak attraction force
}2 k 2 e2
Ed = Ec + − (6.19)
2m∗ 4πεr
Small ε = dielectric constant of the lattice.
2 first terms: Electron in conduction band.
Third term Coulomb potential, r > lattice constant.
2 2
Appears energy level below Ec + }2mk∗ . System similar to Hydrogen atom ⇒ Energy
}2 k2
Figure 6.4: Energy level below Ec + 2m∗
m ε 2
0
Ed − Ec = −13.6 eV · ∗
· (6.20)
m ε
78
Radius m ε
hri = 0.53 Å · = average of distance (6.21)
m∗ ε0
Here 13.6 eV and 0.53 Å are E and r for ground state of hydrogen
Figure 6.5: Hydrogen atom
ε 
≈ 10  ionization energy = Ed − Ec ≈ 0.01 eV
ε0

∗ ⇒
m and orbit radius ≈ 50 Å
≈ 0.1

m
kB T ≈ 0.025 eV > Ed − Ec ⇒ Electron rises from donor state to conduction band. ε
and ε0 are dielctric constant for the lattice and for vacuum.
If εε0 only 5 ⇒ Ed − Ec ≈ 0.04 eV ⇒ not suitable for electronics components.
For acceptor: Similar hydrogen-like system, Eq. (6.20) and (6.21). Hole “disen-
gages”(vapautuu) to valence band.
Figure 6.6: Energy level above Ev
Both energy levels are near to the energy bands. Important energy levels. Exist also
energy levels deep inside the forbidden band:
Reason: Large crystal imperfections. These energy levels are not good.
Deep levels and shallow levels. Impurity levels rather easy to measure (luminescence)
⇒ Exist good information.
Purity is very important. CLEAN. Reason: 10−6 doping would be enough.
Density of crystal imperfections and unwanted impurities must be doping. If not ⇒
wrong energy levels (virhetiloja) inside energy gap.
79
Figure 6.7: Impurity states and ionization energies for Ge,Si and GaAs. D and A mean
donor/acceptor state.
Nowaday the best progress exist with Si: Unwanted impurities in the level of ≈
1013 at/cm3 . This shows the level of quality.
In lectures analyze of Fig. 6.7.
6.1.4 Charge carrier density of doped semiconductor

Basic detail: in room temperature kT > Ed − Ec and kT > Ea − Ev
(
n = density of electrons = density of donor impurities = Nd
⇒
p = density of holes = density of acceptor impurities = Na
This is the influence of doping. Now we look this in more details.

In Fig 6.8 is shown energies as function of location. E = 0 ⇒ Energy levels are descibed
by horizontal lines.
First: n−type semiconductors (with donors).
Occupation probability by using Fermi-Dirac-distribution: Probability to have electron
in energy level Ed (i.e. donor state)
1
f (Ed ) = eEd −EF
(6.22)
kT
+1
80
Figure 6.8: Energy band diagram
⇒ Ionizated donor atoms with density
Nd
Nd+ = [1 − f (Ed )] · Nd = eEd −EF
(6.23)
kT
+1
where total amount of donor atoms = Nd . If Fermi-energy EF far from Ed ⇒ EF −Ed 0

⇒ Nd+ = Nd meaning all donor atoms ionizated.
Acceptors in similar way. Ionizates acceptor atoms with density
Na
Na− = f (Ea )Na = eEa −EF
(6.24)
kT
+1
If EF far from Ea ⇒ Ea − EF 0 ⇒ Na− = Na meaning all acceptor are ionizated.

Calculate Fermi-energy EF .
Earlier n = p and Eq. (6.12) and (6.14). Now charge neutrality
n + Na− = p + Nd+ (6.25)
Using this equation, it is possible to calculate EF and n, p, Na , Nd .

Calculation rather complex. Approximative calculation in book and here. First n-type
semiconductor (Donors, and if Na then anyhow Nd Na ). In very high temperatures
n and p are high, meaning Na and Nd .
⇒ In very high temperatures Na and Nd have no influence to EF .
⇒ In high temperature EF in center of forbidden gap.
Temperature limit T0 where influence of doping disappears: Ni (T0 ) = 12 Nd . One get:
Ed
T0 = √ (6.28)
2kB ln 2 Nc Nv
Nd
where Nc and Nv are effective density of states in conduction band and valence band
81
(Eq. (6.13)).
If Nd = 1017 cm−3 ⇒ T0 = 800 K for Si (far above room temperature).
Below this temperature limit one gets density of electrons and holes
n2i
n = Nd − Na and p= (6.29)
| {z } Nd − Na
majority charge carriers | {z }
minority charge carriers
Result
1. Amount of dominant doping defines the density of dominant charge carriers (now
electrons).
2. Minority charge carrier density is proportional to doping1density and ni (internal

density of charge carriers in undoped semiconductor).
3. Fermi energy EF moves towards the majority band (now conduction band).
Now with n-type material one gets:
Nc
EF = Ec − kB T ln (6.30)
Nd − Na
New temperature limit T1 : when EF increases up to Ec
(Ec − Ed )
T1 = h i (6.31)
Nc
kB ln Nd −Na
If Nd = 1017 cm−3 ⇒ T1 = 40 K for Si. Donors are no longer ionizated and electron
density n Nd (“frozen”)
p−type semiconductor. Similar results. Acceptor-doping is dominant. At very high
temperatures p = n = ni .
n2
Room temperature range: P = Na and n = Nia .
Very low temperature: Charge carrier densities go to zero. Temperature dependence of
charge carrier (hole) density and temperature dependence of Fermi-energy EF similar
to Fig. 6.9.
If very strong doping in semiconductor; Doping more than effective density of states
(Nc or Nv , Eq. (6.13)).
Must be doping ≈ 1019 . . 1021 cm−3 .
Usually is used sentence: Semiconductor is degenerated

 N ⇒ E inside conduction band
d F
Fermi-energy is inside a band
 Na ⇒ EF inside valence band
82
(a) Fermi-energy in Si as a function (b) Electrodensity in Si when Nd = 1016 cm−3
of T when Nd = Na = 1016 cm−3
Figure 6.9
In this case behaviour is like n−type or p−type metal. This possibility is used in places
with the contact.
6.2 Mobility, µ
Mobility of charge carriers is limited by scattering. In principle all disturbances in
periodic potential. Two most important: Phonon (lattice vibrations) and impurities in
doping.
Phonon scattering Similar to photon Fig. 5.30.
Figure 6.10: Phonon scattering
83
Relaxation time τphonon ⇒ eventually one gets
qτphonon
µphonon = ∗
∝ (m∗ )−5/2 T −3/2 (6.35)
m
τphonon = relaxation time = time between collision to phonon.
Mobility µphonon increases when temperature decreases.
Mobility µphonon increases also when effective mass decreases.
Impurity scattering
Scattering from impurities is calculated like collision to obstacle (este) with an area, in
this case so called scattering cross-section.
Figure 6.11: Cross-section area of impurity scattering
Eventually one gets for mobility limited by impurities:
qτImp T 3/2
µImp = ∝ √ (6.39)
m∗ m∗ NImp
τImp = relaxation time = time between collisions to impurities.

NImp = Amount of impurities.
In this case mobility µImp increases when temperature increases.

Mobility µImp increases when effective mass m∗ decreases.
In practical cases exist both: Phonon and impurities. Indipendent of each others ⇒
Scattering probabilities can added together ⇒
1 1 1
= + (6.40)
τ τphonon τImp
1 1 1
= + (6.41)
µ µphonon µImp
This has a name: Mathiessen rule. In low temperatures mobility is limited by impurity
scattering.
84
Mobility increases with increasing temperature up to 70 . . 100 K when phonon scattering
becomes more important. In room temperature mobility is limited by phonon scattering
and decreases with temperature increases.
In Fig. 6.12 is mobility vs. concentration when T = 300 K.
Figure 6.12
Impurity scattering starts to influence when concentration becomes ≈ 1016 cm−3 .

Electron mobility in GaAs very good because effective mass m∗ very small (In GaAs
m∗
mc
= 0.07).
6.3 Generation and recombination of charge carri-

ers
Amount of charge carriers can be influenced by temperature, doping AND BY LIGHT.
Electron is lifted to conduction band using photon energy }ω ⇒ Electron-hole-pair.
This is GENERATION OF CHARGE CARRIERS
RECOMBINATION: Electron from conductivity band goes down to valence band into
an empty state.
Meaning electron goes to a hole.
85
Figure 6.13
In this process, recombination, is emitted one photon; energy difference, ∆E, which
becomes free, is used for }ω.
Recombination also through impurity levels which are inside energy gap. Specially deep
levels are important. Deep levels are called trapping states (loukkutilat), or sometimes
as recombination center.
If energy gap is direct, then recombination is usually directly to valence band. Not
need deep levels. If the energy gap is indirect, then recombination takes place mainly
via deep level. For example in silicon:
G = generation rate (generaatiovilkkaus) =

= transition rate from valence band to conduction band =
= transition/time and volume
R = recombination rate =
= transition rate form conduction band to valence band
Generation because of external electromagnetic radiation, but also because of black

body radiation.
R = A · np (6.42)
Reason: Recombination proportional to occupied initial states in conduction band

(n) and to empty final states in valence band (p), meaning product np. A describes
transition probability. Material parameter.
In similar way
G = B · Nv Nc (6.43)
B = transition probability, depending on excitation activity

Nv = density of states in full valence band
Nc = density of states in empty conduction band
Thermodynamic equilibrium: No external radiation, only black-body radiation ⇒ G0

and R0 where R0 = A · n0 p0 .
86
Equilibrium ⇒ G0 = R0 and therefore ⇒
(6.15)
G0 = R0 = A · n0 p0 = An2i (6.44)
In general case: Net recombination =
(6.44)
∆R = R − R0 = A(np − n2i ) (6.45)
External optical radiation ⇒ Generation Gopt ⇒ charge carrier density changes
∂n ∂p
= Gopt − ∆R = Gopt − A(np − n2i ) = (6.46)
∂t ∂t
This gives movement (transition) of charge carriers between the energy bands. For
example n−type semiconductor;
n = n0 + ∆n and p = p0 + ∆p (6.47)
Recombination in n-p pairs, also generation in n-p pairs ⇒ ∆n = ∆p. Additionally
∆n n0 and ∆p n (6.48)
⇒ Recombination ∆R can be approximated
1
∆R = A(np − n2i ) = . . . ≈ An0 ∆p = ∆p (6.49)
τp
where time constant τp = An1 0 = Recombination lifetime for minority charge carriers.
Radiation ⇒ more charge carriers.
∂
Steady state ⇒ ∂t stabilizes. (6.46) and (6.49) ⇒ Photoconductivity
∆σ = qµp ∆p + qµn ∆n = q(µp + µn )τp Gopt (6.52)
Switch OFF radiation ⇒ Recombination of extra charge carriers

−t
(6.46) ⇒ ∆p(t) = ∆n(t) = ∆p(0) exp (6.53)
τp
This shows that τp is lifetime of minority charge carriers, can be measured using
resistivity (conductivity) measurement.
Fig. 6.14 Shows lifetime in silicon. With usual doping ≈ 1016 cm−3 ⇒ τ ≈ 10 µs.
In GaAs direct gap ⇒ direct recombination and τ ≈ 1 ns with doping level of ≈
1017 cm−3 .
Unequilibrium between energy bands. Appears because of radiation. Time constant =
87
Figure 6.14: Lifetime of minority, charge carriers vs. amount of majority charge carriers
lifetime of recombination. Many orders longer than scattering relaxation, meaning slow.
Unequilibrium is described by quasi Fermi level:
density of electrons and holes

Ec − EFn
n = Nc exp − (6.54)
kT
EFp − Ev

p = Nv exp − (6.55)
kT
where EFn and EFp are quasi Fermi level for electrons and holes. If thermodynamic
equilibrium ⇒ EFn = EFp = EF .
Usually for majority charge carriers quasi Fermi level not change; EFn = EF .
But for minority charge carriers (∆p p0 , p0 small) quasi Fermi level moves towards
the bands (if p ⇒ valence band).
6.4 Diffusion current

In semiconductors often density gradient of current carriers ⇒ small current, diffusion
current. Analysis of diffusion gives eventually total current density (left-right + right-
left) ⇒
∂n
Jdiffusion = qDn (6.62)
∂x
where diffusion constant
1 kB T τ kB T
Dn = vT2 τ = ∗
= µn (6.63)
3 m q
88
Figure 6.15: Gradient of charge carrier density
here
r
3 kB T
vT = Thermal velocity =
m∗
τ = relaxation time = time between collisions
kB T
Dn = · µn is called Einstein relation
q

−x
One example: Electron density depends exponentially on location: n ∝ exp Ln
, Ln =
profile parameter ⇒
∂n Dn
Jdiffusion = qDn = −q ·n (6.64)
∂x Ln
general formulation of current density = J = qvn n ⇒ average velocity, now diffusion
velocity
Dn
vn = (6.65)
Ln

If not exponential n 6∝ exp −x
Ln
⇒ anyhow vn = D Ln
n
. if profile parameter id defined by
∂n/∂x
L−1
n ≡ .
n
In a same manner diffusion current of holes
∂p
Jdiffusion = −qDp (6.66)
∂x
where Dp = kBq T · µp .
Combining drift current density (electrical field) and diffusion current density
J n = qµn nE + qDn ∇n
(6.67)
J p = qµp pE − qDp ∇p
where ∇n and ∇p are gradients in 3 dimensions. (6.67) is the basics for analysing of
89
current-voltage curves in semiconducting components.
6.5 Current caused by temperature gradient

6.5.1 Current density
Thermodynamic equilibrium ⇐⇒ everywhere T = const. If not constant ⇒ flow
and/or current. First approximation: current proportional to gradient ⇒ similar
approach like density gradient.
Figure 6.16: Temperature-gradient. A is border of interest
Current in place x: On one side the temperature is higher ⇒ thermal velocity is higher
⇒ “Free distance”l is longer ⇒ From one side comes particles (electrons) more to the
opposite side than from opposite back. Meaning in Fig. 6.16 left → right more than
right → left.
Within time period of τ (relaxation time) will cross the place x only those electrons
which are within a distance of l, the free distance.
Current density from left → right:
1 1
f + = −q nl− · (6.68)
3 τ
where l− is free distance on left hand side.

Current density to opposite direction f − = −q 13 nl+ · 1
τ
and net current in place x
n − n 1 ∂T kB ∂T
f = f + − f − = −q (l − l+ ) =math
. . . = q l2 = σn (6.74)
3τ 3τ T ∂x q ∂x
q2 τ
where σn = conductivity = m∗
· n.
q
free distance l 3kB T
Here is taken into account that relaxation time
= τ
= v T = m∗
.
Interpretation of Eq. (6.74). Comparing to Eq. (1.6): J = σE.
90
Current density is proportional to conductivity σn . Electron flow is caused by “effec-
tive”electric field, gradient of thermal potential VT = kBq T .
Gradient small and therefore thermal potential small ⇒ current is small.
Apllication: Electric potential and electric power by temperature difference. Thermoele-
ment (usually metal).
For electrons and holes in a same way. The only difference is sign of Eq. (6.74), because
e − → p+ .
6.5.2 Density of heat flow rate (lämpövirrantiheys)

Particles (electrons) carry also thermal energy.
Classical density of heat flow rate can be derived in a same way like Eq. (6.74) but
with moving energy 3k2B T instead of charge
2
3 kB T ∂T
∴ Q = −σn (6.75)
2 q 2 ∂x
Thermal conductivity κ (small kappa) definition
∂T
Q = −κ (6.76)
∂x
2
3 kB T
⇒κ= 2
σn (6.77)
2 q
Meaning thermal conductivity is proportional to electric conductivity with a ratio
2
κ 3 kB
= (6.78)
σn T 2 q
so called Wiedermann-Franz law. This is working for electrons.

In semiconductors and insulators electrons do not move well ⇒ phonons are more
important when thinking about carrying thermal energy.
Analysing motion and scattering of PHONONS (similar way like electron) one will get
for heat flow caused by PHONONS:

1 ∂ U
Qphonons = − vs2 τ (6.79)
3 ∂x V
91
where
vs = sound velocity = velocity of phonons

τ = relaxation time = time between collisions (for phonons)
U energy
= = energy density of vibrating lattice
V volume
∂ U

Using cv = lattice heat capacity = ∂x V
⇒ Thermal conductivity
1
κphonons = vs2 τ cv (6.81)
3
In room temperature so called Debye-approximation is enough
cv = 3kB T nat (6.82)
where nat = atomic density. Thermal conductivity for semiconductors is usually

approximately 1 cmWK . Specially good κ is in diamond and also in sapphire. Phonons,
but no free electrons.
Figure 6.17: Thermal conductivity in room temperature
92
Chapter 7
Preparation of semiconducting
materials
7.1 Crystal growing

Czochralski-method.
Clean Si in liquid form (Tmelt = 1412 °C) Rotating axis is lifted upwards. Start with
Figure 7.1
seed crystal touching liquid and lift slowly. Si-atoms crystallize in locations defined by
crystal structure ⇒ single crystal. Rod diameter = 10 . . 12 cm. Cut 0.4 mm slices,
i.e. silicon wafers.
93
7.2 Selective doping
In selective way n- or p-type areas
a) First SiO2 layer onto Si crystal.
b) Holes to SiO2 layer in those placed areas where n- or p-doping.
c) Impurity atoms onto the wafer.
d) Diffusion of impurity atoms. Atoms penetrate Si but not SiO2 .
Figure 7.2
First step (a) most easily by oxidation. High temperature and usual air. Si+O2 → SiO2 .
Second step (b), removing SiO2 from areas that needed.
This done by PHOTOLITHOGRAPHY.
Photomask technics: Photoresist is plastic that make polymerization in light. Mask and
illumination by UV-light (“negative picture”). Mask is removed. After polymerization
the photoresist is strong. Acid HF is used for removing photoresist and SiO2 from areas
that were not illuminated. On these areas will be pure Si-surface.
Wavelength of UV-light is limit for pattern. Visible light ≈ 0.7 µm, UV-light give limit
0.3 µm, electron beam 0.1 µm.
Smallest transistors ≈ 10 nm (1996).
(c) Structure is inserted to gasmixture, where is doping impurities ⇒ n-type or p-type
doping in places where it is needed.
Points (a)-(c) one more time ⇒ second layer of doping.
Contacts by evaporating a metal layer, usually Al, and by removing useless areas
(Photoresist + Mask + Acid).
94
Figure 7.3
Clean room. Component size ≤ 1 µm ⇒ dust particles give problems if they stick on
the wafer. Specially photolithography-state is very sensitive.
In air 107 dust particles per m3 , particles with size ≥ 1 µm. In clean room 10 000 . . 100 000
times less (4 − 5 decades). Also humidity and temperature must be constant.
7.3 Diffusion and ion-implantation

Diffusion is described in basic material physics. Fick I-law:
∂C(x)
J = −D (7.1)
∂x
J = particle flow, C(x) is conservation, D is diffusion constant. Fick II-law
∂C(x) ∂ 2 C(x)
Time dependence ⇒ =D (7.2)
∂t ∂x2
Differential equation has solution

2Cs x
C(x, t) = √ erfc √ (7.3)
π 2 Dt
Cs = concentration on surface ≈ 1019 . . 1021 cm−3

Z z
erfc = error-function = exp(−y 2 ) dy
0
Diffusion in 2 steps
A. Total amount of impurities.
B. “Atoms in”-diffusion
(A. kokonaisepäpuhtausmäärä ja B. sisäänajodiffuusio)
95
A. Total amount of impurities entering the material
Z ∞
r
Dt
N0 = C(x, t) dx = 2 Cs (7.4)
0 π
Stop after some fixed time value t. Control amount of impurities with time value.
Impurity atoms are in the surface layer.
B. Impurity atoms enter Si to more deep.

Border condiction: N 0 = const ⇒ Diffusion equation (Fick II) gives
N0 x2

C(x, t) = √ exp (7.5)
πDt 4Dt
Rz
[erf h(z) = 0
exp(−y 2 ) dy].
In step B. impurity concentration inside the material is controlled by time and temper-
ature (Fig. 7.4).
Figure 7.4: Diffusion-constant in Si.
96
Ion implantation
Doping-atoms (impurity-atoms) are ionized. Then they are accelerated using electric
field and shot into the pure Si.
Acceleration energy usually 20 . . 200 keV. Penetrates to depth ≤ 1 µm. Crystal partly
distroyed. Need heat treatment. Impurity atoms will be activated ⇒ Shallow levels
will be formed.
Good: Fully controllable. Possible to define in details the amount of impurities.
Figure 7.5: Ion implementation of P in Si, Al and Si3 N4 . Penetration depth (solid line).
97
7.4 Oxidation
Growing of SiO2 layer on Si (page 93):
A. High temperature, 900 . . 1000 °C ⇒ Faster.
B. Wet oxidation ⇒ Faster.
Figure 7.6
H2 O molecules with O2 gas
Si(s) + O2 (g) → SiO2 (s) (7.6)

Si(s) + H2 O(g) → SiO2 (s) + H2 (g) (7.7)
SiO2 layer is limiting the reaction: First diffusion through SiO2 layer.
Thin SiO2 layer ⇒ Reaction speed define the rate of growing. First rate of growing is
linear.
xox ≈ t + τ (7.8)
t is time and τ describes that SiO2 layer exist.

Later, thick SiO2 layer ⇒ The rate of growing is limited by diffusion, and rate has
square root dependence on time
√
xox ≈ t+τ (7.9)
98
7.5 CVD-growing
CVD = Chemical Vapor Deposition. Atoms in gas form to growing chamber. Reaction
Figure 7.7
on surface of Si-wafer. Atoms occupy places according to crystal structure. Growing Si:
SiH4 (g) → Si(s) + 2H2 (g) (7.10)
EPITAXIAL growing. T ≈ 900 . . 1200 °C. Low temperature ⇒ polycrystal.

T below 600 °C ⇒ Amorphous Si.
Growing insulator using CVD:
SiH4 (g) + O2 (g) → SiO2 (s) + 2H2 (g) (7.11)
T ≈ 400 °C.
Good in CVD is low temperature. Growing quality not as good as thermal growing.
7.6 Metal growing

Components . 1 µm.
SiO2 layer protecting components. Make holes to SiO2 in correct places and then grow
1 . . 2 µm metal layer on the component. Al is very suitable metal.
Growing is done by A. Vacuum deposition or B. sputtering
A. Vacuum deposition. Metal is evaporated (heated) by cathode beam, meaning by
electron beam. Metal atoms in gas form drift to wafer and metal atoms grow to a
thin layer.
B. Sputtering. Metal atoms are extracted (taken out) from metal by ionic bombard-
ment.
99
Figure 7.8
Pattern is done in similar way like in chapter 7.2: Mask + photolithography + acid
etching.
Max current density is about 105 A cm−2 . Stronger currents make atoms to move ⇒
problems.
The problems in integrated circuits is usually because of problems in metal coating.
7.7 MBE-method
MBE = Molecular Beam Epitaxy.
Figure 7.9: GaAs−MBE
Used specially for heterojunctions. Strong development starting from 1970’s.

Growing in ultrahigh vacuum, 10−11 torr. Vacuum needed for not to have impurities
and dust.
Initial meterials in own effusion oven (effusion ≈ leak). Heating of initial material ⇒
evaporation ⇒ THERMAL MOLECULE BEAM.
Temperature gives beam intesity. Mechanical shutter controls the time.
As a substrate is used suitable single crystal. Atoms stick on substrate in place defined
by crystal structure.
Substrate cold ⇒ possible to make sharp interfaces.
100
Good: Very good control of layer thickness and content.
Bad: Slow. About one atomic layer per second.
Lattice matching
If crystal structure of substrate is not similar to component ⇒ Deformation of component
(if 10 . . 100 nm) of defect (> 100 nm).
Alx In1−x As is lattice matching with GaAs with x = 0 . . 1.
Gax In1−x Asy P1−y with InP as substrate also good. Electric and optical properties better
than in AlGaAs/GaAs heterostructure.
Gax Si1−x /Si is one example of lattice non-matching system. Lattice constant grows
when x grows.
If only thin layer of GeSi ⇒ no lattice defects. Critical thickness ≈ 100 nm.
101
Chapter 8
Spintronics
In electronics we use electron CHARGE for handling and storage of information.

Spintronics is new area, where we try to use electron SPIN dor handling the information.
Spin =b magnetic moment.
Sometimes insteand of spintronics people use word magnetoelectronics.
8.1 Magnetic semiconductors

DMS = Diluted Magnetic Semiconductors.
In semiconductor is added magnetic impurities, usually Mn. Host material usually
compound semiconductor:
Binary, for example GaAs or GaN. III-V semiconductor.
Tertiary, for example II-IV-V2 .
Magnetic impurity occupy in crystal only one crystal site; adding Mn to GaAs gives
result.
Amount of magnetic impurities: concentration 0.01 % . . 10 %.
Lower limit : effect becomes too small, no effect from impurities. Mn is magnetic
and interaction between Mn atoms depends on distance:
Coulomb-type interaction. Direct. r−2 -dependence, i.e. sharp.
More exotic: RKKY (Ruderman-Kittel-Kasuya-Yosida, 1969) oscillating. Interac-
tion mediated by other electrons.
Upper limit : Crystal structure will deform and not possible to have single crystal.
102
8.2 CMR and GMR phenomenon
Complicated physics is connected with magnetic interactions, this means interesting
phenomenon.
One is influence of magnetic field in resistivity
Figure 8.1
CMR = Colossal Magneto Resistance

GMR = Giant Magneto Resistance
Magnetoresistance = Influence of magnetic field in resistivity. Usually many %, some-

times many 100 %
Rmax − Rmin ∆R
%MR = · 100 % = · 100 %
Rmin R
Reason for magnetoresistance: Moving of electrons is more easy if magnetic moments

of surrounding electrons are aligned parallel.
In other words: Magnetization gradient gives scattering.
Albert Fert, Peter Grünberg: NOBEL 2007.
8.3 Multilayer structure

First thin film from usual semiconductor.
On top of this magnetic semiconductor as thin film and then again thin film of usual
semiconductor. If crystal structure are different ⇒ Tension ⇒ Thickness of thin film
must be small.
Multilayer structure is grown on substrate. Usually buffer layer between the substrate
and the structure.
103
Figure 8.2
Figure 8.3
Multilayer structure gives larger effect if amount of layers are increased.
8.4 Spintronics
In electronics we use charge and voltage ⇒ Binary numbers 1 and 0.
In spintronics
- Memory. No need upgrading.
- Possibility to have very small size. In electronics the limit is quantum mechanics.
Nanophysics.
- Nowadays technical applications only in area of memories (Computer hard-disk
104
Figure 8.4
and diskettes).
One problem is room temperature. Many materials give this magnetic effect only in
low temperature. Transition temperature usually 50 K . . 200 K.
GdGaAs2 with 6 % Mn ⇒ transition temperature 355 K ⇒ Interesting area for research.
105
Repetition (Kertaus)
Classical conductor
- Electrons in metal ⇒ Basic definitions vT hvi = vD , τ , J = σE, σ and ρ, l, µ
- Hall effect
- Frequency dependence
- Optical properties
Quantum mechanics
- Approach from the point of view of practical things
- Minimum amount of theory, but not possible to avoid Schrödinger
- Start with history, meaning with problems in classical physics
- Analysis of Schrödinger equation
- Potential barriers (step, barrier and well)
- Tunneling
Structure of material

- Atom 



- Lattice


These were also in course “Material Physics”
- Crystal structure




- PHONONS 
Free electron model of metals
- Density of states
- Fermi-Dirac
- Fermi-energy
106
- Thermal emission and field emission
Energy-bands
- How crystal structure and periodical potential results in appearance of energy

bands
- Kronig-Penney model
- Wave packet ⇒ Semiclassical equations of motion
- Holes. Direct-indirect energy gap
Semiconductor physics
- Density of states and density of charge carriers; both for electrons and holes; both
in conduction band and in valence band
- DOPING. Acceptors and donors. How additional charge carriers appears:
• Acceptors → holes
• Donors → electrons
- Influence of doping to charge carrier density
- New energy levels inside the gap. Shallow and deep levels.
- Mobility: Scattering from phonon and scattering from impurity.
- Generation and recombination: Photon makes electron-hole pairs. Impurity levels

makes the process easier.
- Current because of density gradient and temperature gradient.
Preparation of Semiconductor materials
- Czochralski-method, Photolithography, CVD-growing, MBE
Spintronics
- Magnetic semiconductors, CMR and GMR phenomenon
107

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Semiconductor and Superconductor

Lectures follow the books:

4 Free-electron model of metals 34

7 Preparation of semiconducting materials 93

Electrons in metal. Free electron gas and positive metal ions.

1.1 Electrical properties

E = 0 ⇒ motion + collision + motion + collision + . . .

− 12 m(vx2 + vy2 + vz2 )

If T = 300 K ⇒ kB T = 0.0258 eV (small).

Electric field E 6= 0 ⇒ F = −qE ⇒ Equation of motion

We investigate time period τ ⇒ electrons move distance ∆x = vD τ

I ∆Q/τ qn∆xA qnvD τ (1.5) q 2 τ n

This gives resistivity

Numerical values. Metal n ≈ amount of atoms ≈ 5 · 1022 electrons/cm3

Now we see why τ is called as “relaxation time”:

This voltage is called Hall-voltage.

1. Usual ohmic voltage parallel to current

2. E H = field perpendicular to current:

In measurements longitudinal voltage gives σ

1.1.3 Frequency dependence of conductivity

where σDC is given in (1.7).

Re[σ(ω)] = σDC /(1 + ω 2 τ 2 )

Low frequency < τ1 ⇒ σ = σDC

High frequency (ωτ  1) ⇒ Re → 0 like ω12 .

J = usual current density with J = σ(ω) · E

Geometrical capacitance is charged when voltage is applied.

Name: PLASMA FREQUENCY

1.2 Optical properties

If additional charge ⇒ Electric field

i.e. lenght of wave vector is connected to λ

(1.32) ⇒ B = B 0 exp[i(k · r − ωt)] (1.42)

In other words: Magnetic field component in plane wave is perpendicular to E and k.

⇒ In electromagnetic wave B and E are ⊥ in comparison to propagation

k 2 = iωµ(σ − iωε) (1.45)

This is called dispersion relation and it gives k = k(ω).

INSULATOR. σ = 0, µ and ε are real constants (non-imaginary) ⇒

Snell law (1.46) can be written in the form

CONDUCTOR. σ = const, real number ⇒

Wave number k: Imaginary part gives attenuation, damping (k 2 = εµω 2 + iσµω).

where δ is called skin depth (Finnish language ≈ penetration depth)

If ωτ  1 ⇒ Eq. (1.53) (τ is the time between collision).

Magnetic field components in similar way B0 + B1 = B2

(v0 = velocity of incoming wave, in vacuum).

2d sin θ = λ · integer (1.60)

Density of waveform ∝ ω 2 ⇒ Energy density ∝ ω 2 .

with n = integer and } = constant.

This has a name Bose-Einstein distribution and it describe behaviour of Bosons

Figure 2.2: Experimental arrangement and explanation

Quantum is called PHONON

D. Bohr model (1913) Classical mechanics: Particle energy is continuous, therefore

Bohr (1913): Angular momentum is quantized

⇒ Only fixed orbits are accepted.

Valid for atoms with one electron (hydrogen-like). n = quantum number.

E. Compton scattering (Phys. Rev. 22, 409 (1923))

Photoelectric effect: All photon energy to electron, photon disappears.

F. Wave nature of electron (de Broglie, PhD-thesis 1924)

Also energy similar to photon E = }ω ⇒

Additional result: Simple interpretation of Bohr quantization rule: (2.17) and

Question: de Broglie is theoretical idea. What about experiments?

1. Linear combinations of Ψ are also solutions of Schrödinger. ⇒ Superposition and

2. Solution is called: WAVEFUNCTION. Complex.

3. |Ψ|2 = Square of wavefunction magnitude = probability distribution.

4. Ψ must be single-valued and finite. Ψ and ∇Ψ continuous.

High frequency (ωτ 1) ⇒ Re → 0 like ω12 .

If ωτ 1 ⇒ Eq. (1.53) (τ is the time between collision).

This equation hasmoreclear interpretation: