Michiel Aerts

Unity quantum yield of photogenerated charges and band-like transport in quantum-dot solids

Solid films of colloidal quantum dots show promise in the manufacture of photodetectors and solar cells. These devices require high yields of photogenerated charges and high carrier mobilities, which are difficult to achieve in quantum-dot films owing to a strong electron-hole interaction and quantum confinement. Here, we show that the quantum yield of photogenerated charges in strongly coupled PbSe quantum-dot films is unity over a large temperature range. At high photoexcitation density, a transition takes place from hopping between localized states to band-like transport. These strongly coupled quantum-dot films have electrical properties that approach those of crystalline bulk semiconductors, while retaining the size tunability and cheap processing properties of colloidal quantum dots.

Photoconductivity of PbSe quantum-dot solids: dependence on ligand anchor group and length.

The assembly of quantum dots is an essential step toward many of their potential applications. To form conductive solids from colloidal quantum dots, ligand exchange is required. Here we study the influence of ligand replacement on the photoconductivity of PbSe quantum-dot solids, using the time-resolved microwave conductivity technique. Bifunctional replacing ligands with amine, thiol, or carboxylic acid anchor groups of various lengths are used to assemble quantum solids via a layer-by-layer dip-coating method. We find that when the ligand lengths are the same, the charge carrier mobility is higher in quantum-dot solids with amine ligands, while in quantum-dot solids with thiol ligands the charge carrier lifetime is longer. If the anchor group is the same, the charge carrier mobility is ligand length dependent. The results show that the diffusion length of charge carriers can reach several hundred nanometers.

Highly efficient carrier multiplication in PbS nanosheets

Semiconductor nanocrystals are promising for use in cheap and highly efficient solar cells. A high efficiency can be achieved by carrier multiplication (CM), which yields multiple electron-hole pairs for a single absorbed photon. Lead chalcogenide nanocrystals are of specific interest, since their band gap can be tuned to be optimal to exploit CM in solar cells. Interestingly, for a given photon energy CM is more efficient in bulk PbS and PbSe, which has been attributed to the higher density of states. Unfortunately, these bulk materials are not useful for solar cells due to their low band gap. Here we demonstrate that two-dimensional PbS nanosheets combine the band gap of a confined system with the high CM efficiency of bulk. Interestingly, in thin PbS nanosheets virtually the entire excess photon energy above the CM threshold is used for CM, in contrast to quantum dots, nanorods and bulk lead chalcogenide materials.

High charge mobility in two-dimensional percolative networks of PbSe quantum dots connected by atomic bonds

Two-dimensional networks of quantum dots connected by atomic bonds have an electronic structure that is distinct from that of arrays of quantum dots coupled by ligand molecules. We prepared atomically coherent two-dimensional percolative networks of PbSe quantum dots connected via atomic bonds. Here, we show that photoexcitation leads to generation of free charges that eventually decay via trapping. The charge mobility probed with an AC electric field increases with frequency from 150±15 cm2 V−1 s−1 at 0.2 terahertz to 260±15 cm2 V−1 s−1 at 0.6 terahertz. Gated four-probe measurements yield a DC electron mobility of 13±2 cm2 V−1 s−1. The terahertz mobilities are much higher than for arrays of quantum dots coupled via surface ligands and are similar to the highest DC mobilities reported for PbSe nanowires. The terahertz mobility increases only slightly with temperature in the range of 15–290 K. The extent of straight segments in the two-dimensional percolative networks limits the mobility, rather than charge scattering by phonons.

Enhanced Hot-Carrier Cooling and Ultrafast Spectral Diffusion in Strongly Coupled PbSe Quantum-Dot Solids

PbSe quantum-dot solids are of great interest for low cost and efficient photodetectors and solar cells. We have prepared PbSe quantum-dot solids with high charge carrier mobilities using layer-by-layer dip-coating with 1,2-ethanediamine as substitute capping ligands. Here we present a time and energy resolved transient absorption spectroscopy study on the kinetics of photogenerated charge carriers, focusing on 0-5 ps after photoexcitation. We compare the observed carrier kinetics to those for quantum dots in dispersion and show that the intraband carrier cooling is significantly faster in quantum-dot solids. In addition we find that carriers diffuse from higher to lower energy sites in the quantum-dot solid within several picoseconds.

Free charges produced by carrier multiplication in strongly coupled PbSe quantum dot films.

We show that in films of strongly coupled PbSe quantum dots multiple electron-hole pairs can be efficiently produced by absorption of a single photon (carrier multiplication). Moreover, in these films carrier multiplication leads to the generation of free, highly mobile charge carriers rather than excitons. Using the time-resolved microwave conductivity technique, we observed the production of more than three electron-hole pairs upon absorption of a single highly energetic photon (5.7E(g)). Free charge carriers produced via carrier multiplication are readily available for use in optoelectronic devices even without employing any complex donor/acceptor architecture or electric fields.

A phonon scattering bottleneck for carrier cooling in lead chalcogenide nanocrystals.

The cooling dynamics of hot charge carriers in colloidal lead chalcogenide nanocrystals is studied by hyperspectral transient absorption spectroscopy. We demonstrate a transient accumulation of charge carriers at a high energy critical point in the Brillouin zone. Using a theoretical study of the cooling rate in lead chalcogenides, we attribute this slowing down of charge carrier cooling to a phonon scattering bottleneck around this critical point. The relevance of this observation for the possible harvesting of the excess energy of hot carriers by schemes such as multiexciton generation is discussed.

Cooling and Auger Recombination of Charges in PbSe Nanorods: Crossover from Cubic to Bimolecular Decay

The cooling and Auger recombination of electron-hole pairs in PbSe quantum dots (QDs) and a series of nanorods (NRs) with similar diameter and varying length was studied by ultrafast pump-probe laser spectroscopy. Hot exciton cooling rates are found to be independent of nanocrystal shape. The energy relaxation rate decreases during cooling of charges, due to reduction of the density of electronic states. Auger recombination occurs via cubic third-order kinetics of uncorrelated charges in the QDs and NRs with length up to 29 nm. On increasing the NR length to 52 nm, a crossover to bimolecular exciton decay is found. This suggests a spatial extent of the one-dimensional exciton of 30-50 nm, which is significantly smaller than the value of 92 nm for the three-dimensional exciton diameter in bulk PbSe. The Auger decay time increases with NR length, which is beneficial for applications in nanocrystal lasers as well as for generation of free charges in photovoltaics.