We describe the structural, optical, and electrical properties of films of spin-cast, oleate-capped PbSe nanocrystals that are treated thermally or chemically in solutions of hydrazine, methylamine, or pyridine to produce electronically coupled nanocrystal solids. Postdeposition heat treatments trigger nanocrystal sintering at approximately 200 degrees C, before a substantial fraction of the oleate capping group evaporates or pyrolyzes. The sintered nanocrystal films have a large hole density and are highly conductive. Most of the amine treatments preserve the size of the nanocrystals and remove much of the oleate, decreasing the separation between nanocrystals and yielding conductive films. X-ray scattering, X-ray photoelectron and optical spectroscopy, electron microscopy, and field-effect transistor electrical measurements are used to compare the impact of these chemical treatments. We find that the concentration of amines adsorbed to the NC films is very low in all cases. Treatments in hydrazine in acetonitrile remove only 2-7% of the oleate yet result in high-mobility n-type transistors. In contrast, ethanol-based hydrazine treatments remove 85-90% of the original oleate load. Treatments in pure ethanol strip 20% of the oleate and create conductive p-type transistors. Methylamine- and pyridine-treated films are also p-type. These chemically treated films oxidize rapidly in air to yield, after short air exposures, highly conductive p-type nanocrystal solids. Our results aid in the rational development of solar cells based on colloidal nanocrystal films.

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.

Recent reports question the validity of pulsed fs-laser experiments for measuring the photon-to-exciton quantum yields (QYs) that result from multiple exciton generation (MEG). The repetitive nature of these experiments opens up an alternative relaxation pathway that may produce artificially high results. We present transient-absorption (TA) data for 4.6 and 6.6 nm diameter PbSe quantum dots (QDs) at a variety of pump photon energies. The data are collected under laminar flow conditions with volumetric flow rates ranging from 0 to 150 mL/min (resulting in Reynolds numbers up to 460). The results are modeled with a spatially resolved population balance of generation, recombination, convective replacement, and accumulation of long-lived excited QDs. By comparing the simulations and experiments, the steady-state population of the long-lived QD-excited states and their kinetics are determined for different experimental conditions. We also improve upon reported photon-to-exciton QYs for PbSe QDs. We find differences in the observed TA dynamics between flowing and static conditions that depend upon photon fluence, pump photon energy, and quality of the QD surfaces. For excitation energies below 2 E g, independent of QD size or photon fluence, we observe no flow rate dependence in the TA dynamics. At excitation energies of hν > 3 E g, we observe differences between static and flowing conditions that are most pronounced for high photon fluences. At 3.7 E g and for 4.6 nm PbSe QDs we find a QY of 1.2 ± 0.1 and at 4.5 E g the QY is 1.55 ± 0.05. With 6.6 nm QDs excited at 4.7 E g we observe no difference between static and flowing conditions and find a QY of 1.61 ± 0.05. We also find that by treating the surface of QDs, we can decrease the charging probability (P g ≈ 5 × 10−5) by a factor of 3−4. The observed variations suggest that different QD samples vary regarding their susceptibility to the creation of long-lived states.