ISSN 0030400X, Optics and Spectroscopy, 2011, Vol. 111, No. 5, pp. 798–807. © Pleiades Publishing, Ltd., 2011.

Original Russian Text © M.Yu. Leonov, A.V. Baranov, A.V. Fedorov, 2011, published in Optika i Spektroskopiya, 2011, Vol. 111, No. 5, pp. 837–846.

CONDENSEDMATTER
SPECTROSCOPY

Transient Intraband Light Absorption by Quantum Dots:

Pump–Probe Spectroscopy
M. Yu. Leonov, A. V. Baranov, and A. V. Fedorov
St. Petersburg University of Information Technologies, Mechanics, and Optics, St. Petersburg, 197101 Russia
email: a_v_fedorov@inbox.ru
Received March 1, 2011

Abstract—We have developed a theory of a transient intraband light absorption by semiconductor quantum
dots. This absorption plays an important role in the twopulse pump–probe method, which enables deter
mining the energy relaxation rates of electron–hole excited states. We have considered all possible schemes
of this process wherein the carrier frequency of optical pump pulses is close to the resonance with the inter
band transition of the quantumdot electronic subsystem, while the carrier frequency of probe pulses is res
onant to the intraband transition. For ensembles of identical and sizedistributed quantum dots, the probe
pulse energy absorption induced by the pump pulse is analyzed in relation to the delay time between the
pulses. We have found that, under certain conditions, this dependence can be described by a single, two, or
three exponentials. The exponents of the exponentials are proportional to the energy relaxation rates of elec
tron–hole excited states.
DOI: 10.1134/S0030400X11120174

INTRODUCTION Previous studies [4, 5] of the energy relaxation of

The study of the energy and phase relaxation pro
cesses of the states of the electron subsystem in semi
conductor quantum dots is one of the most important
problems of the physics of lowdimensional systems.
In quasizerodimensional systems, these processes
are considerably modified compared to bulk ones,
since the threedimensional spatial confinement radi
cally changes the energy spectrum of quantum dots, as
well as various interactions of their elementary excita
tions with each other and with external fields [1].
From the applied point of view, the importance of
studying the relaxation is determined by the fact that
relaxation processes play a key role in operation of var
ious electronic and optoelectronic devices based on
quantum dots (see, e.g., [2]).
The energy and phase relaxation of quantum dots
have been studied in numerous papers; however, the
data available at present are rather contradictory. Dif
ficulties arise because there still is no generally
accepted understanding of which mechanisms domi
nate in determining relaxation processes that occur
upon excitation of states of quantum dots [3]. In addi
tion, the theoretical description of optical investiga
tion methods of the population kinetics of these states
in quantum dots remains insufficiently developed.
Therefore, additional systematic investigations of
relaxation processes themselves and development of
methods, including optical ones, that will be capable
of obtaining reliable information on the dynamics of
transitions in quantum dots are required.
the electronic subsystem of quantum dots considered
processes involving acoustic phonons. It was predicted
that the relaxation rate slows down with decreasing
quantum dot size. However, available experimental
observations of a fast picosecond and even femtosec
ond intraband relaxation in colloidal quantum dots
[6–8] contradict this prediction. At the same time,
data are known on a slow intraband relaxation from
tens of picoseconds [9] to nanoseconds [10] that were
obtained for similar quantum dots and that confirm
this prediction. These results show that the rate of the
intraband relaxation in quantum dots can vary over a
wide range from 108 to 1013 s–1. Data available at
present evidence that the relaxation rates depend on
the growing technique and material of quantum dots
and their size and shape, as well as on the properties of
a matrix in which they are contained.
Let us briefly discuss some energy relaxation mech
anisms that are characteristic of semiconductor quan
tum dots. While, in bulk semiconductors, the fastest
energy relaxation mechanism of the electronic sub
system is determined by its interaction with optical
phonons [11], in quantum dots, this mechanism may
be not too efficient because of a weak “dispersion” of
optical phonons compared to acoustic ones. Due to
the spatial confinement of the energy spectrum, the
transition between a pair of levels Ei and E f of the
electronic subsystem that involves the participation of
an optical phonon can occur only for a quantum dot of
a certain size at which the energy gap between the lev
els E if is close to the phonon energy  Ω . This restric

798
 TRANSIENT INTRABAND LIGHT ABSORPTION
tion can be weakened in the case of a twophoton
relaxation mechanism, in which optical and acoustic
phonons participate [12]. At the same time, it is clear
that the twophoton process is less efficient than the
onephoton one. To explain the experimentally
observed fast energy relaxation, further studies of
relaxation processes involving optical phonons were
undertaken. It was shown that taking into account the
coherent interaction of optical phonons with the elec
tronic subsystem of a quantum dot [13, 14], as well as
taking into account the finiteness of their lifetime [15,
16], makes it possible to obtain a rather high relaxation
rate at detunings from the resonance δ = E if −  Ω as
large as a few tens of millielectronvolts.
Other efficient energy relaxation mechanisms of
the electronic subsystem of quantum dots with partic
ipation of plasmon and plasmon–phonon modes [17–
22], as well as optical phonons [23, 24] localized in
regions located at distances of several tens of nanome
ters from quantum dots, have been proposed apart
from the mechanisms listed above.
It is important to bear in mind that, for smallsize
quantum dots, the energy gap E if can reach hundreds
of millielectronvolts. In this case, processes that
involve the participation of one or two phonons can
not explain the experimentally observed relaxation
rates. To interpret these data, relaxation mechanisms
were proposed that are determined by the interaction
with surface defects of quantum dots [9, 25, 26]; by
multiphoton transitions [27], which are characteristic
of deep impurity centers in bulk crystals [28], as well as
by Auger processes [29] and nonradiative energy
transfer processes [30–32].
Among optical methods of study of energy relax
ation rates of excited states of quantum dots, the
pump–probe pulse method is one of the most promis
ing techniques [33–39]. In terms of this method, sev
eral different schemes can be implemented, which
make it possible to study not only the total energy
relaxation rate (the lifetime) of a particular state of the
electronic subsystem of a quantum dot [40, 41], but
also individual rates of the intraband relaxation of
electrons and holes [42, 43]. In the pump–probe
method, both the twopulse [33] and the threepulse
[43] techniques for measuring the kinetics of absorp
tion [39, 42] and reflection [34, 44] of the probe pulse
are used. It should be noted that, in this method, visi
ble [42], infrared [43], and even terahertz [45] electro
magnetic radiation can be used.
In this work, we develop a theory of the twopulse
pump–probe method for the case in which the carrier
frequency of the pump pulse is close to the resonance
with the interband transition of the quantumdot elec
tronic subsystem, while the carrier frequency of the
probe pulse is resonant to the intraband transition. All
possible schemes of the transient intraband absorption
of the probe pulse induced by the pump radiation are
considered. Based on the reduced density matrix for
OPTICS AND SPECTROSCOPY Vol. 111 No. 5 2011
799
malism [40, 41, 46], the absorption of the probe pulse
energy was calculated for the strong confinement
regime [1] of the electronic subsystem of spherical and
cubic quantum dots. For ensembles of identical and
sizedistributed quantum dots, the dependence of the
probepulse energy absorption on the delay time
between the pulses was analyzed. It was found that,
under certain conditions, this dependence can be
described by a single, two, or three exponentials, with
the exponents of the exponentials being proportional
to the energy relaxation rates of electron–hole excited
states.
INTRABAND ABSORPTION OF A PROBE
PULSE INDUCED BY A PUMP PULSE
Consider a twopulse excitation of a sample with
semiconductor quantum dots. The electromagnetic
fields of the pulses will be described in the classical
approximation (the assumed field approximation),
while their interaction with the quantumdot elec
tronic subsystem will be considered semiclassically.
The electron–hole representation will be chosen for
the electronic subsystem. In this case, the Hamilto
nian of the system quantum dot–pump (pu) and probe
(pr) pulses can be represented as
H = H 0 + H pu + H pr , (1)
where
H0 = ∑ ω n n n (2)
n
is the Hamiltonian of noninteracting electron–hole
pairs in a quantum dot expressed via their eigenvectors
n and eigenenergies  ω n;
∑ (φ )
(pu) −iωput
H pu = pu (t )V n,0 e n 0 + H.c. , (3)
n
H pr = ∑ (φ (pr) −iωprt
pr (t )V n1,n2 e )
n1 n2 + H.c. (4)
n1,n2
are the interaction operators of the pump and probe
pulses with the electronic subsystem of the quantum
dot, which describe the generation of electron–hole
pairs and intraband transitions, respectively; 0 is the
vacuum state of electron–hole pairs; V n(,η0) =
n (−e r)e η 0 , Vn(1η,n)2 = n1 (−e r)e η n2 , er is the dipole
η
moment operator; e is the polarization vector of the
electromagnetic field; ϕ η(t ) timedependent complex
amplitude of the pulse with the carrier frequency ωη ;
and η = pu, pr .
To describe the evolution of states of the quantum
dot under the action of pump and probe pulses, we will
use the formalism of the reduced density matrix [40,
800 LEONOV et al.

|j〉 is the rate of intraband transitions induced by the

ωpr
|i〉
ωpu γii
|0〉
Fig. 1. Cascade scheme of interband–intraband optical
transitions: 0 , i , and j are the ground and excited
states of electron–hole pairs of a quantum dot; ωpu and
ωpr are the carrier frequencies of pump and probe pulses;
and γ ii is the population relaxation rate of the state i .
41, 46], the matrix elements of which have the follow
ing form:
1
i
∑
ρ nm(t) = [ H ,ρ(t)]nm + δ nm θ nkρ kk (t) − γ nmρ nm(t ), (5)
k ≠n
where δ nm is the Kronecker symbol, θnk is the transi
tion rate from the state k to the state n , γ nn is the pop
ulation relaxation rate (the inverse lifetime) of the
state n , γ nm = γ mn = (γ nn + γ mm )/2 + ˆγ nm at m ≠ n is the
rate of the complete dephasing rate of the transition
n ↔ m, and ˆγ nm is the pure dephasing rate of the tran
sition n ↔ m.
In what follows, for simplicity, we will assume that
the pump and probe pulses are defined by the follow
ing expressions:
−σ pu |t | −σ pr |t −τ|
φ pu(t) = E pue , φ pr (t) = E pre
where E pu , σ pu , E pr , and σ pr are the amplitudes, elec
tric field strengths, and spectral widths of the pulses,
respectively, and τ is the delay time between the pulses.
Using (5) and (6), we can calculate the energy
E (τ) of the probe pulse that is absorbed by quantum
( pr )
dots upon the intraband transition m → n (the transi
tion frequency ωn − ωm is close to the resonance with
the frequency ω pr ) and that is defined by the following
expression:
∞ ⎜
E (pr)(τ) = ωpr NK ∫ (t),
(pr)
dtWnm
action of the probe pulse, N is the number of quantum
dots excited by the pump and probe pulses, and K is
the degeneracy multiplicity with respect to the fre
quency of the transition m → n .
Prior to analyzing particular schemes of the intra
band light absorption, we will make several general
points about the initial state of the system under study
and the method of calculation. Assume that, in the ini
tial state, there are no electron–hole pairs in quantum
dots. They arise only under the action of the pump
pulse. We will assume that pulse energies are so small
that we can apply the perturbation theory to describe
optical transitions with expression (5). Since quantum
dots are excited resonantly, from the total set of states
in Hamiltonian (1), we can retain only several signifi
cant states. Let the spectral widths σ pu and σ pr of the
pulses meet the following conditions: σ pu , σ pr Ⰷ γ nm,
and θnm and σ pu τ , σ pr τ Ⰷ 1. The first of these condi
tions can be easily implemented in lowtemperature
experiments. The second condition makes it possible
to radically simplify expressions for the absorbed
energy and means that the experimental data and the
oretical results obtained in this work should be ana
lyzed and compared at delay times τ not too close to
zero. Details and particular features of calculations of
quantities that are similar to the energy absorbed upon
intraband transitions are presented in [40, 41].
Scheme of Light Absorption upon Cascade
Interband–Intraband Transitions
Consider the simplest (cascade) scheme of the
energy absorption of the probe pulse (Fig. 1) by a
quantum dot. In this case, the pump pulse at the car
rier frequency ω pu resonantly excites a certain state i
of electron–hole pairs, the population of which, due
to the interaction with the thermostat relaxes to the
, (6) ground state 0 with the rate γ ii . The probe pulse at the
carrier frequency ω pr that is resonant with the transi
tion frequency between the states i and j transfers
the electron–hole pair to the state j . As a result, the
energy of the probe pulse is absorbed. Clearly, this pro
cess is described in terms of the threelevel model of
the quantum dot, the Hamiltonian of which has the
form
⎛ iω t ⎞
⎜ 0 φ*pu(t)Vi,(0pu)*e pu 0 ⎟
⎜ ⎟
⎜ (pu) −iωput ω ⎟
H= ⎜ φ pu(t )Vi,0 e ωi φ*pr(t)V j(,pri )*e pr ⎟ .
i t
⎟
⎜ (pr) −iωprt ⎟
φ pr (t)V j,i e ω j
⎜ 0 ⎟
(7) ⎝ ⎠

−∞ (8)
where Solving system of equations (5) for the basis 0 , i ,
and j by the method described in [40, 41], we obtain
= −i
−iω t
(pr)
Wnm (t ) φ pr (t )Vn(,prm )e pr ρ mn(t ) + c.c.
 the following expression for the absorbed energy of the

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 TRANSIENT INTRABAND LIGHT ABSORPTION 801

probe pulse upon cascade interband–intraband tran |j〉

sitions:
θij ωpr
(pr)
E cas (τ)
2 2 |i〉
(pu) (pr)⎛ 2σ pu ⎞ ⎛ 2σ pr ⎞ −γ iiτ (9)
=  ωpr NKAcas Acas ⎜ 2 ⎟ ⎜ 2 2 ⎟
e ,
⎝ σ pu + Δ pu ⎠ ⎝ σ pr + Δ pr ⎠
2

ωpu γ (0)
jj
γii
where

(pr) 2 2 (pu) 2 2
V j,i E pr Vi,0 E pu
= , = ,
(pr) (pu)
Acas Acas (10) |0〉
 
2 2

Δ pr = ω j − ωi − ωpr , Δ pu = ωi − ωpu. Fig. 2. Scheme of adjacent interband–intraband optical

transitions: 0 , i , and j are the ground and excited
Therefore, for the cascade scheme, the dependence of states of electron–hole pairs of a quantum dot; ωpu and
(pr)
E cas (τ) on the delay time between the pulses is ωpr are the carrier frequencies of pump and probe pulses;
described by a single exponential, the exponent of γ ii is the population relaxation rate of the state i ; and θij
which is proportional to the relaxation rate γ ii of the (0)
and γ jj are the transition rates from the state j to the
population of the state i . states i and 0 , respectively.

Scheme of Light Absorption upon Adjacent Interband– absorbed energy of the probe pulse in the case of adja
Intraband Transitions cent interband–intraband transitions:
Here, we will consider the scheme of the energy (pr)
E adj (τ)
absorption of the probe pulse (Fig. 2) by a quantum
2 2
(pu) (pr)⎛ ⎞ ⎛ 2σ pr ⎞
2σ pu
dot during adjacent interband–intraband transitions.
In this case, the pump pulse at a carrier frequency ω pu = ωpr NKAadj Aadj ⎜ 2 ⎟ ⎜ 2 2 ⎟
(12)
⎝ σ pu + Δ pu ⎠ ⎝ σ pr + Δ pr ⎠
2
resonantly excites a certain state j of electron–hole
pairs. The population of this state relaxes either to the ⎡⎛ θij ⎞ −γ τ θij ⎤
× ⎢⎜ − 1⎟ e jj − e −γ iiτ ⎥ ,
ground state 0 at a rate γ (0) jj or to a state i at a rate θ ij , ⎣⎝ γ ii − γ jj ⎠ γ ii − γ jj ⎦
the population of which, in turn, relaxes to the ground where
state at a rate γ ii . It is clear that the total relaxation rate
(pr) 2 (pu) 2
of the population of the jth state is γ jj = γ (0) jj + θij . The V j,i E pr
2
V j ,0 E pu
2

= , = ,
(pr) (pu)
carrier frequency ωpr of the probe pulse is resonant Aadj Aadj (13)
 
2 2
with the transition frequency between the states i and
Δ pr = ω j − ωi − ωpr , Δ pu = ω j − ωpu.
j . Therefore, the jth state is the common final state
for the pump and probe pulses. In this process, the It can be seen from these expressions that, unlike cas
probe pulse energy is absorbed as a result of the fact cade interband–intraband transitions, the depen
that light with the frequency ω pr transfers electron– (pr)
dence E adj (τ) on the delay time between the pulses is
hole pairs from the state i (to which they relaxed from described by two exponentials, the exponents of which
the state j backward to the state j . This process is are proportional to the relaxation rates γ ii and γ jj of
described in terms of the threelevel model of the the states i and j , respectively.
quantum dot, the Hamiltonian of which has the form
⎛ iω t ⎞ Scheme of Light Absorption
φ*pu(t )Vi,0 * e pu ⎟
(pu)
⎜ 0 0
⎜ ⎟ upon Cross Interband–Intraband Transitions
⎜
H = ⎜ 0  ωi φ*pr(t )V j(,pri )*eiωprt ⎟⎟ .
⎜ ⎟ Here, we will consider the scheme of the energy
⎜ φ (t )V (pu)e −iω put φpr(t )V j(,pri )e −iωprt ω j ⎟ absorption of the probe pulse (Fig. 3) by a quantum
⎜ pu i, 0 ⎟
⎝ ⎠
dot upon cross interband–intraband transitions. In
(11)
this case, the pump pulse at a carrier frequency ω pu
Using the method of solution of system (5) described resonantly excites a certain state j of electron–hole
in [40, 41], we obtain the following expression for the pairs. The population of this state relaxes either to the

OPTICS AND SPECTROSCOPY Vol. 111 No. 5 2011

802 LEONOV et al.

ground state 0 at a rate γ (0) coupled by the electron–photon interaction with both
jj or to a state i at a rate θ ij ,
the population of which, in turn, relaxes to the ground pulses at a time. In this case, we are dealing with the
fourlevel model of the quantum dot, two levels of
state at a rate γ ii . The total relaxation rate of the pop
which ( 0 and j ) participate in transitions excited by
ulation of the jth state is γ jj = γ (0)
jj + θij . The carrier fre the pump pulse, while transitions between the other
quency ω pr of the probe pulse is resonant with a tran two levels ( i and k ) are caused by the probe pulse.
sition frequency between the states i and k , and the The pairs of these levels are coupled with each other by
energy of the former (ith) state is lower than that of the relaxation processes. The Hamiltonian of this four
state j . In this scheme, there are no states that are level model of the quantum dot has the form

⎛ (pu) iω t ⎞
⎜ 0 0 φ*pu(t)V j,0 *e pu 0 ⎟
⎜ ⎟
⎜ (pr) iω t ⎟
⎜ 0 ωi 0 φ*pr (t)Vk,i *e pr ⎟
H = ⎜ ⎟. (14)
⎜ φ (t )V pu)e −iωput
(
0 ω j 0 ⎟
⎜ pu j ,0 ⎟
⎜ ⎟
−iωprt
⎜
⎝ 0 φ pr (t)Vk(,pri )e 0 ωk ⎟
⎠

Using the method of solution of system (5) for the It can be seen from (15) that, as in the case of adjacent
density matrix that was developed in [40, 41], we interband–intraband transitions, the dependence
obtain the following expression for the absorbed (pr)
E cro (τ) on the delay time between the pulses is
energy of the probe pulse in the case of cross inter described by two exponentials, the exponents of which
band–intraband transitions:
are proportional to the population relaxation rates γ ii
(pr)
E cro (τ) = ωpr NKAcro
(pu) (pr)
Acro and γ jj of the states i and j , respectively.
2 2
⎛ 2σ pu ⎞ ⎛ 2σ pr ⎞ θij −γ jj τ −γ ii τ
(15)
×⎜ 2 ⎟ ⎜ ⎟ (e − e ),
⎝ σ pu + Δ pu ⎠ ⎝ σ pr + Δ pr ⎠ γ ii − γ jj
2 2 2
Scheme of Light Absorption upon Enclosed
where Interband–Intraband Transitions
(pr) 2 2 (pu) 2 2
Consider the scheme of the energy absorption of
Vk,i E pr V j ,0 E pu
= , = ,
(pr) (pu)
Acro Acro (16) the probe pulse (Fig. 4) by a quantum dot upon
 
2 2
enclosed interband–intraband transitions. In this
Δ pr = ωk − ωi − ωpr , Δ pu = ω j − ωpu. case, the pump pulse at a carrier frequency ω pu reso

|k〉 |k〉

θjk
|j〉 |j〉
ωpu θij ωpr ωpu θik θij ωpr

|i〉 |i〉
γ (0)
jj
γii γ (0) γ (0) γii
kk jj

|0〉 |0〉

Fig. 3. Scheme of cross interband–intraband optical tran
sitions: 0 , i , j , and k are the ground and excited
states of electron–hole pairs of a quantum dot; ωpu and
ωpr are the carrier frequencies of pump and probe pulses;
γ ii is the population relaxation rate of the state i ; and θij
(0)
and γ jj are the transition rates from the state j to the
states i and 0 , respectively.
Fig. 4. Scheme of enclosed interband–intraband optical
transitions: 0 , i , j , and k are the ground and excited
states of electron–hole pairs of a quantum dot; ωpu and
ωpr are the carrier frequencies of pump and probe pulses;
γ ii is the population relaxation rate of the state i ; and θij ,
(0) (0)
θik , θ jk , γ kk , and γ jj are the transition rates between cor
responding states.

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 TRANSIENT INTRABAND LIGHT ABSORPTION 803

nantly excites a certain state k of electron–hole quency between the states i and j , the energies of
pairs. The population of this state relaxes either to the which are lower than the energy of the state k .
ground state |0〉 at a rate γ (0)
kk or to states i and j at
In this scheme, as well as in the preceding one,
there are no states that are simultaneously coupled by
with rates θ ik and θ jk , the populations of which, in the electron–photon interaction with the two pulses.
turn, relax to lower lying energy states with rates γ ii , We are dealing with the fourlevel model of the quan
jj , and θ ij .
γ (0) tum dot, two levels of which ( 0 and k ) participate in
transitions excited by the pump pulse, while transi
The total relaxation rates of the populations of the tions between the other two levels ( i and j ) are
kth and jth states are γ kk = γ (0)
kk + θ ik + θ jk and
caused by the probe pulse. The pairs of these levels are
coupled with each other by relaxation processes. The
jj + θij , respectively. The carrier frequency ω pr
γ jj = a (0) Hamiltonian of this fourlevel model of the quantum
of the probe pulse is resonant with the transition fre dot has the form

⎛ )* iωput ⎞
⎜ 0 0 0 φ*pu(t)Vk(,pu
0 e ⎟
⎜ ⎟
⎜ ⎟
⎜ 0 ωi φ*pr(t)V j(,pri )*eiωprt 0 ⎟
H = ⎜
⎜ −iωprt
⎟.
⎟
(17)
⎜ 0 φ pr (t)V j(,pr
i e
)
ω j 0 ⎟
⎜ ⎟
⎜ (pu) −iωput ⎟
⎜ φ (t )V  ωk ⎟
⎝ pu k ,0 e 0 0 ⎠

Applying the same approach as was used to derive ENERGY ABSORPTION OF THE PROBE
expressions (9), (12), and (15), we obtain the following PULSE IN THE STRONG CONFINEMENT
expression for the absorbed energy of the probe pulse REGIME
in the case of enclosed interband–intraband transi It should be noted that expressions (9), (12), (15),
tions: and (18) describe the absorption of the probe pulse by
an ensemble of identical semiconductor quantum
(pr)
Eenc (τ) = ωpr NKAenc
(pu) (pr)
Aenc dots. For an ensemble of quantum dots of different
2 2
sizes, it is necessary to additionally analyze expres
⎛ 2σ ⎞ ⎛ 2σ ⎞ sions (9), (12), (15), and (18) using particular models
× ⎜ 2 pu 2 ⎟ ⎜ 2 pr 2 ⎟ of quantum dots.
⎝ σ pu + Δ pu ⎠ ⎝ σ pr + Δ pr ⎠ To describe the energy spectrum of quantum dots,
⎡⎛ θik θ jk ⎞ −γ kkτ (18) we will use a twoband model of the semiconductor
× ⎢⎜ − ⎟e [1], one of which is the conduction band (c) and the
⎣⎝ γ ii − γ kk γ jj − γ kk ⎠ other is the valence band (v ). Assume that the charac
θ jk −γ τ θik ⎤ teristic size of quantum dots that are embedded into a
+ e jj − e −γ iiτ ⎥ , dielectric maximum is considerably smaller than the
γ jj − γ kk γ ii − γ kk ⎦ exciton Bohr radius Rex of a bulk material from which
where they are prepared [47]. In this case, the electronic sub
system of dots can be considered to be in the strong
confinement regime and the motion of electrons and
(pr) 2 2 (pu) 2 2 holes is confined by infinitely high potential walls [1].
V j,i E pr Vk,0 E pu
= , = ,
(pr) (pu) In the case of spherical quantum dots with a radius
Aenc Aenc (19)
 
2 2
R, twoparticle states of electron–hole pairs are char
Δ pr = ω j − ωi − ωpr , Δ pu = ωk − ωpu. acterized by six quantum numbers
i = {nci, lci, mci, nvi, lvi, mvi }, the first three of which refer
to the electron of the conduction band, while the last
It follows from (18) that, in the case of enclosed inter three quantum numbers pertain to the hole of the
band–intraband transitions, the dependence E enc (pr)
(τ) valence band. The symbols nζ = 1, 2, 3, ..., l ζ = 0, 1, 2, ...,
on the delay time between the pulses is described by and mζ = −l, −l + 1, ..., l − 1, l (ζ = ci,v i ) denote the
three exponentials, the exponents of which are pro principal quantum number, the angular momentum,
portional to the population relaxation rates γ ii , γ jj , and its projection for electrons and holes. The energies
and γ kk of the states i , j , and k , respectively. ωi that correspond to these states, as well as the inter

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804 LEONOV et al.

band Vi,(0pu) and intraband V j(,pr )

i dipole moment matrix
where µ = µ cµv /(µ c + µv ) is the reduced effective mass
elements, are given by [48, 49] of electrons and holes. According to (22)–(25), the
intraband dipole moment matrix elements do not
depend on the band parameters and, therefore, the
 2ξ 2ncilci  2ξ 2nvilvi
ωi = E g + + , (20) band index λ in these expressions can be omitted.
2μ c R 2 2μv R 2
If a semiconductor quantum dot has a shape of a
cube with an edge length L, twoparticle states of elec
| Vi,(0pu)| = δ nci ,nvi δlci ,lvi δ mci ,mvi 2 eP , (21) tron–hole pairs are also described by six quantum
3 Eg numbers i = {nxci , nyci , nz ci , nxvi , nyvi , nzvi } (n = 1, 2, ... for
 = xζ, yζ, zζ and ζ = ci,v i ) and the energies ωi and
corresponding matrix elements Vi,(0pu) and V j(,pr )
(pr)
V j ,i =e ∑ (−1) e ν (pr)
ν nλj l λj mλj | x −ν | nλil λi mλi .
(22) by [48, 49]
i are given

ν=0,±1

(λ = c, v),  ωi = E g
 π (nxci + nyci + nz ci )  π (nxvi + nyvi + nzvi ) (27)
2 2 2 2 2 2 2 2 2 2
Here, E g is the band gap width; ξ nl is the nth zero of + + ,
the spherical Bessel function of the lth order 2μ c L2 2μv L2
( jl (ξ nl ) = 0), µ c and µv are the effective electron and
hole masses; δα,β is the Kronecker symbol; P is the
| Vi,0 | = δ nxci ,nxvi δ nyci ,nyvi δ nzci ,nzvi 2 eP ,
(pu)
(28)
Kane parameter [47]; and eν(pr) and xν are the covariant 3 Eg
cyclic coordinates of the polarization vector of the
probe pulse and of the radius vector of the charge car
rier, respectively, which, for an arbitrary vector b, are i | = e ex
| V j(,pr )
(
(pr)
nx j | x| nxi δ ny j ,nyi δ nz j ,nzi
expressed via its Cartesian coordinates by the follow + ey
(pr)
ny j | y| nyi δ nx j ,nxi δ nz j ,nzi (29)
ing relations: b+1 = −(bx + iby )/ 2 , b0 = bz , and
b−1 = (bx − iby )/ 2;
+ ez
(pr)
nz j | z| nzi δ ny j ,nyi δ nx j ,nxi ,)
where, for α = x, y, z and an odd sum of quantum
nλjlλj mλj | xν| nλilλi mλi
numbers nα j + nαi ,
4Rξnλjlλj ξnλilλi (23)
= χδ
2 ν mλj ,mλi +ν
,
⎛ 2 ⎞ 8Lnα j nαi (nα j +nαi +1)/ 2
⎜ ξ nλjlλj − ξ nλilλi ⎟
2
⎝ ⎠ nα j | α| nαi = (−1) . (30)
π − nαi )
2 2 2 2
(nα j
(l λi ± mλi + 1)(l λi ± mλi + 2)
χ ±1 = δlλj ,lλi +1 For an even sum of quantum numbers nα j + nαi , matrix
2(2l λi + 1)(2l λi + 3)
(24) element (30) is zero. As in the case of spherical quan
(l λi ∓ mλi − 1)(l λi ∓ mλi ) tum dots, the intraband dipole moment matrix ele
− δlλj ,lλi −1,
2(2l λi − 1)(2l λi + 1) ments do not depend on the band parameters; there
fore, the band indices c and v in expressions (29) and
(30) are omitted. It can be seen from (28) that the
(l λi + 1)2 − mλ2i pump pulse can excite electron–hole pairs for which
χ0 = δl ,l +1
(2l λi + 1)(2l λi + 3) λj λi the corresponding quantum numbers of the electron
(25) and hole coincide: nxci = nxvi = nxi , nyci = nyvi = nyi ,
l λi − mλi
2 2
+ δl ,l −1. nz ci = nzvi = nzi . The energies of these pairs are given by
(2l λi − 1)(2l λi + 1) λj λi
 2π2(nx2i + ny2i + nz2i )
It follows from (21) that, in the dipole approximation, ωi = E g + . (31)
pump pulses can excite only electron–hole pairs for 2μL2
which the corresponding electron and hole quantum
numbers coincide: nci = nvi = ni , l ci = lvi = li , It follows from (20), (23), (27), and (30) that the ener
mci = mvi = mi . The energies of these pairs are gies of the levels of electron–hole pairs and the intra
band dipole moment matrix elements depend on the
size of the quantum dot. Therefore, for an ensemble of
 2ξ 2nili dots the size distribution of which is described by the
E i = ωi = E g + , (26)
2μR 2 function F ( x) (where x = R or L for spherical or cubic

OPTICS AND SPECTROSCOPY Vol. 111 No. 5 2011

 TRANSIENT INTRABAND LIGHT ABSORPTION 805

quantum dots), the entire ensemble will contribute to

⎢⎛
⎡
θik (xωpu )
the absorption of the probe pulse energy E q(pr)(τ)
(pr)
E enc (τ) = Qenc(xωpu ) ⎢⎜⎜
⎢ γ (x ) − γ kk (xωpu )
⎣⎝ ii ωpu
(where q = cas, adj, cro, or enc). This circumstance
can be taken into account by averaging of expressions θ jk (xω pu ) ⎞ −γ kk (xωpu )τ
− ⎟e
(9), (12), (15), and (18) γ jj (xωpu ) − γ kk (xωpu )⎟⎠
(36)
∞ θ jk (xωpu ) −γ jj ( xωpu )τ
+ e
∫
E q (τ) = dxF (x)E q (τ). γ jj (xωpu ) − γ kk (xωpu )
(pr) (pr )
(32)
θik (xωpu ) −γ ii ( xωpu )τ ⎤
0
− e ⎥,
The explicit form of the distribution function γ ii (xωpu ) − γ kk (xωpu ) ⎦
depends on the technology of preparation of quantum
dots and, as a rule, is not known in advance. Generally, where
experimental data are analyzed using three types of 8πx ωpuβ q
3
distribution functions (Lifshitz–Slyozov function [50, Qq (x ωpu ) =  ωpr NKAq(pu) Aq(pr)(x ωpu ) F (x ωpu ). (37)
σ
3
51] and normal [52] and lognormal distributions [51]).
Irrespective of the distribution function used to calcu The size of quantum dots resonantly excited by pump
late expression (32), the possibility of representing it in pulses with the carrier frequency ω pu is given by
terms of simple exponential functions such as 1/ 2
Bi exp(−γ ii τ), Bi exp(−γ ii τ) + B j exp(−γ jj τ) , or ⎛ 2 ⎞
x ωpu =⎜ ⎟ , (38)
Bi exp(−γ ii τ) + B j exp(−γ jj τ) + B k exp(−γ kk τ) is deter ⎝ 2β q ( ωpu − E g )⎠
mined by the size dependence of the factors in the
integrand and, primarily, by the strong resonance that where, for spherical quantum dots, β cas = μ/ ξ 2nili ,
arises when Δ pu , Δ pr , or they both turn to zero. In this βadj = βcro = μ/ξ2n jl j , and β enc = μ/ ξ 2nkl k and, for cubic
case, if the pulse widths σ pu and σ pr are so small that, quantum dots, β cas = μ/[π 2 (n x2i + ny2i + nz2i )], βadj =
in the spectral range determined by these parameters βcro = μ/[π 2 (n x2 j + n y2 j + nz2 j )], and βenc =
and, accordingly, in the range of quantum dot sizes, μ/[π 2(nx2k + ny2k + nz2k )].
the variations in other factors in the integrand are
insignificant, the average of the absorbed probepulse It can be seen from (33)–(36) that, by varying the
energy takes the form of the simple exponential func carrier frequency ω pu of pump pulses such that reso
tions mentioned above. In particular, analysis of nantly excite quantum dots of a certain size x ω pu within
expression (32) shows that, if the spectral widths of the the contour F (x ω pu ) of their distribution, one can, in
pump and probe pulses coincide (σpu = σpr = σ) and principle, determine the size dependence of the
their carrier frequencies are resonant with the corre energy relaxation rates γ ii (x ωpu ), γ jj (x ωpu ) , γ kk (x ωpu ),
sponding transition frequencies of the quantum dot θij (x ωpu ) , θ ik (x ωpu ), and θ jk (x ωpu ) . At the same time, it is
electronic subsystem, (32) can be presented as obvious that, from the experimental point of view, the
greatest interest is attracted to schemes of transient
−γ ii ( xωpu )τ
(pr)
E cas (τ) = Qcas (x ωpu )e , (33) intraband light absorption such that give rise to a signal
with a simple dependence on the relaxation parame
ters of the system under study. In this respect, the
(pr)
E adj (τ) schemes of light absorption upon cascade (33) and
cross (35) interband–intraband transitions are the
⎢⎛ ⎞ −γ jj (xωpu )τ
⎡
θij (xωpu ) most attractive.
= Qadj(xωpu ) ⎢⎜⎜ − 1⎟⎟ e (34)
⎢ γ (x ) − γ jj (x ωpu ) ⎠
⎣⎝ ii ωpu
⎤
θij (x ωpu ) −γ ii ( xωpu )τ ⎥ CONCLUSIONS
− e ⎥,
γ ii (x ωpu ) − γ jj (x ωpu ) ⎥
⎦
The basic results of this work can be formulated as
follows. We developed the theoretical description of
the optical pump–probe method that makes it possi
(pr)
E cro (τ) (35) ble to determine the energy relaxation rates of excited
θij (x ωpu ) −γ jj ( xωpu )τ −γ ii ( xωpu )τ ⎞
states of electron–hole pairs in semiconductor quan
⎛
= Qcro(x ωpu ) ⎜⎜ e −e ⎟⎟ , tum dots. We considered the following four possible
γ ii (x ωpu ) − γ jj (x ωpu )⎝ ⎠
schemes of the intraband absorption of probe pulses

OPTICS AND SPECTROSCOPY Vol. 111 No. 5 2011

806 LEONOV et al.
that is induced by pump pulses: the absorption upon
cascade, adjacent, cross, and enclosed interband–
intraband transitions. For these schemes, we calcu
lated the absorbed energy of the probe pulse for an
ensemble of identical quantum dots and for an ensem
ble of sizedistributed dots. We showed that, under
certain conditions, the dependence of the absorbed
energy on the delay time between the pulses can be
described by either single, or two, or three exponen
tials, the exponents of which are proportional to the
energy relaxation rates of excited states of electron–
hole pairs.
ACKNOWLEDGMENTS
This work was supported by the Russian Founda
tion for Basic Research (projects nos. 090200333a
and 090201439a) and by the Ministry of Education
and Science of the Russian Federation (state contract
no. P2324, federal targeted program “Scientific and
Pedagogical Personnel of Innovative Russia” (2009–
2013)).
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