Photoexcitation

Abstract: Photocatalytic and photoelectrochemical water splitting under irradiation by sunlight has received much attention for production of renewable hydrogen from water on a large scale. Many challenges still remain in improving energy conversion efficiency, such as utilizing longer-wavelength photons for hydrogen production, enhancing the reaction efficiency at any given wavelength, and increasing the lifetime of the semiconductor materials. This introductory review covers the fundamental aspects of photocatalytic and photoelectrochemical water splitting. Controlling the semiconducting properties of photocatalysts and photoelectrode materials is the primary concern in developing materials for solar water splitting, because they determine how much photoexcitation occurs in a semiconductor under solar illumination and how many photoexcited carriers reach the surface where water splitting takes place. Given a specific semiconductor material, surface modifications are important not only to activate the semiconductor for water splitting but also to facilitate charge separation and to upgrade the stability of the material under photoexcitation. In addition, reducing resistance loss and forming p-n junction have a significant impact on the efficiency of photoelectrochemical water splitting. Correct evaluation of the photocatalytic and photoelectrochemical activity for water splitting is becoming more important in enabling an accurate comparison of a number of studies based on different systems. In the latter part, recent advances in the water splitting reaction under visible light will be presented with a focus on non-oxide semiconductor materials to give an overview of the various problems and solutions.

Abstract: The study of the photophysical properties of organic–metallic lead halide perovskites, which demonstrate excellent photovoltaic performance in devices with electron- and hole-accepting layers, helps to understand their charge photogeneration and recombination mechanism and unravels their potential for other optoelectronic applications. We report surprisingly high photoluminescence (PL) quantum efficiencies, up to 70%, in these solution-processed crystalline films. We find that photoexcitation in the pristine CH3NH3PbI3–xClx perovskite results in free charge carrier formation within 1 ps and that these free charge carriers undergo bimolecular recombination on time scales of 10s to 100s of ns. To exemplify the high luminescence yield of the CH3NH3PbI3–xClx perovskite, we construct and demonstrate the operation of an optically pumped vertical cavity laser comprising a layer of perovskite between a dielectric mirror and evaporated gold top mirrors. These long carrier lifetimes together with exceptionally high...

Abstract: The status of understanding of the operation of bulk heterojunction (BHJ) solar cells is reviewed. Because the carrier photoexcitation recombination lengths are typically 10 nm in these disordered materials, the length scale for self-assembly must be of order 10–20 nm. Experiments have verified the existence of the BHJ nanostructure, but the morphology remains complex and a limiting factor. Three steps are required for generation of electrical power: i) absorption of photons from the sun; ii) photoinduced charge separation and the generation of mobile carriers; iii) collection of electrons and holes at opposite electrodes. The ultrafast charge transfer process arises from fundamental quantum uncertainty; mobile carriers are directly generated (electrons in the acceptor domains and holes in the donor domains) by the ultrafast charge transfer (≈70%) with ≈30% generated by exciton diffusion to a charge separating heterojunction. Sweep-out of the mobile carriers by the internal field prior to recombination is essential for high performance. Bimolecular recombination dominates in materials where the donor and acceptor phases are pure. Impurities degrade performance by introducing Shockly–Read–Hall decay. The review concludes with a summary of the problems to be solved to achieve the predicted power conversion efficiencies of >20% for a single cell.

Abstract: Excitonic solar cells, within which bound electron-hole pairs have a central role in energy harvesting, have represented a hot field of research over the last two decades due to the compelling prospect of low-cost solar energy. However, in such cells, exciton dissociation and charge collection occur with significant losses in energy, essentially due to poor charge screening. Organic-inorganic perovskites show promise for overcoming such limitations. Here, we use optical spectroscopy to estimate the exciton binding energy in the mixed-halide crystal to be in the range of 50 meV. We show that such a value is consistent with almost full ionization of the exciton population under photovoltaic cell operating conditions. However, increasing the total photoexcitation density, excitonic species become dominant, widening the perspective of this material for a host of optoelectronic applications.

Abstract: We report on reversible, light-induced transformations in (CH3NH3)Pb(BrxI1−x)3. Photoluminescence (PL) spectra of these perovskites develop a new, red-shifted peak at 1.68 eV that grows in intensity under constant, 1-sun illumination in less than a minute. This is accompanied by an increase in sub-bandgap absorption at ∼1.7 eV, indicating the formation of luminescent trap states. Light soaking causes a splitting of X-ray diffraction (XRD) peaks, suggesting segregation into two crystalline phases. Surprisingly, these photo-induced changes are fully reversible; the XRD patterns and the PL and absorption spectra revert to their initial states after the materials are left for a few minutes in the dark. We speculate that photoexcitation may cause halide segregation into iodide-rich minority and bromide-enriched majority domains, the former acting as a recombination center trap. This instability may limit achievable voltages from some mixed-halide perovskite solar cells and could have implications for the photostability of halide perovskites used in optoelectronics.