Auger-assisted electron transfer from photoexcited semiconductor quantum dots.

Although quantum confined nanomaterials, such as quantum dots (QDs) have emerged as a new class of light harvesting and charge separation materials for solar energy conversion, theoretical models for describing photoinduced charge transfer from these materials remain unclear. In this paper, we show that the rate of photoinduced electron transfer from QDs (CdS, CdSe, and CdTe) to molecular acceptors (anthraquinone, methylviologen, and methylene blue) increases at decreasing QD size (and increasing driving force), showing a lack of Marcus inverted regime behavior over an apparent driving force range of ∼0-1.3 V. We account for this unusual driving force dependence by proposing an Auger-assisted electron transfer model in which the transfer of the electron can be coupled to the excitation of the hole, circumventing the unfavorable Franck-Condon overlap in the Marcus inverted regime. This model is supported by computational studies of electron transfer and trapping processes in model QD-acceptor complexes.

Probing spatially dependent photoinduced charge transfer dynamics to TiO2 nanoparticles using single quantum dot modified atomic force microscopy tips.

Using single CdSe/CdS quantum dot (QD) functionalized atomic force microscopy (AFM) tips, we demonstrate that the spatial dependence of photoinduced electron transfer dynamics from the single QD to TiO2 nanoparticles can be controlled and probed with high spatial (subdiffraction-limited) and temporal (limited by fluorescence microscopy) resolutions. This finding suggests the feasibility of using electron donor or acceptor modified AFM tips for simultaneous high resolution imaging of morphology and photoinduced charge transfer dynamics in nanomaterials.

Charging of quantum dots by sulfide redox electrolytes reduces electron injection efficiency in quantum dot sensitized solar cells.

In quantum dot (QD) sensitized solar cells (QDSSCs), redox electrolytes act as hole scavengers to regenerate the QD ground state from its oxidized form, thus enabling a continuous device operation. However, unlike molecular sensitizers, QDs also have redox-active trap states within the band gap, which can be charged in the presence of redox electrolyte. The effects of electrolyte induced charging of QDs on the performance of QDSSCs have not been reported. Here, using steady-state and time-resolved absorption and emission spectroscopy, we show that CdSe/CdS3MLZnCdS2MLZnS2ML core/multishell QDs are charged in the presence of sulfide electrolytes due to the reduction of surface states. As a result, exciton lifetimes in these QDs are shortened due to an Auger recombination process. Such charging induced fast Auger recombination can compete effectively with electron transfer from QDs to TiO2 and reduce the electron injection efficiency in QDSSCs. We believe that the reported charging effects are present for most colloidal nanocrystals in the presence of redox media and have important implications for designing QD-based photovoltaic and photocatalytic devices.

Interfacial charge separation and recombination in InP and quasi-type II InP/CdS core/shell quantum dot-molecular acceptor complexes.

Recent studies of group II-VI colloidal semiconductor heterostuctures, such as CdSe/CdS core/shell quantum dots (QDs) or dot-in-rod nanorods, show that type II and quasi-type II band alignment can facilitate electron transfer and slow down charge recombination in QD-molecular electron acceptor complexes. To explore the general applicability of this wave function engineering approach for controlling charge transfer properties, we investigate exciton relaxation and dissociation dynamics in InP (a group III-V semiconductor) and InP/CdS core/shell (a heterostructure beween group III-V and II-VI semiconductors) QDs by transient absorption spectroscopy. We show that InP/CdS QDs exhibit a quasi-type II band alignment with the 1S electron delocalized throughout the core and shell and the 1S hole confined in the InP core. In InP-methylviologen (MV(2+)) complexes, excitons in the QD can be dissociated by ultrafast electron transfer to MV(2+) from the 1S electron level (with an average time constant of 11.4 ps) as well as 1P and higher electron levels (with a time constant of 0.39 ps), which is followed by charge recombination to regenerate the complex in its ground state (with an average time constant of 47.1 ns). In comparison, InP/CdS-MV(2+) complexes show similar ultrafast charge separation and 5-fold slower charge recombination rates, consistent with the quasi-type II band alignment in these heterostructures. This result demonstrates that wave function engineering in nanoheterostructures of group III-V and II-VI semiconductors provides a promising approach for optimizing their light harvesting and charge separation for solar energy conversion applications.

Unraveling the exciton quenching mechanism of quantum dots on antimony-doped SnO2 films by transient absorption and single dot fluorescence spectroscopy.

Integrating quantum dots (QDs) into modern optoelectronic devices requires an understanding of how a transparent conducting substrate affects the properties of QDs, especially their excited-state dynamics. Here, the exciton quenching dynamics of core/multishell (CdSe/CdS(3ML)ZnCdS(2ML)ZnS(2ML)) quantum dots deposited on glass, tin oxide (SnO2), and antimony (Sb)-doped tin oxide (ATO) films are studied by transient absorption and single QD fluorescence spectroscopic methods. By comparing ensemble-averaged fluorescence decay and transient absorption kinetics, we show that, for QDs on SnO2, the exciton is quenched by electron transfer from the QD to SnO2. At the QD-ATO interface, much faster exciton quenching rates are observed and attributed to fast Auger recombination in charged QDs formed by Fermi level equilibration between the QD and n-doped ATO. Single QDs on SnO2 and ATO show similar blinking dynamics with correlated fluctuations of emission intensities and lifetimes. Compared to QDs on SnO2, QDs on ATO films show larger variation of average exciton quenching rates, which is attributed to a broad distribution of the number of charges and nature of charging sites on the QD surface.

Near unity quantum yield of light-driven redox mediator reduction and efficient H2 generation using colloidal nanorod heterostructures.

The advancement of direct solar-to-fuel conversion technologies requires the development of efficient catalysts as well as efficient materials and novel approaches for light harvesting and charge separation. We report a novel system for unprecedentedly efficient (with near-unity quantum yield) light-driven reduction of methylviologen (MV(2+)), a common redox mediator, using colloidal quasi-type II CdSe/CdS dot-in-rod nanorods as a light absorber and charge separator and mercaptopropionic acid as a sacrificial electron donor. In the presence of Pt nanoparticles, this system can efficiently convert sunlight into H(2), providing a versatile redox mediator-based approach for solar-to-fuel conversion. Compared to related CdSe seed and CdSe/CdS core/shell quantum dots and CdS nanorods, the quantum yields are significantly higher in the CdSe/CdS dot-in-rod structures. Comparison of charge separation, recombination and hole filling rates in these complexes showed that the dot-in-rod structure enables ultrafast electron transfer to methylviologen, fast hole removal by sacrificial electron donor and slow charge recombination, leading to the high quantum yield for MV(2+) photoreduction. Our finding demonstrates that by controlling the composition, size and shape of quantum-confined nanoheterostructures, the electron and hole wave functions can be tailored to produce efficient light harvesting and charge separation materials.

Wave function engineering for efficient extraction of up to nineteen electrons from one CdSe/CdS quasi-type II quantum dot.

Solar-to-fuel conversion devices require not only efficient catalysts to accelerate the reactions, but also light harvesting and charge separation components to absorb multiple photons and to deliver multiple electrons/holes to the catalytic centers. In this paper, we show that the spatial distribution of electron and hole wave functions in CdSe/CdS quasi-type II quantum dots enables simultaneous ultrafast charge separation (0.18 ps to adsorbed Methylviologen), ultraslow charge recombination (0.4 µs), and slow multiple-exciton Auger annihilation (biexciton lifetime 440 ps). Up to nineteen excitons per QD can be generated by absorbing multiple 400 nm photons and all excitons can be dissociated with unity yield by electron transfer to adsorbed methylviologen molecules. Our finding demonstrates that (quasi-) type II nanoheterostructures can be engineered to efficiently dissociate multiple excitons and deliver multiple electrons to acceptors, suggesting their potential applications as light harvesting and charge separation components in artificial photosynthetic devices.

Hole transfer from single quantum dots.

Photoinduced hole transfer dynamics from single CdSe/CdS(3ML)/CdZnS(2ML)/ZnS(2ML) core/multishell quantum dots (QDs) to phenothiazine (PTZ) molecules were studied by single QD fluorescence spectroscopy to investigate the static and dynamic heterogeneities of the hole transfer process as well as its effect on the blinking dynamics of QDs. Ensemble-averaged transient absorption and fluorescence decay measurements show that excitons in QDs dissociate by transferring the valence band hole to PTZ with a time constant of 50 ns for the 1:1 PTZ-QD complex, and the subsequent charge recombination process (i.e., electron transfer from the conduction band of the reduced QD to oxidized PTZ to regenerate the complex in the ground state) occurs mainly on the 100 to 1000 ns time scale. Single QD-PTZ complexes show pronounced correlated fluctuations of fluorescence intensity and lifetime with time. In addition to the dynamic fluctuation, there are considerable heterogeneities of average hole transfer rate among different QD-PTZ complexes. The hole transfer process has little effect on the statistics of the off-states, which is often believed to be positively charged QDs with a valence band hole. Instead, it increases the probability of weakly emissive or "gray" states.

Wave function engineering for ultrafast charge separation and slow charge recombination in type II core/shell quantum dots.

The size dependence of optical and electronic properties of semiconductor quantum dots (QDs) have been extensively studied in various applications ranging from solar energy conversion to biological imaging. Core/shell QDs allow further tuning of these properties by controlling the spatial distributions of the conduction-band electron and valence-band hole wave functions through the choice of the core/shell materials and their size/thickness. It is possible to engineer type II core/shell QDs, such as CdTe/CdSe, in which the lowest energy conduction-band electron is largely localized in the shell while the lowest energy valence-band hole is localized in the core. This spatial distribution enables ultrafast electron transfer to the surface-adsorbed electron acceptors due to enhanced electron density on the shell materials, while simultaneously retarding the charge recombination process because the shell acts as a tunneling barrier for the core localized hole. Using ultrafast transient absorption spectroscopy, we show that in CdTe/CdSe-anthraquinone (AQ) complexes, after the initial ultrafast (~770 fs) intra-QD electron transfer from the CdTe core to the CdSe shell, the shell-localized electron is transferred to the adsorbed AQ with a half-life of 2.7 ps. The subsequent charge recombination from the reduced acceptor, AQ(-), to the hole in the CdTe core has a half-life of 92 ns. Compared to CdSe-AQ complexes, the type II band alignment in CdTe/CdSe QDs maintains similar ultrafast charge separation while retarding the charge recombination by 100-fold. This unique ultrafast charge separation and slow recombination property, coupled with longer single and multiple exciton lifetimes in type II QDs, suggests that they are ideal light-harvesting materials for solar energy conversion.

Poisson-distributed electron-transfer dynamics from single quantum dots to C60 molecules.

Functional quantum dot (QD)-based nanostructures are often constructed through the self-assembly of QDs with binding partners (molecules or other nanoparticles), a process that leads to a statistical distribution of the number of binding partners. Using single QD fluorescence spectroscopy, we probe this distribution and its effect on the function (electron-transfer dynamics) in QD-C60 complexes. Ensemble-averaged transient absorption and fluorescence decay as well as single QD fluorescence decay measurements show that the QD exciton emission was quenched by electron transfer from the QD to C60 molecules and the electron-transfer rate increases with the C60-to-QD ratio. The electron-transfer rate of single QD-C60 complexes fluctuates with time and varies among different QDs. The standard deviation increases linearly with the average of electron-transfer rates of single QD-C60 complexes, and the distributions of both quantities obey Poisson statistics. The observed distributions of single QD-C60 complexes and ensemble-averaged fluorescence decay kinetics can be described by a model that assumes a Poisson distribution of the number of adsorbed C60 molecules per QD. Our findings suggest that, in self-assembled QD nanostructures, the statistical distribution of the number of adsorbed partners can dominate the distributions of the averages and standard deviation of their interfacial dynamical properties.

Controlling charge separation and recombination rates in CdSe/ZnS type I core-shell quantum dots by shell thicknesses.

Type I core/shell quantum dots (QDs) have been shown to improve the stability and conversion efficiency of QD-sensitized solar cells compared to core only QDs. To understand how the shell thickness affects the solar cell performance, its effects on interfacial charge separation and recombination kinetics are investigated. These kinetics are measured in CdSe/ZnS type I core/shell QDs adsorbed with anthroquinone molecules (as electron acceptor) by time-resolved transient absorption spectroscopy. We show that the charge separation and recombination rates decrease exponentially with the shell thickness (d), k(d) = k(0)e(-ßd), with exponential decay factors ß of 0.35 ± 0.03 per Å and 0.91 ± 0.14 per Å, respectively. Model calculations show that these trends can be attributed to the exponential decrease of the 1S electron and hole densities at the QD surface with the shell thickness. The much steeper decrease in charge recombination rate results from a larger hole effective mass (than electron) in the ZnS shell. This finding suggests possible ways of optimizing the charge separation yield and lifetime by controlling the thickness and nature of the shell materials.

Suppressed blinking dynamics of single QDs on ITO.

The exciton quenching dynamics of single CdSe/CdS(3ML)ZnCdS(2ML)ZnS(2ML) core/multishell QDs adsorbed on glass, In2O3, and ITO have been compared. Single QDs on In2O3 show shorter fluorescence lifetimes and higher blinking frequencies than those on glass because of interfacial electron transfer from QDs to In2O3. Compared to glass and In2O3, single QDs on ITO show suppressed blinking activity as well as reduced fluorescence lifetimes. For QDs in contact with the n-doped ITO, the equilibration of their Fermi levels leads to the formation of negatively charged QDs. In these negatively charged QDs, the off states are suppressed because of the effective removal of the valence band holes, and their fluorescence lifetimes are shortened because of exciton Auger recombination and hole transfer processes involving the additional electrons. This study shows that the blinking of single QDs can be effectively suppressed on the surface of ITO. This phenomenon may also be observable for other QDs and on different n-doped semiconductors.

Correlated Single Quantum Dot Blinking and Interfacial Electron Transfer Dynamics.

The electron transfer (ET) dynamics from core/multi-shell (CdSe/CdS(3ML)ZnCdS(2ML)ZnS(2ML)) quantum dots (QDs) to adsorbed Fluorescein (F27) molecules have been studied by single particle spectroscopy to probe the relationship between single QD interfacial electron transfer and blinking dynamics. Electron transfer from the QD to F27 and the subsequent recombination were directly observed by ensemble-averaged transient absorption spectroscopy. Single QD-F27 complexes show correlated fluctuation of fluorescence intensity and lifetime, similar to those observed in free QDs. With increasing ET rate (controlled by F27-to-QD ratio), the lifetime of on states decreases and relative contribution of off states increases. It was shown that ET is active for QDs in on states, the excited state lifetime of which reflects the ET rate, whereas in the off state QD excitons decay by Auger relaxation and ET is not a competitive quenching pathway. Thus, the blinking dynamics of single QDs modulate their interfacial ET activity. Furthermore, interfacial ET provides an additional pathway for generating off states, leading to correlated single QD interfacial ET and blinking dynamics in QD-acceptor complexes. Because blinking is a general phenomenon of single QDs, it appears that the correlated interfacial ET and blinking and the resulting intermittent ET activity are general phenomena for single QDs.