Enhanced Multiple Exciton Dissociation from CdSe Quantum Rods: The Effect of Nanocrystal Shape

A unique ability of semiconductor nanocrystals (NCs) is the generation and accommodation of multiple excitons through either optical or electric current pumping. The development and improvement of NC-based optoelectronic devices that utilize multiple excitons requires the understanding of multiple exciton dynamics and their efficient conversion to emitted photons or external charges prior to exciton–exciton annihilation. Here, we demonstrate that significantly enhanced multiexciton dissociation efficiency can be achieved in CdSe quantum rods (QRs) compared to CdSe quantum dots (QDs). Using transient absorption spectroscopy, we reveal the formation of bound one-dimensional exciton states in CdSe QRs and that multiple exciton Auger recombination occurs primarily via exciton–exciton collision. Furthermore, quantum confinement in the QR radial direction facilitates ultrafast exciton dissociation by interfacial electron transfer to adsorbed acceptors. Under high excitation intensity, more than 21 electrons can be transferred from one CdSe QR to adsorbed methylviologen molecules, greatly exceeding the multiexciton dissociation efficiency of CdSe QDs

Area- and Thickness-Dependent Biexciton Auger Recombination in Colloidal CdSe Nanoplatelets: Breaking the “Universal Volume Scaling Law”

Colloidal nanoplatelets (NPLs) have shown great potentials for lasing applications due to their sharp absorption and emission peaks, large absorption cross sections, large radiative decay rates, and long multiexciton lifetimes. How multiexciton lifetimes depend on material dimensions remains unknown in two-dimensional (2D) materials, despite being a key parameter affecting optical gain threshold and many other properties. Herein, we report a study of room-temperature biexciton Auger recombination time of CdSe NPLs as a function of thickness and lateral area. Comparison of all NPLs shows that the biexciton lifetime does not increase linearly with volume, unlike previously reported “universal volume scaling law” for quantum dots. For NPLs of the same thickness (∼1.8 nm), the biexciton lifetime increase linearly with their lateral area (from 143.7 ± 12.6 to 320.1 ± 17.1 ps when the area increases from 90.5 ± 21.4 to 234.2 ± 41.9 nm²). The biexciton lifetime depends linearly on (1/<i>E</i>_k(e))^7/2 (<i>E</i>_k(e) is the electron confinement energy) or nearly linearly on <i>d</i>⁷ (<i>d</i> is NPL thickness). The observed dependence is consistent with a model in which biexciton Auger recombination rate scales with the product of exciton binary collision frequency and Auger recombination probability in biexciton complexes. The linear increase of Auger lifetimes with NPL lateral areas reflects a 1/area dependence of the binary collision frequency for 2D excitons and the thickness-dependent biexciton Auger recombination time is attributed to its strong dependence on the degree of quantum confinement. This model may be generally applicable to exciton Auger recombination in quantum confined 1D and 2D nanomaterials

Bulk Transport and Interfacial Transfer Dynamics of Photogenerated Carriers in CdSe Quantum Dot Solid Electrodes

Practical solar-to-fuel conversion applications of quantum-confined semiconductor crystals require their integration into electrodes. We show that photogenerated electrons in quantum dot solid electrodes can be transported to the aqueous interface to reduce methyl viologen with 100% quantum efficiency and an effective time constant of 12 ± 2 ps. The charge separated state had a half-life of 200 ± 10 ns, limited by hole transport within the solid

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/CdS_3MLZn­CdS_2MLZn­S_2ML 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

Exciton Localization and Dissociation Dynamics in CdS and CdS–Pt Quantum Confined Nanorods: Effect of Nonuniform Rod Diameters

One-dimensional colloidal multicomponent semiconductor nanorods, such as CdSe–CdS dot-in-rod, have been extensively studied as a promising class of new materials for solar energy conversion because of the possibilities of using the band alignment of component materials and the rod-diameter-dependent quantum confinement effect to control the location of electrons and holes and to incorporate catalysts through the growth of Pt tips. Here we used CdS nanorods as an example to study the effect of nonuniform diameters along the rod on the exciton localization and dissociation dynamics in CdS and (platinum tipped) CdS–Pt nanorods. We showed that, in CdS nanorods prepared by seeded growth, the presence of a bulb with a larger diameter around the CdS seed resulted in an additional absorption band lower in energy than the exciton in the CdS rod. As a result, excitons generated in the CdS rod could undergo ultrafast localization to the bulb region in addition to trapping on the CdS rod. We observed that the Pt tip led to fast exciton dissociation by electron transfer. However, excitons localized on the CdS bulb showed slower average ET rates than those localized in the rod region. Our findings suggested that the effect of rod morphology should be carefully considered in designing multicomponent nanorods for solar energy conversion applications

Mimicking Photosynthesis with Supercomplexed Lipid Nanoassemblies: Design, Performance, and Enhancement Role of Cholesterol

We report here a new approach to mimicking photosynthesis that relies on supercomplexed lipid nanoassemblies to organize small organic species for coordinated light harvesting, energy/electron transfer, and photo-to-electrochemical energy conversion. Specifically, we demonstrate efficient photoinduced electron transfer (PeT) between rhodamine and fullerene assembled together via electrostatically bound liposome and lipid bilayer hosts. The remarkable impact of the lipid matrix on the photoconversion efficiency is further revealed by cholesterol, whose addition is found to modify the distribution and organization of the coassembled rhodamine dyes and thus their photodynamics. This significantly expedites the energy transfer (ET) among rhodamine dyes, as well as the PeT between rhodamines and fullerenes. A respectable 14% photon-to-electron conversion efficiency was achieved for this supercomplexed system containing 5% rhodamines, 5% fullerenes, and 30% cholesterol. The morphology, photodynamics, and photoelectrochemical behavior of these lipid supercomplexes were thoroughly characterized using atomic force microscopy (AFM), fluorescence microscopy, steady-state and time-resolved fluorescence spectroscopy, and transient absorption (TA) and photoaction spectroscopy. A detailed discussion on enhancement mechanisms of cholesterol in this lipid-complexed photosynthesis-mimicking system is provided at the end

Efficient Diffusive Transport of Hot and Cold Excitons in Colloidal Type II CdSe/CdTe Core/Crown Nanoplatelet Heterostructures

Cadmium chalcogenide colloidal quantum wells or nanoplatelets (NPLs), a class of new materials with atomically precise thickness and quantum confinement energy, have shown great potential in optoelectronic applications. Short exciton lifetimes in two-dimensional (2D) NPLs can be improved by the formation of type II heterostructures, whose properties depend critically on the mechanism of exciton transport. Herein, we report a study of room-temperature exciton in-plane transport mechanisms in type-II CdSe/CdTe core/crown (CC) colloidal NPL heterostructures with the same CdSe core and different CdTe crown sizes. Photoluminescence excitation measurements show unity quantum efficiency for transporting excitons created at the crown to the CdSe/CdTe interface (to form lower-energy charge-transfer excitons). At near band edge excitation, the crown-to-core transport time increases with crown size (from 2.7 to 5.6 ps), and this size-dependent transport can be modeled well by 2D diffusion of thermalized excitons in the crown with a diffusion constant of 2.5 ± 0.3 cm²/s (about a factor of 1.6 times smaller than the bulk value). With excitation energy above the band edge, there is an increased contribution of hot exciton transport (up to 7% of the total excitons at 400 nm excitation with diffusion constant that is over twice that of cold excitons). The percentage of hot exciton transport decreases with increasing NPL sizes and decreasing excess excitation photon energy. The observed ultrafast and efficient hot and cold exciton crown-to-core transport suggests their potential applications as light-harvesting and light-emitting materials

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

Low Threshold Multiexciton Optical Gain in Colloidal CdSe/CdTe Core/Crown Type-II Nanoplatelet Heterostructures

Colloidal cadmium chalcogenide core/crown type-II nanoplatelet heterostructures, such as CdSe/CdTe, are promising materials for lasing and light-emitting applications. Their rational design and improvement requires the understanding of the nature of single- and multiexciton states. Using pump fluence and wavelength-dependent ultrafast transient absorption spectroscopy, we have identified three spatially and energetically distinct excitons (in the order of increasing energy): interface-localized charge transfer exciton (X_CT, with electron in the CdSe core bound to the hole in the CdTe crown), and CdTe crown-localized X_CdTe and CdSe core-localized X_CdSe excitons. These exciton levels can be filled sequentially, with each accommodating two excitons (due to electron spin degeneracy) to generate one to six exciton states (with lifetimes of ≫1000, 209, 43.5, 11.8, 5.8, and 4.5 ps, respectively). The spatial separation of these excitons prolongs the lifetime of multiexciton states. Optical gain was observed in tri- (XX_CTX_CdTe) and four (XX_CTXX_CdTe) exciton states. Because of the large absorption cross section of nanoplatelets, an optical gain threshold as low as ∼43 μJ/cm² can be achieved at 550 nm excitation for a colloidal solution sample. This low gain threshold and the long triexciton (gain) lifetime suggest potential applications of these 2D type-II heterostructures as low threshold lasing materials

Strong Electronic Coupling and Ultrafast Electron Transfer between PbS Quantum Dots and TiO₂ Nanocrystalline Films

Hot carrier and multiple exciton extractions from lead salt quantum dots (QDs) to TiO₂ single crystals have been reported. Implementing these ideas on practical solar cells likely requires the use of nanocrystalline TiO₂ thin films to enhance the light harvesting efficiency. Here, we report 6.4 ± 0.4 fs electron transfer time from PbS QDs to TiO₂ nanocrystalline thin films, suggesting the possibility of extracting hot carriers and multiple excitons in solar cells based on these materials