Size and composition dependent multiple exciton generation efficiency in PbS, PbSe, and PbS(x)Se(1-x) alloyed quantum dots.

Using ultrafast transient absorption and time-resolved photoluminescence spectroscopies, we studied multiple exciton generation (MEG) in quantum dots (QDs) consisting of either PbSe, PbS, or a PbSxSe1-x alloy for various QD diameters with corresponding bandgaps (Eg) ranging from 0.6 to 1 eV. For each QD sample, we determine the MEG efficiency, ηMEG, defined in terms of the electron-hole pair creation energy (εeh) such that ηMEG = Eg/εeh. In previous reports, we found that ηMEG is about two times greater in PbSe QDs compared to bulk PbSe, however, little could be said about the QD-size dependence of MEG. In this study, we find for both PbS and PbSxSe1-x alloyed QDs that ηMEG decreases lineally with increasing QD diameter within the strong confinement regime. When the QD radius is normalized by a material-dependent characteristic radius, defined as the radius at which the electron-hole Coulomb and confinement energies are equivalent, PbSe, PbS, and PbSxSe1-x exhibit similar MEG behaviors. Our results suggest that MEG increases with quantum confinement, and we discuss the interplay between a size-dependent MEG rate versus hot exciton cooling.

Comparison of carrier multiplication yields in PbS and PbSe nanocrystals: the role of competing energy-loss processes.

Infrared band gap semiconductor nanocrystals are promising materials for exploring generation III photovoltaic concepts that rely on carrier multiplication or multiple exciton generation, the process in which a single high-energy photon generates more than one electron-hole pair. In this work, we present measurements of carrier multiplication yields and biexciton lifetimes for a large selection of PbS nanocrystals and compare these results to the well-studied PbSe nanocrystals. The similar bulk properties of PbS and PbSe make this an important comparison for discerning the pertinent properties that determine efficient carrier multiplication. We observe that PbS and PbSe have very similar biexciton lifetimes as a function of confinement energy. Together with the similar bulk properties, this suggests that the rates of multiexciton generation, which is the inverse of Auger recombination, are also similar. The carrier multiplication yields in PbS nanocrystals, however, are strikingly lower than those observed for PbSe nanocrystals. We suggest that this implies the rate of competing processes, such as phonon emission, is higher in PbS nanocrystals than in PbSe nanocrystals. Indeed, our estimations for phonon emission mediated by the polar Fröhlich-type interaction indicate that the corresponding energy-loss rate is approximately twice as large in PbS than in PbSe.

Anomalous independence of multiple exciton generation on different group IV-VI quantum dot architectures.

Multiple exciton generation (MEG) in PbSe quantum dots (QDs), PbSe(x)S(1-x) alloy QDs, PbSe/PbS core/shell QDs, and PbSe/PbSe(y)S(1-y) core/alloy-shell QDs was studied with time-resolved optical pump and probe spectroscopy. The optical absorption exhibits a red-shift upon the introduction of a shell around a PbSe core, which increases with the thickness of the shell. According to electronic structure calculations this can be attributed to charge delocalization into the shell. Remarkably, the measured quantum yield of MEG, the hot exciton cooling rate, and the Auger recombination rate of biexcitons are similar for pure PbSe QDs and core/shell QDs with the same core size and varying shell thickness. The higher density of states in the alloy and core/shell QDs provide a faster exciton cooling channel that likely competes with the fast MEG process due to a higher biexciton density of states. Calculations reveal only a minor asymmetric delocalization of holes and electrons over the entire core/shell volume, which may partially explain why the Auger recombination rate does not depend on the presence of a shell.

Comparing multiple exciton generation in quantum dots to impact ionization in bulk semiconductors: implications for enhancement of solar energy conversion.

Multiple exciton generation (MEG) in quantum dots (QDs) and impact ionization (II) in bulk semiconductors are processes that describe producing more than one electron-hole pair per absorbed photon. We derive expressions for the proper way to compare MEG in QDs with II in bulk semiconductors and argue that there are important differences in the photophysics between bulk semiconductors and QDs. Our analysis demonstrates that the fundamental unit of energy required to produce each electron-hole pair in a given QD is the band gap energy. We find that the efficiency of the multiplication process increases by at least 2 in PbSe QDs compared to bulk PbSe, while the competition between cooling and multiplication favors multiplication by a factor of 3 in QDs. We also demonstrate that power conversion efficiencies in QD solar cells exhibiting MEG can greatly exceed conversion efficiencies of their bulk counterparts, especially if the MEG threshold energy can be reduced toward twice the QD band gap energy, which requires a further increase in the MEG efficiency. Finally, we discuss the research challenges associated with achieving the maximum benefit of MEG in solar energy conversion since we show the threshold and efficiency are mathematically related.

Characterization of the unimolecular water elimination reaction from 1-propanol, 3,3,3-propan-1-ol-d3, 3,3,3-trifluoropropan-1-ol, and 3-chloropropan-1-ol.

The unimolecular reactions of 1-propanol, 3,3,3-propan-1-ol-d3, 3,3,3-trifluoropropan-1-ol, and 3-chloropropan-1-ol have been studied by the chemical activation technique. The recombination of CH3, CD3, CF3, and CH2Cl radicals with CH2CH2OH radicals at room temperature was used to generate vibrationally excited CH3CH2CH2OH, CD3CH2CH2OH, CF3CH2CH2OH, and CH2ClCH2CH2OH molecules. The principal unimolecular reaction for propanol and propanol-d3 with 90 kcal mol(-1) of vibrational energy is 1,2-H2O elimination with rate constants of 3.4 x 10(5) and 1.4 x 10(5) s(-1), respectively. For CH2ClCH2CH2OH also with 90 kcal mol(-1) of energy, 2,3-HCl elimination with a rate constant of 3.0 x 10(7) s(-1) is more important than 1,2-H2O elimination; the branching fractions are 0.95 and 0.05. For CF3CH2CH2OH with an energy of 102 kcal mol(-1), 1,2-H2O elimination has a rate constant of 7.9 x 10(5) and 2,3-HF elimination has a rate constant of 2.6 x 10(5) s(-1). Density functional theory was used to obtain models for the molecules and their transition states. The frequencies and moments of inertia from these models were used to calculate RRKM rate constants, which were used to assign threshold energies by comparing calculated and experimental rate constants. This comparison gives the threshold energy for H2O elimination from 1-propanol as 64 kcal mol(-1). The threshold energies for 1,2-H2O and 2,3-HCl elimination from CH2ClCH2CH2OH were 59 and 54 kcal mol(-1), respectively. The threshold energies for H2O and HF elimination from CF3CH2CH2OH are 62 and 70 kcal mol(-1), respectively. The structures of the transition states for elimination of HF, HCl, and H2O are compared.

Variations in the quantum efficiency of multiple exciton generation for a series of chemically treated PbSe nanocrystal films.

We study multiple exciton generation (MEG) in two series of chemically treated PbSe nanocrystal (NC) films. We find that the average number of excitons produced per absorbed photon varies between 1.0 and 2.4 (+/-0.2) at a photon energy of approximately 4E(g) for films consisting of 3.7 nm NCs and between 1.1 and 1.6 (+/-0.1) at hnu approximately 5E(g) for films consisting of 7.4 nm NCs. The variations in MEG depend upon the chemical treatment used to electronically couple the NCs in each film. The single and multiexciton lifetimes also change with the chemical treatment: biexciton lifetimes increase with stronger inter-NC electronic coupling and exciton delocalization, while single exciton lifetimes decrease after most treatments relative to the same NCs in solution. Single exciton lifetimes are particularly affected by surface treatments that dope the films n-type, which we tentatively attribute to an Auger recombination process between a single exciton and an electron produced by ionization of the dopant donor. These results imply that a better understanding of the effects of surface chemistry on film doping, NC carrier dynamics, and inter-NC interactions is necessary to build solar energy conversion devices that can harvest the multiple carriers produced by MEG. Our results show that the MEG efficiency is very sensitive to the condition of the NC surface and suggest that the wide range of MEG efficiencies reported in the recent literature may be a result of uncontrolled differences in NC surface chemistry.