Colloidal PbS nanoplatelets (NPLs) are highly interesting materials for near-infrared optoelectronic applications. We use ultrafast transient optical absorption spectroscopy to study the characteristics and dynamics of photoexcited excitons in ultrathin PbS NPLs with a cubic crystal structure. NPLs are synthesized at near room temperature from lead oleate and thiourea precursors; they show an optical absorption onset at 680 nm (1.8 eV) and photoluminescence at 720 nm (1.7 eV). By postsynthetically treating PbS NPLs with CdCl2, their photoluminescence quantum yield is strongly enhanced from 1.4% to 19.4%. The surface treatment leads to an increased lead to sulfur ratio in the structures and associated reduced nonradiative recombination. Additionally, exciton-phonon interactions in pristine and CdCl2 treated NPLs at frequencies of 1.96 and 2.04 THz are apparent from coherent oscillations in the transient absorption spectra. This study is an important step forward in unraveling and controlling the optical properties of IV-VI semiconductor NPLs.

To improve the stability and carrier mobility of quantum dot (QD) optoelectronic devices, encapsulation or pore infilling processes are advantageous. Atomic layer deposition (ALD) is an ideal technique to infill and overcoat QD films, as it provides excellent control over film growth at the sub-nanometer scale and results in conformal coatings with mild processing conditions. Different thicknesses of crystalline ZnO films deposited on InP QD films are studied with spectrophotometry and time-resolved microwave conductivity measurements. High carrier mobilities of 4 cm² (V s)⁻¹ and charge separation between the QDs and ZnO are observed. Furthermore, the results confirm that the stability of QD thin films is strongly improved when the inorganic ALD coating is applied. Finally, proof-of-concept photovoltaic devices of InP QD films are demonstrated with an ALD-grown ZnO electron extraction layer.

The assembly of colloidal quantum dots (QDs) into dense superstructures holds great promise for the development of novel optoelectronic devices. Several assembly techniques have been explored; however, achieving direct and precise control over the interparticle potential that controls the assembly has proven to be challenging. Here, we exploit the application of critical Casimir forces to drive the growth of QDs into superstructures. We show that the exquisite temperature-dependence of the critical Casimir potential offers new opportunities to control the assembly process and morphology of the resulting QD superstructures. The direct assembly control allows us to elucidate the relation between structural, optical, and conductive properties of the critical Casimir-grown QD superstructures. We find that the choice of the temperature setting the interparticle potential plays a central role in maximizing charge percolation across QD thin-films. These results open up new directions for controlling the assembly of nanostructures and their optoelectronic properties.

Colloidal quantum dots (QDs) allow great flexibility in the design of optoelectronic devices, thanks to their size-dependent optical and electronic properties and the possibility to fabricate thin films with solution-based processing. In particular, in QD-based heterojunctions, the band gap of both components can be controlled by varying the size of the QDs. However, control over the band alignment between the two materials is required to tune the dynamics of carrier transfer across a heterostructure. We demonstrate that ligand exchange strategies can be used to control the band alignment of PbSe and CdSe QDs in a mixed QD solid, shifting it from a type-I to a type-II alignment. The change in alignment is observed in both spectroelectrochemical and transient absorption measurements, leading to a change in the energy of the conduction band edges in the two materials and in the direction of electron transfer upon photoexcitation. Our work demonstrates the possibility to tune the band offset of QD heterostructures via control of the chemical species passivating the QD surface, allowing full control over the energetics of the heterostructure without requiring changes in the QD composition.

Indium antimonide (InSb) quantum dots (QDs) have unique and interesting photophysical properties, but widespread experimentation with InSb QDs is lacking due to the difficulty in synthesizing this material. The key experimental challenge in fabricating InSb QDs is preparing a suitable Sb-precursor in the correct oxidation state that reacts with the In-precursor in a controllable manner. Here, we review and discuss the synthetic strategies for making colloidal InSb QDs and present a new reaction scheme yielding small (∼1 nm diameter) InSb QDs. This was accomplished by employing Sb(NMe₂)₃ as the antimony precursor and by screening different reducing agents that can selectively reduce it to stibine in situ. The released SbH₃, subsequently, reacts with In carboxylate to form small InSb clusters. The absorption features are moderately tunable (from 400 nm to 660 nm) by the amount and rate of reductant addition as well as the temperature of injection and subsequent annealing. Optical properties were probed with transient absorption spectroscopy and show complex time and spectral dependencies.

Thermalization losses limit the photon-to-power conversion of solar cells at the high-energy side of the solar spectrum, as electrons quickly lose their energy relaxing to the band edge. Hot-electron transfer could reduce these losses. Here, we demonstrate fast and efficient hot-electron transfer between lead selenide and cadmium selenide quantum dots assembled in a quantum-dot heterojunction solid. In this system, the energy structure of the absorber material and of the electron extracting material can be easily tuned via a variation of quantum-dot size, allowing us to tailor the energetics of the transfer process for device applications. The efficiency of the transfer process increases with excitation energy as a result of the more favorable competition between hot-electron transfer and electron cooling. The experimental picture is supported by time-domain density functional theory calculations, showing that electron density is transferred from lead selenide to cadmium selenide quantum dots on the sub-picosecond timescale.

Energy levels in the band gap arising from surface states can dominate the optical and electronic properties of semiconductor nanocrystal quantum dots (QDs). Recent theoretical work has predicted that such trap states in II-VI and III-V QDs arise only from two-coordinated anions on the QD surface, offering the hypothesis that Lewis acid (Z-type) ligands should be able to completely passivate these anionic trap states. In this work, we provide experimental support for this hypothesis by demonstrating that Z-type ligation is the primary cause of PL QY increase when passivating undercoordinated CdTe QDs with various metal salts. Optimized treatments with InCl₃ or CdCl₂ afford a near-unity (>90%) photoluminescence quantum yield (PL QY), whereas other metal halogen or carboxylate salts provide a smaller increase in PL QY as a result of weaker binding or steric repulsion. The addition of non-Lewis acidic ligands (amines, alkylammonium chlorides) systematically gives a much smaller but non-negligible increase in the PL QY. We discuss possible reasons for this result, which points toward a more complex and dynamic QD surface. Finally we show that Z-type metal halide ligand treatments also lead to a strong increase in the PL QY of CdSe, CdS, and InP QDs and can increase the efficiency of sintered CdTe solar cells. These results show that surface anions are the dominant source of trap states in II-VI and III-V QDs and that passivation with Lewis acidic Z-type ligands is a general strategy to fix those traps. Our work also provides a method to tune the PL QY of QD samples from nearly zero up to near-unity values, without the need to grow epitaxial shells.

Carrier multiplication is a process in which one absorbed photon excites two or more electrons. This is of great promise to increase the efficiency of photovoltaic devices. Until now, the factors that determine the onset energy of carrier multiplication have not been convincingly explained. We show experimentally that the onset of carrier multiplication in lead chalcogenide quantum confined and bulk crystals is due to asymmetric optical transitions. In such transitions most of the photon energy in excess of the band gap is given to either the hole or the electron. The results are confirmed and explained by theoretical tight-binding calculations of the competition between impact ionization and carrier cooling. These results are a large step forward in understanding carrier multiplication and allow for a screening of materials with an onset of carrier multiplication close to twice the band gap energy. Such materials are of great interest for development of highly efficient photovoltaic devices.

From a niche field over 30 years ago, quantum dots (QDs) have developed into viable materials for many commercial optoelectronic devices. We discuss the advancements in Pb-based QD solar cells (QDSCs) from a viewpoint of the pathways an excited state can take when relaxing back to the ground state. Systematically understanding the fundamental processes occurring in QDs has led to improvements in solar cell efficiency from ~3% to over 13% in 8 years. We compile data from ~200 articles reporting functioning QDSCs to give an overview of the current limitations in the technology. We find that the open circuit voltage limits the device efficiency and propose some strategies for overcoming this limitation.

Solar devices based on semiconductor nanoparticles require the use of conductive ligands; however, replacing the native, insulating ligands with conductive metal chalcogenide complexes introduces structural defects within the crystalline nanostructure that act as traps for charge carriers. We utilized atomically thin semiconductor nanoplatelets as a convenient platform for studying, both microscopically and spectroscopically, the development of defects during ligand exchange with the conductive ligands Na₄SnS₄ and (NH₄)₄Sn₂S₆. These defects can be repaired via mild chemical or thermal routes, through the addition of L-type ligands or wet annealing, respectively. This results in a higher-quality, conductive, colloidally stable nanomaterial that may be used as the active film in optoelectronic devices.