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Systematic investigation of the structure and

photophysical properties of CdSe, CdSe/ZnS QDs and
Cite this: RSC Adv., 2013, 3, 26116
their hybrid with b-carotene†
T. Pazhanivel,ab V. P. Devarajan,a G. Bharathi,a K. Senthil,c V. Ganapathy,d K. Yonge
and D. Nataraj*ab

Received 26th March 2013
Accepted 18th September 2013
DOI: 10.1039/c3ra41482e
www.rsc.org/advances
A systematic investigation was conducted to determine the excitation energy dependent emission
characteristics of CdSe quantum dot–b-carotene and CdSe/ZnS core–shell quantum dot–b-carotene
hybrid samples. The emission intensity was recorded at different excitation energies by continuously
varying the excitation energy from the band edge value of the QDs to a maximum value. In both the
hybrids, the emission intensity increased with an increase of the excitation energy and then a sudden
quenching occurred, which is in contrast with the results from bare samples, where the emission
intensity showed a decreasing trend at all excitation energies. The quantum yields corresponding to the
maximum emission are 47.12% and 69%, for CdSe QD–bC and CdSe/ZnS core–shell QD–bC hybrids,
respectively. At higher excitation energy, electrons were transferred to the molecule's LUMO level,
leaving behind holes in the valance band of the QD, and thus the produced charge separated state
became responsible for the PL quenching in the hybrid sample. We have confirmed this charge
separated state by lifetime measurements. It is because of this PL quenching behaviour of the hybrids
that the nature of the interface band structure was deduced as type I. Furthermore, because of the
involvement of higher energy photons in the quenching process, the transferred electrons in the LUMO
level of the molecule were known as hot electrons. The present paper discusses the excited state
electron dynamics across the interface between the two hybrid materials in detail.

1. Introduction
Size tuneable optical and electronic properties of semi-
conductor quantum dots (QDs) have made them interesting
materials for various applications. Solar cell fabrication is one
of the applications,1–5 in which QDs and their hybrids such as
polymer–QD hybrids,6,7 CNT–QD hybrids8 and polymer–core–
shell QD hybrids9–11 have been used. Tandem photo-electro-
chemical solar cells12 and depleted-heterojunction solar cells13
a
Thinlms & Nanomaterials Research Laboratory, Department of Physics, Bharathiar
University, Coimbatore, India. E-mail: de.natraj2011@gmail.com; Fax: +91-422-
2422387; Tel: +91-422-2428444
b
DRDO-BU CLS, Bharathiar University Campus, Coimbatore, India
c
School of Advanced Materials Science & Engineering, Sungkyunkwan University,
Suwon Campus, Cheoncheon-dong 300, Jangan-gu, Suwon 440-746, South Korea
d
Department of Chemical Engineering and SAINT, Sungkyunkwan University, Suwon
440-746, Republic of Korea
e
Surface Chemistry Laboratory of Electronic Materials, Department of Chemical
Engineering, Pohang University of Science and Technology (POSTECH), Pohang 790-
784, Republic of Korea
† Electronic supplementary information (ESI) available: XRD, TCSPC, laser ash
experimental details, optical absorption and emission spectra for bC, TA spectra
for CdSe/ZnS QDs and extended PL spectrum for CdSe/ZnS–bC hybrid system
are available. See DOI: 10.1039/c3ra41482e
are some other new device designs recently tried for solar cell
fabrication. Though QDs have several advantages over dyes, the
QD sensitized cells are less efficient, because of various possible
carrier loss mechanisms. Trap state assisted recombination
within the QDs, recombination at the interface between the QD
layer and electrolyte, recombination between the QD layer and
oxide electrode and recombination between the adjacent QD
layers are the major carrier loss mechanisms in the device
design. By solving these problems, one can improve the
performance of a QD based solar cell. Recently, there have been
attempts to extract the hot carriers (electrons and holes) from
QDs. If it is possible to utilize these hot carriers (for example,
hot electrons) then the solar energy to power conversion effi-
ciency of the solar cell can be increased further, because of the
increase in the photocurrent or open circuit voltage of the
device. The photocurrent is increased by a process known as
carrier multiplication or multiple exciton generation, and the
threshold energy required for this process to occur is two to
three times greater than the band gap energy of the mate-
rial.14–18 If the incident photon energy is below the threshold
limit of producing multiexcitons, but produces hot electrons by
exciting a few kT above the band edge state, then it is possible to
increase the open circuit voltage of the device by directly
extracting them towards the metal oxide electrode. If the

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extracted hot carriers, (for example, hot electrons) are injected
into the metal oxide electrode, without energy and recombina-
tion losses, then the denition for the open-circuit voltage,
which is usually dened as “the difference between the redox
potential of the electrolyte and the conduction band (CB) edge
state of the QD” could be redened as “the difference between
the redox potential of the electrolyte and the higher energy state
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CB level of the QD”. This fundamental difference in the carrier
extraction process, then, improves the open circuit voltage of
the device. However, the extraction process (of the hot carrier)
has to take place before the ultra fast cooling towards the band
edge states. In a bulk material, hot electron extraction is diffi-
cult, because cooling down is through continuum states on an
ultrafast timescale (Fig. 1). In the absence of a phonon bottle-
neck effect in QDs,19 ‘Auger like’20 processes and ‘trap states’21
are the pathways of cooling and are, in fact, dominant at higher
excitation energies, as reported elsewhere.22 Therefore hot
electron extraction from QDs is also a challenging process.23,24
Recently, Anshu Pandey and Philippe Guyot-Sionnest25 have
extracted hot electrons from CdSe/ZnSe core–shell QDs. They
were irradiated with a resonant 4 mm intraband pulse, aer an
interband excitation pulse, so that the valence band edge elec-
trons were promoted to a higher energy state CB level (1pe) of
the CdSe QD, and from there they were tunnelled out through
the ZnSe outer layer as hot electrons. A similar hot electron
extraction process was also realised in PbSe QDs by Aydil and
Zhu.19 They prepared PbSe QDs with a size distribution of 3.3–
6.7 nm and deposited a layer of them onto a TiO2 pre coated
surface. For a particular size, hot electron extraction was made
possible from PbSe QDs, because the interface is such that the
higher energy state CB electrons of this particular size QD were
able to transfer to the CB level of TiO2. Apart from these
attempts, silicon based thin solar cell devices have also been
constructed proving the hot electron effect in device
performance.26
Fig. 1 Schematic representation of a hot electron cooling process in the bulk
material. Here, the CB states are continuous in nature and therefore the photo-
generated hot electrons relax down towards the CB edge state, on an ultrafast
timescale, and thereby lose their excess energy as heat.
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Here, we report on the successful extraction of hot electrons
from CdSe and CdSe/ZnS core–shell QDs by using the b-caro-
tene (bC) molecule as an electron acceptor. All trans bC27 is a
well known linear conjugated molecule and its structure has a
backbone of eleven carbon double bonds. It is well known that
this molecule can establish charge transfer type interactions28
with iodine and AsF5 and therefore its natural absorption is
reduced or completely disappears. However, the interaction
between bC and nanostructures like QDs, nanowires, nano-
tubes etc., is not well studied. Recently this molecule was
successfully introduced into carbon nanotubes and was inves-
tigated for its structural stability and conformation.29 Here we
have used this molecule to prepare a hybrid with CdSe and
CdSe/ZnS core–shell QDs and investigated their photophysical
properties in detail.
2. Experimental details
2.1. Preparation of CdSe and CdSe/ZnS core–shell QDs
CdSe QDs were prepared by a well-known method, as reported
elsewhere.30 First we prepared 0.2 mmol of selenium stock
solution by dissolving selenium powder in 5 ml octadecene
(ODE) and kept the solution at 180
C for an hour. Then we
prepared cadmium solution by taking CdO powder as a
precursor in a mixture solution of 1 ml oleic acid (OA) and 9 ml
of octadecene, which was then heated to 180
C for an hour until
a clear solution was formed. While increasing the temperature of
the CdO containing solution to 220
C, 5 ml selenium stock
solution was added and the reaction was allowed to run for 15
minutes to obtain large CdSe QDs. The as prepared colloidal QD
solution, aer repeated washing with ethanol, was subjected to
structural and optical characterization. The as obtained nal
product was a semisolid which was suspended in 10 ml ODE for
core–shell preparation. The as prepared Zn and S precursors were
simultaneously added into the already prepared CdSe QD solu-
tion (suspended in ODE), which was also kept at 180
C. Now
aliquots were taken out of this reaction every ve minutes to
obtain core–shell QDs. The removed aliquots were washed
several times with ethanol and re-dispersed in 10 ml of hexane.
To prepare the hybrid sample, different volume of bC solution (1
ml–5 ml) prepared at 0.01 mmol, was mixed with the re-dispersed
QD and QD and core–shell QD solutions.
2.2. Characterization
The crystal structure and size details of the as prepared samples
were obtained using X-ray diffraction (XRD) and high resolution
transmission microscopy (HR-TEM). XRD patterns were recor-
ded by using an XPERT PRO model PANalytical X-ray diffrac-
tometer. HR-TEM images were recorded with a JEOL model
STEM instrument. Optical absorption and steady state photo-
luminescence (PL) experiments were done using a SHIMADZU
3600 UV-Vis-NIR model spectrophotometer and a Horiba Jobin
Yvon spectrouromax 4, respectively. Life time measurements
were conducted using time correlated single photon counting
(TCSPC) and laser ash photolysis methods (details of the
experiments are given in the ESI†).
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3. Results and discussion
3.1. Structure, optical and PL study of CdSe QDs and CdSe
QD–bC hybrids
Fig. S1a† shows the XRD patterns of (i) bare CdSe QDs and (ii)
the CdSe–bC hybrid sample. The diffraction patterns are iden-
tical and correspond to the cubic structure of CdSe. The
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calculated lattice parameter value is 6.102 Å. Fig. S1b† is a high
resolution TEM image of the bare sample and shows the
uniform size (about 4 nm) distribution of the CdSe QDs.
Optical absorption spectra were recorded from the bare CdSe
QD (curve ‘i’ in Fig. 2a) and bio-molecule samples (Fig. S2(a))†
by dissolving them separately in hexane solution. The CdSe QD
sample shows band edge absorption at 2.0 eV which corre-
sponds to the 1sv–1sc transition. In addition to this, we also
noticed two weak absorption bands at 2.12 eV and 2.28 eV,
respectively, due to the 2sv–2sc, and 1pv–1pc transitions.31
These well resolved higher energy state CB levels indicate that
the optical quality of our as prepared CdSe QD sample was
good. We calculated the intraband energy separation between
these two energy levels as 0.16 eV. The absorption spectrum of
bC shows a characteristic wide band in the range between 3.54
and 2.36 eV, with a maximum at 2.73 eV. According to previous
reports this absorption band is assigned to a transition from the
S0 to S2 state of bC.32 The absorption spectrum corresponding to
the hybrid sample consists of both of its components (curve ‘ii’
in Fig. 2a), and this means that there is no charge transfer type
interaction between them. When the molecule is interacting
with a quantum nanostructure, like QDs, then the relative
energy level position between the molecule and nanostructure
is important for the charge transfer type interaction. In our case
we believe that the relative energy level position between the
CdSe QD and bC molecule does not favour charge transfer and
therefore no such interaction is established between them.
Steady state PL characteristics of CdSe QDs and the hybrid
samples were obtained at an excitation energy of 2.06 eV, which
is equivalent to the band edge absorption value of the QDs. The
Fig. 2 (a) Optical absorption spectra of (i) CdSe QD and (ii) CdSe QD–bC hybrid.
The three absorption band positions of the CdSe QDs at 2.0, 2.12 and 2.28 eV,
corresponding to (1sv–1sc), (2sv–2sc) and (1pv–1pc) transitions are indicated by
arrows. The inset of this figure shows schematic representations of the energy
levels, corresponding to the absorption maxima at 2.0, 2.12 and 2.28 eV in the
band structure. (b) Emission spectra of CdSe QDs and the hybrids with different
concentrations of carotene. When the added bC concentration was 5 ml, then a
saturation in the emission was reached.
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quantum yield corresponding to the bare CdSe QD sample,
calculated with reference to rhodamine B, is about 17.62%. In
the case of the hybrid samples, the quantum yield increased
with an increase in the bC concentration. When the added bC
concentration was about 5 ml, then a saturated emission was
noticed as shown in Fig. 2b. We also noticed a gradual shi in
the emission maximum towards the higher energy side, as the
bC concentration was increased from 1 ml to 5 ml (Fig. 2b). The
quantum yield corresponding to the emission maximum is
about 47.12%, and it is about 2.67 times higher than the yield
value calculated for the bare CdSe QD sample. The improve-
ment in the quantum yield and blue shi are due to the surface
passivation effect on the QDs by bC. Because of this passivation
effect, non-radiative relaxation pathways are arrested and
therefore the quantum yield is increased. The reason for the
observed blue shi in the emission maximum could be due to
the induced Stark effect. The attachment of bio-molecules
occurs via electrostatic or covalent forces; therefore, a distri-
bution of these molecules on the QD surface imposes a net
electric eld across the QD core, as reported elsewhere.33 It
could be because of this electric eld assisted Stark effect that
the energy levels of the core QDs are separated, thus resulting in
a blue shi in the emission maximum.
3.2. Excitation energy dependent PL study up to 2.48 eV
Excitation energy dependent PL experiments were conducted on
bare and hybrid samples. The quantum yield of the bare CdSe
QDs was decreased gradually (curve ‘i’ in Fig. 3), from a value of
17.62 to 5.81%, as the excitation energy was increased from the
band edge value of the QD to higher energy values. This gradual
decrease in the quantum yield is usual behavior and has been
observed by others. Unpassivated surface states, associated with
the surface atoms of colloidal QDs, provide a nonradiative
relaxation pathway or channel to the highly excited charge
carriers, and therefore, the higher energy excited charge carriers
are either inhibited or deviated from reaching the band edge
states, from where radiative recombination results.34 In the case
of the hybrids, the quantum yield increased with the increase of
Fig. 3 A plot of excitation energy dependent quantum yield values for bare
(curve ‘i’) and hybrid (curve ‘ii’) samples.
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the excitation energy up to 2.28 eV, and this is unusual behavior.
Beyond this, the quantum yield decreased suddenly (curve ‘ii’ in
Fig. 3), reaching a minimum yield value of 0.25%, at 2.48 eV
excitation energy and above. The initial increase in the
quantum yield is due to the connement of the photoexcited
electrons in the CB offset between the QD and bC molecule.
However, when the electrons were excited beyond the conne-
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ment level then there was a sudden drop in the quantum yield
and that must be due to the transfer of electrons to the LUMO
level of the molecule.
According to previous reports, either CB edge electron
transfer (scheme 1 in Fig. 4) or hole transfer (scheme 2 in Fig. 4)
assisted charge carrier separation is responsible for the
observed uorescence quenching in hybrid samples. However,
in our case the higher energy state CB electron or hot electron
transfer becomes responsible for the uorescence quenching
(scheme 3 in Fig. 4), and excitation energy dependent PL
investigations have shown this clearly. Both the CB edge excited
electrons and valence band (VB) edge created holes do not
transfer to the molecular energy levels and this means that the
nature of the interface between the CdSe QDs (of size about
4 nm) and bC molecules is type I in nature as shown in scheme 3
of Fig. 4. This hybrid sample is, therefore, different from other
hybrids such as CdSe–rhodamine B,5 CdSe–methylene blue23
and CdSe–methyl viologen,24 where the molecule's LUMO level
is just below the CB edge level of the CdSe QD.
The CBoffset between the CdSe QD and bC energy levels is
0.28 eV and we obtained this by subtracting the energy value
corresponding to the start of the emission quenching point (at
2.28 eV) from the optical absorption maximum value at 2.0 eV
(CB edge state of CdSe QD). Using this experimental CBoffset
value in eqn (1), obtained from the interfacial energy diagram
(Fig. 4 ‘scheme 3’),
CBoffset ¼ EAQD  EAbC (1)
where, EAQD and EAbC, respectively, correspond to the electron
affinity values of the CdSe QD and bC, we have calculated EAQD.
Fig. 4 Three different possible combinations of relative energy levels for CdSe QDs
and bC are depicted in three different schemes. Scheme 1: the S2 level of the
carotene is lower than the CB edge state of the QD, and this favours electron
transfer from the QD to bC. Scheme 2: the S0 level of bC is on the higher energy side
of the VB edge state of the QD, and this favours hole transfer into the S0 level.
Scheme 3: the S2 and S0 levels confine the QD energy levels at 2.0, 2.12 and 2.28 eV.
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Before that, EAbC was obtained using eqn (2). For this, the
experimental energy band gap (Egb) (which is 2.57 eV) and the
reported ionization potential (IP) energy (5.84 eV)35 values of
bC were used.
EAbC ¼ Ip  Egb (2)
The obtained electron affinity value of the CdSe QDs is 3.55
eV, which closely matches with the reported experimental and
theoretical EA value of CdSe QDs of similar size.36 Matching the
EA value of the CdSe QDs with that of reported values has
indirectly conrmed the experimental CBoffset value between
these two hybrid systems.
3.3. Lifetime measurement analysis for CdSe QDs and the
hybrid
To conrm the surface passivation effect on the QDs and also to
calculate the electron transfer rate to the LUMO level of bC,
lifetime measurements were conducted by the TCSPC method.
For comparison purposes, a similar study was also conducted
on a bare QD sample. Fig. 5 compares the time resolved PL
decay curves measured at 2.0 eV and 2.48 eV, respectively, cor-
responding to the band edge state and higher energy state CB
level of the CdSe QDs of the bare and hybrid samples. These
emission decay proles were tted using the triexponential
function37 (eqn (3)) and tting parameters such as a and s were
obtained.
t t t
y ¼ a1 e s1 þ a2 e s2 þ a3 e s3 (3)
By substituting the component values of the tting parameters
a1, a2, a3 and s1, s2, s3 into eqn (4), we calculated the average
lifetime value <s> for the electrons in the respective energy
levels. Table 1 summarises the tting parameters and the
calculated <s> values for both bare and hybrid samples at two
different energy levels. The <s> corresponding to the band edge
state of the QD, in its hybridized state with bC is 13.76 ns and
which is high in magnitude when compared to the <s> value of
7.58 ns corresponding to the CB edge state of the bare QD. The
reason for longer lifetime is attributed to the surface
Fig. 5 PL decay curves for bare and CdSe QD–bC hybrid samples recorded at 2.0
eV and 2.48 eV.
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Table 1 Lifetime values of electrons in bare QDs and hybrid samples measured
at 2.48 and 2.0 eV
Emission
Sample (eV) s1 (ns) s2 (ns) s3 (ns)
Pure QDs 2.48 0.2 (8%) 2.5 (45%) 8 (47%)
2.0 0.26 (8%) 2.5 (37%) 8.6 (55%)
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QDs with bC 2.48 0.47 (20%) 1.5 (33%) 5.8 (47%) 4.92
2.0 0.27 (3%) 2.2 (11%) 14 (86%) 13.76
passivation effect on the QDs by bC. The calculated <s> value
corresponding to the higher energy state CB of the QDs, in the
hybridized form with bC, is much shorter than the similar value
measured from the bare QD sample (curve ‘pure 2.48 eV’) and
this must be because of the transfer of electrons to the LUMO
level of the molecule. By substituting the <s> values corre-
sponding to the higher energy level CB of the bare and hybrid
QD samples in eqn (5), we have calculated the electron transfer
rate (ket). The calculated electron transfer rate is 5.35  107 s1
and this value is similar to the reported value calculated for the
transfer of electrons from CdSe QDs to TiO2.38 However, because
of the experimental limitations in measuring the shortest life-
time components at the higher energy level, the calculated rate
constant is an approximate value only.
P
n electrons for a few tens of nanoseconds and therefore any
ai si 2
hsi ¼ i¼1
Pn
ai si
i¼1
1 1
ket ¼  (5)
hsibcCdSe hsiCdSe
3.4. Transient absorption analysis
Finally, to conrm the charge separated state, with electrons in
the LUMO level of bC and holes in the valence band edge state
of CdSe QD, nanosecond transient absorption (TA) measure-
ments were made. The wavelength of the laser source used for
this experiment was 355 nm (3.50 eV). Fig. 6 shows the TA
spectra of the hybrid sample with two negative bleach minima
at 2.75 and 2.0 eV. As these bleach positions match with the
absorption maximum value of bC and the absorption edge value
of the CdSe QDs at 2.75 and 2.0 eV, their origin is expected to
come from these two respective systems. This could not be due
to the direct excitation of either bC or CdSe QDs because their
respective individual bleach proles recover at a much faster
rate. For example, in the case of pure bC the excited state
electrons in the S2 state undergo a fast internal conversion
down to the S1 state within 200 fs. Again, from there the elec-
trons undergo a downward transition to the S0 state in a few
tens of picoseconds.39–41 In the case of the CdSe QDs, the band
edge bleach prole recovers within a few nanoseconds, as
reported elsewhere.42 Therefore the slowly recovering negative
bleach at 2.75 eV must be due to the transferred electrons from
the CdSe QD to the LUMO level of the bC. As the excitation
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Average
lifetime (ns)
6.67
7.58
Fig. 6 The transient absorption (bleach) spectra recorded from the CdSe QD–bC
hybrid sample. The negative bleach positions ‘1’ and ‘2’ correspond to the
presence of holes in the VB edge state of the QDs and to the presence of trans-
ferred electrons in the LUMO level of bC, respectively. The positive bleach position
‘3’ corresponds to the absorption of bC.
energy used in this TA experiment is well above the second
absorption maximum of the QDs, the VB electrons of the
photoexcited CdSe QDs are transferred to the LUMO level of the
bC molecule. The transferred electrons remain there as hot
further transition to this molecular level (followed by the exci-
(4) tation of the molecule (HOMO to LUMO)) is blocked, and as a
consequence the negative bleach is obtained at 2.75 eV. To
make sure that this 2.75 eV negative bleach is from bC, we
measured the difference between the two peak positions at A1
and A2 which is 0.27 eV, agreeing with the vibrational level
separation of bC.
The other slow recovering negative bleach at 2.0 eV is due to
presence of ‘holes’ in the VB edge state of the CdSe QD. This
2.0 eV bleach appears until the holes in the VB edge state of
CdSe QD are depleted by the back transferred electrons from the
LUMO level of the bC. Hot electrons in the molecular LUMO
level back transfer to the CB edge state of the CdSe QDs and
from there they recombine with the holes in the VB level of the
CdSe QDs, and by this process (cooling process) both the
molecule and the QD are brought back to their respective
neutral states. Fig. 7a and b show the time dependent absorp-
tion proles measured at the 2.0 and 2.75 eV peak positions of
the bleach spectra. To determine the average lifetime values
associated with this back transferring process and the cooling
of the charge carriers, we tted the absorption curves measured
at 2.75 and 2.0 eV with Gaussians. A value of 24.44 ns was
obtained from the absorption curves at 2.75 eV and this could
correspond to the average lifetime value for the back trans-
ferring of hot electrons into the CB edge state of the CdSe QDs.
A similar average lifetime value measured from the absorption
curves at 2.0 eV is 30.05 ns, and this corresponds to the time
taken by the back transferred electrons to recombine with the
holes in the VB of CdSe QDs (cooling process). Since the average
lifetime value for the cooling process is higher in magnitude
than that required for the back transferring process, this
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Fig. 7 The time dependent absorption spectra measured at 2.0 eV and 2.75 eV,
corresponding to the CdSe QDs and bC in the hybrid sample. The spectra were
fitted with Gaussians to find the average lifetime values of electrons at the
respective energy levels.
indicates that the recombination process is possible only
aer the arrival back of transferred electrons into the CB edge
state of the CdSe QDs. These differences in the <s> lifetime
values therefore suggest that the back transferring mecha-
nism or pathway of electrons is via the CB edge state of the
CdSe QDs. The slowly recovering negative bleaches at 2.75 and
2.0 eV are, therefore, direct evidence for the existence of hot
electrons.
Type I core–shell structures, such as CdSe/ZnS, are well
known for their enhanced emission yield.43 However, when
their outer surfaces are attached with electron accepting
molecules like benzoquinone or surrounded by metal oxide
nanocrystals (TiO2), then the photoexcited charge carriers are
separated out of the CdSe QDs and the quantum yield from the
core QD is quenched.44 In this surface functionalized type I
CdSe/ZnS core–shell QD, the photoexcited electrons are ther-
malized to the CB edge state of the CdSe QD, and then they
tunnel out to the electron accepting system (molecule or metal
oxide). It is because of this thermalization process that
excess energy possessed by the electrons is lost in the core QD
itself (when it is excited with a higher excitation energy).
Fig. 8 (a) Schematic representation of b-carotene intercalation on the CdSe QD. (b). Schematic representation of the constrained vibrational motion of the –CH]CH–
out of plane vibrational mode at 974 cm1.
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Interestingly, our hybrid system, which is also type I in nature,
has shown different characteristics. It exhibits both uores-
cence enhancement and quenching, and one can tune the
sample between these two states just by varying the excitation
energy. At a lower excitation energy, because of the conne-
ment effect, the quantum yield was increased similar to a
CdSe/ZnS core–shell structure. But once the excitation energy
was raised above a threshold value of 2.25 eV then the elec-
trons were transferred to the LUMO level of the molecule,
leading to the PL quenching. We believe that the electron wave
function overlap with the molecular level is high for the higher
energy state CB electrons of the CdSe QDs, and therefore they
are transferred to the bC.
In this hybrid nanostructure, emission enhancement and
quenching are possible only when bC establishes physical
contact with the QD surface. This situation is equivalent to
introducing a ‘hole’ on the top of a half-lled vessel such that a
water outlet is possible only when the water level rises up to the
‘hole’. In a similar manner electron extraction out of the QD is
possible (in this hybrid) only when electrons are raised above
the CB edge state of the QD. In the oleated CdSe QD, bC
intercalates inbetween the oleic acid molecules as shown in
Fig. 8a and can develop either a weak physical or strong
chemical binding with the QD surface. However, because bC
does not have any functional groups to bind, chemical binding
with the QD surface is not possible. On the other hand, a weak
physical interaction is possible. A similar weak interaction
between the interacting molecules and the QDs is well repor-
ted.5 To conrm the intercalation, FTIR spectrum was recorded.
Fig. 9 (curve b) shows the FTIR spectrum of the CdSe–bC hybrid
sample. Interestingly, we noticed a suppressed vibrational
mode (of bC) at 974 cm1, which usually originates from the
–CH]CH– out of plane vibration of the bC. (For comparison
purposes, the FTIR spectrum was also recorded from bare QD
and pure bC as shown in Fig. 9(a and c).) It can be said that this
out of plane vibrational motion of the –CH]CH– is constrained
in this hybrid sample, and we believe that this constraint is due
to the intercalation of the bC between the oleic acid molecules
(Fig. 8b).
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Fig. 9 The FTIR spectra of (a) CdSe QD, (b) hybrid and (c) bC samples. The
suppressed vibrational mode of the hybrid sample at 974 cm1, in comparison to
the bC sample, is highlighted by a circle.
3.5. Excitation energy dependent PL beyond 2.48 eV
In the excitation energy dependent PL study bC was not excited
up to 2.48 eV. If bC was also excited then it would inuence the
emission process of the hybrid sample. To determine the nature
of the inuence, the excitation energy dependent PL study was
extended beyond 2.48 eV. When the excitation energy was
around 2.75 eV, then a weak emission band started to appear at
2.0 eV as shown in Fig. 10. As this emission maximum matched
the band edge value of the CdSe QDs, it could originate from the
CdSe QD, and either charge or energy transfer induced inter-
action between bC and the QD may be responsible for it.
As the LUMO level of the molecule is at a higher energy
position, the excited molecules can transfer their electrons to
the CB edge state of the CdSe QD, leaving behind the holes in its
Fig. 10 The excitation energy dependent emission behaviour in the range from
2.26 to 2.95 eV.
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HOMO level. These holes will be then preferentially occupied by
the electrons from the VB edge state of the QD, and as a
consequence holes are introduced in the VB edge state of the
QD. When these introduced holes recombine with the trans-
ferred electrons in the CB of the QD, then band edge emission is
possible, or otherwise if the holes are introduced from the QD's
deep VB states into the HOMO level of the molecule, followed by
the excitation of the QD, then they could be depleted immedi-
ately followed by the recombination process with the excited
electrons in the CB edge state of QD. By this process bC and QD
are neutralised. Now once again electron–hole pairs may be
introduced into the QDs, followed by the excitation of the
molecule, as discussed before, and this could lead to a weak
band edge emission. However, the above charge transfer
induced emission must occur at all higher excitation energies.
However, the experimental results have shown (Fig. 10) that this
weak emission appears only when the excitation energy
matches the absorption maximum of bC at 2.75 eV. This means
that the charge transfer induced process is not responsible for
this weak emission. The other possibility is through the energy
transfer assisted process. The emission spectrum of bC is in the
range from 2.48 to 1.91 eV (Fig. S2(b))† (the emission spectrum
of bC given is similar to that reported elsewhere45) and as it is
overlapping with the absorption band position of the acceptor
CdSe QD at 2.0 eV, energy transfer assisted band edge emission
from the CdSe QDs is possible.46 Some of the bC molecules
which were not in contact with the QD surface, but still in close
proximity can have an energy transfer type interaction with the
QDs, and make them emit at the band edge value.
4. CdSe/ZnS core–shell with bC hybrid
system
4.1. Structure, optical and PL emission analysis of CdSe/ZnS
and its hybrid
Fig. S3† shows the XRD diffraction pattern of (i) the bare core–
shell QDs and (ii) the core–shell QD–bC hybrid samples. The
XRD pattern consists of diffraction peaks from both the core
CdSe QDs and the ZnS shell layer. The diffraction peaks at 2q ¼
25.3, 42.2 and 49.7
correspond to the CdSe QDs and the peaks
at 2q ¼ 28.5, 33.0 and 47.5
correspond to the ZnS shell layer.47
The optical absorption spectrum was also recorded from the
core–shell QD and its hybrid samples. The spectrum corre-
sponding to the core–shell QD shows a band edge state
absorption at 1.97 eV (1sv–1sc) of the core CdSe QD. Higher
energy states of the core QD were also resolved at 2.10 and 2.21
eV, which respectively correspond to (2sv–2sc) and (1pv–1pc)
transitions in the absorption spectrum. The spectrum corre-
sponding to the core–shell QD–bC hybrid sample shows bands
of the core–shell QD and bC as in Fig. 11a (curve ‘ii’). Here,
interestingly, bC's absorption band position is red shied, and
this could be possible only if the molecule undergoes a
conformation change from the trans to the cis isomer.48 The
prepared core–shell QDs are monodispersed in nature and
therefore bC seems to undergo a conformation change from the
trans to the cis isomer, and thus becomes responsible for the red
shi in the absorption maximum. One more interesting
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Fig. 11 (a) The optical absorption spectra of the CdSe/ZnS core shell QD and its
hybrid with different concentrations of bC. The inset of this figure is an enlarged
view of the absorption region and it indicates the red shift (dotted line) in the
absorption of the hybrid sample. (b) The emission spectra of the core–shell QD and
its hybrid with different concentrations of bC. The inset of this figure is the enlarged
view of the highlighted emission region, which shows a gradual blue shift.
observation is that the absorption maximum of the CdSe/ZnS
QDs is also red shied with respect to the absorption maximum
of the CdSe QDs (Fig. 11a). Though the size of the core CdSe QD
remains the same in both the samples, because the ZnS shell
layer was grown over the already prepared core CdSe QDs, there
is a red shi in the absorption maximum of the CdSe/ZnS and
that is due to the delocalization of excitons into the ZnS shell
layer as reported elsewhere.49
The as prepared core–shell QD’s quantum yield is about
53.7% and this matches the previously reported value.50 The
reason for the increased quantum yield, in comparison with the
yield value of the bare QD sample, is the surface passivation
effect on CdSe QD by the ZnS shell layer. We have also noticed a
red shi in the emission maximum, as observed by others, and
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this is due to the delocalization of excitons into the ZnS shell
layer.49 These observed results have, thus, conrmed the surface
passivation effect on CdSe QDs by the ZnS shell layer. Emission
spectra were recorded from the core–shell QD–bC hybrid
sample at 2.06 eV, with different concentrations of bC (1 ml–
5 ml). A maximum yield of 69% was obtained with a 5 ml
concentration of bC. The observed further increase in the
quantum yield could be due to the surface passivation effect of
bC on the ZnS shell layer of the core–shell QDs (Fig. 11b). Defect
states present in the ZnS layer are passivated by bC and hence
the presence of relaxation process through these defect states is
deduced and therefore the quantum yield is increased further.
Fig. 12a and b show a schematic representation of the surface
passivation effect on the ZnS shell layer. A slight blue shi was
seen in the emission maximum (Fig. 11b), and the reason for
this could be the surface passivation effect on the ZnS shell layer
by bC. When the delocalization of excitons into the ZnS shell
layer is responsible for the red shi in the emission maximum
of the core–shell QDs, the observed blue shi in the emission
maximum must be due to the decrease in the “exciton delo-
calization effect” into the shell layer. The observed results
therefore support the surface passivation of the ZnS shell layer
and the consequent enhancement in the emission yield.
4.2. Excitation energy dependent PL behaviour of the CdSe/
ZnS–bC hybrid system
We observed the emission behaviour of the core–shell–bC
hybrid sample by exciting it at higher energies, well above the
second absorption maximum of the core CdSe/ZnS QD at
2.21 eV. Fig. 13 shows the excitation energy dependent
quenching behaviour of the CdSe/ZnS and CdSe/ZnS–bC
samples. Here also the emission quenching started suddenly,
once the excitation energy was increased beyond the absorption
maximum (curve ‘ii’ in Fig. 13) at 2.21 eV. However, up to
2.21 eV, the emission intensity was increased and this means
that the excited electrons up to this energy level are conned in
the core QD. The sudden quenching was due to the transfer of
higher energy (hot) electrons from the CdSe QD to the LUMO
level of the bC. Though a similar higher energy CB electron
transfer process becomes responsible for the quenching in
the CdSe–bC and CdTe–bC51 hybrid systems, here the electron
Fig. 12 (a) Schematic diagram of a ZnS passivated CdSe QD and the relative energy
levels. The “dashes” in the ZnS are the surface states. The photo excited electrons are
relaxing through the surface states of the ZnS, and this process limits the emission
yield. (b) The carotene passivated core–shell QD. Here surface states are removed,
therefore the electron relaxation processes through these levels are blocked.
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Fig. 14 The relative energy level positions of the LUMO level of the molecule
and the higher energy state CB level of the QD, separated by a ZnS barrier.
Tunnelling occurs when the levels match.

4.4. Transient absorption analysis of the CdSe/ZnS core–

shell and its hybrids
We also recorded bleach spectra from the core–shell–bC hybrid
sample and conrmed the presence of transferred hot electrons
Fig. 13 A plot of excitation energy dependent quantum yield values for bare in the LUMO level of the molecule. Fig. 16a shows the transient
CdSe/ZnS (curve ‘i’) and CdSe/ZnS–bC hybrids (curve ‘ii’) samples. absorption spectra or bleach spectra of the core–shell–bC
hybrid sample which shows two negative bleach minima at 2.69
and 1.97 eV, respectively, due to the presence of transferred
transfer process occurs via tunneling through the ZnS shell electrons in the LUMO level of bC and due to the presence of
layer. It has to be pointed out that the emission quenching is holes in the VB edge state of the core CdSe QDs. Both the
not complete as was noticed in the case of the CdSe–bC and negative bleaches recovered slowly, because of the back transfer
CdTe–bC hybrid systems. We believe that the mismatching of process. Once the negative bleach at 2.69 eV recovered
energy levels across the barrier (ZnS layer), limits the tunneling completely then the positive bleach started to appear at 2.69 eV
probability, because of the violation of the tunnelling condi- due to the band edge absorption of the molecule. This positive
tions (Fig. 14). bleach position of the molecule is red shied because of the
conformation change as discussed before. We also noticed one
more positive bleach at 2.25 eV, as observed by several others in
4.3. Lifetime measurements of the CdSe/ZnS core–shell QDs the core–shell structure, and this is due to the Stark effect.31 The
and the hybrid system Stark eld is developed inside the QD when its surface is
Fig. 15 shows the TCSPC spectra recorded from the CdSe/ZnS passivated by the ZnS shell layer, and consequently the energy
core–shell QD sample, in comparison with that of the bare CdSe levels are split. When the absorption takes place, with the
QDs sample. The <s> value, at the CB edge state of the ZnS
passivated CdSe core QD sample, is 17.55 ns and which is high
in magnitude when compared to the value of 7.5 ns measured
from the CB edge state of the bare CdSe QD sample. This higher
lifetime value is usually attributed to the surface passivation
effect as reported elsewhere.52
Furthermore, to determine the electron transfer rate from
the core CdSe/ZnS QD to the bC molecule, TCSPC spectra were
recorded from the hybrid sample as well. Table ST1†
summarizes the <s> values for the CdSe/ZnS core–shell and its
hybrid. The measured lifetime values also support the surface
passivation effect on the core–shell QD sample by the mole-
cule. For example an increase in the <s> value at the CB edge
state of the core CdSe/ZnS QD, in the presence bC, is due to the
surface passivation effect of bC on the ZnS shell layer. The <s>
of the hybrid sample at 2.48 eV is 11.04 ns and which is much
lower than a similar value from the core–shell QD measured
from a similar energy position. This difference in lifetime
value is due to the transfer of hot electrons from the core–shell Fig. 15 The PL decay curves of CdSe QD, CdSe/ZnS core–shell QD and CdSe/
QD to the bC. ZnS–bC hybrid samples measured at 1.97 and 2.48 eV.

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Fig. 16 (a) Transient absorption spectra recorded from the CdSe/ZnS core–shell QD–bC hybrid sample. The negative bleach positions ‘1’ and ‘2’, respectively,
correspond to the presence of holes in the VB edge state of the QD and to the presence of transferred electrons in the LUMO level of the bC. The positive bleach position
‘3’ corresponds to the absorption of bC and the positive bleach position ‘4’ corresponds to the Stark effect assisted positive absorption. (b) The time dependent
transient absorption profile measured at 1.97 and 2.69 eV of the CdSe/ZnS QD–bC hybrid sample.
involvement of these split energy levels then the positive bleach
starts to appear at 2.25 eV. We have also noticed a similar
positive absorption bleach at 2.25 eV from the bare CdSe/ZnS
core–shell QD sample as shown in Fig. S4.†
The <s> value for the back transfer process was obtained by
tting the bleach spectra at 2.69 eV (Fig. 16b) and this resulted
in a value of 39 ns. This value is high in magnitude when
compared to a similar value obtained at 2.75 eV from the ZnS
passivation free CdSe QD–bC hybrid sample. The obtained
higher lifetime value suggests that the transferred electrons
spend more time in the bC molecule, in the case of the core–
shell QD–bC hybrid sample, than in the case of the CdSe QD–bC
hybrid, and that must obviously be due to the presence of the
ZnS shell layer, which blocks the easy back transfer of electrons
from bC to the core QD in the core–shell structure. This delayed
back transfer pathway is again via the CB edge state of the QD.
The electrons tunnel through the ZnS layer and step down to the
CB edge state of the CdSe QD and from there they recombining
with the holes in the VB edge state of the CdSe QD. It is for this
reason that the negative bleach at 1.97 eV recovers aer the
recovery of the negative bleach at 2.69 eV. The <s> value
obtained from the bleach prole at 1.97 eV is 41 ns, which is
high in magnitude when compared to the lifetime value calcu-
lated at 2.69 eV and this difference in lifetime value conrms
the back transfer pathway. We also recorded the emission
spectrum from the core–shell–bC hybrid system by extending
the excitation energy range up to 2.95 eV (Fig. S5†), in a similar
way as we did in the case of the CdSe QD–bC hybrid system.
Here, we couldn't see the weak emission band at 2.75 eV as we
have seen previously in CdSe–bC hybrid system. This could be
because the luminescence was not quenched completely in the
case of the core–shell–bC hybrid sample and therefore the
emission from the core CdSe QD, due to energy transfer type
interaction (if any), could not be observed in this sample.
5. Conclusion
In summary, we found that the photoluminescence behaviour
of the CdSe QDs, CdSe/ZnS core–shell QDs and the hybrid with
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bC samples are excitation energy dependent and therefore both
the emission enhancement and quenching were tuneable in
these systems. Importantly, we demonstrated that it is possible
to extract hot electrons from the photoexcited CdSe and CdSe/
ZnS core–shell QDs by using bC as an electron acceptor. The
relative energy level positions of the QD and bC favour hot
electron transfer from the higher energy state CB level of the QD
into the LUMO level of the bC. In the case of the CdSe/ZnS core–
shell system, the ZnS shell layer passivates the CdSe QD surface
and therefore the quantum yield was increased to 53.7%. At the
same time, in the case of the CdSe/ZnS–bC hybrid system, the
ZnS shell layer is passivated by bC and hence, the quantum yield
is improved further to 69%. In the CdSe–bC hybrid system, the
charge separated state, with electrons in the LUMO level of bC
and holes in the VB of the QD, existed for a much longer time (a
few tens of ns) and therefore the slowing down of the cooling
process was possible in our hybrid sample. This cooling process
was still slowed down in the CdSe/ZnS–bC hybrid system,
because the ZnS shell layer blocked the easy ow of electrons
back to the core QD. If these hot electrons, present in the LUMO
level of the bC can be further extracted to the electrodes of a
solar cell device, without any energy loss, then the energy
conversion efficiency of the cell could be increased further, and
our future research will be on this problem.
Acknowledgements
We would like to thank ER & IPR of DRDO, New Delhi for
providing funds for this project. We thank Dr P. Ramamurthy,
Director, National Centre for Ultrafast Processes, Chennai for
conducting the Time Resolved Photoluminescence Studies. We
also thank Dr P. V. L. Rao, Director and Dr K. Kadirvelu, joint
Director of DRDO-BU CLS, Bharathiar University, Coimbatore
for extending the centre facility.
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