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Lead-halide perovskites have triggered the latest breakthrough in photovoltaic technology. Despite the great promise shown by these materials, their instability towards water even in the presence of low amounts of moisture makes them, a priori, unsuitable for their direct use as light harvesters in aqueous solution for the production of hydrogen through water splitting. Here, we present a simple method that enables their use in photoelectrocatalytic hydrogen evolution while immersed in an aqueous solution. Field's metal, a fusible InBiSn alloy, is used to efficiently protect the perovskite from water while simultaneously allowing the photogenerated electrons to reach a Pt hydrogen evolution catalyst. A record photocurrent density of -9.8 mA cm(-2) at 0 V versus RHE with an onset potential as positive as 0.95±0.03 V versus RHE is obtained. The photoelectrodes show remarkable stability retaining more than 80% of their initial photocurrent for ∼1 h under continuous illumination.

Metal-halide perovskites are at the frontier of optoelectronic research due to solution processability and excellent semiconductor properties. Here we use transient absorption spectroscopy to study hot-carrier distributions in CH3NH3PbI3 and quantify key semiconductor parameters. Above bandgap, non-resonant excitation creates quasi-thermalized carrier distributions within 100 fs. During carrier cooling, a sub-bandgap transient absorption signal arises at ∼1.6 eV, which is explained by the interplay of bandgap renormalization and hot-carrier distributions. At higher excitation densities, a ‘phonon bottleneck' substantially slows carrier cooling. This effect indicates a low contribution from inelastic carrier-impurity or phonon–impurity scattering in these polycrystalline materials, which supports high charge-carrier mobilities. Photoinduced reflectivity changes distort the shape of transient absorption spectra and must be included to extract physical constants. Using a simple band-filling model that accounts for these changes, we determine a small effective mass of mr=0.14 mo, which agrees with band structure calculations and high photovoltaic performance., The use of organic–inorganic metal-halide perovskites in hot-carrier devices depends on deepening the understanding of photoexcitations in these materials. Here, Price et al. use transient absorption spectroscopy to study hot-carrier distributions in CH3NH3PbI3 and quantify key semiconductors parameters.

Solution-processed metal halide perovskite semiconductors, such as CH3NH3PbI3, have exhibited remarkable performance in solar cells, despite having non-negligible density of defect states. A likely candidate is halide vacancies within the perovskite crystals, or the presence of metallic lead, both generated due to the imbalanced I/Pb stoichiometry which could evolve during crystallization. Herein, we show that the addition of hypophosphorous acid (HPA) in the precursor solution can significantly improve the film quality, both electronically and topologically, and enhance the photoluminescence intensity, which leads to more efficient and reproducible photovoltaic devices. We demonstrate that the HPA can reduce the oxidized I2 back into I−, and our results indicate that this facilitates an improved stoichiometry in the perovskite crystal and a reduced density of metallic lead., An imbalance in I/Pb stoichiometry is thought to lead to defects in metal halide films. Here, Zhang et al. show that the addition of hypophosphorous acid in the precursor solution can significantly improve the film quality and enhance the photoluminescence intensity, leading to improved photovoltaic devices.

Funder: HKU | University Research Committee, University of Hong Kong (HKU Research Committee); doi: https://doi.org/10.13039/501100003802, Organic solar cells based on non-fullerene acceptors can show high charge generation yields despite near-zero donor–acceptor energy offsets to drive charge separation and overcome the mutual Coulomb attraction between electron and hole. Here, we use time-resolved optical spectroscopy to show that free charges in these systems are generated by thermally activated dissociation of interfacial charge-transfer states that occurs over hundreds of picoseconds at room temperature, three orders of magnitude slower than comparable fullerene-based systems. Upon free electron–hole encounters at later times, both charge-transfer states and emissive excitons are regenerated, thus setting up an equilibrium between excitons, charge-transfer states and free charges. Our results suggest that the formation of long-lived and disorder-free charge-transfer states in these systems enables them to operate closely to quasi-thermodynamic conditions with no requirement for energy offsets to drive interfacial charge separation and achieve suppressed non-radiative recombination.

Perovskite light-emitting diodes have recently broken the 20% barrier for external quantum efficiency. These values cannot be explained with classical models for optical outcoupling. Here, we analyse the role of photon recycling (PR) in assisting light extraction from perovskite light-emitting diodes. Spatially-resolved photoluminescence and electroluminescence measurements combined with optical modelling show that repetitive re-absorption and re-emission of photons trapped in substrate and waveguide modes significantly enhance light extraction when the radiation efficiency is sufficiently high. In this manner, PR can contribute more than 70% to the overall emission, in agreement with recently-reported high efficiencies. While an outcoupling efficiency of 100% is theoretically possible with PR, parasitic absorption losses due to absorption from the electrodes are shown to limit practical efficiencies in current device architectures. To overcome the present limits, we propose a future configuration with a reduced injection electrode area to drive the efficiency toward 100%., Perovskite light-emitting diodes have shown unexpected high external quantum efficiency of 20%, breaking the ray-optics limit. Here Cho et al. reveal that photon recycling is responsible for the enhancement and propose photonic structures to further improve the device efficiency.

We report a fully efficient singlet exciton fission material with high ambient chemical stability. 10,21-Bis(triisopropylsilylethynyl)tetrabenzo[a,c,l,n]pentacene (TTBP) combines an acene core with triphenylene wings that protect the formal pentacene from chemical degradation. The electronic energy levels position singlet exciton fission to be endothermic, similar to tetracene despite the triphenylenes. TTBP exhibits rapid early time singlet fission with quantitative yield of triplet pairs within 100 ps followed by thermally activated separation to free triplet excitons over 65 ns. TTBP exhibits high photoluminescence quantum efficiency, close to 100% when dilute and 20% for solid films, arising from triplet-triplet annihilation. In using such a system for exciton multiplication in a solar cell, maximum thermodynamic performance requires radiative decay of the triplet population, observed here as emission from the singlet formed by recombination of triplet pairs. Combining chemical stabilisation with efficient endothermic fission provides a promising avenue towards singlet fission materials for use in photovoltaics., Designing optimised molecules for singlet fission is crucial to improve the efficiency of solar cells beyond its theoretical limit. Here, the authors investigate pentacene derivative TTBP, which exhibits high stability and luminescence yield, and find it highly suitable for exciton multiplication purposes.

Covalent organic frameworks (COFs) are an emerging class of highly tuneable crystalline, porous materials. Here we report the first COFs that change their electronic structure reversibly depending on the surrounding atmosphere. These COFs can act as solid-state supramolecular solvatochromic sensors that show a strong colour change when exposed to humidity or solvent vapours, dependent on vapour concentration and solvent polarity. The excellent accessibility of the pores in vertically oriented films results in ultrafast response times below 200 ms, outperforming commercially available humidity sensors by more than an order of magnitude. Employing a solvatochromic COF film as a vapour-sensitive light filter, we demonstrate a fast humidity sensor with full reversibility and stability over at least 4000 cycles. Considering their immense chemical diversity and modular design, COFs with fine-tuned solvatochromic properties could broaden the range of possible applications for these materials in sensing and optoelectronics.

Efficiency roll-off is a major issue for most types of light-emitting diodes (LEDs), and its origins remain controversial. Here we present investigations of the efficiency roll-off in perovskite LEDs based on two-dimensional layered perovskites. By simultaneously measuring electroluminescence and photoluminescence on a working device, supported by transient photoluminescence decay measurements, we conclude that the efficiency roll-off in perovskite LEDs is mainly due to luminescence quenching which is likely caused by non-radiative Auger recombination. This detrimental effect can be suppressed by increasing the width of quantum wells, which can be easily realized in the layered perovskites by tuning the ratio of large and small organic cations in the precursor solution. This approach leads to the realization of a perovskite LED with a record external quantum efficiency of 12.7%, and the efficiency remains to be high, at approximately 10%, under a high current density of 500 mA cm−2., Large drop in efficiency at high brightness has been holding back the development of various light-emitting diodes including halide perovskite. Here Zou et al. achieve high quantum efficiency of 10% under a high current density of 500 mA cm−2 in perovskite-based diodes by reducing luminescence quenching.