6320

2009, 113, 6320–6323

Published on Web 03/31/2009

Spectral Switching of Type-II Quantum Dots by Charging

Jiwon Bang, Bonghwan Chon, Nayoun Won, Jutaek Nam, Taiha Joo, and Sungjee Kim*
Department of Chemistry, Pohang UniVersity of Science & Technology, San 31, Hyojadong,
Namgu, Pohang 790-784, South Korea
ReceiVed: January 19, 2009; ReVised Manuscript ReceiVed: March 19, 2009

We report photoluminescence (PL) spectral switching of quantum dots (QDs) by chemically controlling transfers
of electrons in and out of the type-II heterostructures. When electron charged, CdTe/CdSe (core/shell) QDs
show huge PL blue shifts (up to ∼100 nm) whereas PL of CdSe/CdTe (core/shell) QDs red-shifts. We
demonstrate reversible spectral switching of type-II QDs by repeated charging and neutralization processes.
The PL spectral shifts are due to the interactions between injected spectrator electrons and type-II character
excitons. Electron charged CdTe/CdSe QDs show PL blue shifts because of the strong repulsions between
the shell-localized excitonic electrons and injected spectrator electrons. It is opposite for CdSe/CdTe QDs,
where injected electrons in surface states attract the holes in the shells. We investigate the interactions of
spectrator electrons and excitons as varying the dimensions of type-II QDs. We also compare the type-II
QDs with type-I QDs such as CdSe, CdTe, and CdTeSe alloyed QDs. We showcase unique optical properties
of charged type-II QDs, which have many potential applications such as electro-optic modulators.

The properties of charged semiconductor quantum dots (QDs)
attract great interest for their potential applications such as
electro-optical devices.1-7 Reversible fluorescence quenching
of CdSe QDs has been demonstrated by charging.5,6 Charged
QDs show significantly reduced threshold for stimulated emis-
sions, promising applications toward efficient lasers.8 However,
the studies on charged QDs have been limited to type-I QDs.
On the other hand, type-II QDs are being extensively explored
for potential applications including biological tagging,9 lasers,10-12
and solar cells.13-15 Type-II QDs can have electron-hole pairs
that are spatially separated, and their effective band gaps are
heavily governed by their band offsets of the cores and
shells.16-22 Spatially separated excitons in type-II QDs show
unique properties such as slow Auger and radiative decay rates,22
blue shifts of the biexciton energy and single exciton optical
gains.10-12 Charging type-I QDs typically results in changes in
photoluminescence (PL) intensities.1,23 Herein, we report revers-
ible PL spectral switching of type-II CdTe/CdSe (core/shell,
C/S) and CdSe/CdTe (C/S) QDs by charging. Unique PL
properties of the charged type-II QDs are attributed to the novel
type-II characteristic carrier separations and their interactions
with spectrator electrons.
Preparations of colloidal type-II CdTe/CdSe (C/S) and CdSe/
CdTe (C/S) QDs and electron transfers in and out of the QDs
are carried out by similar methods reported previously.16,19,23,24
(See the Supporting Information (SI).) As-prepared QDs are
dispersed in anhydrous hexanes and electrons are injected into
the QDs using sodium particles under inert atmosphere. This
charging process is known to be slow owing to the low mobility
of QDs and sodium particles.1 Figure 1a shows PL wavelength
shift of a CdTe/CdSe (2.3 nm radius core/1.8 nm thickness shell)
QD sample during electron injection for 8 days. As electrons
* To whom correspondence should be addressed. Tel: 82-54-279-2108.
Fax: 82-54-279-1498. E-mail: sungjee@postech.ac.kr.
10.1021/jp900530a CCC: $40.75
being accumulated on QDs over time, the PL continuously shifts
to the blue. The spectral shift reaches as large as ∼100 nm.
Figure 1b shows the absorption spectra of CdTe/CdSe (C/S)
QDs in initial uncharged state and when electron charged for 8
days. Attenuation of absorption transitions near the band edge
is observed. The attenuation of absorption transition is neither
predominant nor concurrent with the PL shift. This suggests
that injected electrons fill surface states of QDs first and occupy
delocalized states over the shells. Similar behaviors have been
also observed for type-I QDs.1,23 As control experiments, CdSe
QDs and CdTe QDs are charged over a month and the PL shifts
are found within a few nm presumably due to surface changes
(Figure S1). Huge spectral shift of type-II QDs can be explained
based on Coulombic interactions between injected spectrator
electrons and generated excitons.26 CdTe/CdSe (C/S) QDs have
lower potentials for electrons in CdSe shells than in CdTe
cores.16-19 As a result, electrons are more localized in the shells
whereas holes mostly reside in the cores. The chemically
injected electrons are either trapped on surface states or localized
in the shells due to the type-II character. When the injected
spectrator electrons interact with excitons, electron-electron
repulsions are expected to be stronger than the electron-hole
attractions. This results in the progressive blue shift of the
excitonic peak during the charging process. As the charging
proceeds, the number of spectrator electrons should increase.
In addition, initially surface trapped electrons can move inside
the shells. Figure 1c shows the change of PL quantum yield
(QY) during the charging process. Type-II CdTe/CdSe (C/S)
QDs typically show the PL QY ∼ 5%. The left open square in
figure 1c represent the PL QY of CdTe/CdSe (C/S) QD sample
before the charging process. As charging proceeds, PL continu-
ously decreases by Auger processes and generations of quench-
ing surface sites. The open square over the arrow represents
the regained PL QY after neutralization on day 8. Neutralization,
 2009 American Chemical Society
Letters J. Phys. Chem. C, Vol. 113, No. 16, 2009 6321

Figure 1. (a) Normalized PL spectra of a CdTe/CdSe (C/S) QD sample in initial uncharged state (black) and when electron charged for 2 (red),
5 (green), and 8 days (blue). (b) Absorption spectra of CdTe/CdSe (C/S) QDs in initial uncharged state (black) and when electron charged for 8
days (blue). (c) PL intensity change during the charging process. Uncharged and charged QD states are represented by open and closed squares,
respectively. The arrow on day 8 denotes neutralization step.

Figure 2. (a) Normalized PL spectra, (b) absorption spectra, and (c) normalized PL decays of CdTe QDs (green), and CdTe/CdSe (C/S) QDs in
initial uncharged state (black), in electron charged state (blue) and after neutralization (red). (d) Repeated PL spectral switching of a CdTe/CdSe
(C/S) QD sample by multiple charging/neutralization processes. Open and closed circles denote emission wavelengths of a CdTe/CdSe (C/S) QD
sample in uncharged and charged states, respectively. Solid and broken arrows represent charging and neutralization processes, respectively.

or removal of injected electrons from QDs, is made by following
previously reported method of intentional exposure of the
samples to air.1,23 The number of injected electrons may be
correlated with the degree of spectral shift or the PL QY change.
Unfortunately, our experimental setup does not allow quantifica-
tion of injected electrons. It has been reported that electrochemi-
cal cells can be fabricated to study the number of electrons
transferred in and out of QDs.6 Further research is required in
this direction.
Upon neutralizing charged type-II QDs, the PL returns back
to the initial spectral position. Type-II QDs can show PL spectral
switching by charging/neutralization. Figure 2a demonstrates
the reversibility of the spectral switching. Initially 766 nm (PL
peak) emitting CdTe/CdSe (C/S) QD sample is electron charged
for 3 days. The PL blue shifts to 733 nm, and returns back to
768 nm upon neutralization. Slight tailing of the PL spectrum
is accompanied by the neutralization due to little aggregations.
It is noted that the PL spectrum of charged QDs does not overlap
with that of bare CdTe QDs. The bare CdTe QDs are the cores
for the CdSe shell deposition. Along with the reversible PL
spectral switching, reversible absorption bleaching is observed
as in Figure 2b. The absorption of CdTe/CdSe (C/S) QD
becomes attenuated near the band edge when electron charged
for 3 days. The injected spectrator electrons can occupy the
conduction levels and reduce the oscillator strength of the band
edge transitions.1,23,25 Upon neutralization of the charged CdTe/
CdSe (C/S) QD sample, attenuated band edge absorption is
almost recovered. Figure 2c shows the PL decays of the 4
samples that are used for Figure 2, panels a and b. Intensity-
weighted average lifetimes28 are obtained using biexponential
and triexponential fittings. (See the SI for time-resolved PL
measurement setup and the data analysis.) When fitted by
biexponential decays, bare CdTe QD, initial CdTe/CdSe (C/S)
QD before charging, charged CdTe/CdSe (C/S) QD and
neutralized CdTe/CdSe (C/S) QD samples show the lifetimes
of 6.3, 34, 8.7, and 68 ns, respectively (Table S1). In case of
triexponential fitting, the lifetimes are 11 ns, 42 ns, 16 and 82
ns, respectively with the same order (Table S1). PL QYs of the
initial CdTe/CdSe (C/S) QD, charged CdTe/CdSe (C/S) QD,
and neutralized CdTe/CdSe (C/S) QD samples are 2.5%, 0.03%,
and 7.0%, respectively. The lifetimes for bare CdTe QD and
initial CdTe/CdSe (C/S) QD samples are similar to the previ-
ously reported lifetimes.16-18,29 Charged state CdTe/CdSe (C/
S) QD shows dramatically shortened lifetime when compared
to initially uncharged or neutralized state. When biexponential
(triexponential) decay fitting is used, the lifetime reduces from
34 ns (42 ns) to 8.7 ns (16 ns) as the QD sample becomes
electron charged. The decrease of lifetime upon charging is
particularly dominant for slow component of the decay (τ2 for
biexponential and τ3 for triexponential fitting in Table S1). The
slow component lifetime decreases from 37 ns (47 ns) to 10 ns
(24 ns). On the other hand, changes of fast components are not
as dramatic as the slow component. The lifetime τ1 (τ1, τ2) in
biexponential (triexponential) fitting changes from 0.67 ns (0.19
6322 J. Phys. Chem. C, Vol. 113, No. 16, 2009
ns, 2.6 ns) to 0.55 ns (0.23 ns, 2.8 ns) from initial uncharged to
charged state. Quatro-exponential fitting is also used for the
liftetime analysis, where similar lifetime behaviors are observed
(Table S1). We speculate that the dominant nonradiative
channels become quite different for the cases when the quantum
dots are neutral in uncharged state and when electron charged.
When quantum dots are excited at a low excitation intensity
(less than 1 e-h pair produced per dot), nonradiative decay
channels are thought mainly generated from surface trap sites
and internal defect sites. When electrons are injected into
quantum dots, Auger processes between injected spectrator
electrons and exciton or surface(or interface)-trapped hole may
become dominant. Auger processes of charged quantum dots
are expected to be very efficient. Obviously, we cannot rule
out the possibility that the charging process generates efficient
surface-oriented nonradiative channels. Unfortunately, there have
been little quantitative studies for surface oriented nonradiative
decay kinetics and Auger processes for type-II quantum dots.
We estimate the Auger lifetime of CdTe/CdSe (C/S) QDs to
be longer than type-I QDs with similar size.22 This may explain
the increase of τ1 (from 0.19 to 0.23 ns) and τ2 (from 2.6 to 2.8
ns) in triexponential fitting and τ1 (from 0.088 to 0.15 ns) and
τ2 (from 0.83 to 1.1 ns) in quatro-exponential fitting (Table S1).
It is not feasible to directly correlate the lifetime kinetics with
QY in our case. However, nonradiative decay channels of QD
including Auger process are thought to be faster than radiative
decays.17,22 Although the low QY of charged QD sample
severely limits interpretations on radiative channels from the
lifetime data, one can assume that the changes in slowest
component are heavily dependent on the radiative channel.
When electrons are injected into CdTe/CdSe (C/S) QDs, the
excitonic electron-hole pair overlap should increase as the
electron-electron repulsions in the shells dominate. Therefore,
the exciton becomes less spatially separated and can show fast
decays.22 Long-lived exciton dynamics of charged type-II QD
becomes similar to that of type-I bare CdTe QD. This can be
well visualized when the PL decay spectra are normalized by
the area (Figure S2). Type-II characteristic slow decay of CdTe/
CdSe QD reappears upon neutralization. However, samples often
show significant PL brightening after neutralization that is
accompanied by prolonged PL decays on both fast and slow
components (Figure S3). The origin of QY increase is not clear,
yet presumably due to oxidative surface reconstructions which
remove Se0 quenching sites.6,30
Figure 2d demonstrates the reversible switching capability
of type-II QD by repeated charging/neutralization process.
Initially ∼840 nm emitting CdTe/CdSe (C/S) QD sample is
electron charged until it blue-shifts to ∼760 nm (the first solid
arrow in Figure 2d). The spectral shift is comparable to the PL
bandwidth. In the second and fifth cycle, the neutralization is
made intentionally partial so as to show the modulating
capability. The emission wavelength can be flexibly tuned by
controlling the degree of charging. The switching can be made
as many times until QDs lose the colloidal stability. Typically
QDs can survive up to 10 cycles of repeated charging/
neutralization processes in solution. Solid state QD charging
devices are expected to overcome the colloidal stability limita-
tion for electro-optic modulating applications.4-6
In Figure 3a, CdTe/CdSe (C/S) QDs with identical cores and
shells with different thicknesses are prepared. (See Figure S4
for TEM images.) PL peak appears at longer wavelengths for
the QDs with thicker shells because of the enhanced type-II
characteristics. They are charged for 5 days using an identical
condition including the amount of charging agent per QD. QDs
Letters
Figure 3. (a) Normalized PL spectra of CdTe/CdSe (C/S) QD samples
in neutral states (open squares) and in their charged states after charging
for 5 days (closed squares). The QD samples have identical cores of
CdTe (2.3 nm radius) and different CdSe shell thicknesses of 0.5 nm
(blue) 1.4 nm (green) and 1.8 nm (red). (b) Normalized PL spectra of
alloyed CdTeSe QD samples with different size in their neutral states
(open squares) and after charging for 5 days (closed squares).
Figure 4. Normalized PL spectra of CdSe/CdTe (C/S) QDs in initial
uncharged state (black), in electron charged state (blue) and after
neutralization (red).
with thicker shells, hence more type-II character QDs, show
larger spectral shift by charging. The QD sample with the
thickest shell shows 80 meV blue shift, while the other two
show 33 and 29 meV in the order of decreasing shell thickness.
Actually, injected electrons per QD should be smaller for the
thicker shell QDs. The charging process is governed by
diffusion, and larger QDs should be less susceptible to charging
because of the low mobility.1 Size-dependent electron repulsion
effect is not considered. Type-II character dependent spectral
shift is observed consistently from the charging day 1. It is
believed that the number of injected electrons per QD is not
large enough to significantly consider the repulsion effect. For
comparison, alloyed CdTeSe QDs with homogeneous internal
structures are prepared by following previous reports.31 (See
SI for the synthetic procedure and Figure S5 for optical
properties and TEM image). Figure 3b shows PL spectra of
different size CdTeSe alloy QDs. Though alloyed QDs emits
at similar wavelengths as the type-II QDs, they only show
insignificant spectral shifts by charging.
CdSe/CdTe (C/S) QDs are prepared to investigate the case
of spatially reversed electron-hole localizations. As shown in
Figure 4, initially 775 nm (PL peak) emitting CdSe/CdTe (C/
S) QD sample shows red-shifted PL at 798 nm upon charging
for 2 days, and returns back to 773 nm upon neutralization.
The PL red-shift makes a sharp contrast with blue-shift of the
counterpart CdTe/CdSe (C/S) QD sample shown in Figure 2a.
CdSe/CdTe (C/S) QDs have electrons mostly confined in cores
and holes that reside mostly in shells. Electrons on surface states
of CdTe shells should attract excitonic holes in the shells more
strongly than they repel electrons in the cores. As charging
proceeds, injected electrons accumulate on the CdTe shell
surface states and the PL continuously red-shifts. However,
CdSe/CdTe (C/S) QDs quickly lose fluorescence for longer
charging processes. They seem to easily create nonradiative
channels via surface hole traps, especially in combination with
Letters
the injected electrons. In this case, holes are localized in the
shells, and injected electrons are supposed to fill the cores via
surface states. It seems that the PL completely quenches before
the injected electrons reach the cores. The surface charged
electrons seem to enhance type-II characteristics by attracting
excitonic holes, which results in the red-shift upon charging.
Lifetime measurements should corroborate our analysis, which
is unfortunately still limited by the very low PL QYs.
In conclusion, we have demonstrated that QD spectral
switching can be well engineered by controlling the transfers
of electrons in and out of type-II QD heterostructures. Huge
and reversible spectral shifts up or down by charging/ neutral-
ization processes clearly showcase the unique properties of type-
II QDs and their application potentials.
Acknowledgment. This work was supported by KOSEF grant
funded by the Korea government (MOST) (M10703001036-
08M0300-03610, KRF-2008-331-C00140, M10755020003-
07N5502-00310, R0A-2008-000-20114-0(2008)), Ministry of
Health & Welfare (A060660) and by the Korea Research
Foundation Grant funded by the Korean Government (MOE-
HRD) (KRF-2005-005-J13102).
Supporting Information Available: Detail experimental
procedure, UV-vis spectra, PL spectra, PL decay data, and
TEM figure. This material is available free of charge via the
Internet at http://pubs.acs.org.
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JP900530A