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Semiconductor core-shell quantum

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Pratima Sen

Journal of Applied Physics

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Semiconductor core-shell quantum dot: A low temperature nano-sensor
material
Saikat Chattopadhyay, Pratima Sen, Joseph Thomas Andrews, and Pranay Kumar Sen

Citation: J. Appl. Phys. 111, 034310 (2012); doi: 10.1063/1.3681309

View online: http://dx.doi.org/10.1063/1.3681309
View Table of Contents: http://jap.aip.org/resource/1/JAPIAU/v111/i3
Published by the American Institute of Physics.

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 JOURNAL OF APPLIED PHYSICS 111, 034310 (2012)

Semiconductor core-shell quantum dot: A low temperature nano-sensor

material
Saikat Chattopadhyay,1 Pratima Sen,1,a) Joseph Thomas Andrews,2
and Pranay Kumar Sen2
1
Laser Bhawan, School of Physics, Devi Ahilya University, Indore-452 017, India
2
Department of Applied Physics, Shri G. S. Institute of Technology and Science, Indore-452003, India
(Received 2 August 2011; accepted 7 January 2012; published online 9 February 2012)
This paper presents an analytical study of temperature dependent photoluminescence (PL) in core-
shell quantum dots (CSQDs) made of most frequently used II-VI semiconducting materials. The
analysis incorporates the temperature dependent radiative recombination processes in the calculation
of the integrated PL intensity. The PL intensity has been derived using semiclassical density matrix
formalism for the CSQDs exhibiting excitonic and biexcitonic features. The numerical estimates
show that the PL intensity response and PL peak shifts are non-trivial at low temperature in such
CSQDs and can be useful in the design of a temperature sensor. V C 2012 American Institute of

Physics. [doi:10.1063/1.3681309]

I. INTRODUCTION was studied by Peng et al.5 using alkoxysilanized dye as a

reference and found the ratiometric fluorescence of the nano-
Temperature is a significant fundamental thermodynami-
particles as extremely temperature sensitive near room temper-
cal property of matter and is required to be measured and con-
ature and can be suitably exploited in development of
trolled in scientific experiments as well as for industrial
temperature nano-sensors in cellular sensing, and imaging.
purpose. Luminescence thermometry is a versatile non-contact
Very recently, a number of workers6–8 have proposed that the
optical technique for the measurement of temperature and can
nanoparticles or semiconductor QDs could be used in lumines-
overcome many of the problems and limitations of the conven-
cence thermometry to develop temperature sensors for various
tional temperature measurement methods. The luminescence
applications including medical and industrial purposes depend-
temperature measurement technique exploits the temperature
ing on their steady state photoluminescence properties.
dependent changes in the luminescence properties such as the
The luminescence properties of a bare semiconductor QD
decay lifetime of the fluorescence, the excitation spectra, and
can be modified by using appropriate shell of an organic or
the wavelength or the energy of the fluorescence. Different
inorganic material on it. In general, deposition of shell causes
luminescent materials and compounds are used as optical tem-
red-shift in PL peak and improve the PL quantum efficiency
perature probes including organic dyes, inorganic phosphors,
due to the proper passivation of surface dangling bonds and
and luminescent coordination complexes. Conventional phos-
nonradiative recombination sites with strong confinement of
phors with micron size grains are likely to be replaced by nano-
electrons and holes inside the core.9 In our opinion, the ther-
phosphors that are envisaged as potential candidate materials
mal response of the core and shell material together will
with much less scattering in accordance with Rayleigh’s crite-
decide the temperature sensitivity of the core-shell quantum
rion. Moreover, such nanophosphors enhance emitted light
dot (CSQD). The basic requirements needed to determine the
such that the detection becomes much easier and the nanopar-
PL intensity are (i) the excitation mechanism that can generate
ticles have better quantum efficiency due to its confinement
population in various excited states of the system and (ii) radi-
effect. Therefore, it is possible to design and fabricate more
ative as well as nonradiative recombination processes that can
sensitive temperature sensors using nanoparticles.1–4
yield the PL intensity. Furthermore, from device making point
The concept of nanoparticle luminescent thermometry
of view, it is necessary to examine the temperature sensitivity
using semiconductor quantum dots (QDs) for a wide range of
of PL intensity in different materials. In view of this discus-
applications in low temperature environments is well known.
sion, we have theoretically investigated the effect of tempera-
Walker et al.2 reported the steady-state photoluminescence
ture on the PL intensity of different CSQDs by taking into
(PL) properties of CdSe quantum dots (QDs) for the tempera-
account the temperature dependence of energy levels, dephas-
ture range from 100 to 315 K. Depending on PL peak shift,
ing mechanisms, and exciton-phonon interaction.
they have proposed that the CdSe QDs may be used as tempera-
ture indicators for temperature-sensitive coatings. Wang et al.1
II. THEORETICAL FORMULATIONS
analyzed the temperature response of several pure and doped
semiconductor nanoparticles for the temperature ranging from The temperature dependence of PL can be used to deter-
room temperature to 423 K and found a linear response above mine the information about energy level structure in semi-
the room temperature, which can be conveniently applied for conductors. In CSQDs, discrete exciton and biexciton energy
temperature sensing. Ratiometric fluorescence of nanoparticles states exist. The energies of these states depend on the quan-
tum dot size as well as the band offset between the core and
a)
Electronic mail: pratimasen@gmail.com. the shell materials. The distinct exciton and biexciton peaks

0021-8979/2012/111(3)/034310/8/$30.00 111, 034310-1 C 2012 American Institute of Physics

V

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034310-2 Chattopadhyay et al. J. Appl. Phys. 111, 034310 (2012)

in the PL spectra can be observed only at temperatures where esses taking part in the deexcitation mechanism are consid-
the binding energies of excitons/biexcitons are larger than ered in Sec. II C.
the thermal energy. The changes in the PL peak energy and Our ultimate objective to demonstrate analytically the
spectral-width are governed by thermally stimulated transfer possibility of making a low temperature nano-sensor is
processes, confining potentials, exciton/biexciton energies examined in Sec. III where we have also carried out the nu-
etc. At high temperatures where the thermal energy exceeds merical analysis based on the theoretical formulation for
the exciton/biexciton binding energy, the independent charge three different types of CSQDs.
carriers play an important role. Dawson et al.10 have shown
that at elevated temperature the carrier dynamics is domi- A. Exciton and biexciton binding energies
nated by independent carrier relaxation. In the present theo-
We consider a type-I spherical core shell quantum dot
retical formulation we have restricted ourselves to low
with the bandgap energy of the core material being smaller
temperatures where exciton-phonon relaxation mechanism
than that of the shell material. The geometry and the dimen-
as well as direct radiative recombination process contribute
sions of the dot is illustrated in Fig. 1.
to the photoluminescence. However, we have neglected the
Here, a is the radius of the core and b is the radius of the
contribution of defect states on PL intensity.
CSQD as a whole such that the annular shell thickness is
The PL intensity in II–VI semiconductor quantum dots
d ¼ (b - a). The two-dimensional electron and hole confine-
is reported to be polarization sensitive,11 and the emission in-
ment potentials are given by14
tensity is proportional to the product of the probability of
occupation of the excited state and the probability of empty Vc; v 2
Ve; h ðrÞ ¼ ðr  a2 Þ; (3)
ground state. The decay of the excited state could arise due a2
to radiative as well as nonradiative decay mechanisms. Con-
sequently, knowledge of initial population generated in the ~
r being the quasi-particle position satisfying the condition
excited state due to photoexcitation as well as the decay a < r < b. The subscripts e, h, c, and v denote the electron,
processes involved are of basic importance in the calculation hole, conduction band, and valence band, respectively. Vc
of PL intensity. Irrespective of the decay mechanism, the and Vv are the conduction and valence band offsets between
integrated PL intensity is reported to be express as12 the core and the shell. The quasi-particles in the CSQD expe-
rience strong confinement within the core due to the presence
I0 of the peripheral shell. The buffer layer further confines the
IðTÞ ¼ ; (1)
1 þ aexpðET =kTÞ electrons and holes within the shell. Hence, the particles
inside the core experience a double confinement like struc-
where a and ET are the process rate parameter and activation ture. The single particle wave functions under such situation
energy, respectively. The expression for the integrated PL in- can be described using WKB approximation as14,15
tensity in CSQD was given by13 8  ð a 
> pAffiffiffiffi
> S
exp j j dr for b < r < a;
jj
>
N0 >
> b
IPL ðTÞ ¼ s srad ; (2) >
>  ð a 
1 þ rad eðEa =kTÞ
<
þ A p
sa sesc /j ðrÞ ¼ pCffiffiffiffi sin kj dr þ
4
for a < r < a;
>
> k j a
b
>
>  ð 
with sa, srad, and sesc being the fitting parameter, radiative as : pAffiffiffiffi
>
S
exp  jj dr for a < r < b;
>
>
well as the thermal escape rate and N0 is the initial carrier jj a
population density that can be derived from the generation (4)
rate. We assume that the radiative recombination and thermal
escape rates are inversely proportional to the inhomogeneous
broadening (Cinh ) and the broadening arising due to exciton-
acoustic phonon (cph ), exciton-LO phonon coupling (CLO ).
Equations (1) and (2) have been obtained using the clas-
sical rate equations. In the present paper, we have used semi-
classical treatment in which quasi-particles-like electrons,
holes, excitons etc. are treated quantum mechanically while
the excitation caused by the electromagnetic radiation is
treated classically as waves. We have calculated the initial
population by using the density matrix analysis. The activa-
tion energies used in the above Eqs. (1) and (2) correspond
to the energies of the exciton and biexciton states. Accord-
ingly, we have obtained the energies of the exciton and biex-
citon states in Sec. II A. In order to determine PL intensity,
in Sec. II B we have taken into account the excitation of the
QD by the electromagnetic radiation via the dipole type of
radiation-matter interaction to obtain the population density FIG. 1. Schematic diagram of a core-shell quantum dot (CSQD) and dimen-
in the excitonic/biexcitonic states. The recombination proc- sions as assumed in present calculation.

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034310-3 Chattopadhyay et al. J. Appl. Phys. 111, 034310 (2012)

with jj ¼ ikj and j ¼ e, h. AC and AS are the normalization and

constants for core and shell region, respectively, and
hx0bx ¼ 2hx0ex  jDbx j: (10b)
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
mVe; h ðr2  a2 Þ aT
The term ðTþbÞ 2
has its origin in the temperature sensitive
kj ¼ : (5)
h2 a2 bandgap of semiconductors and is usually given by the Var-
shni formula. A more appropriate form of it has been sug-
For a bare quantum dot, we restrict the value of the running gested by Viña et al.,17,18 and all the forms show good
parameter r in the range a < r < a while the contribution of agreement within the temperature range 15 K–300 K.19 It is
shell is obtained by assigning appropriate values to the run- worthy to mention that we have taken due care to choose the
ning parameter r as b < r < -a and a < r < b in the forth- appropriate bandgap energies and Varshni parameters for
coming calculations. Apart from this, the change in the both the core (re < a) and the shell (a < re < b). Dex and Dbx
physical parameters regarding energy and effective mass of are the binding energies of exciton and biexciton, respec-
electron has been incorporated in the core and shell region. tively, in a CSQD and expressed as14,20,21
The WKB wave functions defined by Eq. (4) are the single
e2 
  

particle envelope functions. Under effective mass approxi- Dex ða; bÞ ¼ wX ða; b; re ; rh Þ  Ve þ
 w ða; b; re ; rh Þ
mation, the total wave functions we and wh can be written as 0 r  X
e2 
  
the product of the envelope function and the Bloch function 
þ wX ða; b; re ; rh Þ  Vh þ w ða; b; r ;
e hr Þ
(ue, uh) and given by  r  X 0

we ða; b; re Þ ¼ /e ða; bÞ  ue ðre Þ (6) (11a)

and
and
e2 
  

wh ða; b; rh Þ ¼ /h ða; bÞ  uh ðrh Þ: (7) Dbx ða; bÞ ¼ we ða; b; re ; rh Þ  Ve þ w ða; b; r ;
e hr Þ
0 r  e
e2 
 
Here, ~r e and ~
 
r h represent the position vectors of electron and 
 wh ða; b; re ; rh Þ  Vh þ
 w ða; b; re ; rh Þ
hole, respectively. 0 r  h
The interaction of near-resonant electromagnetic radia-
e2 
  

tion with the QDs generates photo-induced bound one þ we ða; b; re ; rh Þ  Vh þ
 w ða; b; re ; rh Þ
electron-hole (e-h) pairs known as excitons. In QDs, the e-h 0 r  e
e2 
   
pair formation is influenced by the confinement potential in 
 wh ða; b; re ; rh Þ  Ve þ w ða; b; r e ; r h Þ :
addition to the Coulombic term. Within Hartree approxima- r  h 0
tion,16 the exchange ground state wave function (wX ) can be (11b)
written as
In writing the above equations, we have taken into account
wX ða; b; re ; rh Þ ¼ /e ða; bÞ:ue ðre Þ  /h ða; bÞ:uh ðrh Þ: (8)
the temperature influenced bandgap shrinkage in semicon-
When inter-exciton separation approaches bulk exciton Bohr ductors by incorporating the Varshni contributions.17 In
radius aB, the Coulombic interaction forces existing between CSQD, band offset plays an important role in the confine-
these excitons lead to the creation of bound two electron- ment of the carriers within the core or shell materials. The
hole pairs well known as biexcitons similar to the case of temperature dependent bandgap shrinkage can also affect
formation of H2-molecule. Hence, the description of the the band offsets and due consideration has been given to it in
interaction of radiation with such small QD system requires the present analysis.
a three-level ladder system comprising of ground j0i, exciton In the interaction picture, the interactions of both excitons
jexi and biexciton jbxi states. Accordingly, we define the and biexcitons with radiation are taken to be of dipole type
unperturbed Hamiltonian as such that the interaction Hamiltonian HI can be written as22

0 l^0ex  E 0
2 3 2 3
x0 0 0
H0 ¼ h4 0 xex 0 5; (9) HI ¼ 4 l^ex0  E 0 l^exbx  E 5: (12)
6 7
0 0 xbx 0 l^bxex  E 0
where hxi is the ground state energy of the ith state with the Here, l^ ij (i, j ¼ 0, ex, bx) is the element of the transition
subscript i (¼ 0, ex and bx) corresponding to the ground, dipole moment matrix operator and E [¼ E0exp (ixt)] is the
exciton, and biexciton states, respectively. The transition excitation electromagnetic field with amplitude E0 and fre-
energies corresponding to these levels are temperature sensi- quency x and it is taken to be parallel to the transition dipole
tive and given by17 moment operators l ^ ij . The transition dipole moment opera-
tors corresponding to the transitions between the exciton *
aT 2 ground states (l0ex) and biexciton * exciton states (lexbx)
hx0ex ¼ 
 hðxex  x0 Þ ¼ hxg   jDex j (10a)
ðT þ bÞ are defined as22,23

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034310-4 Chattopadhyay et al. J. Appl. Phys. 111, 034310 (2012)

epcv Equation (15) has been solved using time dependent pertur-
^ 0ex ða; bÞ ¼
l j/ ða; bÞ  /h ða; bÞj; (13a)
m0 x0ex e bation technique to obtain the density matrix elements of
various orders. For the present formulation, we need to know
and the zeroth and second-order components q(0) and q2. The
1 epcv first order density matrix q1 does not play any role in the
^ exbx ða; bÞ ¼ 
l j/ ða; bÞ  /h ða; bÞj3 : (13b) estimation of the PL emission intensity and are not consid-
2 m0 xexbx e
ered henceforth. Standard mathematical procedure yields26
Here, pcv is the interband transition momentum matrix ele- 2
A 0 B
3
ment and is defined as24 qð2Þ ¼ 4 0 C 0 5: (18)
vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
u

m0
 ffi D 0 F
u3
u 1
me
jpct j ¼ u m0  : (14) Here,
t2 2 1
þ
hxg hxg þ Dso
!
4X20ex 1 1
A¼ þ ðq000  q0ee Þ; (19a)
x Dþ0e D 0e
Here, m0 is free electron mass, me is the effective mass of
electron, and Dso is the spin-orbit splitting energy for the 4X0ex Xexbx ðq0ee  q0bb Þ ðq000  q0ee Þ
 
core and shell materials of the CSQD under consideration, B¼ þ ; (19b)
x Dþ0b Dþ
0e
hxg is the bandgap energy.
and 
   
1 1 1
B. Population density in excitonic and biexcitonic C¼ Ax þ 4 þ þ  ðq0ee  q0bb Þ X2exbx ;
x  2iCðTÞ Deb Deb
states
(19c)
The excitation source generates the population in the
ðq000 q0ee Þ ðq0ee q0bb Þ
 
exciton and biexciton states. As discussed earlier, we have 4X0ex Xexbx  
D¼ þ ; (19d)
considered dipole type radiation-matter interaction. With H0 x Dþ
0b Dþ
eb
and HI being the ground state and interaction Hamiltonians,
the equation of motion of the density matrix q can be written and
as25 Ax
F¼ : (19e)
 
@q x  2iCðTÞ
i
hq_ ¼ ½ðHo þ HI Þ; q þ ih ; (15)
@t relax
In the above equations, D6 6
0e ¼ x6x0ex þ iCðTÞ, Deb ¼ x
6
 6xexbx þ iCðTÞ, D0b ¼ x62x0ex  Dbx þ iCðTÞ, and Xij
where @q@t relax ¼ CðTÞq (T) being the temperature dependent ¼ lij E0 =2h is the Rabi frequency.
relaxation parameter that depends on the recombination
In Eq. (18), the parameters A, C, and F represent the ex-
processes. We have focused our attention to the radiative and
citation intensity dependent populations in ground, exciton,
non-radiative recombination processes. The latter being de-
and biexciton states, respectively. The occupation in the
pendent on the exciton-phonon interaction. Also, q is defined
exciton level is caused by the photoinduced transition of
using a generalized 3  3 density matrix as
electrons from ground state to the exciton state and relaxa-
2
q00 q0e q0b
3 tion of the population from the biexcitonic state to excitonic
q ¼ 4 qe0 qee qeb 5: (16) state. The former contribution is represented by the term pro-
ð0Þ ð0Þ
qb0 qbe qbb portional to ðq00  qee Þ and the latter is represented by the
ð0Þ ð0Þ
term ðqee  qbb Þ in Eq. (19c). In general, at room tempera-
The diagonal elements represent the population in the ground ð0Þ
ture, ðqð0Þ
ee  qbb Þ is negligibly small and one may neglect
ðq00 Þ, exciton ðqee Þ, and biexciton ðqbb Þ states while the
the contribution of the corresponding terms. These terms
off-diagonal elements represent the elements that undergo
maximize and give rise to PL peak intensity at resonance
transitions among the states represented by their subscripts.
with the exciton and biexcitonic transitions frequencies,
At finite temperature T, the initial state population q(0) for
respectively. The broadening of the peak is determined by
ground, exciton and biexciton state are given by
CðTÞ that depends on various recombination processes.
ð0Þ ð0Þ ð0Þ
q00 ¼ 1  qee  qbb ; (17a)
C. Radiative and nonradiative recombination

hjDex j
 processes
ð0Þ
qee ¼ exp ; (17b)
kB T In the present calculations, we have incorporated the
losses occurring due to radiative and nonradiative decay proc-
and esses. Chen et al.27 have considered the thermal broadening of
  the exciton peak through the exciton-phonon interaction. The
ð0Þ hðjDex j þ jDbx jÞ
qbb ¼ exp : (17c) temperature dependent full width at half maximum (FWHM)
kB T was taken as

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034310-5 Chattopadhyay et al. J. Appl. Phys. 111, 034310 (2012)

CLO where g is a constant. Since the transition energies are tem-

C ¼ Cinh þ cph T þ h
 i; (20)
exp
hxLO
1 perature sensitive as is evident from Eq. (10a), one can
kB T expect its influence on both the PL emission intensity and
the PL peak shift. The transition energies can be modified in
where, Cinh , cph , CLO , hxLO , and kB T are the inhomogeneous a CSQD by changing the shell width.14 Since the recombina-
peak width at zero temperature, the exciton-acoustic phonon tion processes are temperature dependent, one can expect a
coupling strength, exciton-longitudinal optical (LO) phonon change in the FWHM of the PL peak with increasing temper-
coupling strength, the LO phonon energy, and thermal ature. These interpretations suggest that a temperature probe
energy, respectively. We have taken Cinh as temperature in- using a semiconductor core-shell quantum dot can be
dependent but depends on the radiative recombination pro- designed by calibrating the change in the PL intensity and
cess. Due to the strong overlapping of electron and hole the PL peak energy shift with respect to the ambient temper-
wave functions, the radiative recombination rate in quantum ature. We have examined these features in five different
dot is modified via an overlap integral parameter K and given types of bare and core-shell quantum dots made of II-VI
by11 semiconductor crystals.
4e2 xn
s1
rad  Cinh ¼ hpcv i2 K 2 : (21) A. PL intensity as a measure of temperature
3m20 c3 h
From Eqs. (10), one can notice that the PL intensity
for the medium with background material refractive index n. varies with temperature due to the temperature dependence
For the present case K ¼ /e ða; bÞ:/h ða; bÞ. The electron- of exciton/biexciton energies and recombination times.
phonon interaction in semiconductor nano-crystal has been Equations (21) and (22) further suggest that the PL sensitiv-
addressed by Takagahara,28 where he has shown that the ity in the quantum dots depends upon both the dot size and
coupling constant cph is size dependent and is controlled not the temperature T through the different parameters like
only by the electron-phonon interaction but also by exciton CðTÞ, Dex , Dbx etc. Lubyshev et al.29 and Xu et al.30 have
wave function. Valerini et al.13 have also mentioned about shown that the thermal quenching of PL in QDs can be
the enhancement in the exciton-acoustic phonon coupling attributed to the thermal activation of charge carrier from the
constant with reduced dimensionality of the nano-crystal. confined well to the barrier. The confinement potential in a
They have also studied the role of different nonradiative CSQD depends on the band offset parameter that is further
processes in CdSe/ZnSe QDs. It has been reported that the dependent on the bandgap of the core and the shell materials.
acoustic phonon contributes significantly at low tempera- Accordingly, we have calculated the temperature dependent
ture.27 The values of the relevant material parameters are PL intensity in two bare QDs viz. CdSe and ZnSe as well as
given in Table I. in CdSe/ZnSe, CdSe/ZnS, and ZnSe/ZnS CSQDs. The exci-
tation photon energy in each case is chosen to be temperature
III. RESULTS AND DISCUSSION independent exciton resonance frequency.
Figure 2 illustrates the temperature variation of the pho-
The PL intensity IPL arises due to the radiative decay toluminescence intensity of bare CdSe and ZnSe QDs of ra-
from the exciton state and is proportional to the vacancy in dius a ¼ 2.0 nm. The figure shows that ZnSe QDs, which
the ground state and the occupation in excitonic state. The have a larger bandgap and smaller exciton Bohr radius
usage of Eqs. (19a) and (19c) along with the mathematical
definition that the net population can be expressed in terms
of the product of the form C(1-A) yields
  
4 1 1
ð0Þ ð0Þ

IPL ¼ g X20ex þ þ  q00  qee
x  2iCðTÞ D0e D0e
 

1 1 ð0Þ ð0Þ

2
þ þ q  q X
Dþ
eb D
eb
ee bb exbx

4X20ex 1
   
1  0 0

 1 þ  q00  qee ; (22)
x Dþ0e D0e

TABLE I. Bandgap and Varshni parameters of the selected II–VI semicon-

ductor materials (Ref. 19).

a
Materials Bandgap (eV) a (104 eV/K) b (K) (106 eV/K2)
b

CdSe 1.766 6.96 281 2.48

ZnSe 2.8071 5.58 187 2.98 FIG. 2. (Color online) Temperature dependent photoluminescence intensity
ZnS 3.8652 10 600 1.67 for bare CdSe and ZnSe quantum dots of radius a ¼ 2.0 nm under low tem-
perature regime (5 K–78 K).

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034310-6 Chattopadhyay et al.
FIG. 3. (Color online) Temperature dependent photoluminescence intensity
for two core shell quantum dots having same core material (CdSe) with core
radius, a ¼ 2.0 nm and different shell materials (i.e., ZnS and ZnSe) with
same shell thickness, d ¼ 0.2 nm. CdSe bare quantum dot photolumines-
cence intensity variation with temperature is also plotted here to understand
the effect of shell on a bare quantum dot at low temperature.
compared to CdSe QD, yield better PL intensity variations as
compared to CdSe QDs. The temperature sensitivity of PL
intensity was found to saturate above 100 K while the PL in-
tensity decreases linearly with the lowering of the tempera-
ture below 50 K in ZnSe QDs. The improved temperature
sensitivity of ZnSe QDs can be assigned to the larger value
of (a/b) in this system as compared to that of CdSe (Table I).
In order to examine the role of temperature sensitivity of
the shell, we have obtained PL intensity of CSQDs having
the same core with two different shell materials. Figure 3
demonstrates the temperature dependence of PL intensity of
CdSe/ZnS and CdSe/ZnSe CSQDs as well as that of a bare
CdSe QD. It is clear from the figure that coating CdSe QD
with a shell made up of a semiconductor material with larger
bandgap results in an increase in the PL intensity. However,
coating CdSe with ZnSe exhibits sharp fall with increasing
temperature below 30 K while the temperature variation is
not very sharp if the CdSe QD is coated with ZnS shell. Thus
a low temperature probe of CdSe/ZnSe CSQD appears to be
more potential than a CdSe/ZnS CSQD probe. From the fig-
ure, it can be further seen that at temperature above 40 K, the
PL intensity variations are small in both CSQDs. We define
relative temperature dependent parameters arel(¼ ashell/acore)
and brel(¼ bshell/bcore). From Table II, one can notice that
(arel/brel) is larger in a CdSe/ZnSe CSQD as compared
to that in CdSe/ZnS CSQD. This larger (arel/brel) value is
TABLE II. Band offset values and effective Varshni parameters for selected
II–VI core-shell quantum dots.
VBO CBO aðshellÞ bðshellÞ
a ¼ b ¼
Materials (eV) (eV) rel aðcoreÞ rel bðcoreÞ
CdSe/ZnSe (Ref. 31) 0.23 0.75 0.802 0.666
CdSe/ZnS (Ref. 32) 0.6 1.44 1.437 2.135
ZnSe/ZnS (Ref. 33) 0.58 0.03 1.792 3.209
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J. Appl. Phys. 111, 034310 (2012)
FIG. 4. (Color online) Temperature dependent photoluminescence intensity
variation at low temperature (5 K–78 K) in CdSe/ZnS, ZnSe/ZnS, and ZnSe.
responsible for larger temperature sensitivity of the CdSe/
ZnSe CSQDs.
To examine the contribution of temperature sensitivity
of core, we have obtained PL intensity of CSQDs having
same shell with different core materials. In Fig. 4, the PL in-
tensity variation as a function of temperature has been plot-
ted for CdSe/ZnS, ZnSe/ZnS, and ZnSe QDs. We changed
the core material keeping the shell to be the same as ZnS to
examine the explicit PL response in the core material at low
temperature. The figure reveals that the sensitivity of CdSe/
ZnS CSQDs is better. The reason for this can again be attrib-
uted to (arel/brel) ratio as is evident from Table II.
B. PL peak shift as a measure of temperature
Most of the available literatures show that the excitation
sources selected for experimental study of PL spectra in
II-VI semiconductor QDs are Ti:sapphire laser or Arþ laser.
We consider the excitation of the QDs by using a Ti:sapphire
laser. The PL spectra for all the five samples (two bare and
three core-shell QDs) are plotted in Fig. 5. The inset in the
figures have been plotted for the bare QDs. It is found that
the PL intensity in CSQDs can be increased by nearly an
order of magnitude through the proper choice of the shell
material. This finding establishes the utility of a shell on the
core of the QDs. The figures also exhibit red shifts in the PL
peaks with increasing temperature. The redshift has been cal-
culated and found to be around 1013 s-1 for the temperature
range 10 K-75 K. Both Valerini et al.13 and Walker et al.2
have experimentally observed the redshift in PL peak with
increasing temperature. Walker et al.2 suggested that signifi-
cant temperature dependence of luminescence combined
with its insensitivity to oxygen quenching establishes CdSe/
arel 1 ZnS QDs as optical temperature indicator. On the basis of
(10 )
brel the theoretical analysis made in the present paper, we find
that the temperature probe using CSQD can be made by cali-
12.04
6.73
brating the probe via PL intensity variations as a function of
5.58 temperature. Although the analysis made in the present paper
have been carried out for a single quantum dot, in practice
034310-7 Chattopadhyay et al. J. Appl. Phys. 111, 034310 (2012)

interaction based relaxation times for calculating the PL in-

tensity. It is observed that an increase in temperature leads to
redshift of the PL peak. Also the PL intensity decreases with
increasing temperature.
The numerical analysis has been made for CdSe and
ZnSe bare quantum dots as well as CdSe/ZnS, CdSe/ZnSe,
and ZnSe/ZnS CSQDs. It is found that the presence of a
shell improves the PL intensity. Also the matching of core
and shell materials is important for making a nano-sensor.
After examining the effect of temperature sensitivities of
core (CdSe/ZnS, ZnSe/ZnS) and shell materials (CdSe/ZnSe,
CdSe/ZnS) on the temperature dependent PL intensity, we
observe that the ratio of the relative parameters defined in
terms of (arel/brel) plays a significant role in the selection of
the core/shell materials for making a low temperature nano-
sensor using a core-shell II-VI semiconductor quantum dot.

ACKNOWLEDGMENTS
The financial support received from the Department of
Science and Technology (DST), New Delhi, India is grate-
fully acknowledged by the authors.

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