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9 results for: All records
Author ORCID ID is 0000000152387487
Full Text and Citations
  1. Artificial photosynthetic approaches require the combination of light absorbers interfaced with overlayers that enhance charge transport and collection to perform catalytic reactions.
  2. Chemical transformations that occur on photoactive materials, such as photoelectrochemical water splitting, are strongly influenced by the surface properties as well as by the surrounding environment. Herein, we elucidate the effects of oxygen and water surface adsorption on band alignment, interfacial charge transfer, and charge-carrier transport by using complementary Kelvin probe measurements and photoconductive atomic force microscopy on bismuth vanadate. By observing variations in surface potential, we show that adsorbed oxygen acts as an electron-trap state at the surface of bismuth vanadate, whereas adsorbed water results in formation of a dipole layer without inducing interfacial charge transfer. The apparent changemore » of trap state density under dry or humid nitrogen, as well as under oxygen-rich atmosphere, proves that surface adsorbates influence charge-carrier transport properties in the material. The finding that oxygen introduces electronically active states on the surface of bismuth vanadate may have important implications for understanding functional characteristics of water splitting photoanodes, devising strategies to passivate interfacial trap states, and elucidating important couplings between energetics and charge transport in reaction environments.« less
  3. Mixed cation metal halide perovskites with increased power conversion efficiency, negligible hysteresis, and improved long-term stability under illumination, moisture, and thermal stressing have emerged as promising compounds for photovoltaic and optoelectronic applications. In this paper, we shed light on photoinduced halide demixing using in situ photoluminescence spectroscopy and in situ synchrotron X-ray diffraction (XRD) to directly compare the evolution of composition and phase changes in CH(NH 2) 2CsPb-halide (FACsPb-) and CH 3NH 3Pb-halide (MAPb-) perovskites upon illumination, thereby providing insights into why FACs-perovskites are less prone to halide demixing than MA-perovskites. We find that halide demixing occurs in both materials.more » However, the I-rich domains formed during demixing accumulate strain in FACsPb-perovskites but readily relax in MA-perovskites. The accumulated strain energy is expected to act as a stabilizing force against halide demixing and may explain the higher Br composition threshold for demixing to occur in FACsPb-halides. In addition, we find that while halide demixing leads to a quenching of the high-energy photoluminescence emission from MA-perovskites, the emission is enhanced from FACs-perovskites. This behavior points to a reduction of nonradiative recombination centers in FACs-perovskites arising from the demixing process and buildup of strain. FACsPb-halide perovskites exhibit excellent intrinsic material properties with photoluminescence quantum yields that are comparable to MA-perovskites. Finally, because improved stability is achieved without sacrificing electronic properties, these compositions are better candidates for photovoltaic applications, especially as wide bandgap absorbers in tandem cells.« less
    Cited by 1
  4. We present that the operando quantification of surface and bulk losses is key to developing strategies for optimizing photoelectrodes and realizing high efficiency photoelectrochemical solar energy conversion systems. This is particularly true for emerging thin film semiconductors, in which photocarrier diffusion lengths, surface and bulk recombination processes, and charge separation and extraction limitations are poorly understood. Insights into mechanisms of efficiency loss can guide strategies for nanostructuring photoelectrodes, engineering interfaces, and incorporating catalysts. However, few experimental methods are available for direct characterization of dominant loss processes under photoelectrochemical operating conditions. In this work, we provide insight into the function andmore » limitations of an emerging semiconductor photoanode, γ-Cu 3V 2O 8, by quantifying the spatial collection efficiency (SCE), which is defined as the fraction of photogenerated charge carriers at each point below the surface that contributes to the measured current. Analyzing SCE profiles at different operating potentials shows that increasing the applied potential primarily acts to reduce surface recombination rather than to increase the thickness of the space charge region under the semiconductor/electrolyte interface. Comparing SCE profiles obtained with and without a sacrificial reagent allows surface losses from electronically active defect states to be distinguished from performance bottlenecks arising from slow reaction kinetics. Combining these insights promotes a complete understanding of the photoanode performance and its potential as a water splitting photoanode. More generally, application of the SCE extraction method can aid in the discovery and evaluation of new materials for solar water splitting devices by providing mechanistic details underlying photocurrent generation and loss.« less
    Cited by 1
  5. Photoelectrochemical water splitting is a promising approach for renewable production of hydrogen from solar energy and requires interfacing advanced water-splitting catalysts with semiconductors. Understanding the mechanism of function of such electrocatalysts at the atomic scale and under realistic working conditions is a challenging, yet important, task for advancing efficient and stable function. This is particularly true for the case of oxygen evolution catalysts and, here, we study a highly active Co 3O 4/Co(OH) 2 biphasic electrocatalyst on Si by means of operando ambient-pressure X-ray photoelectron spectroscopy performed at the solid/liquid electrified interface. Spectral simulation and multiplet fitting reveal that themore » catalyst undergoes chemical-structural transformations as a function of the applied anodic potential, with complete conversion of the Co(OH) 2 and partial conversion of the spinel Co 3O 4 phases to CoO(OH) under precatalytic electrochemical conditions. Furthermore, we observe new spectral features in both Co 2p and O 1s core-level regions to emerge under oxygen evolution reaction conditions on CoO(OH). The operando photoelectron spectra support assignment of these newly observed features to highly active Co 4+ centers under catalytic conditions. Comparison of these results to those from a pure phase spinel Co 3O 4 catalyst supports this interpretation and reveals that the presence of Co(OH) 2 enhances catalytic activity by promoting transformations to CoO(OH). The direct investigation of electrified interfaces presented in this work can be extended to different materials under realistic catalytic conditions, thereby providing a powerful tool for mechanism discovery and an enabling capability for catalyst design.« less
    Cited by 17Full Text Available
  6. Organometal halide perovskite semiconductors have emerged as promising candidates for optoelectronic applications because of the outstanding charge carrier transport properties, achieved with low-temperature synthesis. In this paper, we present highly sensitive sub-bandgap external quantum efficiency (EQE) measurements of Au/spiro-OMeTAD/CH 3NH 3Pb(I 1–xBr x) 3/TiO 2/FTO/glass photovoltaic devices. The room-temperature spectra show exponential band tails with a sharp onset characterized by low Urbach energies (E u) over the full halide composition space. The Urbach energies are 15–23 meV, lower than those for most semiconductors with similar bandgaps (especially with E g > 1.9 eV). Intentional aging of CH 3NH 3Pb(I 1–xBrmore » x) 3 for up to 2300 h, reveals no change in E u, despite the appearance of the PbI 2 phase due to decomposition, and confirms a high degree of crystal ordering. Moreover, sub-bandgap EQE measurements reveal an extended band of sub-bandgap electronic states that can be fit with one or two point defects for pure CH 3NH 3PbI 3 or mixed CH 3NH 3Pb(I 1–xBr x) 3 compositions, respectively. Finally, the study provides experimental evidence of defect states close to the midgap that could impact photocarrier recombination and energy conversion efficiency in higher bandgap CH 3NH 3Pb(I 1–xBr x) 3 alloys.« less
    Cited by 12Full Text Available
  7. Development of practical systems for photoelectrochemical conversion of solar energy to chemical fuel requires light absorbers that are efficient, durable, and scalable. Because no material currently meets all three requirements, intensive semiconductor discovery efforts are underway, with a major focus on complex metal oxides. Discovery and development of next-generation light absorbers can be accelerated by gaining mechanistic insights into the function of existing systems. BiVO 4 embodies many key characteristics of the broader class of transition-metal oxides. Thus, it is well-suited as a platform for elucidating the critical roles of charge localization, defects, and chemical interactions on photoelectrochemical performance characteristics.more » In this work, we discuss how comprehensive characterization of electronic structure and semiconductor properties can advance theoretical models, approaches to addressing inefficiencies and instabilities, and prediction of new materials. Studies of BiVO 4 provide a general framework for understanding mechanisms in emerging materials and a foundation for discovering new ones.« less

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