Measuring electron and hole transfer in core/shell nanoheterostructures.

Using femtosecond transient absorption and time-resolved photoluminescence spectroscopy, we studied the electron versus hole dynamics in photoexcited quasi-type-II heterostructured nanocrystals with fixed CdTe core radii and varying CdSe shell coverage. By choosing the pump wavelength in resonance with the core or the shell states, respectively, we were able to measure the excited electron and hole dynamics selectively. Both, the core- and the shell-excited CdTe/CdSe nanocrystals showed the same spectral emission and photoluminescence lifetimes, indicating that ultrafast electron and hole transfer across the core/shell interface resulted in the identical long-lived charge transfer state. Both charge carriers have subpicosecond transfer rates through the interface, but the subsequent relaxation rates of the hole (τ(dec) ∼ 800 ps) and electron (τ(avg) ∼ 8 ps) are extremely different. On the basis of the presented transient absorption measurements and fitting of the steady-state spectra, we find that the electron transfer occurs in the Marcus inverted region and mixing between the CdTe exciton and charge transfer states takes place and therefore needs to be considered in the analysis.

Emergent properties resulting from type-II band alignment in semiconductor nanoheterostructures.

The development of elegant synthetic methodologies for the preparation of monocomponent nanocrystalline particles has opened many possibilities for the preparation of heterostructured semiconductor nanostructures. Each of the integrated nanodomains is characterized by its individual physical properties, surface chemistry, and morphology, yet, these multicomponent hybrid particles present ideal systems for the investigation of the synergetic properties that arise from the material combination in a non-additive fashion. Of particular interest are type-II heterostructures, where the relative band alignment of their constituent semiconductor materials promotes a spatial separation of the electron and hole following photoexcitation, a highly desirable property for photovoltaic applications. This article highlights recent progress in both synthetic strategies, which allow for material and architectural modulation of novel nanoheterostructures, as well as the experimental work that provides insight into the photophysical properties of type-II heterostructures. The effects of external factors, such as electric fields, temperature, and solvent are explored in conjunction with exciton and multiexciton dynamics and charge transfer processes typical for type-II semiconductor heterostructures.

Noninjection gram-scale synthesis of monodisperse pyramidal CuInS2 nanocrystals and their size-dependent properties.

CuInS2 nanocrystals are viewed as very good candidates for solar harvesting and light emitting applications. Here we report an optimized noninjection method for the synthesis of monodisperse pyramidal CuInS2 nanocrystals with sizes ranging from 3 to 8 nm. This synthetic route is able to yield large amounts of high quality nanoparticles, usually in the gram scale for one batch experiment. The structure and surface studies showed that the resulting nanocrystals are pyramids of CuInS2 tetragonal phase with well-defined facets, while their surface is functionalized with dodecanethiol capping ligands. Spectroscopic and electrochemical measurements revealed size-dependent optical and electrical properties of CuInS2 nanocrystals, demonstrating quantum confinement effects in these systems. The size-dependent optical bandgaps of CuInS2 nanocrystals were found to be consistent with the finite-depth well effective mass approximation (EMA) calculations, which provide a convenient method to estimate the diameter of CuInS2 pyramids. Additionally we have also determined some important physical parameters, including bandgaps and energy levels, for this system, which are crucial for the integration of CuInS2 nanocrystals in potential device applications.

Temperature and solvent dependence of CdSe/CdTe heterostructure nanorod spectra.

Charge separation is known to occur in heterostructure nanocrystals with type II alignment. Transfer rates have been inferred from ultrafast measurements, but other elements relevant to this process, such as the role of the solvent and the internal degrees of freedom, are still poorly understood. The present study investigates temperature and solvent effects on the optical properties of the charge-separated state in CdSe/CdTe collinear nanorods. The importance of the surrounding medium in the steady state photoluminescence is suggested both in the solvent and temperature studies. The latter also provides evidence that a charge-separated bound state is formed at the interface of the two materials, while states where electron and hole behave as free carriers are only accessible through an activated process in which the interfacial exciton is dissociated. Finally, using a dipole-dielectric continuum model, we found that the optical properties of the charge-separated state in these nanocrystals change as a function of solvent polarity.

Quantitative modeling of the role of surface traps in CdSe/CdS/ZnS nanocrystal photoluminescence decay dynamics.

Charge carrier trapping is an important phenomenon in nanocrystal (NC) decay dynamics because it reduces photoluminescence (PL) quantum efficiencies and obscures efforts to understand the interaction of NC excitons with their surroundings. Particularly crucial to our understanding of excitation dynamics in, e.g., multiNC assemblies, would be a way of differentiating between processes involving trap states and those that do not. Direct optical measurement of NC trap state processes is not usually possible because they have negligible transition dipole moments; however, they are known to indirectly affect exciton photoluminescence. Here, we develop a framework, based on Marcus electron transfer theory, to determine NC trap state dynamics from time-resolved NC exciton PL measurements. Our results demonstrate the sensitivity of PL to interfacial dynamics, indicating that the technique can be used as an indirect but effective probe of trap distribution changes. We anticipate that this study represents a step toward understanding how excitons in nanocrystals interact with their surroundings: a quality that must be optimized for their efficient application in photovoltaics, photodetectors, or chemical sensors.

CdSe nanoparticle elasticity and surface energy.

The acoustic phonon modes of colloidal CdSe nanoparticles in solution (293 K) are passively measured by a third order ultrafast heterodyne cross-polarized transient grating measurement. Using the observed size-dependence of the acoustic phonon frequency, the elastic properties of the nanoparticles are determined. The size-dependence of the elastic modulus is then used to ascertain information about the relative surface energies of the nanocrystals and suggests the extent and depth of surface reconstruction.

Control of exciton spin relaxation by electron-hole decoupling in type-II nanocrystal heterostructures.

The electron spin flip relaxation dynamics in type II CdSe/CdTe nanorod heterostructures are investigated by an ultrafast polarization transient grating technique. Photoexcited charge separation in the heterostructures suppresses the electron-hole exchange interaction and their recombination, which reduces the electron spin relaxation rate in CdSe nanocrystals by 1 order of magnitude compared to exciton relaxation. The electron orientation is preserved during charge transfer from CdTe to CdSe, and its relaxation time constant is found to be approximately 5 ps at 293 K in the CdSe part of these nanorods. This finding suggests that hole spin relaxation determines the exciton fine structure relaxation rate and therefore control of exciton spin relaxation in semiconductor nanostructures is possible by delocalizing or translating the hole density relative to the electron.

Nanorod heterostructures showing photoinduced charge separation.

Size- and shape-dependent property modifications of semiconductor nanocrystals have been a subject of intense interest because of their potential for future engineering devices. The bandgap and related optical-property tuning of these materials are mainly governed by the nature of their band edges. In addition, fusing one type of nanocrystal over another enables further control of material properties that are dependent on the relative alignments of their energy levels. On a molecular scale, the synthesis of supramolecular compounds has inspired advances in theories for photoinduced charge transfer. Heterostructured nanocrystals potentially provide a nanoscale analog of such systems. A method for preparing heterostructured nanocrystals of complex morphologies showing photoinduced charge separation is presented. It is shown that the energy and lifetime of the charge-transfer photoluminescence band can be tuned by changing the relative alignment of band edges in CdSe/CdTe heterostructure nanorods. The long-lived charge transfer states in these type II semiconductors may make them attractive for photovoltaic applications.