Letter

pubs.acs.org/JPCL

Ultrafast Charge Separation from Highly Reductive ZnTe/CdSe Type

II Quantum Dots
Shengye Jin,†,‡,∥ Jun Zhang,†,∥ Richard D. Schaller,†,§ Tijana Rajh,*,† and Gary P. Wiederrecht*,†,‡
†
Center for Nanoscale Materials, Argonne National Laboratory, Argonne, Illinois 60439, United States
‡
Argonne−Northwestern Solar Energy Research Center, Northwestern University, Evanston, Illinois 60208, United States
§
Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States
*
S Supporting Information

ABSTRACT: The low electron affinity of ZnTe quantum dots (QDs)

makes it of interest for critically important photocatalytic processes.
However, studies of charge transfer from such materials to adsorbates
have not been reported. Here, the ultrafast internal and external charge
separation dynamics in ZnTe/CdSe core/shell type II QDs have been
studied through femtosecond transient absorption spectroscopy. The
internal electron transfer time from a ZnTe core to a CdSe shell was
found to be 0.67 ps, while the external electron transfer time from QDs
to adsorbed molecules was found to be <0.2 ps. Such a fast external
charge separation time is due to the extraordinarily high conduction
band energy potential of this QD composition. This study indicates the
preservation of high photodriven reductive abilities in the ZnTe/CdSe
core/shell type II heterostructures.
SECTION: Spectroscopy, Photochemistry, and Excited States

C ore/shell type II semiconductor quantum dots (QDs) are

of great interest for photovoltaic and photocatalytic
applications because the edge-state positions of the core and
shell allow for the separation of photon-induced electron hole
pairs across the core−shell interface.1−10 This is in sharp
contrast to type I QDs, where both the electron and hole are
confined in either the core or shell. Type II QDs possess many
unique properties, such as long charge carrier lifetimes,3,7 fast
charge separation dynamics,10,11 and red-extended absorption
spectra.10 Among the various semiconductor materials used to
fabricate type II QDs, ZnTe draws particular interest because of
its low electron affinity (high conduction band (CB) energy
level: −2.7 eV vs Vac. in bulk with a 2.3 eV band gap).12,13 Such
a high CB offers substantial benefits when forming a type II
heterostructure by offering a large energy range over which to
select different core or shell materials. The high CB also allows
for additional freedom to tune the degree of quantum
confinement by changing core size and shell thickness to
achieve efficient electron and hole separation. Comparison of
the examples of CdTe/CdSe and ZnTe/CdSe shown in Figure
1a illustrate this point. In a CdTe/CdSe core/shell type II QD,
the limited energy difference between CBs in these two
materials requires a large CdSe shell thickness to maintain a
type II band alignment.5 However, in a ZnTe/CdSe core/shell
QD, the significantly higher CB energy level of ZnTe allows a
much thinner CdSe shell to still achieve efficient separation of
the electron and hole. A thinner shell thickness means stronger
quantum confinement and hence higher electron energy levels
in it. Therefore, ZnTe/CdSe QDs can afford higher photo-
driven reductive potentials than other type II heterostructures.
The core/shell structure also acts to protect the ZnTe core
from irreversible photooxidation damage while largely main-
taining its highly reductive properties.
Most current studies on ZnTe materials primarily focus on
synthesis.14−16 A few studies report the photophysical proper-
ties of type II heterostructures containing ZnTe as the shell for
hole trapping.17−19 However, the photoinduced internal and
external charge separation and recombination dynamics in type
II heterostructures with ZnTe as the core are still unknown, but
crucial for utilizing ZnTe materials in solar energy conversion.
In this Letter, we report the studies of internal and external
charge separation and recombination dynamics in a ZnTe/
CdSe core/shell type II QD as well as a QD−AQ
(anthraquinone-2,3-dicarboxylic acid) complex as shown in
Figure 1b. Following photoexcitation, an internal electron
transfer (ET) process (kIET) can occur from the ZnTe core to
the CdSe shell because of the type II energy alignment, which is
followed by an external ET (kEET) from the CdSe shell to AQs.
The separated electron and hole can recombine through
internal (kIR) or external (kER) charge recombination processes.
Through transient absorption (TA) studies we found that the
internal ET time is ∼0.67 ps, and the external ET time is <0.2
ps, which is ∼10-fold faster than that in CdTe/CdSe type II
Received: July 5, 2012
Accepted: July 19, 2012
Published: July 23, 2012

© 2012 American Chemical Society 2052 dx.doi.org/10.1021/jz3008886 | J. Phys. Chem. Lett. 2012, 3, 2052−2058
The Journal of Physical Chemistry Letters
Figure 1. (a) Energy level diagrams of ZnTe/CdSe and CdTe/CdSe
core/shell type II QDs. Solid blocks indicate bulk CB and VB energy
levels. Dashed lines are the estimated lowest energy electron and hole
levels considering quantum confinement. (b) The photoinduced
internal and external ET and recombination processes in ZnTe/
CdSe−AQ complexes.
QDs.10 The findings in this study reveal efficient photophysical
and photochemical properties in ZnTe/CdSe type II QDs and
pave the road for their future applications in photocatalytic
reactions.
The synthesis of the ZnTe seed and the ZnTe/CdSe core/
shell QDs, and the TA measurement setup are described in the
Supporting Information (SI). The SEM images of the ZnTe
seed and ZnTe/CdSe QDs are shown in Figure S1 (SI). Their
diameters are estimated to be 4.6 and 5.8 nm, respectively. The
thickness of the CdSe shell is then determined to be 0.6 nm.
With the addition of the shell, the stability was found to
dramatically improve relative to the ZnTe seed, with a shelf life
of at least several months. The ultraviolet−visible (UV−vis)
absorption and emission spectra of ZnTe/CdSe QDs and the
corresponding ZnTe seeds are shown in Figure 2. The ZnTe
seed exhibits the first exciton absorption peak at 500 nm, and
no photoluminescence is observed.14 For ZnTe/CdSe QDs,
two absorption peaks at 500 and 600 nm are observed.
Furthermore, an emission band emerges that is centered at 652
nm, indicating the formation of the expected type II
material.11,20,21 The energy level diagram of these ZnTe/
CdSe type II QDs is plotted in the inset in Figure 2. The
fluorescence decay of the ZnTe/CdSe QDs is shown in Figure
S2. The fitting of the decay indicates the presence of a slow
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Figure 2. UV−vis absorption (solid) and emission (dashed) spectra of
ZnTe/CdSe core/shell type II QDs, as well as the absorption of the
ZnTe seeds (no emission is observed in ZnTe seeds). The energy level
diagram of the QD is shown in the inset. Solid blocks indicate bulk CB
and valence band (VB) energy levels. The arrows indicate three
possible electronic transitions (T1, T2, and T3), which are also
marked on the corresponding absorption bands. T1 is assigned to the
transition from the lowest energy valence-band 1sh level in ZnTe
(−5.1 eV) to a delocalized conduction-band electron level in ZnTe
(−2.6 eV). T2 is assigned to the spatially indirect transition from the
valence-band 1sh in ZnTe (−5.1 eV) to the lowest energy conduction-
band 1se level in CdSe (−3.1 eV). T3 is assigned to the transition from
the lowest energy delocalized valence-band hole level (−5.6 eV) to the
conduction-band 1se level in CdSe (−3.1 eV).
lifetime component with a time constant of ∼40 ns. Such a long
exciton lifetime is not observed in the TA kinetics of a ZnTe
seed QD (Figure S5), and is strong evidence of the spatial
separation of the electron in CdSe and the hole in ZnTe.11,20,21
The fast component with a lifetime of 0.25 ns in the
fluorescence decay may be partially due to the electron and/
or hole transfer to the defect states in and around the QDs.
The TA spectra of ZnTe/CdSe QDs at different delay times
after excitation at 400 nm are shown in Figure 3a. Consistent
with its UV−vis absorption spectrum, clear bleach bands
centered at 500 and 600 nm are observed. The bleaches are due
to the state-filling of the electron in the CB and the hole in the
VB levels associated with their absorption bands.22,23 Because
of the higher degeneracy and closely spaced energy levels in the
VB (hole effective mass is larger than the electron in ZnTe and
CdSe),22,23 the formation and recovery of the bleach signals
mainly reflect the dynamics of the electrons in the CB levels. In
addition to the bleach peaks, there is a positive absorption
signal in the region red of 650 nm. A similar positive TA feature
is also observed in the ZnTe seed QDs (see Figure S5a). This
positive signal is attributed to the photoinduced absorption of
valence holes in the ZnTe core (see SI and Figure S3 for
details), consistent with the assignment in similar type II QDs
in a previous report.24 The TA kinetics probed at 500 and 600
nm are shown in Figure 3b,c. The kinetics at 600 nm exhibit the
formation of bleach signal within ∼1.5 ps, while the bleach
band at 500 nm forms within ∼0.6 ps (Figure 3c). Their
recovery kinetics are nearly identical (Figure 3b). Since the
absorption band at 600 nm is at the lowest energy level and
near the emission peak, it is assigned to the spatially indirect
transition from the lowest energy valence band 1s hole (1sh)
level in ZnTe to the lowest energy CB 1s electron level (1se) in
CdSe, denoted as T2 in Figure 2. Our effective mass
calculations show that the lowest energy electrons and holes
are largely localized in the CdSe shell and ZnTe core (Figure
S4), respectively, confirming the type II band alignment. The
dx.doi.org/10.1021/jz3008886 | J. Phys. Chem. Lett. 2012, 3, 2052−2058
The Journal of Physical Chemistry Letters Letter

Figure 3. (a) TA spectra of ZnTe/CdSe type II QDs at indicated delay times after 400 nm excitation. (b) TA kinetics of the QDs probed at
indicated wavelengths (transitions) and (c) their extended view in the early time window. The kinetics of the T1 transition were obtained by
subtraction (see main text for the details). The black solid lines are the fits to eqs S1−S3.

Figure 4. (a) TA spectra of free ZnTe/CdSe QDs at indicated delay times after 585 nm excitation. (b) TA kinetics of the QDs probed at indicated
wavelengths (transitions) and (c) their extended view in the early time window.

1se and 1sh energy levels are calculated to be −3.1 and −5.1 eV,
respectively, as shown in the inset in Figure 2, indicating a value
of 2.0 eV for transition T2. This value agrees well with the
measured value of 2.07 eV at the absorption band of 600 nm,
supporting our assignment for T2.
The TA measurements on identical QD samples were also
carried out with an excitation at 585 nm, where only transition
T2 at 600 nm is excited. The TA spectra at different delay times
after 585 nm excitation are shown in Figure 4a, still showing
bleaches of the 500 and 600 nm absorption bands. The kinetics
probed at these two bands are almost identical (Figure 4b), and
the bleach signals form faster (within 0.3 ps) (Figure 4c) than
those using 400 nm excitation. These results indicate that the
transitions at 500 nm involve the same 1se level in the CdSe
shell as T2 at 600 nm, and the electronic occupation of the level
is through excitation of T2. From the calculated energy level of
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1se in CdSe and the measured transition energy (500 nm), the
energy level in the valence band for the transition at 500 nm is
estimated to be −5.6 eV, which is very close to the valence-
band level of the CdSe shell. We therefore assign the
absorption band at 500 nm to the transition from the lowest
energy delocalized valence-band hole level to the 1se level in the
CdSe shell, as shown for the transition T3 in Figure 2.
Another TA feature that is significantly different at different
excitation wavelengths is the ratio of the bleach amplitudes at
500 and 600 nm bands (ΔA500 nm/ΔA600 nm). With 585 nm
excitation, the ratio is ∼0.85 over the whole time window (see
Figure 4a). However, the ratio increases to ∼1.1 with 400 nm
excitation in the early time (within the first 2 ps), and then
reduces to ∼0.85 (see Figure 3a), suggesting that the bleach
band at 500 nm has a contribution from another transition
(namely T1) when excited at 400 nm. The kinetics of T1
dx.doi.org/10.1021/jz3008886 | J. Phys. Chem. Lett. 2012, 3, 2052−2058
The Journal of Physical Chemistry Letters
Figure 5. TA spectra of ZnTe/CdSe−AQ complexes at indicated delay times after (a) 400 nm excitation and (b) 585 nm excitation. (c) TA kinetics
probed at 680 nm with 400 and 585 nm excitations and (d) their extended view in the early time window. The black solid lines are the fits according
to eqs S4 and S5.
(ΔA(t)T1) can be obtained by subtracting the T3 contribution
(ΔA(t)T3): ΔA(t)T1 = ΔA(t)500nm − ΔA(t)T3, with ΔA(t)500nm
= ΔA(t)T1+T3 and ΔA(t)T3 = 0.85ΔA(t)T2 at 600 nm. The
kinetics of T1 are also plotted in Figure 3b,c. The T1
contribution is only present with a high energy excitation and
can be attributed to the transition from the 1sh level in ZnTe to
a delocalized conduction-band electron level, as shown in the
inset in Figure 2. On the basis of the calculated 1sh level in the
ZnTe core and the measured transition energy (500 nm), the
energy level in the CB involved in the T1 transition is estimated
to be at −2.6 eV.
The correlation between the kinetics at T1, T2, and T3
transitions indicates the presence of an internal charge
separation process from the ZnTe core to the CdSe shell.
With 400 nm excitation (see Figure 3c), the bleach of the T1
band forms within ∼0.3 ps, due to the formation of excitons in
the ZnTe core. It quickly decays within ∼2 ps and leads to the
growth of the bleach signals of T2 and T3, indicating an
internal ET process from the ZnTe core to the 1se level in the
CdSe shell. The kinetics at 500 nm have contributions from
both T1 and T3 transitions, and therefore exhibit faster bleach
formation kinetics than T2 at 600 nm. The contribution from
T1 becomes negligible after 2 ps, and then the kinetics at 500
and 600 nm become identical (see Figure 3b), reflecting the
same electron depopulation process from the 1se level in the
CdSe shell through electron hole recombination and/or
relaxation to defect states. With excitation at 585 nm, the
transitions T1 and T3 are hardly excited, and the filling of
electrons at the 1se level in the CdSe shell is through exclusive
excitation of T2, which generates the bleach signals at both T2
and T3 bands (Figure 4).
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The fit of the kinetics in Figure 3b,c according to eqs S1−S3
yields an internal ET time constant (1/kIET) of 0.67 ps from the
ZnTe core to the CdSe shell. This internal charge separation
time is similar to reported values in CdTe/CdSe10 and ZnSe/
CdS25 type II nanocrystals. The internal charge recombination
dynamics are stretched over a long time scale from picoseconds
to tens of nanoseconds as observed in TA kinetics (Figure 3b)
and fluorescence lifetimes (Figure S2), with an averaged time
constant of 115 ps. It is much slower than the recombination
kinetics in the ZnTe seed, whose time constant is 23 ps (Figure
S5), consistent with the slow electron−hole recombination rate
expected in the type II core/shell QDs.
To study the photoinduced external charge separation and
recombination dynamics from ZnTe/CdSe type II QDs, we
chose AQ as the electron acceptor. AQ molecules have been
utilized as electron acceptors to probe the charge separation
and recombination dynamics in other QDs.10,26 The reduction
potential of AQ is −4.0 eV (vs Vac.), indicating that the ET
from ZnTe/CdSe to AQ is energetically allowed. The
preparation of the QD−AQ complexes is described in the SI.
The UV−vis absorption spectrum of the ZnTe/CdSe-AQ
complex is shown in Figure S6. The average number of the
adsorbed AQ molecules per QD is estimated to be 1−2 (see
Figure S6 for the details). The fluorescence of the QDs is
dramatically quenched by AQ.
The TA spectra of this QD−AQ complex at different delay
times after 400 and 585 nm excitations are shown in Figure 5a
and b, respectively. Unlike the TA spectra of free QDs, a broad
induced absorption band centered at ∼680 nm was observed
with a signal amplitude almost 2-fold larger than free QDs. This
positive absorption is attributed to the formation of anion
dx.doi.org/10.1021/jz3008886 | J. Phys. Chem. Lett. 2012, 3, 2052−2058
The Journal of Physical Chemistry Letters
radical AQ¯ following the external charge separation. This
assignment is consistent with the reported absorption spectrum
of AQ¯ in the literature,10,26 and confirms the occurrence of
external charge separation that produces a charge-separated
state ZnTe+/CdSe−AQ¯ with a hole in the ZnTe core and an
electron on AQ. Another TA feature in QD−AQ complexes
that is considerably different than free QDs is the depletion of
the bleach signals at 500 and 600 nm bands (more than 5-fold
less compared to free QDs). For free QDs, the TA signals at
500 and 600 nm (T2 and T3 transitions) are mainly due to the
filling of electrons in the 1se level in the CdSe shell after
internal ET. However, for the QD−AQ complex, the depletion
of the bleach signals at T2 and T3 bands imply an ultrafast
external ET process. The remaining TA spectral signals at 500
and 600 nm bands contain contributions mainly from the Stark-
effect-induced TA features.10,26−29
The Stark effect is generated in the charge separated state
(ZnTe+/CdSe−AQ¯) where the electron on AQ and hole in
the ZnTe core produce a local electric field and hence modulate
the absorption spectrum of QDs, inducing corresponding
bleach signals. This effect has been broadly observed and
reported in bare CdSe QDs with surface trapped charges or in
an externally applied DC field,27−29 as well as CdSe/ZnS−AQ
and CdTe/CdSe−AQ ET systems.10,26 Furthermore, the
excitation of T1 with 400 nm light produces a shift of the
bleach peak from 490 nm to 475 nm on the time scale of the
internal and external charge separation process in <2 ps (see
Figure 5a). This is due to the formation of the Stark effect and
AQ¯ positive signal as the charge separation process proceeds.
With 585 nm excitation, the Stark-effect-induced bleach appears
at 475 nm at very early times due to the ultrafast external ET
that occurs in <0.2 ps (see Figure 5b). Similarly, a Stark effect
should also be present in ZnTe/CdSe QDs due to photoexcited
charge carriers (a hole in ZnTe core and an electron in CdSe
shell). However, the TA signals are dominated by the state-
filling-induced features and the Stark-effect-induced signals are
relatively much smaller and therefore not observed in the TA
spectra shown in Figures 3 and 4.
The TA kinetics probed at 680 nm (absorption of AQ¯) with
400 and 585 nm excitations are plotted and compared in Figure
5c,d. These kinetics indicate the external charge separation
(signal formation) and recombination (signal decay) processes.
The whole charge separation process in the QD−AQ complex
can be understood from the following reaction:
With 400 nm excitation, the external charge separation starts
from the ZnTe core, including both internal ET (from ZnTe to
CdSe) and external ET (from CdSe to AQ) steps. However,
with 585 nm excitation, the external charge separation process
starts from the CdSe shell and includes only the external ET
step. As shown in Figure 5d, the kinetics using 585 nm
excitation are faster than those observed using 400 nm
excitation, indicating a faster charge separation process. These
kinetics are similar in the decay region (Figure 5c) because they
follow the same charge recombination process from AQ¯ to the
hole in the ZnTe core. These kinetics are well fit according to
eq S4. Fitting the kinetics with 585 nm excitation yields the
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external ET time (1/kEET) from the CdSe shell to AQ to be
<0.2 ps (within the limit of our instrument response function).
A similar external ET time was observed from a sample with 3-
fold less AQ, in agreement with the above estimation of 1−2
AQs per QD (on average) in the presented data. The external
ET kinetics (kEET > ∼5 ps−1) is at least 3 times faster than the
internal ET kinetics (kIET = ∼1.4 ps−1), and hence the
population of ZnTe+/CdSe¯−AQ can be significantly sup-
pressed in the charge separation process. This explains the
observed depletion of bleach signals at the 500 (T3) and 600
(T2) nm absorption bands in the TA spectra (Figure 5a,b).
Fitting the kinetics with 400 nm excitation yields a charge
separation time of 0.71 ps, which is very close to the internal
ET time (0.67 ps), suggesting that the external charge
separation process is limited by the internal ET step when
initiated from the ZnTe core. The averaged external charge
recombination time from AQ¯ to the hole in ZnTe/CdSe is
found to be about 300 ps (1/kER) at both excitations.
The ultrafast external ET dynamics (<0.2 ps) from ZnTe/
CdSe type II QDs to AQs is at least 10-fold faster than those
for CdTe/CdSe type II QDs (2.7 ps)10 or CdSe type I QDs
(3.4 ps)26 to the same AQ molecules with similar molecule-to-
QD ratios. This can be caused by the high CB energy level of
ZnTe and the thin CdSe shell in ZnTe/CdSe type II QDs,
which lead to a larger driving force (−ΔG) for the external ET.
A significantly enhanced ET rate induced by an increased
driving force has been broadly observed in different ET
systems.30−32 For example, it was reported that an increase of
driving force from ca. −0.3 eV to ca. −0.9 eV (tuned by the size
of QDs) led to a nearly 3 orders of magnitude enhancement in
the ET rate from CdSe QDs to TiO2 nanoparticles.31 In the
studied ZnTe/CdSe−AQ complexes, the driving force for the
external ET is calculated to be −0.9 eV, based upon the energy
difference between the 1se level of the CdSe shell (−3.1 eV)
and the reduction potential of AQ (−4.0 eV). For comparison,
the driving force for external ET from the compared CdTe/
CdSe type II QDs to AQ (with an external ET time of 2.7 ps) is
only ca. −0.2 eV.10 An order of magnitude improvement in the
ET dynamics (0.2 ps in ZnTe/CdSe vs 2.7 ps in CdTe/CdSe)
should therefore be caused by the large increase in the driving
force.
It should also be noted that the external charge
recombination dynamics (∼300 ps) from AQ¯ to the hole in
the studied ZnTe/CdSe QDs is 2 orders of magnitude faster
than that (92 ns) in the compared CdTe/CdSe type II QDs.10y
This is caused by the thinner CdSe shell in ZnTe/CdSe QDs.
The electron on AQ recombines with the hole confined in the
core by tunneling through the CdSe shell. Therefore, the charge
recombination dynamics are mainly determined by the
thickness of the CdSe shell, which is 0.6 nm in the studied
ZnTe/CdSe QD and 1.6 nm in the compared CdTe/CdSe
QDs. While considering the practical applications of these type
II materials in photodriven reductions, a thin shell should be
preferred for the fast regeneration of the holes in the core to
quickly bring the materials back to a neutral state. We note that
the CdSe shell thickness can be adjusted to permit longer
charge recombination times if the specific photocatalytic
process requires more time for the charge separated state to
be available.
The above-discussed ultrafast charge separation and
recombination dynamics indicate attractive advantages in the
ZnTe/CdSe core/shell type II QDs. First, the ZnTe/CdSe
QDs still maintain the benefits from the type II energy
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The Journal of Physical Chemistry Letters
alignment. They have a long charge carrier lifetime relative to
the ZnTe type I seeds, ultrafast charge separation dynamics,
and red-extended absorption spectra. More importantly, the
ZnTe/CdSe QDs accomplish this while having a higher
reductive potential compared to other type II heterostructures.
Furthermore, the higher reductive potential of ZnTe enables a
greater range of tunability in the core−shell structure by
changing the size of the ZnTe core and the thickness of the
CdSe shell. For example, our TA studies show that the
extraordinarily high CB energy level of ZnTe core allows for a
very thin CdSe shell (0.6 nm) in order to achieve efficient type
II energy alignment. The observed 10-fold faster external ET in
the ZnTe/CdSe QD compared to other type II QDs can be
attributed to its thin CdSe shell (large quantum confinement),
which leads to a stronger electronic coupling (a larger electron
density) and a much higher electron energy level in the CB.
This leads to an overall larger driving force for ET and hence a
faster ET rate. Ultimately, the stronger photodriven reductive
ability brought about by the higher CB energy level in the
ZnTe/CdSe QD, combined with the fast rate constants for ET,
should enable the ZnTe/CdSe QDs to reduce a greater range
of materials that are not energetically reducible by other type II
heterostructures upon photoillumination. These dynamical
studies strongly support the use of ZnTe nanomaterials for
photocatalysis, photovoltaics, and solar energy conversion
applications.
■
ASSOCIATED CONTENT
*
S Supporting Information
Synthesis and experimental setup, SEM images, fluorescence
decay, electron and hole distribution function, details of TA
analysis, and UV−vis absorption spectrum. This material is
available free of charge via the Internet at http://pubs.acs.org.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: rajh@anl.gov (T.R.); wiederrecht@anl.gov (G.P.W.).
Author Contributions
∥
These authors contributed equally.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
S.J. acknowledges support for a postdoctoral fellowship from
the ANSER Center, an Energy Frontier Research Center
funded by the U.S. Department of Energy, Office of Science,
Office of Basic Energy Sciences, under Award Number DE-
SC0001059. Use of the Center for Nanoscale Materials, and
support of J.Z., R.S., T.R., and G.P.W., is funded by the U.S.
Department of Energy, Office of Science, Office of Basic Energy
Sciences through Contract No. DE-AC02-06CH11357.
■
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