Understanding cooling of hot charge carriers in semiconductor quantum dots (QDs) is of fundamental interest and useful to enhance the performance of QDs in photovoltaics. We study electron and hole cooling dynamics in PbSe QDs up to high energies where carrier multiplication occurs. We characterize distinct cooling steps of hot electrons and holes and build up a broadband cooling spectrum for both charge carriers. Cooling of electrons is slower than of holes. At energies near the band gap we find cooling times between successive electronic energy levels in the order of 0.5 ps. We argue that here the large spacing between successive electronic energy levels requires cooling to occur by energy transfer to vibrational modes of ligand molecules or phonon modes associated with the QD surface. At high excess energy the energy loss rate of electrons is 1–5 eV/ps and exceeds 8 eV/ps for holes. Here charge carrier cooling can be understood in terms of emission of LO phonons with a higher density-of-states in the valence band than the conduction band. The complete mapping of the broadband cooling spectrum for both charge carriers in PbSe QDs is a big step toward understanding and controlling the cooling of hot charge carriers in colloidal QDs.Keywords: carrier cooling; carrier dynamics; electronic structure; nanocrystal; quantum dot; transient absorption spectroscopy;

In this work, we demonstrate that a preferential Ga-for-Zn cation exchange is responsible for the increase in photoluminescence that is observed when gallium oleate is added to InZnP alloy QDs. By exposing InZnP QDs with varying Zn/In ratios to gallium oleate and monitoring their optical properties, composition, and size, we conclude that Ga3+ preferentially replaces Zn2+, leading to the formation of InZnP/InGaP core/graded-shell QDs. This cation exchange reaction results in a large increase of the QD photoluminescence, but only for InZnP QDs with Zn/In ≥ 0.5. For InP QDs that do not contain zinc, Ga is most likely incorporated only on the quantum dot surface, and a PL enhancement is not observed. After further growth of a GaP shell and a lattice-matched ZnSeS outer shell, the cation-exchanged InZnP/InGaP QDs continue to exhibit superior PL QY (over 70%) and stability under long-term illumination (840 h, 5 weeks) compared to InZnP cores with the same shells. These results provide important mechanistic insights into recent improvements in InP-based QDs for luminescent applications.

In semiconductor quantum dots (QDs), charge carrier cooling is in direct competition with processes such as carrier multiplication or hot charge extraction that may improve the light conversion efficiency of photovoltaic devices. Understanding charge carrier cooling is therefore of great interest. We investigate high-energy optical transitions in PbSe QDs using hyperspectral transient absorption spectroscopy. We observe bleaching of optical transitions involving higher valence and conduction bands upon band edge excitation. The kinetics of rise of the bleach of these transitions after a pump laser pulse allow us to monitor, for the first time, cooling of hot electrons and hot holes separately. Our results show that holes cool significantly faster than electrons in PbSe QDs. This is in contrast to the common assumption that electrons and holes behave similarly in Pb chalcogenide QDs and has important implications for the utilization of hot charge carriers in photovoltaic devices.Keywords: band structure; charge carrier cooling; electron acceptor; nanocrystal; quantum dot; transient absorption spectroscopy;

Charge transfer in semiconductor heterojunctions is largely governed by the offset in the energy levels of the constituent materials. Unfortunately, literature values for such energy level offsets vary widely and are usually based on energy levels of the individual materials rather than of actual heterojunctions. Here we present a new method to determine absolute energy levels and energy level offsets in situ for films containing CdSe and PbSe quantum dots. Using spectroelectrochemistry, we find a type I offset at the CdSe-PbSe heterojunction. Whereas the energy level offset follows the expected size-dependent trend, the absolute positions of the 1Se level in the individual CdSe or PbSe quantum dots does not. This level varies by more than 0.5 eV, depending on film composition and surface defect concentration. Rather than extrapolating energy level offsets from measurements on pure CdSe or PbSe quantum-dot films, we suggest measuring energy level offsets in heterojunctions in situ.

Stability of quantum dot (QD) films is an issue of concern for applications in devices such as solar cells, LEDs, and transistors. This paper analyzes and optimizes the passivation of such QD films using gas-phase deposition, resulting in enhanced stability. Crucially, we deposited alumina at economically attractive conditions, room temperature and atmospheric pressure, on (1,2-ethanediamine) capped PbSe QD films using an approach based on atomic layer deposition (ALD), with trimethylaluminum (TMA) and water as precursors. We performed coating experiments from 1 to 25 cycles on the QD films, finding that alumina formed from the first exposure of TMA. X-ray photoelectron spectroscopy points to the presence of oxygen-rich compounds on the bare QD films, most likely from entrapped solvent molecules during the assembly of the QD films. These oxygenated compounds and the amine groups of the organic ligands react with TMA in the first cycle, resulting in a fast growth of alumina. Using 10 cycles resulted in a QD film that was optically stable for at least 27 days. Depositing alumina at ambient conditions is preferred, since the production of the QD films is also carried out at room temperature and atmospheric pressure, allowing combination of both processes in a single go.

Charge trapping is an ubiquitous process in colloidal quantum-dot solids and a major limitation to the efficiency of quantum dot based devices such as solar cells, LEDs, and thermoelectrics. Although empirical approaches led to a reduction of trapping and thereby efficiency enhancements, the exact chemical nature of the trapping mechanism remains largely unidentified. In this study, we determine the density of trap states in CdTe quantum-dot solids both experimentally, using a combination of electrochemical control of the Fermi level with ultrafast transient absorption and time-resolved photoluminescence spectroscopy, and theoretically, via density functional theory calculations. We find a high density of very efficient electron traps centered ∼0.42 eV above the valence band. Electrochemical filling of these traps increases the electron lifetime and the photoluminescence quantum yield by more than an order of magnitude. The trapping rate constant for holes is an order of magnitude lower that for electrons. These observations can be explained by Auger-mediated electron trapping. From density functional theory calculations we infer that the traps are formed by dicoordinated Te atoms at the quantum dot surface. The combination of our unique experimental determination of the density of trap states with the theoretical modeling of the quantum dot surface allows us to identify the trapping mechanism and chemical reaction at play during charge trapping in these quantum dots.

Understanding and controlling charge transfer between different kinds of colloidal quantum dots (QDs) is important for devices such as light-emitting diodes and solar cells and for thermoelectric applications. Here we study photoinduced electron transfer between CdTe and CdSe QDs in a QD film. We find that very efficient electron trapping in CdTe QDs obstructs electron transfer to CdSe QDs under most conditions. Only the use of thiol ligands results in somewhat slower electron trapping; in this case the competition between trapping and electron transfer results in a small fraction of electrons being transferred to CdSe. However, we demonstrate that electron trapping can be controlled and even avoided altogether by using the unique combination of electrochemistry and transient absorption spectroscopy. When the Fermi level is raised electrochemically, traps are filled with electrons and electron transfer from CdTe to CdSe QDs occurs with unity efficiency. These results show the great importance of knowing and controlling the Fermi level in QD films and open up the possibility of studying the density of trap states in QD films as well as the systematic investigation of the intrinsic electron transfer rates in donor–acceptor films.Keywords: charge transfer; defect; electrochemistry; Fermi level; ligands; quantum dot; transient absorption spectroscopy; trapping

Ligand exchange is a much-used method to increase the conductivity of colloidal quantum-dot films by replacing long insulating ligands on quantum-dot surfaces with shorter ones. Here we show that while some ligands indeed replace the original ones as expected, others may be used to controllably remove the native ligands and induce epitaxial necking of specific crystal facets. In particular, we demonstrate that amines strip lead oleate from the (100) surfaces of PbSe quantum dots. This leads to necking of QDs and results in cubic superlattices of epitaxially connected QDs. The number of amine head-groups as well as the carbon chain length of linear diamines is shown to control the extent of necking. DFT calculations show that removal of Pb(oleate)2 from (100) surfaces is exothermic for all amines, but the driving force increases as monoamines < long diamines < short diamines < tetramines. The neck formation and cubic ordering results in a higher optical absorption cross section and higher charge carrier mobilities, thereby showing that the use of the proper multidentate amine molecules is a powerful tool to create supercrystals of epitaxially connected PbSe QDs with controlled electronic coupling.Keywords: charge transport; density functional theory; ligands; photovoltaics; quantum dots; self-assembly;

Films of colloidal quantum dots (QDs) show great promise for application in optoelectronic devices. Great advances have been made in recent years in designing efficient QD solar cells and LEDs. A very important aspect in the design of devices based on QD films is the knowledge of their absolute energy levels. Unfortunately, reported energy levels vary markedly depending on the employed measurement technique and the environment of the sample. In this report, we determine absolute energy levels of QD films by electrochemical charge injection. The concomitant change in optical absorption of the film allows quantification of the number of charges in quantum-confined levels and thereby their energetic position. We show here that the size of voids in the QD films (i.e., the space between the quantum dots) determines the amount of charges that may be injected into the films. This effect is attributed to size exclusion of countercharges from the electrolyte solution. Further, the energy of the QD levels depends on subtle changes in the QD film and the supporting electrolyte: the size of the cation and the QD ligand length. These nontrivial effects can be explained by the proximity of the cation to the QD surface and a concomitant lowering of the electrochemical potential. Our findings help explain the wide range of reported values for QD energy levels and redefine the limit of applicability of electrochemical measurements on QD films. Finally, the finding that the energy of QD levels depends on ligand length and counterion size may be exploited in optimized designs of QD sensitized solar cells.Keywords: electrochemical charging; energy level; layer by layer; ligand; quantum dot; spectroelectrochemistry; surface functionalization

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.Keywords: carrier lifetime; carrier mobility; photoconductivity. layer-by-layer assembly; quantum dots; solar cells

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 (5.7Eg). 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.

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.

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.Keywords: CdSe; CdTe; charge separation; photoconductivity; quantum dots

Highly photoconductive films of CdSe nanocrystals have been prepared by exchanging the original bulky ligands with 1,2-ethanedithiol (EDT) and 1,2-ethanediamine (EDA). Different methods to achieve this exchange, layer-by-layer (LbL) deposition and soaking of drop-casted films, have been compared in detail. Introduction of EDT and EDA by the soaking method results in a broadening of the optical absorption due to disorder in the film. In contrast, the width of the absorption features is unaffected in the LbL films, while the position of the first optical absorption peak is red-shifted by tens of millielectronvolts. The photoluminescence is completely quenched for the LbL films. These findings are characteristic for strong and homogeneous electronic coupling between the quantum dots (QDs) in the LbL films. The photoconductivity of these films was studied with the time-resolved microwave conductivity (TRMC) technique. With this electrodeless technique effects of electrode injection on charge transport are avoided, so that information about the intrinsic mobility of charge carriers is obtained. We find that in simple drop-casted films the conductivity is mainly imaginary and dominated by the polarizability of photogenerated excitons. When the orginal ligands are exchanged by soaking or by the LbL procedure, the conductivity becomes real and dominated by interparticle transport of free charge carriers. It is found that the product of the exciton dissociation yield and the charge carrier mobility is 4 × 10−3 cm2/(V s) in the LbL grown films with EDA capping molecules. This implies that a surprisingly high fraction of free carriers is generated or, alternatively, that the carrier mobility is higher than all previously reported mobility values for layers of CdSe QDs.

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 cm2/(V·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 μs 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%.Keywords: annealing; photoconductivity; quantum dot; supercrystal; TiO2

Efficient carrier multiplication has been reported for several semiconductor nanocrystals: PbSe, PbS, PbTe, CdSe, InAs, and Si. Some of these reports have been challenged by studies claiming that carrier multiplication does not occur in CdSe, CdTe, and InAs nanocrystals, thus raising legitimate doubts concerning the occurrence of carrier multiplication in the remaining materials. Here, conclusive evidence is given for its occurrence in PbSe nanocrystals using femtosecond transient photobleaching. In addition, it is shown that a correct determination of carrier-multiplication efficiency requires spectral integration over the photobleach feature. The carrier multiplication efficiency we obtain is significantly lower than what has been reported previously, and it remains an open question whether it is higher in nanocrystals than it is in bulk semiconductors.

The temperature dependence of the electrical conductivity of assemblies of ZnO nanocrystals, studied with an electrochemically gated transistor is very accurately described by the relation ln σ = ln σ0 − (T0/T)x with x = 2/3 over the entire temperature range from 7 to 200 K, independent of charge concentration and dielectric environment. These results cannot be explained by existing models but are supported by results on Au nanocrystals where an identical temperature dependence was observed (Zabet-Khosousi et al., Phys. Rev. Lett. 2006, 96 (15), 156403). We propose an adaptation of the Efros−Shklovskii variable-range hopping model by introducing an expression for nonresonant tunneling based on local energy fluctuations, which yields exactly the temperature dependence that is observed experimentally.

The second peak in the optical absorption spectrum of PbSe nanocrystals is arguably the most discussed optical transition in semiconductor nanocrystals. Ten years of scientific debate have produced many theoretical and experimental claims for the assignment of this feature as the 1Pe1Ph as well as the 1Sh,e1Pe,h transitions. We studied the nature of this absorption feature by pump−probe spectroscopy, exactly controlling the occupation of the states involved, and present conclusive evidence that the optical transition involves neither 1Se nor 1Sh states. This suggests that it is the 1Ph1Pe transition that gives rise to the second peak in the absorption spectrum of PbSe nanocrystals.