Carrier Induced Changes in the Optical

Responses of Semiconductors
A report on Reading Course-I
submitted towards the partial fulfillment of the requirement for the degree of

Doctor of Philosophy (Physics)

From
Homi Bhabha National Institute, Mumbai

Submitted By

Durga Prasad Khatua

Under guidance of

Dr. J. Jayabalan
Nano Science Laboratory
Material Science Division
Raja Ramanna Centre For Advanced Technology

Indore - 452013.

August 9, 2018
Contents

1 Introduction 3
1.1 Energy bands and energy levels in semiconductors . . . . . . . . . . . . . . . . . 5
1.2 Semiconductor quantum structures . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.3 Optical Response of a Classical Oscillator . . . . . . . . . . . . . . . . . . . . . . 9
1.4 Kramers-Kronig Relation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

2 Effect of excited carriers on optical response of semiconductor 13

2.1 Band Filling Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
2.2 Band gap Shrinkage Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
2.3 Free Carrier Absorption Process . . . . . . . . . . . . . . . . . . . . . . . . . . . 19

3 Estimation of change in optical response due to excited carriers 21

3.1 Contribution of band filling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
3.2 Contribution of band gap shrinkage . . . . . . . . . . . . . . . . . . . . . . . . . 24
3.3 Contribution of free carrier absorption . . . . . . . . . . . . . . . . . . . . . . . 25
3.4 Estimation of the total change in the optical response . . . . . . . . . . . . . . . 26

4 Summary 29

1
 Syllabus for Reading Course - 1

Carrier induced changes in the optical response of semiconductors

1. Band filling,

2. Band gap renormalization/shrinkage,

3. Free carrier absorption,

4. Contribution of these processes to the refractive index of the material,

5. Estimation of these effects at different photon energies for a given semiconductor (e.g.
GaAs).

2
Chapter 1

Introduction

Active research is being carried out to develop materials for new applications as well as for
improving the efficiency of present devices. Materials required for such applications should
have various contradictory requirements which are not met by any normal materials. Reducing
the size of the material and combining different types of materials can be used for achieving the
task designing the properties. Devices that are made by nanostructuring would have compact
size, lower power consumption, and would also reduce the overall cost of production. In genenal
efficient devices should also have fast response and fast switching speed etc.[1, 2, 3]. In order to
design such nanostructured materials understanding has to be developed how the structuring
modifies the properties of the material itself. In order to design such fast device components
it is essential to study the carrier excitation and relaxation mechanisms in such nanomaterials.
In a metals and semiconductors carrier excitation and relaxations happens in few femtoseconds
to few tens of nanoseconds [4, 5, 6, 7].

When the photon having energy above the band gap is incident on a semiconducting material
then electrons in the valance band gets excited to the conduction band. Depending on the
photon energy the electrons may get excited to deep inside the conduction band. These electrons
in the conduction band will respond to the any other incident optical beam in a different manner
than that when they are in valence band. In time these electrons thermalize by electron-
electron and electron-phonon scattering and relax to the band edge. Then from the electrons
and holes recombine at the band edge through radiative process. The decay is non-radiative
when the carriers relax within a band. While the recombination between bands are generally
radiative depending on the band gap. These dynamical changes in the state of electron and
holes changes the material properties. Further, most of these changes happen in ultrafast

3
subpicosecond and picosecond timescales. The pump-probe experiments using optical pulses
like transient reflectivity or transient absorption can be performed to study the excitation and
relaxation processes. A detailed understanding of carrier dynamics is necessary for designing
and optimizing the material for device application. Thus the designed new material can make
the performance of that device more efficient.

For the measurement of the property of a material it is essential to disturb it to certain

extent. For example if we have to measure the electrical conductivity it is essential to apply
voltage across the material and measure the amount of current that passes through the material.
In case of measurement of absorption coefficient measurement it is essential to pass the light of
particular intensity though the material. In all these measurements it is essential to make sure
that the voltage that is applied should not lead to breakdown of the material understudy or
the applied intensity should not be large that the material becomes nonlinear. If the properties
of the material gets changed then the properties that are measured are no longer same as that
of the original material. In general measurement of the properties of the material at various
voltage or intensity itself is the direct way to estimate whether the material is unperturbed
or in a perturbed state. For optical measurements, if the measured signal is linear with the
intensity then one can always extrapolate the property to estimate its value at zero intensity.

In carrier dynamics measurements we excite the material with a light pulse and study how
the properties of material changes in time after this excitation. The properties of material like
absorption coefficient or reflectivity at a particular wavelength or the intensity of light emitted
from the material can all be used for the studies of transient changes in the properties of the
material. The amount of change in the absorption coefficient or the reflectivity of material with
respect to time would give the information about the transient properties of the material. Even
in this measurement it is essential to check that the properties of the material is not changed
substantially with respect to its original state.

In the following sections an introduction to the properties of semiconductors are discussed

followed by various quantum structures that can be formed using confinements. The changes
in the optical properties of semiconductors can be understood by a simple lorentz model which
is also discussed. Kramers-Kronig relation which will be used extensively to model the optical
response of materials is also discussed in this chapter.

4
1.1 Energy bands and energy levels in semiconductors

To understand many of the optical properties of semiconductor it is essential to understand

its band structure. For infra red (IR) and visible regime the structure of band near the band
edge is sufficient to explain most of the observed optical response of semiconductors. When two
atoms are far apart from each other the interaction between them is negligible and the energy
levels of each atom remains same and has the same properties. However, in bulk these atoms
comes close to each other and interact resulting in complete modification of their properties.
As an example let consider the band formation in carbon atom. Carbon has six electrons with
a outer shell configuration 2s2 2p2 . The 2s and 2p orbitals are close in energy and can hybridize
to form sp3 orbitals. There are 4 electrons in the sp3 orbitals. This is a common property of
Group IV elements of periodic table. These hybrid orbitals interacts with the hybrid orbitals
of other nearby atoms. These two orbitals, one from each atom, interact to form a bonding and
an anti-bonding orbital. As each C-atom can contribute one electron there will be 2 electrons
in each bonding orbitals and anti-bonding orbital will be empty. Thus each C-atom can form
bond with 4 other C-atoms and all the bonding orbitals will be full. In bulk material, bonding
orbitals form a energy band called valence band, which is full for temperatures close to 0 K.
Anti-bonding orbitals form another energy band called conduction band and are is completely
empty [8, 9]. The valence band and conduction band are separated by a forbidden energy gap
called band gap. For measurements at IR and visible regime the carrier dynamics near the band
edge is mostly sufficient. Near the band edge the band structure can be well approximated to
a parabola. Fig.1.1 shows the band structure of semiconductor near band edge.

Based on the band structure, semiconductors can be classified into two main types, direct
band gap and indirect band gap semiconductors. In direct band gap semiconductors lower
energy state of conduction band and higher energy state of valence band are situated at same
→
−
k value. In this case electrons from valence band can be excited to the edge of conduction
band directly by a photon. This is due to the fact that photon has very less momentum. When
a electron is conduction band it can recombine with the hole in the valence band and emit
a photon. This process is called as luminescence and it also happens nearly vertically in the
(E, k) diagram which is also observable in case of direct band gap materials. Examples of direct
bandgap materials are InAs and GaAs. In case of indirect band gap semiconductors the lowest
energy state of conduction band and higher energy state of valence band are situated at different
→
−
k values. In this case it is not possible to excite the material directly by a photon at the band
edge as the momentum is not conserved. However if a phonon is involved in the transition the
momentum can be conserved. This is also true for the relaxation of electrons to the valence

5
Figure 1.1: The band structure of (a) direct and (b) indirect band gap semiconductor near
band edge. Eg is the band gap of the material.

band. Examples of indirect bandgap materials are Si and Ge. Whether the material has direct
band gap or indirect band gap, can be identified by measuring its absorption spectrum near
the band edge. Absorption coefficient for direct and indirect band gap materials varies as,
p
α ∝ E − Eg (1.1)
α ∝ (E − Eg + Ep )2 (1.2)

where Eg is the band gap and Ep is the phonon energy.

Once carriers are excited in a semiconductor, i.e. electrons to the conduction band and
holes in the valence band, They can interact with each other by coulombic interaction to form
a bound quasi particle called exciton. The excitons have hydrogen like wave functions and
energy states. The formation of exciton is an important process in semiconductors. Many of
the optical relaxation processes in semiconductors depend on the excitons. Exciton has lower
energy than the total energy of electron and hole when they are not interacting. These excitonic
energy levels occur just below the band gap of the semiconductor. Compared to a hydrogen
atom exciton has very less binding energy and hence has much larger size. Depending upon
the binding energy and Bohr’s radius, excitons are can be classified into Frankel excitons and

6
Wannier-Mott excitons. Frankel excitons are generally found in materials having small dielectric
constant. In this case the interaction between hole and electron is very strong and tends to
form excitons Bohr radius smaller than unit cell. The binding energy of Frankel excitons are
of the order of 0.1 eV - 1 eV. The Wannier-Mott excitons are found in materials having large
dielectric constants. The high dielectric screens the Columbic interaction between the electrons
and holes resulting in large Bohr radius. Binding energies in this case are of the order of 0.1
eV. Apart from these two types of excitons there are also surface excitons that exist on the
surface of the material. These excitons form due to the dangling bonds that are present on the
surface of materials.

Besides conduction band and valence band some other bands are also found in semicon-
ductors which are introduced by defects or impurities or by the semiconductor itself. In the
following we discuss some of these important states which contributes to the optical response
and carrier dynamics in semiconductors. When semiconductor terminates at the surface, the
atoms at the boundary has a band structure which is different from these which are inside
the material. The unsaturated bonds present at the surface is called as dangling bonds. New
electronic states appear in the material due to these dangling bonds which are called as the
surface states. Surface states can act as donor or acceptor of electrons and surface states are
generally found in the forbidden region of energy band. Apart from surface states there are
also trap states present in semiconductors. Traps are metastable states formed due the defects
or impurities. Traps capture the electrons from higher energy states and retain it for a long
time. These trap states also appear in the forbidden region of the band gap.

1.2 Semiconductor quantum structures

When the size of a material is reduced to nanometer length scales its properties are no longer
same as that of bulk. A semiconductor structure having length in one dimension in the range
of few tens of nanometer are generally called as semiconductor nanostructures. The typical
length scale is the Bohr radius of the exciton. When the size of the material, in at least one
dimension becomes less than the Bohr radius the material states showing quantum size effects.
As a result of this confinement the physical and chemical properties of the semiconductor gets
changed drastically. Due to confinement the energy bands becomes discretized and also leads
to increase of band gap. Bulk material are less flexible over band gap engineering and density
of states modification. For example by applying temperature and pressure band gap can be
changed but up to only a limited range. Using the quantum confinement effect it is possible to

7
tune the properties of the semiconductor to a wide range.

In free carrier approximation the total energy of a charge carrier can be written as the sum
of kinetic energies along three directions (Eni ). If E is the total energy of the carrier then,

~2 ~ 2 ~2 2
E = Enx + Eny + Enz = |k| = (k + ky2 + kz2 ), (1.3)
2m 2m x
ni π
where ~k = (kx , ky , kz ) is the wave vector of the carrier. The wave vector has a form ki = ,
Li
where Li is size of the material in ith direction and ni is the quantum number (1,2,3...). In case
of a bulk material the all Li ’s are large and hence the energy levels becomes continuous.

Quantum Well : A semiconductor quantum well is a two dimensional structure in which

a low band gap material is sandwiched between two wide band gap material. The thickness of
the confined layer is of few nanometer order. In reality the potential well formed has a finite
depth. However several properties of the material can be understood by assuming the potential
well to have infinite depth. The SE can be solved for this potential well and wave functions
for electrons and holes can be obtained. For a quantum well having reduced dimention along
X-direction, the total energy of the carrier in this case can be written as,

~2 2
E = Enx + (k + kz2 ). (1.4)
2m y

For small Lx the gap between the energy levels for each nx will be very large while the other
two energies varies continuously.

Quantum Wire: In Quantum wire the confinement is done in two directions. The total
energy of a carrier in this case is given by

~2 2
E = Enx + Eny + k , (1.5)
2m z

n2x π 2 ~2 n2y π 2 ~2
where Enx = , Eny = and Lx , Ly are size of the quantum well in x and y
2mL2x 2mL2y
directions.

Quantum Dot: In quantum dots carriers are confined in all the three directions and the
total energy for a carrier inside the dot is,

n2x π 2 ~2 n2y π 2 ~2 n2z π 2 ~2

E= + + , (1.6)
2mL2x 2mL2y 2mL2z

8
where nx , ny , nz are integers and Lx , Ly , Lz are size of confinement in X, Y, Z direction.

1.3 Optical Response of a Classical Oscillator

For understanding the optical response of materials and how it will change with respect to
small change in resonance frequency can be obtained from the classical Lorentz model. In
classical theory light is treated as electromagnetic wave and atom or molecule as classical
dipole oscillator. According to this model electron is bound to nucleus of atom by a force
which behaves like Hook’s law i.e. spring like force. If electric field is applied, it interacts with
the charge of electron causing compression or stretching as in a spring, which would set electron
in oscillation. Let ω0 be the resonance frequency of this system. Due to this time varying dipole
is produced and its magnitude given by p = −ex(t) where x(t) is the time varying displacement
of electron from the equilibrium position. The displacement x of electron is governed by the
equation
m0 ẍ + m0 γ ẋ + m0 ω02 x2 = −eE, (1.7)

where γ is damping rate, e is electric charge, E is electric field of light. Here the first term on
left side represents acceleration, the second term corresponds to the damping process and third
term represents the restoring force. The term in right side represents driving force due applied
electric field. Using a time dependent electric field,

E(t) = E0 exp(−iωt − φ), (1.8)

the magnitude of macroscopic dipole moment of the material is can be derived and is given by,

N e2 E
P = −N eX = , (1.9)
m0 [ω02 − ω 2 − iγω]

where N is the number of atoms present per unit volume. From above equation it is clear that
response of dipole is negligible if frequency of light is very different from the resonant frequency.
Using Eq.1.9 the complex relative dielectric constant (r = 1 + i2 ) can be written as

N e2 (ω02 − ω 2 )
1 = 1 + χ + 2 (1.10)
m0 0 [(ω02 − ω 2 ) + (γω)2 ]
N e2 (γω)
2 = 2 (1.11)
m0 0 [(ω02 − ω 2 ) + (γω)2 ]

9
From these expressions for dielectric constants the absorption coefficient (α) and refractive
index (n) of material can be estimated. As an example, the frequency dependence of α and n
for a resonator having resonance at 100 THz is plotted in Fig.1.2.

To understand how the optical properties of materials will change with any small change
in properties of material we show the plot of α and n for two more resonances, once above
(102 THz) and one below (97 THz) in Fig. 1.3. If by any process the resonance frequency of
the material changes its optical properties will change accordingly. In Fig. 1.3 we also show
the frequency dependence of ∆α and ∆n. When the resonance shifts to higher frequency, for
probing frequencies lower than the resonance the ∆n is positive. On the other hand for the same
spectral regime when resonance shifts to the lower frequencies, the ∆n is negative. Similarly
for the case of change in absorption, when the resonance shifts to higher frequency, the ∆α is
positive for probe wavelengths below the resonance and is negative when the resonance shifts
to lower frequency. Later when we study the band filling and band gap shrinkage process
where the band gap increases or reduces similar change in optical properties can be expected
for wavelengths below band gap.

Figure 1.2: Frequency dependence of refractive index and absorption coefficient

10
Figure 1.3: (a)The dependence refractive index and absorption coefficient with frequency for a
system with different resonance frequencies(97 THz,100 THz, 102 THz) (b) show the variation
of change in refractive index when resonance frequency changes from the original value, (c)
show the variation of change in absorption coefficient for the same as in (b).

1.4 Kramers-Kronig Relation

Kramers-Kronig relation is a bidirectional mathematical relation which relates real and imagi-
nary part of a analytic complex function in the upper half plane. It is used to find the real part
of a response function if its imaginary part is known for any system which response function
is analytic and casual. According to causality, the effect can’t precede the cause i.e scattered
wave cannot exist before the incident wave reached the scattering center. From the discussion
on dipole oscillator we see that refractive index and absorption coefficient are not indepen-
dent. Applying law of causality and complex number analysis, a general relationship between
real and imaginary part of the refractive index can be derived. These relationship is called

11
Kramer-Kronig relation and it can be written as [10]
Z ∞ 0 0
2 ω κ(ω ) 0
n(ω) = 1 + P dω (1.12)
π 0 ω02 − ω2
∞ 0
−2ω
Z
n(ω ) 0
κ(ω) = P 02 2
dω (1.13)
π 0 ω −ω
where P indicates the principal part of the integration. Kramer-Kronig relation is very helpful
to calculate n from κ and vice versa.

In case of optical response, using this relation, it is possible to obtain dispersion curve if
the experimental data of absorption spectra is available without a separate measurement. Let
the dependence of optical absorption coefficient on photon energy (E) is given by α(E). The
dispersion relation for refractive index n(E) can be expressed using Eq.1.12,
Z ∞ 0 0
2 E κ(E ) 0
n(E) = 1 + P 02 2
dE . (1.14)
π 0 E −E
0 0 0
Since κ(E ) = hcα(E )/4πE , we can rewrite the above equation as
Z ∞ 0
ch α(E ) 0
n(E) = 1 + 2 P 02 2
dE (1.15)
2π 0 E −E

Thus if we know α(E) then we can always calculate n(E) using the above equation.

12
Chapter 2

Effect of excited carriers on optical

response of semiconductor

In the present study we mainly focus on understanding the changes that happens to the absorp-
tion coefficient and reflectivity at a measurement wavelength when the carries are in excited
state. Further it is also essential to understand how the change in absorption/reflectivity varies
with the excited carrier density.

Once carriers are excited several processes can modify the optical properties of the material.
In case of semiconductor there are three major process by which the change in optical properties
can be understood.

1. Band filling effect

2. Band gap normalization and

3. free carrier absorption.

For interaction of semiconductor with visible spectrum understanding of carrier dynamics near
the band edge is sufficient in most of the cases. Near the band edge the band structure of
semiconductor can be well approximated to be parabolic in nature. Further for simplicity we
concentrate on direct band gap materials for these studies.

The optical absorption coefficient of a direct gap semiconductor of band gap (Eg ) is for a

13
Figure 2.1: The schematic diagram of band structure of a direct-gap semiconductor near band
edge along with few possible transitions.

photon energy, E = ~ω, is given by,

Cp
α0 (E) = E − Eg for E ≥ Eg and
E
α0 (E) = 0 for E < Eg . (2.1)

Here C is a constant involving material properties. Figure.2.1 shows a schematic of a direct gap
semiconductor band structure near its band edge. The valence bands in III-V semiconductors
are degenerate at the band edge with light- and heavy- hole bands. Both of these bands
contribute to the absorption process[11]. Depending on the photon energy, excitation can take
place from light hole band to conduction band and from heavy hole band to conduction band as
shown in Fig.2.1. The total absorption coefficient with the contribution from these two process

14
is given by

Chh p Clh p
α0 (E) = E − Eg + E − Eg , for E ≥ Eg and
E E
α0 (E) = 0 for E < Eg . (2.2)

Here Chh and Clh refer to the material contents that corresponds to heavy- and light-holes,
respectively and are given by, !
3/2
µehh
Chh = C 3/2 3/2
, (2.3)
µehh + µelh
and !
3/2
µelh
Clh = C 3/2 3/2
, (2.4)
µelh + µehh
where µehh and µelh are given by,
 −1
1 1
µehh = + (2.5)
me mhh

and  −1
1 1
µelh = + . (2.6)
me mlh
Here me , mhh , and mlh are the effective masses of electrons, heavy-holes and light-holes re-
spectively. Equation.2.2 gives the absorption coefficient of semiconductor when there are no
carriers in the excited state. Once carriers are excited the absorption coefficient will change
due to various processes. When photons of energy larger than the bandgap of the material is
incident on the semiconductor, carriers will be excited. In case of transient experiments this
excitation of carriers is done by the pump pulse. Electrons from the valance band gets excited
to the conduction band creating heavy or light holes in the corresponding bands. Consider the
situation after these carriers have sufficient time to relax to the band edge. Now the material is
different from that of the original unfilled state where there are no electrons or no holes in the
conduction or valence bands respectively. Now if another photon of same or different energy
as that of the original photon falls on the semiconductor, its reaction (absorption or reflection)
to this photon will be different. The carrier excitation can be done by optical means as that
discussed in this report or also by electrical means. The reaction to the next photon will depend
on the number of states filled in the edge of the band gap.

In the following sections we discuss the, band filling, band gap shrinkage and free carrier
absorption processes along with simple theoretical description to estimate the change in optical
response of the semiconductor.

15
Figure 2.2: Schematic diagram for demonstrating the effect of band filling on optical transitions.

2.1 Band Filling Effect

Since electrons are fermions once a level is filled no other electron can occupy that level. This
implies that once electrons are filled in the conduction band further excitation of electrons
from the valance band to conduction band in the same state will be prevented. Similarly if
the valence band has holes further excitation from these states will once again reduce due
to the non-availability of electrons. Filling the electrons in conduction band or holes in the
valance band respectively can be done by optical excitation. In this case the excited carrier
densities for electrons and holes are equal. Under thermalized condition the excited carriers, the
electrons, will occupy the states near the edge of conduction band while the holes will occupy
the states near the band edge (top) of the valence band. Now if the material is illuminated with
wavelength that corresponds to the bandgap since these levels are already filled the absorption at
this wavelength will reduce. The filling of band that lead to decrease in absorption coefficient is
called as band filling effect. If photon of higher energy are used for excitation still the absorption
can take place. Thus one effectively assume that the band gap of the material has increased
due to the band filling effect.

If Ea and Eb are energies of a state in valence and conduction band, absorption coefficient

16
of injected semiconductor is given by,

α(N, P, E) = α0 (E) [fv (Ea ) − fc (Eb )] (2.7)

where N and P are concentration of free electrons and free holes respectively, α0 is the absorp-
tion coefficient of pure material, fc (Eb ) is the probability of a conduction band state of energy
Eb being occupied by electron and fv (Ea ) is the probability of valence band state of energy Ea
being occupied by electron. Ea and Eb are uniquely defined for a given photon energy and are
given by,
 
me
Eah,al = (Eg − E) − Eg and (2.8)
me + mhh,lh
 
mhh,lh
Ebh,bl = (Eg − E) . (2.9)
me + mhh,lh

The functions fc (Eb ) and fv (Ea ) represent the Fermi-Dirac distribution function and is given
by
1
fv,c (Ea,b ) = , (2.10)
1 + exp[(Ea,b − EFv,c )/kB T ]
where EFv,c is carrier dependent quasi-Fermi level, T is absolute temperature and kB is Boltz-
mann’s constant.

In case of transient measurements we are interested in the change in absorption coefficient

or change in reflectivity. The change in absorption (∆α) due to excitation of carriers due to
band filling is given by,
∆α(N, P, E) = α(N, P, E) − α0 (E). (2.11)

Considering the contributions from heavy holes and light holes the above expression can be
written as,

Chh p Clh p
∆α(N, P, E) = E − Eg [fv (Eah )−fc (Ebh )−1]+ E − Eg [fv (Eal )−fc (Ebl )−1]. (2.12)
E E

This expression can be used for the estimation of band filling effect for any direct gap semicon-
ductor.

17
 Figure 2.3: Schematic diagram showing the process of band-gap shrinkage.

2.2 Band gap Shrinkage Process

When carriers are excited in a semiconductor and reaches a thermalized state, the bottom of
the conduction band will be occupied by the electrons. If the concentration of electrons is very
high, the wave functions of these electrons will overlap. Due to coulomb force, electrons will
repel each other and the same spin electrons will avoid one another due to Pauli’s exclusion
principle. This will result in lowering of the energy of conduction band edge by forming tails of
density of states at the band edge. Due to a similar effect for the holes there will be a increase
in energy of valence band edge. The shift in conduction band energy and increase in the valence
band energy will lead to reduction of the band gap[11, 3, 12]. This effect is called band-gap
shrinkage (Fig.2.3.). Band gap shrinkage is a result of the mutual exchange and coulombic
interaction between the carriers excited.

The overall shrinkage in the band gap is related to the density of excited carriers. For a
case where the inter charge distance is small or comparable to the Bohr radius of electron or

18
hole an expression for the band gap shrinkage is given by [11, 13],
   1/3
e 3
∆Eg = − N 1/3 (2.13)
2π0 s π

where N is the concentration of electrons or holes in their corresponding excited states. For
lower concentrations the expression for band gap shrinkage can be written as[11],
 1/3
Csh N
∆Eg (N ) = 1− N ≥ Nc (2.14)
s Nc
∆Eg (N ) = 0 N < Nc (2.15)

where Csh is a fitting parameter and Nc is critical free carrier concentration which is 1.4 times
Mott density of the material. The change in absorption, ∆α, due to band gap shrinkage is
given by,
C
∆α(N, E) = [(E − Eg − ∆Eg (N ))1/2 − (E − Eg )1/2 ]. (2.16)
E

2.3 Free Carrier Absorption Process

Figure 2.4: Schematic diagram showing the free carrier absorption process.

Beside the above mentioned two processes, the refractive index can also get changed due
to the absorption of a photon by the free carriers (electrons in conduction band and holes in

19
valence band). In this process a free carrier absorbs photon and go to the higher energy state
within the band and hence this process is also called as intraband absorption. An illustration
of the process of free carrier absorption is shown in the Fig.2.4. This process is proportional
to concentration of carriers and square of wavelength. According to Drude model, change in
refractive index for the case of free carriers can be written as[11],

e2 λ2
  
N P
∆n = − + (2.17)
8π 2 c2 0 n me mh

From above expression we see that ∆n is always negative and increases with increase in carrier
density and decrease with increase in photon energy.

20
Chapter 3

Estimation of change in optical

response due to excited carriers

In this chapter we present the results of our estimation of change in absorption and change
in refractive index for a direct band-gab semiconductor GaAs due to carrier excitation. Using
the reported values for properties of GaAs like, band gap, effective masses, and other number
densities we have estimated the change in absorption coefficient and change in refractive index
for various photon energies.

3.1 Contribution of band filling

For given density of electrons in conduction band, N , and holes in valence band, P , the new
Fermi levels EFc and EFv can be calculated using Nilsson approximation and are given by [8, 14],
 " r !#−1/4 
 
N N N N
EFc = ln + 64 + 0.05524 64 +  kB T (3.1)
Nc Nc Nc Nc
  " r !#−1/4  
 
P P P P
EFv = − ln + 64 + 0.05524 64 +  − Eg  kB T. (3.2)
Nv Nv Nv Nv

Here
 3/2
me,dh kB T
Nc,v = 2 , (3.3)
2π~2

21
Figure 3.1: The dependence of change in absorption coefficient with the photon energy for
GaAs due to band filling effect. The excitation density N is specified in units of cm−3 .

where me is the effective mass of electron and mdh is the density of states effective mass for
holes. The effect of band filling has been calculated using Eq.2.12 for a given carrier density.
Figure 3.1 shows the effect of band filling in changing the absorption coefficient of GaAs at
different excited carrier densities. Clearly for all the cases the absorption reduces and hence
the change in absorption is always negative. Further the change happens only at energies above
band gap. We find that just above the band gap the change in absorption for a given excitation
density is maximum and the over all change reduces at higher photon energies. As the density
of excited carriers increases one can see that the maximum change in absorption also increases.
For a density of 1016 cm−3 the maximum change is about -2 × 10−2 cm−1 while for a excitation
density of 1018 cm−3 the maximum change is nearly -8 × 10−1 cm−1 .

For samples that does not transmit the beam, and for samples having substrate that blocks
the light the transient measurements can be performed by measuring the change in reflectivity
of the sample. For the estimation of change in refractive index we use the Kramers-Kronig
relation (Eq. 1.15). Using this relation we can calculate the relation between ∆α and ∆n and

22
Figure 3.2: (a)The dependence of change in refractive index with the photon energy for GaAs
due to band filling effect and (b) the variation of maximum change in refractive index due to
band filling effect for different excitation densities. The excitation density N is specified in
units of cm−3 .

is given by,
Z ∞ 0
2c~ ∆α(N, P, E ) 0
∆n = 2 dE . (3.4)
e 0 E 02 − E 2

In Fig.3.2(a) we show the change in the refractive index of GaAs for the excitation densities
same as that calculated for change in absorption coefficients. Unlike the change in absorption
the refractive index below the band gap also changes. For all the excitation densities the
change in refactive index (∆n) is negative below band gap and becomes positive just above
the band gap. The maximum ∆n happens to be nearby the band edge. As the photon energy
reduces the total change in refractive index also reduces. Similarly for photon energies much
above the band gap the ∆n also reduces. The maximum ∆n for a given excitation density is
negative. Figure 3.1 (b) shows the variation of maximum negative change in refractive index
for different excitation densities. The rate of increase of maximum variation of ∆n is more for
lower excitation densities and reduces as the excitation density increases.

23
Figure 3.3: The variation of change in absorption coefficient with respect to the input photon
energy for GaAs due to band gap shrinkage effect (N is in units of cm−3 .)

3.2 Contribution of band gap shrinkage

The contribution of band gap shrinkage to the ∆α has been calculated using Eq.2.16 when
excited at different carrier densities. Figure 3.3 shows the calculated results for ∆α of GaAs
due to this process. Unlike the band filling effect the band gap shinkage contributes to change
in absorption below the band gap also. This is due to the fact that the band gap reduces due
to band gap shrinkage process. Further ∆α is always found to be positive irrespective of the
probing wavelength. Just above the new band edge the ∆α starts increasing and reaches a
maximum just above the original band gap. For photon energies above the original band gap
the ∆α starts reducing with the increase in photon energy. As the density of excited carriers
increases the energy at which ∆α starts increasing also reduces. Further, the maximum change
in absorption also increases. During an absorption based transient experiment if measurement
is performed just below the band gap it will be easy to identify which of the process, band filling
or band gap shrinkage is playing the role in changing the optical properties of semiconductor.

24
Figure 3.4: (a) The variation of change in refractive index with respect to the input photon
energy for GaAs due to band gap shrinkage effect and (b) the variation of maximum change
in refractive index due to band gab shrinkage effect for different excitation densities. The
excitation density N is specified in units of cm−3 .

If there is no change in absorption below the original band means that band gap shrinkage is
not playing any role.

Once again using Kramers-Kronig relation we have estimated the change in refractive index
due to band gap shirnkage and is shown in Fig.3.4 (a). In this case the ∆n below the band gap
is positive and quickly changes it sign between the photon energies that corresponds to new
band gap and the old one. Above the original band gap the ∆n is negative and reduces with
increase in photon energies. Figure 3.3 (b) shows the variation of maximum change in refractive
index for different excitation densities. The rate of increase of the maximum variation of ∆n
with excitation density is this case also reduces with increase in excitation density.

3.3 Contribution of free carrier absorption

For the estimation the effect of free carrier absorption on the refractive index of GaAs for
different excitation densities we have used Eq.2.17. In Fig. 3.5(a) we show the photon energy
dependence of ∆n. Clearly one can see that there is no change in the behavior near the band
gap of the GaAs. This is due to the fact that free carrier absorption is happening inside the
conduction band and has no dependence on the band gap. This behavior is similar to that of

25
bulk metal. The effect of free carrier absorption on ∆n is always negative. As photon energy
increases the magnitude of ∆n reduces. Figure. 3.5(b) shows the variation of ∆n at band gap
energy of GaAs, 1.42 eV, for various excitation densities. In the present case the ∆n changes
linearly with number of excited carriers.

Figure 3.5: (a)The dependence of change in refractive index on photon energy due to free
carrier absorption in GaAs and (b) the variation of change in refractive index due to free
carrier absorption at 1.42 eV for different excitation densities (N is in units of cm−3 ).

3.4 Estimation of the total change in the optical re-

sponse

In reality when carriers are excited in a semiconductor all the above mentioned processes the
band-filling, band gap shrinkage and free carrier absorption will contribute to the total change
in absorption or reflectivity of the sample. For simplicity, all these processes are assumed to
be independent of each other. Hence the total change in the optical response of the material
can be calculated by summing the contribution of all the individual processes. Figure.3.6 (a)
shows the total combined effect for the change in absorption coefficient for GaAs for an excited
carrier density of 2 × 1017 cm−3 . The individual contributions were also shown in the same
graph. The change in absorption ∆α is zero for photon energies below the new band gap
which is decided by the band gap shrinkage process. However just at the original band gap

26
energy the contribution from band filling starts reducing the overall change in absorption and
at higher photon energies it finally becomes negative. At even higher photon energies since
the contribution from band filling effect reduces once again the effect of band gap shrinkage
takes over and the ∆α becomes positive. Further the contribution by free carrier absorption is
negligible for this excitation density and the ∆α is dominated by band filling effect and band
gap shrinkage process only. Using Kramers-Kronig relation, total change in refractive index
that corresponds to the above mentioned density is also calculated and plotted in Fig. 3.7 (a).
Unlike the case of ∆α, the free carrier absorption also contributes to the ∆n. However still its
contribution to the overall ∆n is lower compared to that of the other two processes. Figure 3.7
(b) shows the variation of maximum change in refractive index on the negative side for different
excitation densities which is linear with respect to excitation density.

Figure 3.6: The variation of change in absorption with respect to the input photon energy for
GaAs due to all the three processes band filling band gap shrinkage and free carrier absorption
processes. The excitation density N is specified in units of cm−3 .

27
Figure 3.7: (a) Same as that of Fig.3.6 but for change in refractive index and (b) the variation
of maximum change in refractive index on the negative side due to the total combined effect
for different excitation densities. The excitation density N is specified in units of cm−3 .

28
Chapter 4

Summary

In ultrafast pump-probe techniques using a strong pump pulse carriers are excited in the semi-
conductor sample. The optical properties of the excited material will be different from that
of the original due to band filling, band gap shrinkage or free carrier absorption. The change
caused by the pump pulse is then monitored by using a weak probe pulse of any photon energy.
A broad white light spectrum can also be used for measuring the total change in the properties
of the sample.

In this reading course the origin of various changes that causes change in optical response
of an excited semiconductor are studied. Programs were written in Python language to calcu-
late individual contribution due to the band filling effect, band gap shrinkage or free carrier
absorption. The change in the absorption of the semiconductor is calculated at first and using
Kramer-Kronig relation the change in the refractive index was also estimated. We find that the
contribution from these processes are different at different excitation densities. Among these
three processes the effect of band-filling was found to be strong even at low excited carrier
densities.

At low excitation densities, the change in absorption or change in refractive index was
found to be linear with the excitation density for a given probe wavelength. This is due to the
fact that at low excitation densities only band-filling contributes to the change in the optical
response. However as the excitation density increases the band gap shrinkage starts playing
a role and they have the opposite effect. The linear relation between excitation density and
change in the absorption or change in refractive index is no longer valid. Such nonlinear relation
between the carrier density and change in the optical properties can make carrier dynamics
studies complicated. Consider a simple case where photoluminescence life time is measured

29
by transient measurements. If the change in optical properties is directly proportional to the
number of excited carriers then just by fitting the exponential decay function to the measured
change in the optical properties one can obtain the life times. In a similar way all the changes
in the optical response can be directly correlated to the carrier density. The calculated optical
response of the semiconductor and its relation to the excited carrier density will be directly
useful for understanding the carrier dynamics in semiconductor materials and its quantum
structures.

30
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