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Journal of Luminescence 155 (2014) 330337

Contents lists available at ScienceDirect

Journal of Luminescence
journal homepage: www.elsevier.com/locate/jlumin

Probing photoluminescence dynamics of colloidal CdSe/ZnS core/


shell nanoparticles
Gurvir Kaur, S.K. Tripathi n
Centre of Advanced Study in Physics, Department of Physics, Panjab University, Chandigarh 160014, India

art ic l e i nf o a b s t r a c t

Article history: The paper presents the synthesis of thiol capped CdSe/ZnS core/shell nanoparticles with CdSe core and
Received 8 February 2014 ZnS shell. The thickness of the ZnS shell has been controlled by the regulating the amount of Zn/S
Received in revised form precursors for reaction. The steady and transient photoluminescence properties substantiate the growth
5 June 2014
of ZnS shell over the CdSe cores. High resolution transmission electron microscope and the X-ray
Accepted 25 June 2014
Available online 2 July 2014
diffraction patterns reveal nanocrystalline particles of an average size 3.4 nm packed in wurtzite lattice.
Photoluminescence excitation spectra as well as the excitationemission matrix of CdSe and CdSe/ZnS
Keywords: evidence the growth of ZnS for Type I hetero-junction without interfering the energy states of core. By
Quantum dots this method, ZnS layer of 8.84 is optimum for uorescence enhancement of the core/shell quantum
Core/shell structures
dots. The multiexponential uorescence decay of the quantum dots represents independent radiative
Photoluminescence
recombinations with overlapped energies. It is revealed that the average uorescence lifetimes of
Time resolved uorescence spectroscopy
quantum dots decreased with increase in ZnS shell, which is due to the enhanced contribution from
initially populated excitonic recombination and the reduction in the surface trap states with shell
growth.
& 2014 Elsevier B.V. All rights reserved.

1. Introduction The origin of the dark-exciton state is basically a spin triplet state
that is forbidden for optical transitions by the spin-selection rule.
Quantum dots (QDs) are quasi-zero-dimensional nanoscale Spin exchange splitting energy is small (omeV) for the bulk mate-
materials having carriers restricted in all three directions that lead rials however the quantum connement in semiconductor nanos-
to a unique electronic structure different from that of the atomic tructures raise the splitting energy that cannot be overcome by
and bulk materials [1]. The extensive studies of colloidal QDs thermal effects and the dark-exciton state come visible [8,9].
have been motivated by their promising photonic or photovoltaic QDs do possess large number of atoms at the surface with
applications for example light-emitting devices [2], lasers [3], solar dangling bonds that creates trap states for the charge carriers and
cells [4] and uorescent labels [5]. Photons of sufcient energy act as non-radiative recombination centres. Although organic
create electrons and holes in semiconductors where the electrons molecules have the tendencies to control the particle size and
populate the excited states. Energy relaxation of these excitons dispersity of semiconductor nanocrystals but lack in passivating
establishes quasi-equilibrium populations of electron and hole the surface sites efciently [10]. Inorganic materials that speci-
quantized states and lead to a complex de-excitation process. cally with higher band gap in comparison to the core nanoparticles
De-excitation involves radiative electronhole (eh) recombination are of great interest and being employed to passivate the surface of
(uorescence), non-radiative (phonon-assisted eh) recombination, the core [6]. CdSe/ZnS core/shell nanoparticles are among the
carrier trapping at defect/surface states and Auger recombination most utilized materials in biological assays for therapy and
[6]. Size of QDs has signicant affect on the radiative and non- diagnosis and in photovoltaics [11]. The heterostructure so gener-
radiative recombination of the eh pairs. One of the most char- ated lead to the enhanced uorescence quantum yield that
acteristic photoluminescence (PL) properties of QDs is the observa- consecutively affects the exciton recombination time [12]. Chemi-
tion of an optically passive state, the so-called dark-exciton state [7]. cal routes for synthesizing highly uorescent and tunable uores-
cence emission from CdSe/ZnS QDs are well established [13],
however the work on the uorescence dynamics of such compo-
sites is in scarce. Time, wavelength, temperature, polarization-
n
Corresponding author. Tel.: 91 172 2534462; fax: 91 172 2783336. resolved luminescence studies possibly clarify the nature of
E-mail addresses: surya@pu.ac.in, surya_tr@yahoo.com (S.K. Tripathi). the absorbing and luminescent states and exciton recombination

http://dx.doi.org/10.1016/j.jlumin.2014.06.052
0022-2313/& 2014 Elsevier B.V. All rights reserved.
G. Kaur, S.K. Tripathi / Journal of Luminescence 155 (2014) 330337 331

processes [14,15]. Fluorescence relaxation dynamics of CdSe, CdTe reactions were performed in standard glassware using deionised
and CdS nanocrystals is well studied [1,14,16,17]. In CdSe QDs, (DI) water.
at room temperature the photoinduced carriers cool in less than
200 fs, relax in 150 ps, recombine at the band edge in 150 ns 2.2. Synthesis
and result into a multiexponential decay [17]. Temperature
dependent time resolved uorescence spectroscopy (TRFS) is able Sodium selenosulphate (Na2SeSO3) prepared by reuxing a
to reveal the dark and bright exciton state in CdSe nanocrystals solution containing 0.1 M Na2SO3 and 0.05 M Selenium powder
[14]. Capping reagents, such as thiol also inuence the exciton for 6 h. The transparent solution was cooled and kept overnight in
luminescence and decay kinetics of CdTe and CdSe QDs [18]. dark to settle down the unreacted Se. In case black residues are
Prodding the nature of recombination processes, their depen- observed the solution is ltered and stored in dark to use as the
dence on the shape, size and type of material is necessary from selenium source for CdSe QDs. The capping reagent MAA (0.6 M)
the fundamental and applied physics point of view. Recently, and (CH3COO)2Cd  2H2O (0.05 M) are mixed and stirred well for
core/shell and multishell nanostructures (CdSe/CdS, CdTe/CdSe, complexation. The turbid white solution of Cd complex is adjusted
and CdSe/CdS/ZnS) are being explored for their remarkable to 910 pH by adding freshly prepared NaOH (1 M) solution.
optical properties, such as suppressed uorescence blinking and Finally added Se source to the mixture maintaining (Cd2 :Se2  ::
enhanced multiexciton emission states [1921]. Fluorescence 2:1) and carried the reuxing for 79 h at 60 1C. The yellow-
dynamics of such composite systems, CdSe/CdS/ZnS [21,22], orange solution indicates CdSe nanoparticles formation. The
CdTe/CdSe [23], CdTe/CdS [24], CdSe/CdS [12,19] and InP/ZnS particles were separated and washed using acetone. After several
[25] are been recently studied. Energy-dependent TRFS experi- washings the QDs were dispersed again in water for characteriza-
ment for CdTe/CdSe, found that the relationship between the tion and application [28].
radiative lifetime and the size of QDs can be well described by CdSe/ZnS core/shell QDs have been produced by controlled
the quantum connement effect [23]. For CdSe/CdS ultrafast growth of ZnS over the MAA capped CdSe QDs. To a solution
spectroscopy techniques revealed the optical signatures of neutral of CdSe nanoparticles (10 ml) added 0.05 M Na2S and 0.05 M
and charged excitonic and multiexcitonic states, where the Auger (CH3COO)2Zn  2H2O solutions alternatively in small xed aliquots
recombination of biexcitons was not suppressed, while there was with continuous stirring at room temperature. Objective is to
optical gain and amplied spontaneous emission from multi- prepare three samples of CdSe/ZnS QDs by varying the amount of
exciton states and from long-lived charged-exciton states [19]. Zn and S (i.e. 0.3, 0.5, 0.7 ml each). The amount of precursor's
A paper on calculation of radiative recombination lifetime theore- control the thickness of ZnS shell and the respective samples are
tically for core/shell QDs has been reported in 2012, which named CdSe/ZnS I, CdSe/ZnS II and CdSe/ZnS III.
predicted decrease in the lifetime with increase in the shell
thickness around the core QD [26]. Overall there are very few 2.3. Characterization
publications in this eld and that on specic materials only. This
limits the knowledge over relaxation dynamics and pathways, 2.3.1. Transmission electron microscopy (TEM)
which need to be explored widely for better applications in A FEI Tecnai G2 transmission electron microscope operating at
photophysics and biological imaging. an acceleration voltage of 200 kV was used for high resolution
This paper concerns with the synthesis and uorescence images of individual QDs to analyse size, size distribution, and the
properties of mercaptoacetic acid (MAA) capped CdSe/ZnS core/ structure of core/shell nanocrystals. The nanocrystals were depos-
shell nanostructures at room temperature. CdSe/ZnS core/shell ited from diluted solutions onto copper grids with carbon coating.
QDs have been chemically synthesized and the thickness of shell
has been controlled by the amount of Zn/S precursors. Transmis-
2.3.2. Powder X-ray diffraction (XRD)
sion electron micrographs and the X-ray diffraction predicted the
Wide-angle X-ray diffraction (WAXS) was performed with Spin-
morphology and crytallinity of the QDs. The study involves
ner 3064 XPERT-PRO X-ray diffractometer using Cu K (1.54 )
analysis of samples via steady state UVvisible absorption, emis-
radiation. Measurements were performed in a 2 range from 151 to
sion, excitation and the time resolved uorescence spectroscopy.
601.
We have probed the effects induced by ZnS accumulation over the
CdSe surface on the uorescence relaxation dynamics of lumines-
cent CdSe nanocrystal. Superposition of Quantum Connement 2.3.3. Infra-red absorption
Energy (SQCE) model has been used to calculate the thickness of Fourier transform-infrared (FT-IR) spectra of MAA, CdSe and
the ZnS shell from the optical bandgap of the composite core/shell CdSe/ZnS were taken on Perkin-Elmer (Spectrum 400-FTIR) Spec-
structures [27]. trometer.

2.3.4. Steady state absorption and uorescence


2. Experimental UVvis absorption spectra were taken with Single Beam
Spectrophotometer (SpectroScan 30). PL and photoluminescence
2.1. Materials excitation (PLE) spectra were taken with a Shimadzu Spectro-
uorophotometer (RF-5301PC) using 1 cm  1 cm quartz cuvette.
The reagents were of analytical grade and used without further The relative uorescence quantum yields were measured relative
purication. Cadmium acetate dihydrate [(CH3COO)2Cd  2H2O] to rhodamine 6 G (in ethanol) using the gradient method. The
was purchased from Qualigen Fine Chemicals, Selenium [Se] equation followed is [29]:
powder and rhodamine 6 G from Loba Chemie Pvt. Ltd., Sodium
mQ D  n  2
sulphite anhydrous [Na2SO3] from Merck specialities Pvt. Ltd., QYQ D QYRh 1
mRh n'
Sodium sulphide [Na2S] akes from New India Chemical Enter-
prises (Cochin-24, India), Sodium hydroxide [NaOH] from Ranbaxy where QYRh 0.95 is the QY of rhodamine 6 G dissolved in ethanol,
laboratories Ltd. Zinc acetate pure [(CH3COO)2Zn  2H2O] and mQ D and mRh are the slopes of curves of QDs and the rhodamine
mercaptoacetic acid, MAA [C2H4O2S] extra pure with concentra- 6 G respectively, the curves are obtained by plotting integrated
tion 80% was purchased from Central Drug House Ltd. All the uorescence intensity vs optical density of different concentration
332 G. Kaur, S.K. Tripathi / Journal of Luminescence 155 (2014) 330337

solutions. n 1.33 and n0 1.36 are the refractive indices of the structure and the peaks at 2 23.21 (1 0 0), 25.51 (0 0 2), 27.51
solvents in which the QDs and the dye are dissolved, respectively. (1 0 1) and 35.51 (1 0 2) are quite broad and overlapped due to small
crystal size. The straight lines show the position of diffraction peaks
2.3.5. Time resolved uorescence spectroscopy for CdSe powder having pure hexagonal structure [31]. ZnS nano-
Time-resolved PL measurements were performed to probe the crystals can possibly crystallize in cubic as well as hexagonal
uorescence mechanism of the colloidal QDs. Edinburgh FL920 structures where the hexagonal structure is favourable at high
Fluorescence Life Time Spectrometer has been employed for all the temperatures. For CdSe/ZnS the diffraction peaks emerged more but
measurements where the time-correlated single photon counting with not much change in the FWHM of the respective peaks. The
is used to measure the decay of exciton luminescence. broad hump in the region 40501 is clearly visible and is interpreted
as the superposition of diffraction peaks for planes (1 1 0), (1 0 3) and

3. Results and discussion

3.1. Morphology and crystallography of quantum dots

Fig. 1 shows the TEM micrographs of CdSe and CdSe/ZnS samples.


The size of CdSe QDs is less than 5 nm and the QDs are not completely
dispersed but exist in micro sized clusters. Lattice fringes are visible at
high resolution, which are shown by drawing circle in Fig. 1(b)
(diameter corresponds to 3.271.2 nm on scale). The fringe regions
range 24.4 nm in diameter and correspond to the particle size. The
inter fringe spacing  3.4 matches with the interplanar spacing of
(2 0 0) hexagonal lattice planes [28,30]. The CdSe/ZnS particles have
larger size (4.071.2 nm) in comparison to CdSe QDs (Fig. 1(c)) but the
boundary of the core and shell material is not very distinguishable and
the lattice fringes for CdSe/ZnS (Fig. 1(d)) are continuous without any
kind of distortions. This indicates epitaxial growth of ZnS shell which
is reected by the optical properties of the material.
The crystallinity of the materials with dimensions in nanometres
is quite essential to investigate and is studied from X-ray diffraction
(XRD). The material dried on the Corning 7059 glass substrate is used Fig. 2. X-ray diffraction patterns of (i) CdSe (black) and (ii) CdSe/ZnS (red) QDs. (For
for the study. Fig. 2 compares the XRD patterns of CdSe and CdSe/ZnS interpretation of the references to color in this gure legend, the reader is referred
core/shell samples. The pattern of CdSe matches with that of wurtzite to the web version of this article.)

Fig. 1. TEM and HR-TEM micrographs: (a) CdSe QDs, (b) CdSe QDs at higher resolution, (c) CdSe/ZnS QDs and (d) CdSe/ZnS QDs at higher resolution.
G. Kaur, S.K. Tripathi / Journal of Luminescence 155 (2014) 330337 333

(2 0 0). Owing to a similar XRD pattern for CdSe and CdSe/ZnS be attributed to the stretching vibration of CQO, at 1406 and
nanostructures, the formation of an alloy upon encapsulating ZnS is 1298 cm  1 to CO stretching and in-plane bending of OH bonds
not likely. The lattice constants a and c for hexagonal CdSe and 1195 cm  1 may be the twisting of CH2 [37]. For MAA capped
and CdSe/ZnS structures are determined from the plane spacing CdSe the absorbed H2O give a broad absorption band around
equation [32]: 3434 cm  1. The characteristic absorption bands for CQO and
! CO vibration at 1715 and 1298 cm  1 are absent in turn the
2 2 2
1 4 h hk k l
2 absorption bands at  1578 and 1407 cm  1 correspond to asym-
2 a2 c2
dhkl 3 metric and symmetric stretching, respectively in carboxylate group.
For planes (1 0 0) and (0 0 2) of CdSe QDs the dhkl values are There are bands at 631 and 678 cm  1 due to the stretching
3.84 and 3.45 , respectively and lattice parameters a and c comes frequency of CdSe and CdS bonds, but no absorption correspond-
out to be 4.43 and 6.90 , respectively (c=a 1.55). The values of ing to SH vibrations (v 2560 cm  1) is observed. This indicates
lattice parameters are comparable to that reported for CdSe that the sulphur of sulfhydryl group coordinates with Cd on the
experimentally and theoretically [33]. Upon growth of ZnS the nanocrystal surface and the hydrophilic carboxylate groups face
diffraction pattern shifts to higher 2 values resulting into the outwards [38]. FT-IR of CdSe/ZnS shows similar bands (v 3408,
lattice parameters a 3.80 and c 6.90 . The reduction of a 1574, 1415, 654 and 623 cm  1) as that for CdSe with only small
could be attributed smaller lattice constants for ZnS or may be due displacements in some bands, it concludes MAA binding at
to the strain caused by the growth of ZnS [34]. It is expected that the surface has not been affected by growth of the ZnS shell over
the thicker shells will shift the peaks to higher angles transform- the CdSe NC. Actually the CdS bond is dynamic which allow the
ing the diffraction pattern from CdSe towards ZnS [35]. However, growth of ZnS over the CdSe surface. The IR absorption bands in the
large lattice mismatch for CdSe (CdSe 6.05 ) and ZnS (ZnS region 700600 cm  1 justies that the thiol groups of MAA forms
5.41 ) lattice do not allow the alloying of elements [30]. coordinate bond with metal ions (Cd2 and Zn2 ) present at the
Sherrer's relation in full width at half maximum (FWHM) of the NCs surface and the hydrophilic carboxylate groups facing outwards
diffracted peak and the crystallite size has been used to calculate make NCs water-soluble and stable due to negative charge on the
the crystallite size. The relation is [36]: surface [28].

D 0:91 = cos 3
where D is the average crystallite size, is the wavelength of the 3.3. UV-visible absorption and uorescence of quantum dots
incident X-ray (1.54 ), is the (FWHM) of X-ray diffraction and
is Bragg's angle. The peak centred at 25.51 (CdSe) and 25.71 Fig. 4 illustrates the absorption and emission spectra of MAA-
(CdSe/ZnS) with FWHM (obtained by Gauss t to the respective capped CdSe and CdSe/ZnS (CdSe/ZnS I, CdSe/ZnS II and CdSe/ZnS
peaks) 2.82 and 2.12, respectively were used for calculation. The III) QDs in the UVvisible region. It is observed that CdSe QDs have
crystallite sizes as calculated are 2.8 and 3.8 nm for CdSe and broad absorption band in the UV region which extends to the
CdSe/ZnS, respectively. visible region with absorption edge at 525 nm. The absorption
edge shifted to lower wavelength in comparison to the bulk CdSe
crystal (bulk  690 nm corresponding to 1.74 eV). Upon addition of
3.2. IR absorption
Zn/S precursors to the CdSe QDs the shoulder in the absorption
band shift to higher wavelength with increase in the amount
Absorption in IR region gives us signicant knowledge about the
of precursors in relation to the parent material. While there are no
binding of MAA to CdSe and CdSe/ZnS QD surfaces. Fig. 3 presents
absorption characteristics of ZnS clusters, the red shift in the
the FT-IR spectra of MAA, CdSe and CdSe/ZnS. MAA, has character-
absorption shoulder is attributed to relaxation of quantum con-
istic IR peaks at 3470, 2568, 1715, 1407, 1298 and 1195 cm  1. The
nement in the CdSe QDs resulting to the growth of the ZnS
strong absorption peak at 3470 cm  1 arises from the hydroxyl bond
shell [11,13]. The luminescence of the QDs has been observed with
(OH stretching) and at 2568 cm  1 corresponds to the stretching
different excitation wavelengths ex and formed the excitation-
vibration of SH bond. The absorption peaks at 1715 cm  1 should
emission matrix for the QDs. Fig. 4 presents the emission corre-
sponding to ex 400 nm. CdSe QDs are luminescent with

Fig. 3. FT-IR Spectra of mercaptoacetic acid, CdSe QDs and CdSe/ZnS QDs (bottom Fig. 4. Absorption spectra (lines) and photoluminescence (doted) spectra
to top). (Ex  400 nm) of CdSe and CdSe/ZnS core/shell nanoparticles.
334 G. Kaur, S.K. Tripathi / Journal of Luminescence 155 (2014) 330337

maximum intensity at 539 nm. The addition of Zn/S precursors effective band-gap energy. Saran et al. [27] took up the SQCE for
signicantly increased the luminescence intensity of CdSe QDs up the calculation of shell thickness and justied experimentally.
to the addition of 0.7 ml Zn/S i.e. for CdSe/ZnS III. Quantum yield of The model can employed only for estimating shell thickness
the CdSe/ZnS III QDs is calculated (from Eq. (1)) to be 25%, which is in core/shell QDs belonging to Type-I quantum connement
more than the double of CdSe QDs (10%). The increase in intensity (3-dimension) found in QDs and not to the anisotropic quantum
is accompanied by a small red shift of 6 nm. The red shift and rods or wires. In case of uneven shell thickness, it estimates an
increase in the PL intensity are interpreted and taken as a average shell thickness due to superposition between core and
conrmation of accumulation of ZnS over the surface of CdSe shell material. Morphology of the CdSe/ZnS core/shell system is
NCs. The shell so grown is sufcient to conne the exciton to the spherical from TEM, so the model can implied for the samples. The
CdSe core with only partial leakage into the shell. model requires the particle size for homogenous CdSe QDs that
The present reaction conditions favour the growth of ZnS layer has been estimated from the absorbance spectra and the quantum
over the CdSe surface. The reactions mechanism for the CdSe connement equation developed by Brus (Eq. (6)) [42,43]. Accord-
synthesis is well reported [28]. Accordingly the hydrolytic decom- ing to the statement the overall band gap energy (obtained from
position of Sodiumselenosulfate in alkaline media releases Sele- absorbance spectra, Eq. (4)) of the core/shell QD, can be attributed
nide ions gradually, which react with Cd2 ions to form CdSe. The to a superimposition of core and shell band gaps and presented as
growth of ZnS shell is aided by the incomplete coordinated surface follows:
atoms of the bare CdSe nanocrystals which are highly active and ECdSe=ZnS;d 2 ECdSe;d EZnS;d 2  EZnS;d  7
invites the possibility of epitaxial overgrowth of ZnS represented
by [39]: where, ECdSe;d corresponds to CdSe core energy gap with size d,
2 ECdSe=ZnS;d 2 corresponds to CdSe/ZnS core/shell energy gap with
Zn Na2 S 2OH -ZnS 2NaOH 4
size d 2 (, represents the shell thickness). EZnS;d and EZnS;d 2
Growth of shell generally needs to restrict the nucleation of the represent the energy gap that of ZnS particles of size d and d 2,
shell material and demands the addition of shell precursors in respectively. The energy gap for each CdSe/ZnS QD sample is listed
small aliquots and alternatively. Also growth temperature must be in Table 1 and that for other terms can be written in the terms of
lower than of the core nanoparticles. Overall the synthesis of Brus formula as
core/shell structures is an art and requires the optimization of
ECdSe;d  1:741:6  10  19
concentration and amount of the precursors along with adequate
reaction temperature [40]. 2:154786  10  36 1:054554  10  28
2
 8
CdSe is a direct band gap material, so the absorption coefcient d d
() of the QDs have a relation with the optical band gap (Eg ) of the
material. Plot of h2 against photon energy h shows a linear EZnS;d  3:541:6  10  19
behaviour in certain region. Extapolation of this region gives an 1:00513  10  36 0:99556  10  28
intercept on x-axis which is equal to the optical energy band gap 2
 9
d d
for direct (Eg ) transitions anchored in the expression [41]:
Ah  Eg 1=2 EZnS;d 2  3:541:6  10  19
5
h 1:00513  10  36 0:99556  10  28
 10
Here A is a constant related to the extent of the band tailing. d 2 2 d 2
The band gap of CdSe QDs comes out to be 2.47 eV and decreases
Using Eqs. (8), (9) and (10) the Eq. (7) takes the form of Eq. (11).
to 2.36 eV with growth of ZnS shell. It is noted that the optical
band gap is larger than that of bulk CdSe (1.74 eV) due to quantum ECdSe=ZnS;d 2  1:741:6  10  19
connement but is smaller than that of shell material (3.54 eV). It
1:14965  10  36 0:05899  10  28
infers the growth of ZnS shell over the CdSe nanocrystals. In case 2

d d
of the nucleation or alloying of ZnS, the optical band gap of QDs
must have increased. 1:00513  10  36 0:99556  10  28
 11
Further Brus equation has been employed to calculate the mean d 2 2 d 2
particle size of QDs using optical band gap [42]. The Brus equation
This Eq. (11) is quadratic for thickness and gives two routes
is a relationship between nanoparticle band gap EgQ D , bulk band
one positive and other negative, where the positive one corre-
gap EgBulk (1.74 eV for CdSe) and the mean particle diameter d,
sponds to the thickness of ZnS shell. The shell thickness is 4.42
expressed as follows:
!  for CdSe/ZnS I, 6.32 for CdSe/ZnS II and 8.86 for CdSe/ZnS III.

h
2
1 1 3:6e2 Thus the shell thickness () increases with addition Zn/S precursor
EgQ D EgBulk 2 n  6
n
2d me mh 4o d solution and for greater than 0.7 ml Zn/S precursors the lumines-
cence intensity decreases. The shell growth thus achieved is less
where h is Plank's constant, is the dielectric constant of semi- than one nm and is not visible in the TEM micrographs but is
conductor, e the charge of electron, mne me mo and mnh mh mo . sufcient to passivate the surface dangling bonds and enhance
Here me 0:13 and mh 0:46 are the effective masses of electron
and hole for CdSe, respectively, and mo is the mass of an electron. Table 1
Values of universal constants are mo 9.1  10  31 kg, 8.854  List of parameters determined from optical measurements.
10  12 F/m, e 1.6  10  19C and h 6.626  10  34 Js. It gives the
Sample Amount of Energy Emission FWHM of Shell
CdSe particles of size 3.86 nm and the value is comparable to that
Zn and S gap peak emission peak thickness ()
predicted from TEM and the XRD peak broadening. This expres- precursors (eV) (nm) (nm) () (SQCE)
sion cannot be employed to calculate the particle size of the core/
shell QDs as the excitons are not relaxed equally throughout the CdSe 0 2.47 539 90 0
volume and the heterojunction (CdSe/ZnS) restricts the exciton CdSe/ZnS-I 0.3 ml 2.42 539 90 4.42
CdSe/ZnS-II 0.5 ml 2.39 542 90 6.32
wave function. In such core/shell nanoparticle the band-gap CdSe/ZnS-III 0.7 ml 2.36 544 90 8.86
energies of core and shell materials are super-imposed to give
G. Kaur, S.K. Tripathi / Journal of Luminescence 155 (2014) 330337 335

the PL. Sharan et al. also checked the optimum shell thickness
0.689 nm (corresponding to maximum quantum yield) for ZnS
shell over a 4.26 nm CdSe core. The shell thickness is sufcient to
enhance the PL, while not enough thick to contribute its own
characteristics to the composite material.

3.4. Excitationemission matrix and the photoluminescence


excitation spectroscopy of CdSe/ZnS core/shell quantum dots

The emission spectra of the samples have been collected at


different excitation wavelengths in the range 300420 nm and are
plotted as contour or topographical plots where the excitation and
emission coordinates of observable uorescence peaks are used to
identify different uorophore moieties. This is called uorescence
excitationemission matrix (EEM) spectroscopy and is a powerful
and widely used technique for characterizing the uorescent
organic or inorganic systems [29,44]. Fig. 5 is presenting the
contours corresponding to CdSe and CdSe/ZnS structures. Semi-
conductor QDs do not contain any uorescent moiety but are itself
uorophores giving their special character different from the other
conventional entities. The pattern is almost same for all the QD
samples but different from the conventional entities, where the
contour shapes are not oblique but almost spherical. Comparing
both the maximum intensity region is greater for the CdSe/ZnS
core/shell system and the PL is less sensitive to the excitation
wavelength 340380 nm.
Further, the uorescence intensity at 539 nm was measured
as a function of the excitation wavelength (280530 nm),
which means the excitation prole of the emission has been
obtained by collecting a xed window of the emission spectrum
and scanning the excitation energy. Such measurement is called
PLE spectra and leads to a narrowed and almost homogeneous
spectrum. Fig. 6 shows the PLE spectra for the CdSe and different
samples of CdSe/ZnS. The spectra allowed us to observe absorption
features of the sample at room temperature which were not so
clear in the absorption spectra. Along with the lowest energy
transition (1S3/2(h)1S(e)), the higher energy transitions are also
visible [45]. The PLE spectrum of core-shell system is parallel to
the core itself with enhancement in the emission corresponding to
each absorption wavelength. It clearly evidences the epitaxial
growth of ZnS shell over the CdSe core and indicates that the Fig. 5. Fluorescence excitationemission contours of (a) CdSe and (b) CdSe/
growth of ZnS has not affected the energy levels of the core [28]. ZnS QDs.

3.5. Time resolved uorescence spectroscopy

Time-resolved uorescence spectroscopy (TRFS) is a powerful


technique to probe energy relaxation and recombination dynamics
of the carriers in CdSe nanostructures. Multiexponential PL decay
mechanisms for ensembles of different sized as well as for
the single crystal CdSe QDs have been reported by the researchers.
Fig. 7 shows room temperature time-resolved uorescence spectra
of CdSe and CdSe/ZnS QDs. The transition has been studied at the
peak wavelength, observed in steady state PL spectra, with
excitation at 405 nm. Tri-exponential decay model described by
the following equation:
3
Ft Ao Ai exp  t=i 12
i1

where 1, 2 and 3 represent the lifetime for each uorescence


decay and A1, A2 and A3 are respective amplitudes; shows the best
tting to the decay curves (r-square  0.99). Average lifetime was
calculated using the following equation [24]:
3 3
Ai 2i = Ai i 13
i1 i1
Fig. 6. PLE scans for various CdSe/ZnS QDs in comparison to CdSe cores (i) CdSe
The values of the parameters A1, A2, A3, 1, 2 and 3 obtained by core, (ii) CdSe/ZnS I, (iii) CdSe/ZnS II and (iv) CdSe/ZnS III.
336 G. Kaur, S.K. Tripathi / Journal of Luminescence 155 (2014) 330337

increases. On the basis of these results and above discussion the


smallest lifetime 3 is possibly due to initially populated excitonic
recombination, 2 for band edge excitonic and the 1 for the deep
trap recombinations. ZnS shell in CdSe/ZnS I is 4.42 , which is less
than a monolayer and is able to reduce the contribution from deep
trap states to almost 50%. The uorescence contribution from
initially populated excitonic states increased by 20% (CdSe/ZnS III
in comparison to CdSe NCs) with shell growth. Overall there is
decrease in each recombination lifetime with shell growth. Thus,
the overcoating with ZnS suppresses deep trap emission by
passivating most of the vacancies and trap sites on the crystallite
surface, resulting in PL which is dominated by band-edge and
initially populated excitonic recombinations [12].

4. Conclusions

The synthesis method is feasible to generate CdSe/ZnS core/


shell nanoparticles by growing a ZnS layer over CdSe QDs. Capping
Fig. 7. Photoluminescence decay curves for CdSe, CdSe/ZnS I, CdSe/ZnS II and CdSe/
reagent MAA is dynamic and allow accumulation of Zn/S over
ZnS III QDs with excitation wavelength 406 nm and emission 539 nm. the CdSe surface where the been ZnS thickness is controlled by
regulating the amount of Zn/S precursors. The steady and transient
uorescence of colloidal CdSe conrmed the growth of ZnS
shell. High resolution transmission electron micrographs and
Table 2
The tted values of lifetimes 1, 2, 3, the percentage of the respective amplitudes X-ray diffraction patterns reveal nanocrystalline particles of size
A1, A2, A3 and average life time of the uorescence decay curve for CdSe and CdSe/ 3.4 1.2 nm with wurtzite lattice. SQCE model predicted the shell
ZnS QDs. thickness of ZnS (4.428.86 ), which is not visible in the TEM
images but affects the uorescence properties. PLE spectra as well
Sample A1(%) 1 (ns) A2 (%) 2 (ns) A3 (%) 3 (ns) (ns)
as the excitationemission matrix of CdSe and CdSe/ZnS also
CdSe 25 55.98 34 7.63 41 0.94 47.34 evidence the growth of ZnS, generating a Type I hetero-junction
CdSe/ZnS-I 13 47.49 33 5.91 54 0.78 35.69 which has not affected the energy states of core. Charge carrier
CdSe/ZnS-II 11 45.80 32 5.595 57 0.75 33.22 relaxation and charge transfer dynamics in CdSe QDs and CdSe/
CdSe/ZnS-III 10 40.77 31 4.96 59 0.66 28.67
ZnS core/shell QDs has been probed by measuring time-resolved
uorescence spectra at room temperature. It is revealed that the
tting are summarized in Table 2. Fluorescence decay lifetimes for average uorescence lifetimes decreased from 47.32 ns to 28.67 ns
CdSe (em 539 nm) are 55.98, 7.63 and 0.94 ns. The amplitude is for CdSe/ZnS, which is due to the enhanced contribution from
the highest for the smallest lifetime, which means this transition initially populated excitonic recombination and the reduction in
contributes maximum to the uorescence of the QDs. Upon the the surface trap states with shell growth.
growth of ZnS over the CdSe QDs, the lifetime for each transition
decreases, which mean the transitions, are faster for the core/shell
Acknowledgements
structure. Interestingly, the amplitude of the smallest lifetime
increases from 0.41 to 0.59 with increase in the shell thickness.
This work is nancially supported by UGC (Major Research
Thus, indicates its dominant contribution to the total uorescence.
Project: F. no. 42-781/2013 (SR)), New Delhi. Ms. Gurvir Kaur is
The uorescence lifetimes of CdSe QDs as well as for CdSe/ZnS
thankful to CSIR, New Delhi for providing the fellowship. We are also
core/shell are comparable to that reported by Hines et al. for CdSe/
thankful to Chairman, Department of Bio-Chemistry, P.U. Chandigarh
ZnS system [11]. The results also agree with that reported by
for their co-operation for uorescence data acquisition.
Califano et al. for CdSe nanocrystals [1]. The group theoretically
addressed that recombination lifetimes of the dark and bright
excitons in CdSe nanocrystals ranging from 2 to 4 nm in diameter. References
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