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Charge Separation and Recombination in CdTe/CdSe Core/Shell Nanocrystals as a Function of Shell Coverage: Probing the Onset of the Quasi Type-II Regime
Chi-Hung Chuang, Shun S. Lo, Gregory D. Scholes,*, and Clemens Burda*,
Center for Chemical Dynamics and Nanomaterials Research, Department of Chemistry, Case Western Reserve University, 10900 Euclid Avenue, Cleveland, Ohio 44106, and Department of Chemistry, 80 St. George Street, Institute for Optical Sciences, and Center for Quantum Information and Quantum Control, University of Toronto, Toronto, Ontario, M5S 3H6 Canada

ABSTRACT Femtosecond transient absorption (TA) is used to investigate population dynamics of electronic states in CdTe/CdSe core/shell nanocrystals (NCs) with varying CdSe shell coverage. Upon CdSe shell growth, the CdTe/CdSe NCs show a gradual evolution of surface passivation toward a quasi-type-II charge separation regime. Our results indicate that ultrafast electron transfer (ET) through the interface of CdTe/CdSe NCs becomes measurable as the CdSe shell approaches the quasi-type-II regime which we experimentally determined to be at 0.4 nm (shell) for a 3.4 nm CdTe core. This work reports the first measurement using femtosecond TA to study the electronic states in CdTe/CdSe NCs and spectroscopically observe the evolution of an ultrafast charge transfer (CT) in such a core/ shell system. Time-resolved photoluminescence (PL) spectroscopy is used to study the radiative lifetimes of the CdTe/CdSe NCs. One monolayer CdSe coverage leads to longer-lived PL, which is red-shifted by 140 nm compared to the CdTe core PL. It is concluded that this is due to greater electron-hole separation providing a longer-lived CT state. SECTION Nanoparticles and Nanostructures

eterostructured semiconductor nanocrystals (NCs) display novel optical properties due to the spatiotemporal separation of charge carriers.1-12 Photoexcitation of type-II NC heterostructures, that is, those composed of semiconductor materials with a staggered band offset, is followed by charge transfer (CT) across the interface between the materials. The resulting CTstate can be long-lived in CdTe/CdSe core/shell NCs, and therefore has great potential for transferring electrons efficiently from the CdSe shell into a surrounding matrix prior to electron-hole recombination.1,4,5,8 In addition, CT emission from type-II NCs is of lower energy than photoluminescence (PL) from either NC component, thus providing a way to obtain near-infrared emission. In this context, CT processes through the interface and recombination dynamics of the CT states in heterostructures have been studied in the past few years.13-19 Direct access to spectroscopic and kinetic data can be obtained from femtosecond pump-probe spectroscopy. Recently, therefore, femtosecond transient absorption (TA) pump-probe spectroscopy of type-II heterostructured NCs has been reported in the literature, including CdSe/CdTe (tetrapods and nanorods),13,14 (ZnSe/CdS)/CdS nanorods,15,16 CdTe/CdS quantum dots,17 CdSe/ZnTe nanowires,18 and ZnSe/ CdS/ZnSe nanobarbells.19 CdSe/CdTe nanorods were studied by Fiebig et al. using broadband pump-probe spectroscopy to simultaneously monitor the dynamics of CdSe1S, CdTe1S,

and CT bands.14 Zamkov et al.15 have reported the carrier dynamics in type-II (ZnSe/CdS)/CdS heteronanorods, which produce spatially extended excitons along the main axis of the structure. Another type-II system, ZnSe/CdS/ZnSe nanobarbells, was studied with TA spectroscopy by the same group.19 It has been established that external conditions, such as solvent polarity16 and surface ligand species,17 have measurable effects on the excited state dynamics of heterostructures. However, a systematic study of excited state dynamics as a function of shell coverage in the submonolayer regime for CdTe/CdSe core/shell NCs has not yet been reported. The goal is to answer the question at which point CT sets in and how it will affect the photophysics of this heterostructured system. Here we report the results of this study using femtosecond timeresolved pump-probe measurements. In this letter, we present the preparation of CdTe and a series of CdTe/CdSe core/shell heterostructured NCs with increasing shell coverage. Optical properties of these NCs were characterized by absorption and PL spectroscopy, as well as morphological characterization by electron microscopy. With femtosecond pump-probe measurements, the
Received Date: June 19, 2010 Accepted Date: August 2, 2010 Published on Web Date: August 10, 2010

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population dynamics of the electronic states in CdTe/CdSe core/shell NCs were investigated as a function of shell coverage. In addition, the evolution of the charge separation was studied by femtosecond pump-probe measurements and picosecond time-resolved PL spectroscopy to determine the shell coverage-dependent charge recombination rates. By choosing CdTe as the core material coated with a CdSe shell, we obtained quasi-type-II core/shell heterostructures. We synthesized a series of CdTe/CdSe heterostructure NCs with different CdSe shell coverage. All of the CdTe/CdSe NCs were washed and redispersed in toluene for measurements (see Supporting Information for detailed synthesis). UVvisible (UV-vis) absorption and PL spectra were recorded using a Varian Cary 50 and Varian Eclipse fluorescence spectrometer, respectively. Size distributions of the prepared

Figure 1. UV-vis absorption (solid lines) and PL (dashed lines) spectra of CdTe/CdSe core/shell heterostructured NCs with a 3.4 nm CdTe core and increasing CdSe shell thickness. Labels correspond to Table 1. Absorption and PL spectra are shifted vertically for clarity. The CdTe and CdSe transitions in absorption spectra are marked by asterisks (lowest exciton state of CdTe, XCdTe) and diamonds (lowest exciton state of CdSe, XCdSe), respectively.

NCs were determined by transmission electron microscopy (TEM) with a Philips CM12 at 60 kVand a high-resolution TEM (HRTEM) Tecnai F30 (FEI) at 300 kV. Femtosecond TA measurements were conducted using a Clark MXR 2001 fs laser system producing 780 nm, 150 fs pulses from a regenerative amplifier. The laser pulse train is split to generate a white light continuum probe pulse in a sapphire crystal and a tunable pump pulse. For TA and PL lifetime experiments, the tunable pump pulse is generated using an optical parametric amplifier (TOPAS, Light Conversion). PL dynamics were measured with a time-resolved streak camera (Optronis) equipped with a monochromator (DK240 0.25 m, Spectral Products). All femtosecond laser experiments were carried out in a 2 mm quartz cuvette at room temperature. The instrumental time resolution was determined to be 150 fs via a pump-probe cross-correlation analysis (Supporting Information Figure S1). Figure 1 shows the absorption and PL spectra of the CdTe core and 7 CdTe/CdSe core/shell NCs with increasing shell coverage. The size of the CdTe core is 3.4 ( 0.3 nm in diameter, determined by TEM. As the core is subsequently coated with a CdSe shell, we observe the lowest exciton band, starting with the CdTe core, red-shifted from 527 to 661 nm. These exciton transitions (X,CdTe) of the eight prepared NC samples are tabulated in Table 1. We also found another band forming, on the blue side of the CdTe absorption (denoted by diamonds), which gradually begins to appear for CdTe/CdSe 3, and as the shell thickness increases, this band becomes more prominent. This band is assigned as the lowest CdSe exciton state (XCdSe),3,4 although minor high energy transitions (nS, nP, ... n > 1) of the CdTe core contribute to the absorbance at this wavelength. The corresponding PL spectra are also shown in Figure 1. We tabulate the PL bands (PL) in Table 1. A 140 nm red-shift (relative to 546 nm) of the emission from the core to CdTe/CdSe 7 is found. Following the theoretical model of the electronic structure in quasi-type-II NCs proposed by Klimov's group,2 the hole is localized in the CdTe core, but the electron is delocalized over the entire CdTe/CdSe volume as long as the shell is thin. Upon photoexcitation, these structures produce partial separation between electrons and holes. This model considers the reduced quantum confinement effects due to the additional coating, yielding the red-shifted emission in our CdTe/ CdSe NCs even with a constant CdTe core. Strain at the interface can also contribute to the observed red shift. Once the shell is thick enough (CdTe/CdSe 7), the electrons and

Table 1. Summary of the Optical Properties of CdTe/CdSe Heterostructured NCsa

sample CdTe core CdTe/CdSe 1 CdTe/CdSe 2 CdTe/CdSe 3 CdTe/CdSe 4 CdTe/CdSe 5 CdTe/CdSe 6 CdTe/CdSe 7
a

X,CdTe 527/2.35 536/2.31 558/2.22 579/2.14 595/2.08 622/1.99 645/1.92 661/1.88

PL (PL) 546/2.27 (1.8%) 558/2.22 (3.3%) 578/2.15 (11.3%) 595/2.08 (17.7%) 611/2.03 (25.5%) 639/1.94 (33.8%) 663/1.87 (33.7%) 686/1.81 (32.3%)
b

Stokes shift b 19/0.08 22/0.09 20/0.07 16/0.06 16/0.05 17/0.05 18/0.05 25/0.07

bandwidths of PL (FWHM) 34/0.14 36/0.14 33/0.13 32/0.12 32/0.11 34/0.11 42/0.12 48/0.13

All spectral positions, Stokes shift, and bandwidths in nanometer/eV. Stokes shift is the difference between the PL maximum and the exciton absorption bands of CdTe states.

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Figure 2. TEM images of (a) CdTe/CdSe 4 and (b) CdTe/CdSe 7 heteronanocrystals. The uniformity and monodispersity in particle-size distribution are shown. (c,d) Diameter distribution of CdTe/CdSe 4 and CdTe/CdSe 7 NCs. The average diameters of CdTe/CdSe 4 and CdTe/ CdSe 7 NCs are 3.8 ( 0.2 and 4.2 ( 0.3 nm, respectively.

holes can be further separated. On the basis of Stokes shift, red tail absorption, and PL bandwidth analysis, we expect that CdTe/CdSe 7 approaches the quasi-type-II regime with a measurable CT.1,2 Quantum yields (QYs) of the CdTe/CdSe NCs were also measured (PL in Table 1). Compared with the bare CdTe core, the shell deposition produces much improved QYs. The highest QY (34%) was detected for CdTe/CdSe 5 NCs, and decreased slightly for samples 6 and 7 (Table 1). The morphology of CdTe/CdSe NCs was characterized by TEM. Figure 2a,b reveals excellent homogeneity of our NC samples. Both CdTe/CdSe 4 and CdTe/CdSe 7 NCs, shown in Figure 2a,b, respectively, are uniform in shape and monodisperse in size. By examining more than 200 NCs, we determined the size distribution and average diameter of CdTe/CdSe 4 (Figure 2c) and CdTe/CdSe 7 (Figure 2d) NCs. The average diameter of CdTe/CdSe 4 and CdTe/CdSe 7 NCs are 3.8 and 4.2 nm, respectively, with standard deviations of 0.2 (5%) and 0.3 nm (7%). We estimated shell coverage by subtracting CdTe cores (3.4 nm) from CdTe/CdSe NCs and obtained a 0.4 nm CdSe shell thickness in CdTe/CdSe 7. Starting with the CdTe core, each core/shell sample has an average of 0.06 nm increase in shell thickness. According to previous reports,7 the 0.4 nm CdSe shell in CdTe/ CdSe 7 completes the first monolayer formation. QYs, TEM, and HRTEM (Supporting Information Figure S2) results indicate that the prepared CdTe/CdSe NCs are of good quality and suitable for time-resolved ensemble studies via TA measurements. We tuned the pump wavelength resonant to the lowest CdTe exciton state for each sample (X,CdTe in Table 1) without pumping the CdSe shell states. With 150 fs white light continuum pulses as the probe light, we obtained the TA spectra shown in Figure 3 (raw data in Figure S3). The pump power (less than 0.05 mW) was carefully controlled to avoid multiexciton production in the NCs. The average number of electron-hole excitations (Neh) per particle is estimated to be less than 1 and is summarized in Table 2. Figure 3 shows the TA spectra recorded at 1.6 ps after excitation. By comparing bleach positions with the absorption spectra in Figure 1, we were able to assign the origin of the observed bleaching at longer wavelength corresponding to the 1S(e)-1S(h) transition of CdTe (labeled by asterisks). Furthermore, the peak of

Figure 3. TA spectra of the CdTe core and CdTe/CdSe heterostructured NCs with increasing shell coverage. The spectra were recorded at 1.6 ps after excitation that was resonant to the CdTe state. The transient spectra are shifted vertically for clarity. The CdTe and CdSe states are labeled by asterisks (XCdTe) and diamonds (XCdSe), respectively. Evolution of the spectral positions for the CdTe and CdSe bleaching as a function of shell coverage is shown. The spectra are shown in arbitrary intensity for clarity and esthetics. For raw spectra, see Supporting Information Figure S3.

the bleach band red-shifted as the CdSe shell increased. The bands on the blue side of CdTe, denoted by diamonds, are the lowest exciton transition of CdSe states. Compared with steady-state UV-vis spectra, the intensity ratio between CdSe and CdTe states (ICdSe/ICdTe) is, however, small in the TA spectra. This change in relative intensity is caused by the low population of the high energy states (nS, nP, ... n > 1) in CdTe at 1.6 ps delay time. For additional discussion on discerning electron versus hole dynamics, please see the Supporting Information.

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Table 2. Analysis of the Kinetic Parameters from TA Spectroscopy and PL Lifetime Measurements
sample CdTe core CdTe/CdSe 1 CdTe/CdSe 2 CdTe/CdSe 3 CdTe/CdSe 4 CdTe/CdSe 5 CdTe/CdSe 6 CdTe/CdSe 7
a

rise/fsa 300 200 300 300 200 400 400 400

b

dec,1/psa 0.49 ( 0.04 (85%)b <0.3 0.44 ( 0.02 (93%) 0.67 ( 0.04 (85%) 0.70 ( 0.05 (70%) 1.00 ( 0.07 (63%) 0.52 ( 0.05 (59%) 2.42 ( 0.35 (38%)

dec,2/psa 8.70 ( 0.64 (15%)b 6.41 ( 0.49 (7%) 7.49 ( 0.6 (15%) 10.3 ( 0.6 (30%) 19.2 ( 1.1 (37%) 15.7 ( 0.7 (41%) 23.9 ( 1.7 (62%)

Nehc 0.62 0.64 0.33 0.34 0.35 0.36 0.38 0.39

c

PL/nsd 15.3 ( 0.2 26.5 ( 0.3 27.5 ( 0.2 28.7 ( 0.2 29.4 ( 0.2 31.2 ( 0.2 35.1 ( 0.2 37.5 ( 0.2

Measured @ X,CdTe (see text and Figure 1). The values in parentheses show the signal amplitude of the component. Neh is an average number of excitations (electron-hole pairs) per NC after low power excitation in pump-probe measurements. d Measured @ PL (Table 1 and Figure 1).

By analyzing the TA spectra and their kinetics, the bleaching signals not only provide the time it takes for the bleaching to reach its intensity maximum (the bleach rise time, rise, to populate the lowest core state), but also the bleach decay time, indicating further electronic relaxation to even lower electronic states. We first focus on the population dynamics of the CdTe states by varying the CdSe shell coverage. The bleaching of CdTe transitions within the initial 180 ps is best fit with a biexponential decay function yielding components 1 (dec,1) and 2 (dec,2). The fitting results are summarized in Table 2 (see fitting curves in Supporting Information Figure S4). In each sample, we find the recovery generally consisted of a fast component with 1 ps time constant, followed by a 15 ps decay except for the CdTe/CdSe 1. In the case of CdTe core, about 85% of the bleach decays very fast with a 0.49 ps time constant, and this fast component is followed by a 8.70 ps decay (15% of the signal). On the basis of previous reports, these components are due to electron relaxation from the CdTe state to surface-defect related states.6,15,20-23 The CdTe/ CdSe 1 has a very short recovery time constant (<0.3 ps). It seems that the incomplete CdSe coating yields instantaneous carrier trapping after photoexcitation. The large red-shift at the core/shell spectra suggests that, upon shell growth, CdTe/CdSe NCs have increasing CT character and create an additional relaxation pathway, which is the CTacross the interface. Both surface-defect-related relaxation ( dec,1) and CT across the CdTe/CdSe interface have decay time constants of <1 ps. At the beginning of the shell growth, the surface-defect-related relaxation seems dominant. As the CdSe shell gets thick enough, the CT dynamics increases in contribution until in CdTe/CdSe 7 a charge separation becomes measurable. This point is further confirmed when we analyze the population kinetics of CT and CdSe states. Since bulk CdTe/CdSe has a typical type-II band alignment, we anticipate the formation of a CTstate and studied its population dynamics for the prepared core/shell NCs. Figure 4 shows the kinetics of core/shell systems 3, 5, and 7 at the wavelength of the CT and CdSe states. In CdTe/CdSe 3, we found that the TA kinetics started with a rapid rise to its maximum followed by a fast decay, which we measured through six sets of the kinetics at different wavelengths from 580 to 605 nm. We found that these kinetic characteristics were similar for CdTe/CdSe 1-3. However, for CdTe/CdSe 4-7, we found a gradually increasing buildup dynamics with

Figure 4. TA dynamics of CdTe/CdSe heterostructured NCs. (a) Picosecond dynamics of the CdTe state at 580 nm in CdTe/CdSe 3 (black squares). Beyond the CdTe band, the dynamics are recorded in 5 nm increments. The dynamics of CdTe/CdSe 5 and 7 are shown in panels b and c, respectively. (d) The dynamics of the CdSe state in CdTe/CdSe NCs. For more detailed information, see the Supporting Information, Figure S5.

a slower rise time on the order of 400 fs. On the basis of the fact that CdTe/CdSe 7 has the thickest shell (about 1 monolayer of CdSe), we conclude that this is the buildup of the CT state due to electron transfer (ET) from the photoexcited CdTe core across the interface to the CdSe shell. Hence, we directly observe here the formation of the CT state for CdTe/CdSe. Figure 4d shows the kinetics at CdSe states from CdTe/ CdSe 3 to CdTe/CdSe 7. In CdTe/CdSe 3 to 6, we find that the kinetics started with a rapid rise to its maximum followed by an exponential decay. However, a gradual change of these traces occurs from sample 4 to 6. In CdTe/CdSe 7 we found slower population of the CdSe-related states. The bleaching builds with a 400 fs time constant, which is consistent with

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(red tail in absorption, red-shifted PL, and increasing PL lifetimes) as well as for passivation of surface trap states (increasing PL QYs).

SUPPORTING INFORMATION AVAILABLE Detailed synthesis

of CdTe cores and CdTe/CdSe core/shell NCs; determination of QYs; TA spectra of CdTe and CdTe/CdSe NCs; biexponential fits at the core states; PL intensity decay and single exponential fits; a pump-probe cross-correlation; HRTEM images of CdTe and CdTe/ CdSe 7 QDs; TA dynamics of CdTe/CdSe 3 to CdTe/CdSe 7. This material is available free of charge via the Internet at http://pubs. acs.org.

AUTHOR INFORMATION Corresponding Author:

Figure 5. PL intensity decay curves of CdTe/CdSe core/shell heterostructured NCs with a 3.4 nm CdTe core and increasing CdSe shell coverage measured with a streak camera. The PL intensity is shown in a logarithmic scale. All of the PL intensity decay curves are fit with single exponential decay functions yielding the radiative lifetimes tabulated in Table 2. *To whom correspondence should be addressed. (C.B.) E-mail: burda@case.edu; phone: (216) 368-5918; fax: (216) 368-3006. (G.D.S.) E-mail: gscholes@chem.utoronto.ca; phone: (416) 946-7532; fax: (416) 978-8775.

ACKNOWLEDGMENT This research was supported by NSF

the buildup of the CT state.14,19 This observation is consistent with UV-vis and PL results, with the red shift increase, absorption and PL broadening toward CdTe/CdSe 7. The population of the CT state in these NCs is followed by the charge recombination, yielding the observed emission. The radiative lifetimes of the CdTe/CdSe NCs were examined with time-resolved PL spectroscopy (Figure 5). The prepared NCs exhibited increasing PL lifetimes as the shell grew (raw data in Supporting Information Figure S6). We could fit the PL intensity decays with single exponential functions similar to others21 and determined the PL lifetimes tabulated in Table 2. The radiative lifetime gradually increased from 15 ns (CdTe cores) to 38 ns (CdTe/CdSe 7), which corroborates the model that the charge separation occurs more completely, resulting in smaller overlap of electron and hole wave functions and therefore in long-lived CT states. In addition, the longer lifetimes and increasing QYs indicate that passivation of surface trap states also occurs by CdSe capping of the CdTe core. In this work we presented the preparation of 3.4 nm CdTe and derivative CdTe/CdSe NCs, and the optical properties of these NCs were characterized by absorption and PL spectroscopy. TEM of the CdTe/CdSe heterostructured NCs confirmed the uniformity and monodispersity of the samples. Upon CdSe shell growth on the CdTe cores, the electronic structure of the core/shell NCs showed gradual evolution to a quasitype-II CT behavior, evidenced by the PL bands that redshifted into the near-infrared spectral region with increasing PL bandwidth and lifetime. This work reports the first measurement using femtosecond TA spectroscopy to investigate the population dynamics of electronic states in a series of CdTe/CdSe NCs. The dynamics for core, shell, and CT states were analyzed to fit with exponential decay functions. Our results indicate that ultrafast CTacross the interface of the NCs occurs as the CdSe shell coverage (0.4 nm) reaches one monolayer. Time-resolved PL spectroscopy was used to study the radiative lifetimes of the CdTe/CdSe NCs. With increasing CdSe shell, there is clear evidence for formation of a CT state

Career (CHE-0239688) and NIRT (CTS-0608896) for C.B. G.D.S. would like to thank NSERC.

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