Colloidal semiconductor quantum dots (QDs) are a highly promising materials platform for implementing solution-processable light-emitting diodes (LEDs). They combine high photostability of traditional inorganic semiconductors with chemical flexibility of molecular systems, which makes them well-suited for large-area applications such as television screens, solid-state lighting, and outdoor signage. Additional beneficial features include size-controlled emission wavelengths, narrow bandwidths, and nearly perfect emission efficiencies. State-of-the-art QD-LEDs exhibit high internal quantum efficiencies approaching unity. However, these peak values are observed only at low current densities ( J) and correspondingly low brightnesses, whereas at higher J, the efficiency usually exhibits a quick roll-off. This efficiency droop limits achievable brightness levels and decreases device longevity due to excessive heat generation. Here, we demonstrate QD-LEDs operating with high internal efficiencies (up to 70%) virtually droop-free up to unprecedented brightness of >100,000 cd m (at ∼500 mA cm). This exceptional performance is derived from specially engineered QDs that feature a compositionally graded interlayer and a final barrier layer. This QD design allows for improved balance between electron and hole injections combined with considerably suppressed Auger recombination, which helps mitigate efficiency losses due to charge imbalance at high currents. These results indicate a significant potential of newly developed QDs as enablers of future ultrabright, highly efficient devices for both indoor and outdoor applications.

Luminescent CuInS 2 (CIS) quantum dots (QDs) exhibit highly efficient intragap emission and long, hundreds-ofnanoseconds radiative lifetimes. These spectral properties, distinct from structurally similar II−VI QDs, can be explained by the involvement of intragap defect states containing a localized hole capable of coupling with a conduction band electron for a radiative transition. However, the absolute energies of the intragap and band-edge states, the structure of the emissive defect(s), and the role and origin of nonemissive decay channels still remain poorly understood. Here, we address these questions by applying methods of spectral electrochemistry. Cyclic voltammetry measurements reveal a well-defined intragap state whose redox potential is close to that of the Cu x defect state (where x = 1+ or 2+). The energy offset of this state from the valence band accounts well for the apparent photoluminescence Stokes shift observed in optical spectra. These results provide direct evidence that Cu-related defects serve as emission centers responsible for strong intragap emission from CIS QDs. We then use in situ spectroelectrochemistry to reveal two distinct emission pathways based on the differing oxidation states of Cu defects, which can be controlled by altering QD stoichiometry (1+ for stoichiometric QDs and 2+ for Cu-deficient QDs).

The use of semiconductor nanocrystal quantum dots (QDs) in optoelectronic devices typically requires postsynthetic chemical surface treatments to enhance electronic coupling between QDs and allow for efficient charge transport in QD films. Despite their importance in solar cells and infrared (IR) light-emitting diodes and photodetectors, advances in these chemical treatments for lead chalcogenide (PbE; E = S, Se, Te) QDs have lagged behind those of, for instance, II-VI semiconductor QDs. Here, we introduce a method for fast and effective ligand exchange for PbE QDs in solution, resulting in QDs completely passivated by a wide range of small anionic ligands. Due to electrostatic stabilization, these QDs are readily dispersible in polar solvents, in which they form highly concentrated solutions that remain stable for months. QDs of all three Pb chalcogenides retain their photoluminescence, allowing for a detailed study of the effect of the surface ionic double layer on electronic passivation of QD surfaces, which we find can be explained using the hard/soft acid-base theory. Importantly, we prepare highly conductive films of PbS, PbSe, and PbTe QDs by directly casting from solution without further chemical treatment, as determined by field-effect transistor measurements. This method allows for precise control over the surface chemistry, and therefore the transport properties of deposited films. It also permits single-step deposition of films of unprecedented thickness via continuous processing techniques, as we demonstrate by preparing a dense, smooth, 5.3-μm-thick PbSe QD film via doctor-blading. As such, it offers important advantages over laborious layer-by-layer methods for solar cells and photodetectors, while opening the door to new possibilities in ionizing-radiation detectors.

The light reaction in natural photosynthesis is generally recognized as one of the most efficient mechanisms for converting solar energy into other energy sources. We report herein on a novel strategy for generating H(2) fuel via an artificial Z-scheme mechanism by mimicking the natural photosynthesis that occurs in green plants. Designing a desirable photocatalyst by mimicking the Z-scheme mechanism leads to a conduction band that is sufficiently high to reduce protons, thus decreasing the probability of charge recombination. We combined two visible light sensitive photocatalysts, CdS and carbon-doped TiO(2), with different band structures. The used of this combination, that is, CdS/Au/TiO(1.96)C(0.04), resulted in the successful transfer of photogenerated electrons to a higher energy level in the form of the letter 'Z'. The system produced about a 4 times higher amount of H(2) under irradiation by visible light than CdS/Au/TiO(2). The findings reported herein describe an innovative route to harvesting energy by mimicking natural photosynthesis, and is independent of fossil fuels.

Colloidal quantum dots (QDs) of I–III–VI ternary compounds such as copper indium sulfide (CIS) and copper indium selenide (CISe) have been under intense investigation due to both their unusual photophysical properties and considerable technological utility. These materials feature a toxic-element-free composition, a tunable bandgap that covers near-infrared and visible spectral energies, and a highly efficient photoluminescence (PL) whose spectrum is located in the reabsorption-free intragap region. These properties make them attractive for light-emission and light-harvesting applications including photovoltaics and luminescent solar concentrators. Despite a large body of literature on device-related studies of CISe­(S) QDs, the understanding of their fundamental photophysical properties is surprisingly poor. Two particular subjects that are still heavily debated in the literature include the mechanism(s) for strong intragap emission and the reason(s) for a poorly defined (featureless) absorption edge, which often “tails” below the nominal bandgap. Here, we address these questions by conducting comprehensive spectroscopic studies of CIS QD samples with varied Cu-to-In ratios using resonant PL and PL excitation, femtosecond transient absorption, and magnetic circular dichroism measurements. These studies reveal a strong effect of stoichiometry on the concentration of Cu1+ vs Cu2+ defects (occurring as CuIn ″ and CuCu • species, respectively), and their effects on QD optical properties. In particular, we demonstrate that the increase in the relative amount of Cu2+ vs Cu1+ centers suppresses intragap absorption associated with Cu1+ states and sharpens band-edge absorption. In addition, we show that both Cu1+ and Cu2+ centers are emissive but are characterized by distinct activation mechanisms and slightly different emission energies due to different crystal lattice environments. An important overall conclusion of this study is that the relative importance of the Cu2+ vs Cu1+ emission/absorption channels can be controlled by tuning the Cu-to-In ratio, suggesting that the control of sample stoichiometry represents a powerful tool for achieving functionalities (e.g., strong intragap emission) that are not accessible with ideal, defect-free materials.