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The electrochemical CO2 reduction reaction (CO2RR) using Cu-based catalysts holds great potential for producing valuable multi-carbon products from renewable energy. However, the chemical and structural state of Cu catalyst surfaces during the CO2RR remains a matter of debate. Here, we show the structural evolution of the near-surface region of polycrystalline Cu electrodes under in situ conditions through a combination of grazing incidence X-ray absorption spectroscopy (GIXAS) and X-ray diffraction (GIXRD). The in situ GIXAS reveals that the surface oxide layer is fully reduced to metallic Cu before the onset potential for CO2RR, and the catalyst maintains the metallic state across the potentials relevant to the CO2RR. We also find a preferential surface reconstruction of the polycrystalline Cu surface toward (100) facets in the presence of CO2. Quantitative analysis of the reconstruction profiles reveals that the degree of reconstruction increases with increasingly negative applied potentials, and it persists when the applied potential returns to more positive values. These findings show that the surface of Cu electrocatalysts is dynamic during the CO2RR, and emphasize the importance of in situ characterization to understand the surface structure and its role in electrocatalysis.

Si photocathodes integrated with Ag-supported dendritic Cu catalysts are used to perform light-driven reduction of CO2 to C2 and C3 products in aqueous solution. A back illumination geometry with an n-type Si absorber was used to permit the use of absorbing metallic catalysts. Selective carrier collection was accomplished by a p+ implantation on the illumination side and an n+ implantation followed by atomic layer deposition of TiO2 on the electrolyte site. The Ag-supported dendritic Cu CO2 reduction catalyst was formed by evaporation of Ag followed by high-rate electrodeposition of Cu to form a high surface area structure. Under simulated 1 sun illumination in 0.1 M CsHCO3 saturated with CO2, the photovoltage generated by the Si (∼600 mV) enables C2 and C3 products to be produced at -0.4 vs. RHE. Texturing of both sides of the Si increases the light-limited current density, due to reduced reflection on the illumination side, and also deceases the onset potential. Under simulated diurnal illumination conditions photocathodes maintain over 60% faradaic efficiency to hydrocarbon and oxygenate products (mainly ethylene, ethanol, propanol) for several days. After 10 days of testing, contamination from the counter electrode is observed, which causes an increase in hydrogen production. This effect is mitigated by a regeneration procedure which restores the original catalyst selectivity. A tandem, self-powered CO2 reduction device was formed by coupling a Si photocathode with two series-connected semitransparent CH3NH3PbI3 perovskite solar cells, achieving an efficiency for the conversion of sunlight to hydrocarbons and oxygenates of 1.5% (3.5% for all products).

Harnessing solar energy to drive photoelectrochemical reactions is widely studied for sustainable fuel production and versatile energy storage over different timescales. However, the majority of solar photoelectrochemical cells cannot drive the overall photosynthesis reactions without the assistance of an external power source. A device for simultaneous and direct production of renewable fuels and electrical power from sunlight is now proposed. This hybrid photoelectrochemical and photovoltaic device allows tunable control over the branching ratio between two high-value products of solar energy conversion, requires relatively simple modification to existing photovoltaic technologies, and circumvents the photocurrent mismatches that lead to significant loss in tandem photoelectrochemical systems comprising chemically stable photoelectrodes. Our proof-of-concept device is based on a transition metal oxide photoanode monolithically integrated onto silicon that possesses both front- and backside photovoltaic junctions. This integrated assembly drives spontaneous overall water splitting with no external power source, while also producing electricity near the maximum power point of the backside photovoltaic junction. The concept that photogenerated charge carriers can be controllably directed to produce electricity and chemical fuel provides an opportunity to significantly increase the energy return on energy invested in solar fuels systems and can be adapted to a variety of architectures assembled from different materials.

Irradiation of high-temperature superconductor YBa2Cu3O7 (YBCO) with high-energy He+ ions is known to cause structural changes in the YBCO film, decreasing the critical temperature TC and finally leading to a superconductor-to-insulator transition. This allows one to pattern narrow insulating regions with a focused ion beam (FIB) and thus fabricate nanoscale Josephson junctions on YBCO films. Moreover, such ion irradiation is known to cause structural changes in the YBCO film. However, details of how these structural changes occur in nanoscale devices produced by FIB remain unknown. Using nanofocus X-ray diffraction, we study the changes in the YBCO crystal lattice and investigate how the nature of these changes depends on the size of the irradiated regions. These data provide an important understanding of how oxide superconductors can be tailored at the nanometer scale for various applications. [ABSTRACT FROM AUTHOR]

The spatial collection efficiency portrays the driving forces and loss mechanisms in photovoltaic and photoelectrochemical devices. It is defined as the fraction of photogenerated charge carriers created at a specific point within the device that contribute to the photocurrent. In stratified planar structures, the spatial collection efficiency can be extracted out of photocurrent action spectra measurements empirically, with few a priori assumptions. Although this method was applied to photovoltaic cells made of well-understood materials, it has never been used to study unconventional materials such as metal-oxide semiconductors that are often employed in photoelectrochemical cells. This perspective shows the opportunities that this method has to offer for investigating new materials and devices with unknown properties. The relative simplicity of the method, and its applicability to operando performance characterization, makes it an important tool for analysis and design of new photovoltaic and photoelectrochemical materials and devices. Understanding the optoelectronic and transport properties of semiconductors is essential for producing high-efficiency photovoltaic and photoelectrochemical cells. To this end, empirical extraction of the spatial collection efficiency (i.e., the fraction of photogenerated charge carriers created at a specific point within the device that contribute to the photocurrent) is a useful, nondestructive, analytical tool to study new materials, junctions, and devices. This perspective describes how the spatial collection efficiency can be extracted by combining photocurrent action spectra with optical absorption profiles. The result is high-resolution depth profiles of device functionality with very few assumptions, which paves the way to operando semiconductor tomography. The challenges and opportunities that this method offers for analysis of complex materials are discussed. Since the method is based on widely used spectral response measurements, it can be an important addition to the toolbox of analytical methods for material research for future solar energy conversion systems. Quantifying transport and loss mechanisms is a key step in producing high-efficiency solar energy conversion and storage devices. Empirical extraction of the spatial collection efficiency under real operating conditions is a useful analytical tool for studying such processes. We describe how the spatial collection efficiency can be extracted and apply the method to a α-Fe2O3 water splitting photoanode. The extracted spatial collection efficiency profiles provide significant insights on driving forces and the advanced optoelectronic properties of α-Fe2O3.

Safe and practical solar-driven hydrogen generators must be capable of efficient and stable operation under diurnal cycling with full separation of gaseous H2 and O2 products. In this study, a novel architecture that fulfills all of these requirements is presented. The approach is inherently scalable and provides versatility for operation under diverse electrolyte and lighting conditions. The concept is validated using a 1 cm2 triple-junction photovoltaic cell with its illuminated photocathode protected by a composite coating comprising an organic encapsulant with an embedded catalytic support. The device is compatible with operation under conditions ranging from 1 m H2SO4 to 1 m KOH, enabling flexibility in selection of semiconductor, electrolyte, membrane, and catalyst. Stable operation at a solar-to-hydrogen conversion efficiency of >10% is demonstrated under continuous operation, as well as under diurnal light cycling for at least 4 d, with simulated sunlight. Operational characteristics are validated by extended time outdoor testing. A membrane ensures products are separated, with nonexplosive gas streams generated for both alkaline and acidic systems. Analysis of operational characteristics under different lighting conditions is enabled by comparison of a device model to experimental data.

Artificial photosystems are advanced by the development of conformal catalytic materials that promote desired chemical transformations, while also maintaining stability and minimizing parasitic light absorption for integration on surfaces of semiconductor light absorbers. Here, we demonstrate that multifunctional, nanoscale catalysts that enable high-performance photoelectrochemical energy conversion can be engineered by plasma-enhanced atomic layer deposition. The collective properties of tailored Co3O4/Co(OH)2 thin films simultaneously provide high activity for water splitting, permit efficient interfacial charge transport from semiconductor substrates, and enhance durability of chemically sensitive interfaces. These films comprise compact and continuous nanocrystalline Co3O4 spinel that is impervious to phase transformation and impermeable to ions, thereby providing effective protection of the underlying substrate. Moreover, a secondary phase of structurally disordered and chemically labile Co(OH)2 is introduced to ensure a high concentration of catalytically active sites. Application of this coating to photovoltaic p+n-Si junctions yields best reported performance characteristics for crystalline Si photoanodes.

Formation of planar heterojunction perovskite solar cells exhibiting both high efficiency and stability under continuous operation remains a challenge. Here, we show this can be achieved by using a defective TiO2 thin film as the electron transport layer. TiO2 layers with native defects are deposited by electron beam evaporation in an oxygen-deficient environment. Deep-level hole traps are introduced in the TiO2 layers and contribute to a high photoconductive gain and reduced photocatalytic activity. The high photoconductivity of the TiO2 electron transport layer leads to improved efficiency for the fabricated planar devices. A maximum power conversion efficiency of 19.0% and an average PCE of 17.5% are achieved. In addition, the reduced photocatalytic activity of the TiO2 layer leads to enhanced long-term stability for the planar devices. Under continuous operation near the maximum power point, an efficiency of over 15.4% is demonstrated for 100 h.

Artificial photosynthesis relies on the availability of semiconductors that are chemically stable and can efficiently capture solar energy. Although metal oxide semiconductors have been investigated for their promise to resist oxidative attack, materials in this class can suffer from chemical and photochemical instability. Here we present a methodology for evaluating corrosion mechanisms and apply it to bismuth vanadate, a state-of-the-art photoanode. Analysis of changing morphology and composition under solar water splitting conditions reveals chemical instabilities that are not predicted from thermodynamic considerations of stable solid oxide phases, as represented by the Pourbaix diagram for the system. Computational modelling indicates that photoexcited charge carriers accumulated at the surface destabilize the lattice, and that self-passivation by formation of a chemically stable surface phase is kinetically hindered. Although chemical stability of metal oxides cannot be assumed, insight into corrosion mechanisms aids development of protection strategies and discovery of semiconductors with improved stability.

III-V photovoltaics (PVs) have demonstrated the highest power conversion efficiencies for both single- and multi-junction cells. However, expensive epitaxial growth substrates, low precursor utilization rates, long growth times, and large equipment investments restrict applications to concentrated and space photovoltaics (PVs). Here, we demonstrate the first vapor-liquid-solid (VLS) growth of high-quality III-V thin-films on metal foils as a promising platform for large-area terrestrial PVs overcoming the above obstacles. We demonstrate 1-3 μm thick InP thin-films on Mo foils with ultra-large grain size up to 100 μm, which is ~100 times larger than those obtained by conventional growth processes. The films exhibit electron mobilities as high as 500 cm²/V-s and minority carrier lifetimes as long as 2.5 ns. Furthermore, under 1-sun equivalent illumination, photoluminescence efficiency measurements indicate that an open circuit voltage of up to 930 mV can be achieved, only 40 mV lower than measured on a single crystal reference wafer.

We are developing two-dimensional 16 x 25 pixel detector arrays of bothunstressed and stressed Ge:Ga photoconductive detectors for far-infraredastronomy from SOFIA. The arrays, based on earlier 5 x 5 detector arrays usedon the KAO, will be for our new instrument, the Far Infrared Field Imaging LineSpectrometer (FIFI LS). The unstressed Ge:Ga detector array will cover thewavelength range from 40 to 120 microns, and the stressed Ge:Ga detector arrayfrom 120 to 210 microns. The detector arrays will be operated with multiplexedintegrating amplifiers with cryogenic readout electronics located close to thedetector arrays. The design of the stressed detector array and results ofcurrent measurements on several prototype 16 pixel linear arrays are reported.They demonstrate the feasibility of the current concept. ***This paper does notinclude Figures due to astro-ph size limitations. Please download entire fileat http://fifi-ls.mpe-garching.mpg.de/spie.det.ps.gz ***

Bolometers designed to detect submillimeter radiation also respond to cosmic, gamma, and x rays. Because detectors cannot be fully shielded from such energy sources, it is necessary to understand the effect of a photon or cosmic-ray particle being absorbed. The resulting signal (known as a glitch) can then be removed from raw data. We present measurements using an Americium-241 gamma radiation source to irradiate a prototype bolometer for the High Frequency Instrument in the Planck Surveyor satellite. Our measurements showed no variation in response depending on where the radiation was absorbed, demonstrating that the bolometer absorber and thermistor thermalize quickly. The bolometer has previously been fully characterized both electrically and optically. We find that using optically measured time constants underestimates the time taken for the detector to recover from a radiation absorption event. However, a full thermal model for the bolometer, with parameters taken from electrical and optical measurements, provides accurate time constants. Slight deviations from the model were seen at high energies; these can be accounted for by use of an extended model. OCIS codes: 040.0040, 040.3060, 040.7480.

In order to further understand the pulsed-laser melting (PLM) of Mn and N implanted GaAs, which we have used to synthesize thin films of the ferromagnetic semiconductor Ga1-xMnxAs and the highly mismatched alloy GaNxAs1-x, we have simulated PLM of amorphous (a-) and crystalline (c-) GaAs. We present a numerical solution to the one-dimensional heat equation, accounting for phase-dependent reflectivity, optical skin depth, and latent heat, and a temperature-dependent thermal conductivity and specific heat. By comparing the simulations with experimental time-resolved reflectivity and melt depth versus laser fluence, we identify a set of thermophysical and optical properties for the crystalline, amorphous, and liquid phases of GaAs that give reasonable agreement between experiment and simulation. This work resulted in the estimation of thermal conductivity, melting temperature and latent heat of fusion of a-GaAs of 0.008 W/cm K at 300 K, 1350 K, and 2650 J/cm3, respectively. These materials properties also allow the prediction of the solidification velocity of crystalline and ion-amorphized GaAs. [ABSTRACT FROM AUTHOR]

Several analyses are conducted to explain the photovoltaic activity taking place in the several different homojunction ZnTe solar cells. An increase in the light absorption of the cells is shown to lead to a drop in the short circuit current.

Several simulation studies are conducted to explain the pulsed laser melting (PLM) taking place in the Mn and N implanted GaAs systems. The complete thermophysical and optical properties of the system are also explained.

We present the design and performance of a feedhorn-coupled bolometer array intended for a sensitive 350-[micro]m photometer camera. Silicon nitride micromesh absorbers minimize the suspended mass and heat capacity of the bolometers. The temperature transducers, neutron-transmutation-doped Ge thermistors, are attached to the absorber with In bump bonds. Vapor-deposited electrical leads address the thermistors and determine the thermal conductance of the bolometers. The bolometer array demonstrates a dark noise-equivalent power of 2.9 x [10.sup.-17] W/[square root of Hz] and a mean heat capacity of 1.3 pJ/K at 390 mK. We measure the optical efficiency of the bolometer and feedhorn to be 0.45-0.65 by comparing the response to blackbody calibration sources. The bolometer array demonstrates theoretical noise performance arising from the photon and the phonon and Johnson noise, with photon noise dominant under the design background conditions. We measure the ratio of total noise to photon noise to be 1.21 under an absorbed optical power of 2.4 pW. Excess noise is negligible for audio frequencies as low as 30 mHz. We summarize the trade-offs between bare and feedhorn-coupled detectors and discuss the estimated performance limits of micromesh bolometers. The bolometer array demonstrates the sensitivity required for photon noise-limited performance from a spaceborne, passively cooled telescope. OCIS codes: 040.0040, 040.3060, 040.1240.