A brief overview on Semiconductors

Brief summary of what you have seen in Lecture « Physics of devices » (3rd year)
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Additionnal features
 Semiconductors

A) Intrinsic carrier concentration

B) Doping

C) Band structure taking into account spin-orbit term

D) Bandgap as a function of temperature

E) Excitons
I) Accurate control of charge contrary to metal, thanks to the presence of a gap and
controlled doping

Microelectronics IV-IV semiconductors: Si, Ge

Devices: junctions, transistors,
Integrated circuits, microprocessors…
 Silicon fcc
Si has diamond structure with two identical atoms per primitive cell
- Minimum of the con-
Γ 0 duction band located close
to the X point at 0.85 2π/a
L <111>
in the ⟨100⟩ direction.
X <001>
Γ
K <011> - Max of the valence band is
in Γ (not at the same point
in k space) as the top of the
valence band.

Such a band structure

is called indirect.

Minimum of the conduction band in k0

Isoenergy surfaces for conduction band close to the minimum

There are six equivalent ⟨100⟩ directions: there are six equivalent minima of the conduction band
 Germanium fcc
Ge has diamond structure with two identical atoms per primitive cell
- The conduction minima
are at the L point in the
⟨111⟩ direction. Due to
symmetry there are eight
equivalent conduction-
Γ 0 band minima.
L <111> - The top of the valence
X <001> band is in Γ
Γ
K <011>

indirect band structure

Conduction band
minimum

Due to symmetry there are eight equivalent conduction-band minima.

II) Forbidden gap Optoelectronics
Light emitters with tunable wavelength (direct gap semiconductors)
Telecommunications through optical fibers: Laser diodes, light amplifiers based on
III-V Semiconductors GaAs, InAs, AlAs …

GaAs Zinc-blende structure

fcc two identical atoms per primitive cell

EL
Ex Γ 0
L <111>
X <001>
EG Γ
K <011>
Isoenergy surfaces for
conduction band
close to the minimum
 Ligthing: GaN (wide bandgap) based blue Light emitting diodes, white leds

Light detectors
Energy: Solar cells (Si, CdTe,…)
Telecommunications: photodiodes (InGaAs, …)
Imaging: CCD camera (Si…)
A) Intrinsic carrier concentration
Fermi distribution: f(E) is the probability of
occupation of a state of energy E or
equivalently the average number of
electrons that occupies a state of energy E
n number of electrons in the conduction band

c  (E) density of states

c (E)

p number of holes in the valence band

v f (E)

 (E) →

v (E)
 electron vs electron-hole picture

ρc (E)

f (E)
f (E)

fh(E)= 1- f (E)
ρv (E)
electron-hole picture

Full electron picture

 Boltzmann approximation
non degenerate electron (or hole) gaz

c with and  c(E) = (1/2π2) (2me */ћ2)3/2 (E-Ec)1/2

Density of states in the bottom of conduction

band in the parabolic approximation of the band
Ec-µ(T) >> kT => f (E) ⋍ exp [–(Ec-µ(T))/kT] Boltzmann approximation
OK at 300K

n(T)=Nc(T) exp [–(Ec-µ(T))/kT] with Nc(T) =(2/h3) (2m*e kT)3/2

Called effective critical density in the conduction band

v with  v (E) = (1/2π2) (2mh */ ћ 2)3/2 (Ev - E)1/2

Density of states in the top of the valence band in
the parabolic approximation of the band

µ(T) - Ev >> kT => 1-f (E) ⋍ exp (E-µ(T))/kT)

p(T)=Nv(T) exp [–(µ(T) -Ev)/kT] with Nv(T) =(2/h3) (2m*h kT)3/2

Called effective critical density in the valence band
intrinsic semiconductor
n (T) = p(T) = ni (T) => ni (T)2 = * *

independent from chemical potential

Mass-action law

One can also express the chemical potential µ (T) = (Ec+Ev)/2 +(3/4)kT ln(mh*/me*)
as a function of temperature
 Intrinsic carrier concentration

300K

effective critical density

in the conduction band

effective critical density

in the valence band
 Conductivity
Rod of intrinsic silicon (1 cm long, diameter of 1mm)

At room temperature, the intrinsic concentration the silicon is ni = 1.5x1016 per m3.
The electron and hole mobilities are μe = 0.13m2 V−1 s−1 and μh = 0.05m2 V−1 s−1.

Let us calculate the conductivity σ: σ = n e μe + p e μh = ni e ( μe + μh )

→ very poor conductivity → doping is required

Doping is the incorporation of impurities into a semiconductor (in a controlled

manner)
B) Doping We treat the electron in excess
as belonging to an hydrogenic atom

Positive 1
excess charge

Electron
coming for As atom
(it could be P in Si, etc…)

in a material : replace ε0 with ε0εr and me with me*

Donor levels

Acceptor levels
 Ionisation energy

Ionization energy

Donor
Donorlevels
levels

Acceptor levels
C) Band structure taking into account spin-orbit term
Electrons move around the positively charged nucleus at relativistic speeds → the electric
field of the nucleus is seen as an effective magnetic field by the electron spin

HSO= = with

Potential due to nuclei

Ex in GaAs

HSO is responsible
for this splitting
D) Bandgap as a function of temperature

GaAs Si

GaP C -diamond

The average distance between atoms increases

when T increases (dilatation), so their interactions
decrease, and thus the bandgap decreases
Varshni law
E) Excitons

A) « one-electron » theory
2
The Hamiltonian corresponding to the N electrons is: H= σ𝑁𝑖=1 𝒑𝒊 + 𝑉(𝒓𝒊 )
2𝑚
where V(ri) is the potentiel energy felt by electron i due to all the nuclei and other electrons
This potentiel is the same for all the electrons.
This Hamiltonian is the sum of the N Hamiltonians of N independant electrons
(« one-electron » theory )

The energy of the semiconducteur with N electrons is: E= σ𝑁

𝑖=1 𝐸𝑖

For electron i:
Ei

This band diagram is the same for all the N electrons

Eg
ki
In this model: Ei

Eg one electron in the conduction band

E of the semiconductor (N electrons)
ki
(one hole in the valence band)
Continuum of excited states
Ei
E first excited state= Eg

E fundamental state = 0 Eg No electron in the conduction band

ki

Corresponding absorption coefficient in this model:

Abs coefficient α
Abs coefficient α :
I=IO exp (- α L)
(L is the length
of the semiconductor) E
Eg
But experimentally, at low temperature, several (at least one) absorption peaks appear
below the bandgap

Abs coefficient α

These peaks correspond to Exciton states

E
Eg
Exciton states are not predicted by the « one electron » model

E of the semiconductor (N electrons)

E excited state= Eg corresponding to an electron-hole pair (unbound)

Exciton states
E fundamental state= 0
B) Many body theory

Exciton states are not predicted by the « one-electron » model. It is necessary to take
into account electron-electron interactions (many-body theory) to get these states as
solutions of H.
This many-body therory is extremely complicated, but the result is simple from the point
of view of the energy:
The exciton energies can be calculated using a pseudo-hydrogen atom model constituted
by an electron and a hole bound by Coulomb interaction
𝒑𝑒 2 𝒑ℎ 2 𝑞𝑒 𝑞ℎ
The effective Hamiltonian writes: Hexc = + +
2 𝑚𝑒* 2 𝑚ℎ* 4𝜋𝜀0 𝜀𝑟 (𝒓𝒆 −𝒓𝒉 )

E of the semiconductor (N electrons)

E for pseudo-hydrogen atom

Eg corresponding to an electron-hole pair (unbound) E= « 0 » for the pseudo-

hydrogen atom
Exciton states
n=2 E= -Ry*/n2

n=1
E fundamental state= 0
 Excitons in bulk

Qualitative treatment: assume parabolic bands:

two body problem: split it into CM and relative motion by variable change:

center of mass relative motion

of e-h pair
 Above the gap
Excitons: discrete + continuous
Below the gap: spectrum
(Sommerf
Excitons
theingap:
hydrogenic
Below bulk
levels Above the gap:
hydrogenic
Electron-hole Coulomb R*
levels
attraction 2 two-particle
2
K ex problem (Sommerfe
En (K ) Eg exc ( ) S( ) in
Rn*2 2K 2M2
En (K ) Eg ex exc ( ) S( ) inte
Above2 Mthe gap: enhancement2 x
Relative Below
motionthe gap:
part: hydrogenic-type problem n2
hydrogenic levels (Sommerfeld) factor S( x)
1 2 ex 2 x
2K(k2 )2 SEffective
( x) Rydberg
R* 2 x
kexc exc ( ) S( ) interband ( ) 1 *e 4
exc
ex
K )) = Eg
EEnn(k(exc
n2 2M e
R* ,
* 2 41 2
/ 2
M = me *+ mh* 2 x
R * R*2 e ,
µ * =S(m
( xe)*mh*)/(m2e*+m x h*)
x
2 2 2
1 e BohraB g E
radius ,
2*e2
*e4 1 a1B 1 ,
* 2
R* , * * *
R ~1-10 *e,
2 2 2 me mmeV,h aB *~
For GaAs, R*~1-10 meV, aB ~50-150 Å
Observable
2 R*~1-10 meV, aonly B *~
(Observable only at low temperatures for GaAs)
aB
* 2
, me* mh* only a
M Observable
e
kexc R*~1-10 meV, aB *~50-150 Å shallow
Observable only at low temperatures
 Excitons:
Excitons:absorption
absorptionspectrum
spectrum
Absorption effects
absorption is
absorption is finiteand
finite continuousatatthe
andcontinuous theband
bandedge:
edge:
R.J.
R.J.Elliott,
Elliott,Phys.
Phys.Rev.
Rev.108,
108,1384
1384(1957)
(1957)
Absorption coefficient
Absorption coefficient

n=1
n=1

n=2 with 3D Sommerfeld factor

n=2 with 3D Sommerfeld factor
n=3
n=3

without exciton effect

without exciton effect

Eg R3D* Eg Energy E
Eg R3D* Eg Energy E

C. Weisbuch, R.G. Ulbrich (1976)

C. Weisbuch, R.G. Ulbrich (1976)
Analytic
Analyticexpression
expressionfor
for with
withexcitonic
excitoniceffects:
effects:
C.C.Tanguy,
Tanguy,Phys.
Phys.Rev.
Rev.Lett.
Lett.75,
75,4090
4090(1995);
(1995);76,
76,716
716(1996)
(1996)
Exciton binding energy for some “inorganic” bulk materials
 Exciton binding energy for typical organic (involving Carbon) materials

Binding energy > kT= 25 meV at room temperature => excitons are robust at room temperature
Major role in Organic Solar Cells, Organic LEDs (OLED)
at room temperature!!

AMOLED used in Samsung Galaxy Note

(active-matrix organic light-emitting diode)
New trends in semiconductor field: 2D semiconductors
Transition metal dichalcogenides MX2 (M Metal, X chalcogen) monolayer
S S
S Mo
MoS2 Mo Mo Primitive cell

Top view

Monolayer: direct gap

interesting optical properties

Other TMDCs: MoSe2, WS2, WSe2, MoTe2….


As for organic semiconductors, binding energy > kT= 25 meV at room temperature =>
excitons are robust at room temperature

Emitters
Detectors
Intensity

Photon
energy (eV)
Optoelectronics Photoresponse 400nm-600nm

Ultra-sensible phototransistor

Lopez-Sanchez et al,
Nature Nanotech (2013)

APL 104, 193508 (2014)