Nanocrystal quantum dots have favourable light-emitting properties. They show photoluminescence with high quantum yields, and their emission colours depend on the nanocrystal size--owing to the quantum-confinement effect--and are therefore tunable. However, nanocrystals are difficult to use in optical amplification and lasing. Because of an almost exact balance between absorption and stimulated emission in nanoparticles excited with single electron-hole pairs (excitons), optical gain can only occur in nanocrystals that contain at least two excitons. A complication associated with this multiexcitonic nature of light amplification is fast optical-gain decay induced by non-radiative Auger recombination, a process in which one exciton recombines by transferring its energy to another. Here we demonstrate a practical approach for obtaining optical gain in the single-exciton regime that eliminates the problem of Auger decay. Specifically, we develop core/shell hetero-nanocrystals engineered in such a way as to spatially separate electrons and holes between the core and the shell (type-II heterostructures). The resulting imbalance between negative and positive charges produces a strong local electric field, which induces a giant ( approximately 100 meV or greater) transient Stark shift of the absorption spectrum with respect to the luminescence line of singly excited nanocrystals. This effect breaks the exact balance between absorption and stimulated emission, and allows us to demonstrate optical amplification due to single excitons.

One consequence of strong spatial confinement of electronic wave functions in semiconductor nanocrystals (NCs) is a significant enhancement in carrier-carrier Coulomb interactions. This effect leads to a number of novel physical phenomena including ultrafast decay of multiple electron-hole pairs (multiexcitons) by Auger recombination and high-efficiency generation of mutiexcitons by single photons via carrier multiplication (CM). Significant recent interest in multiexciton phenomena in NCs has been stimulated by studies of NC lasing, as well as potential applications of CM in solar-energy conversion. The focus of this Account is on CM. In this process, the kinetic energy of a "hot" electron (or a "hot" hole) does not dissipate as heat but is, instead, transferred via the Coulomb interaction to the valence-band electron, exciting it across the energy gap. Because of restrictions imposed by energy and translational-momentum conservation, as well as rapid energy loss due to phonon emission, CM is inefficient in bulk semiconductors, particularly at energies relevant to solar energy conversion. On the other hand, the CM efficiency can potentially be enhanced in zero-dimensional NCs because of factors such as a wide separation between discrete electronic states, which inhibits phonon emission ("phonon bottleneck"), enhanced Coulomb interactions, and relaxation in translational-momentum conservation. Here, we investigate CM in PbSe NCs by applying time-resolved photoluminescence and transient absorption. Both techniques show clear signatures of CM with efficiencies that are in good agreement with each other. NCs of the same energy gap show moderate batch-to-batch variations (within approximately 30%) in apparent multiexciton yields and larger variations (more than a factor of 3) due to differences in sample conditions (stirred vs static solutions). These results indicate that NC surface properties may affect the CM process. They also point toward potential interference from extraneous effects such as NC photoionization that can distort the results of CM studies. CM yields measured under conditions when extraneous effects are suppressed via intense sample stirring and the use of extremely low pump levels (0.02-0.03 photons absorbed per NC per pulse) reveal that both the electron-hole creation energy and the CM threshold are reduced compared with those in bulk solids. These results indicate a confinement-induced enhancement in the CM process in NC materials. Further optimization of CM performance should be possible by utilizing more complex (for example, shaped-controlled or heterostructured) NCs that allow for facile manipulation of carrier-carrier interactions, as well as single and multiexciton energies and dynamics.

Generation of multiple electron-hole pairs (excitons) by single photons, known as carrier multiplication (CM), has the potential to appreciably improve the performance of solar photovoltaics. In semiconductor nanocrystals, this effect usually has been detected using a distinct dynamical signature of multiexcitons associated with their fast Auger recombination. Here, we show that uncontrolled photocharging of the nanocrystal core can lead to exaggeration of the Auger decay component and, as a result, significant deviations of the apparent CM efficiencies from their true values. Specifically, we observe that for the same sample, apparent multiexciton yields can differ by a factor of approximately 3 depending on whether the nanocrystal solution is static or stirred. We show that this discrepancy is consistent with photoinduced charging of the nanocrystals in static solutions, the effect of which is minimized in the stirred case where the charged nanocrystals are swept from the excitation volume between sequential excitation pulses. Using side-by-side measurements of CM efficiencies and nanocrystal charging, we show that the CM results obtained under static conditions converge to the values measured for stirred solutions after we accurately account for the effects of photocharging. This study helps to clarify the recent controversy over CM in nanocrystals and highlights some of the issues that must be carefully considered in spectroscopic studies of this process.

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Effects of air exposure on surface properties, electronic structure, and carrier relaxation dynamics in colloidal PbSe nanocrystals (NCs) were studied using X-ray photoelectron spectroscopy, transmission electron microscopy, and steady-state and time-resolved photoluminescence (PL) spectroscopies. We show that exposure of NC hexane solutions to air under ambient conditions leads to rapid oxidation of NCs such that up to 50% of their volume is transformed into PbO, SeO2, or PbSeO3 within 24 h. The oxidation is a thermally activated process, spontaneous at room temperature. The oxidation-induced reduction in the size of the PbSe "core" increases quantum confinement, causing shifts of the PL band and the absorption onset to higher energies. The exposure of NC solutions to air also causes rapid (within minutes) quenching of PL intensity followed by slow (within hours) recovery during which the PL quantum yield can reach values exceeding those observed prior to the air exposure. The short-term PL quenching is attributed to enhanced carrier trapping induced by adsorption of oxygen onto the NC surface, while the PL recovery at longer times is predominantly due to reduction in the efficiency of the "intrinsic" nonradiative interband recombination caused by the increase of the band gap in oxidized NCs. Although the analysis of subnanosecond relaxation dynamics in air-exposed NCs is complicated by a significant enhancement in fast carrier trapping, our picosecond PL measurements suggest that air exposure likely has only a weak effect on Auger recombination and also does not significantly affect the efficiency of carrier multiplication. We also show that the effects of air exposure are partially suppressed in PbSe/CdSe core/shell structures.

Time-resolved sum-frequency vibrational spectroscopy permits the study of hitherto neglected ultrafast vibrational dynamics of neat water interfaces. Measurements on interfacial bonded OH stretch modes revealed relaxation behavior on sub-picosecond time scales in close resemblance to that of bulk water. Vibrational excitation is followed by spectral diffusion, vibrational relaxation, and thermalization in the hydrogen-bonding network. Dephasing of the excitation occurs in

Electronic relaxation in photoexcited graphenes is central to their photoreactivity and their optoelectrical applications such as photodetectors and solar cells. Herein we report on the first ensemble studies of electronic energy relaxation pathways in colloidal graphene quantum dots with uniform size. We show that the photoexcited graphene quantum dots have a significant probability of relaxing into triplet states and emit both phosphorescence and fluorescence at room temperature, with relative intensities depending on the excitation energy. Because of the long lifetime and reactivity of triplet electronic states, our results could have significant implications for applications of graphenes.

Colloidal nanocrystal quantum dots (NQDs) of narrow band gap materials are of substantial general interest because of their unparalleled potential as infrared fluorophores. While PbSe NQDs are a promising class of infrared-active nanocrystals due to high emission quantum yields and a wide useful spectral range, typical synthetic methods are sensitive to a variety of factors, including the influence of solvent/ligand impurities that render reproducibility difficult. In this work, we specifically examine the effects of diphenylphosphine and 1,2-hexadecanediol, as surrogates for putative trioctylphosphine-based reducing impurities, on the synthesis of PbSe NQDs. Specifically, we compare their influence on NQD size, chemical yield, and photoluminescence quantum yield. While both additives substantially increase the chemical yield of the synthesis, they demonstrate markedly different effects on emission quantum yield of the product NQDs. We further examine the effects of reaction temperature and oleic acid concentration on the diol-assisted synthesis. Increased oleic acid concentration led to somewhat higher growth rates and larger NQDs but at the expense of lower chemical yield. Temperature was found to have an even greater effect on growth rate and NQD size. Neither temperature nor oleic acid concentration was found to have noticeable effects on NQD emission quantum yield. Finally, we use numerical simulations to support the conjecture that the increased yield is likely a result of faster monomer formation, consistent with the activation of an additional reaction pathway by the reducing species.