From sphere to multipod: thermally induced transitions of CdSe nanocrystals studied by molecular dynamics simulations.

Molecular dynamics (MD) simulations are used to show that a spherical zinc blende (ZB) nanocrystal (NC) can transform into a tetrapod or an octapod as a result of heating, by a local zincblende-to-wurtzite phase transformation taking place in the NC. The partial sphere-to-tetrapod or sphere-to-octapod transition occurs within simulation times of 30 ns and depends on both temperature and NC size. Surprisingly, the wurtzite (WZ) subdomains are not formed through a slip mechanism but are mediated by the formation of highly mobile Cd vacancies on the ZB{111} Cd atomic planes. The total potential energy of a tetrapod is found to be lower than that of a ZB sphere at the same numbers of atoms. The simulation results are in good agreement with experimental high-resolution transmission electron microscopy (HR-TEM) data obtained on heated colloidal CdSe NCs.

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.

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.

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.

Conductive response of a photo-excited sample in a radio-frequent driven resonance cavity.

An expression is derived for the perturbative response of a lumped resonance circuit to a sudden change in the circuit parameters. This expression is shown to describe also the photo-induced conductivity of a semiconductor mounted in a single-mode microwave cavity. The power dissipated in the cavity is measured in the two dimensions corresponding to time (after photo-excitation of the sample) and frequency (of the microwave driving source). Analysis of the experimental data for different semiconductor materials demonstrates the general applicability of the presented analytical expression here, by retrieving the time dependence of the sample's photo-induced conductivity.

Photoconductivity enhancement in multilayers of CdSe and CdTe quantum dots.

Charge separation at the interface between CdSe and CdTe quantum dots was investigated by comparing the photoconductivity of films consisting of only CdSe or CdTe quantum dots to that of films with alternating layers of CdSe and CdTe quantum dots. The photoconductivity for alternating layers is three times higher than for the single component layers. Different possible mechanisms are discussed, and it is concluded that the dissociation of photoexcited excitons into spatially separated mobile charge carriers at the CdSe/CdTe QD interfaces is the most likely explanation. Given that the yield of charge carrier photogeneration in the multilayer sample is at most one, and under the assumption that the mobility of QD layers in unchanged, we conclude that the yield of charge carrier photogeneration in the single component samples is at most one-third. The thickness of the individual CdSe and CdTe layers was varied, resulting in different distances between the CdSe/CdTe interfaces. The photoconductivity increased with respect to films of only CdSe or CdTe when these interfaces were separated by only one or two quantum dot layers, which implies that exciton diffusion is inefficient.

Supercrystals of CdSe quantum dots with high charge mobility and efficient electron transfer to TiO2.

Thermal annealing of thin films of CdSe/CdS core/shell quantum dots induces superordering of the nanocrystals and a significant reduction of the interparticle spacing. This results in a drastic enhancement of the quantum yield for charge carrier photogeneration and the charge carrier mobility. The mobile electrons have a mobility as high as 0.1 cm(2)/(V x s), which represents an increase of 4 orders of magnitude over non-annealed QD films and exceeds existing literature data on the electron mobility in CdSe quantum dot films. The lifetime of mobile electrons is longer than that of the exciton. A fraction of the mobile electrons gets trapped at levels below the conduction band of the CdSe nanocrystals. These electrons slowly diffuse over 50-300 nm on longer times up to 20 micros and undergo transfer to a TiO2 substrate. The yield for electron injection in TiO2 from both mobile and trapped electrons is found to be >16%.

Study of electronic defects in CdSe quantum dots and their involvement in quantum dot solar cells.

To enhance efficiencies of quantum dot CdSe/TiO(2) based solar cells, understanding of the space charge at the CdSe/TiO(2) interface is crucial. In this paper, the presence of a shallow acceptor in the CdSe quantum dots is found by means of a detailed impedance and Mott-Schottky (C(-2)-phi) study. Furthermore, it is clearly shown that this acceptor density decreases strongly with increasing quantum dot size. The presence of these defect states may give rise to Auger recombination in small quantum dots and therewith decrease the efficiency of quantum-dot-sensitized solar cells.