Intermixing at the InxSy/Cu2ZnSn(S,Se)4 Heterojunction and Its Impact on the Chemical and Electronic Interface Structure

We report on the chemical and electronic structure of the interface between a thermally co-evaporated InxSy buffer and a Cu2ZnSn(S,Se)4 (CZTSSe) absorber for thin-film solar cells. To date, such cells have achieved energy conversion efficiencies up to 8.6%. Using surface-sensitive X-ray and UV photoelectron spectroscopy, combined with inverse photoemission and bulk-sensitive soft X-ray emission spectroscopy, we find a complex character of the buffer layer. It includes oxygen, as well as selenium and copper that diffused from the absorber into the InxSy buffer, exhibits an electronic band gap of 2.50 ± 0.18 eV at the surface, and leads to a small cliff in the conduction band alignment at the InxSy/CZTSSe interface. After an efficiency-increasing annealing step at 180 °C in nitrogen atmosphere, additional selenium diffusion leads to a reduced band gap at the buffer layer surface (2.28 ± 0.18 eV)

Molybdenum Disulfide Catalytic Coatings via Atomic Layer Deposition for Solar Hydrogen Production from Copper Gallium Diselenide Photocathodes

We demonstrate that applying atomic layer deposition-derived molybdenum disulfide (MoS2) catalytic coatings on copper gallium diselenide (CGSe) thin film absorbers can lead to efficient wide band gap photocathodes for photoelectrochemical hydrogen production. We have prepared a device that is free of precious metals, employing a CGSe absorber and a cadmium sulfide (CdS) buffer layer, a titanium dioxide (TiO2) interfacial layer, and a MoS2 catalytic layer. The resulting MoS2/TiO2/CdS/CGSe photocathode exhibits a photocurrent onset of +0.53 V vs RHE and a saturation photocurrent density of -10 mA cm-2, with stable operation for >5 h in acidic electrolyte. Spectroscopic investigations of this device architecture indicate that overlayer degradation occurs inhomogeneously, ultimately exposing the underlying CGSe absorber

Local electronic structure of the peptide bond probed by resonant inelastic soft X-ray scattering.

The local valence orbital structure of solid glycine, diglycine, and triglycine is studied using soft X-ray emission spectroscopy (XES), resonant inelastic soft X-ray scattering (RIXS) maps, and spectra calculations based on density-functional theory. Using a building block approach, the contributions of the different functional groups of the peptides are separated. Cuts through the RIXS maps furthermore allow monitoring selective excitations of the amino and peptide functional units, leading to a modification of the currently established assignment of spectral contributions. The results thus paint a new-and-improved picture of the peptide bond, enhance the understanding of larger molecules with peptide bonds, and simplify the investigation of such molecules in aqueous environment

Nutritional Quality of Leaves and Unripe Fruit Consumed as Famine Foods by the Flying Foxes of Samoa

Many tropical herbivores alter their diets throughout the year in response to different levels of food availability. Fruit bats, including Pteropus samoensis Peale and Pteropus tonganus Quoy & Gaimard, are phytophagous species that may increase their consumption of foods such as unripe fruit and leaves in periods of low fruit diversity and volume. These periods include the tropical dry season or following the frequent hurricanes that batter the Samoan Archipelago. We examined the nutritional composition of leaves and immature fruits and compared the levels of organic and mineral nutrients with those of ripe fruit. We used principal components analysis (PCA) to examine patterns of variation in nutrient components of leaves, unripe fruit, and ripe fruit, as well as to compare the mean levels of nutrients. Overall, unripe fruit provided levels of nutrients comparable with those of ripe fruit of the same species for many organic and mineral components. Unripe fruit were only half as rich in iron as ripe fruit, but unripe fruit had high levels of calcium compared with ripe fruit of the same species. Leaves are often cited as a rich source of protein for fruit bats, and our results were consistent with this suggestion. Leaves were also found to be rich in zinc, manganese, and calcium. Therefore, flying foxes and other herbivores probably do not avoid unripe fruits and leaves because of their low nutrient levels. It may be that these famine foods are not normally consumed because of the presence of secondary compounds, low concentrations of palatable sugars, or a distasteful and hard pericarp on unripe fruits

Coupling methylammonium and formamidinium cations with halide anions: Hybrid orbitals, hydrogen bonding, and the role of dynamics

The electronic structures of four precursors for organic–inorganic hybrid perovskites, namely, methylammonium chloride and iodide, as well as formamidinium bromide and iodide, are investigated by X-ray emission (XE) spectroscopy at the carbon and nitrogen K-edges. The XE spectra are analyzed based on density functional theory calculations. We simulate the XE spectra at the Kohn–Sham level for ground-state geometries and carry out detailed analyses of the molecular orbitals and the electronic density of states to give a thorough understanding of the spectra. Major parts of the spectra can be described by the model of the corresponding isolated organic cation, whereas high-emission energy peaks in the nitrogen K-edge XE spectra arise from electronic transitions involving hybrids of the molecular and atomic orbitals of the cations and halides, respectively. We find that the interaction of the methylammonium cation is stronger with the chlorine than with the iodine anion. Furthermore, our detailed theoretical analysis highlights the strong influence of ultrafast proton dynamics in the core-excited states, which is an intrinsic effect of the XE process. The inclusion of this effect is necessary for an accurate description of the experimental nitrogen K-edge X-ray emission spectra and gives information on the hydrogen-bonding strengths in the different precursor materials

Adaptive Optics Imaging of IRAS 18276-1431: a bipolar pre-planetary nebula with circumstellar "searchlight beams" and "arcs"

We present high-angular resolution images of the post-AGB nebula IRAS18276-1431 (also known as OH17.7-2.0) obtained with the Keck II Adaptive Optics (AO) system in its Natural Guide Star (NGS) mode in the Kp, Lp, and Ms near-infrared bands. We also present supporting optical F606W and F814W HST images as well as interferometric observations of the 12CO(J=1-0), 13CO(J=1-0), and 2.6mm continuum emission with OVRO. The envelope of IRAS18276-1431 displays a clear bipolar morphology in our optical and NIR images with two lobes separated by a dark waist and surrounded by a faint 4.5"x3.4" halo. Our Kp-band image reveals two pairs of radial ``searchlight beams'' emerging from the nebula center and several intersecting, arc-like features. From our CO data we derive a mass of M>0.38[D/3kpc]^2 Msun and an expansion velocity v_exp=17km/s for the molecular envelope. The density in the halo follows a radial power-law proportional to r^-3, which is consistent with a mass-loss rate increasing with time. Analysis of the NIR colors indicates the presence of a compact central source of ~300-500K dust illuminating the nebula in addition to the central star. Modeling of the thermal IR suggests a two-shell structure in the dust envelope: 1) an outer shell with inner and outer radius R_in~1.6E16cm and R_out>~1.25E17cm, dust temperature T_d~105-50K, and a mean mass-loss rate of Mdot~1E-3Msun/yr; and 2) an inner shell with R_in~6.3E14cm, T_dust~500-105K, and Mdot~3E-5Msun/yr. An additional population of big dust grains (radius a>~0.4mm) with T_dust=150-20K and mass M_dust=(0.16-1.6)E-3 [D/3kpc]^2 Msun can account for the observed sub-mm and mm flux excess. The mass of the envelope enclosed within R_out=1.25E17cm derived from SED modeling is ~1[D/3kpc]^2 Msun.Comment: 46 pages, 14 figures, 3 tables, accepted for publication in ApJ. Figures 12 & 13 in low resolution. Full resolution versions are available upon request to the first autho

Spectroscopic investigation of the deeply buried Cu In,Ga S,Se 2 Mo interface in thin film solar cells

The Cu In,Ga S,Se 2 Mo interface in thin film solar cells has been investigated by surface sensitive photoelectron spectroscopy, bulk sensitive X ray emission spectroscopy, and atomic force microscopy. It is possible to access this deeply buried interface by using a suitable lift off technique, which allows to investigate the back side of the absorber layer as well as the front side of the Mo back contact. We find a layer of Mo S,Se 2 on the surface of the Mo back contact and a copper poor stoichiometry at the back side of the Cu In,Ga S,Se 2 absorber. Furthermore, we observe that the Na content at the Cu In,Ga S,Se 2 Mo interface as well as at the inner grain boundaries in the back contact region is significantly lower than at the absorber front surfac

Near-infrared observations of water-ice in OH/IR stars

A search for the near-infrared water-ice absorption band was made in a number of very red OH/IR stars which are known to exhibit the 10um silicate absorption. As a by-product, accurate positions of these highly reddened objects are obtained. We derived a dust mass loss rate for each object by modelling the spectral energy distribution and the gas mass loss rate by solving the equation of motion for the dust drag wind. The derived mass loss rates show a strong correlation with the silicate optical depth as well as that of the water-ice. The stars have a high mass loss rate (> 1.0E-4 Msun/yr) with an average gas-to-dust mass ratio of 110. In objects which show the 3.1um water-ice absorption, the near-IR slope is much steeper than those with no water-ice. Comparison between our calculated mass loss rates and those derived from OH and CO observations indicates that these stars have recently increased their mass loss rates.Comment: 10 pages, 6 figures : accepted for publication in A&

Interchannel Coupling in the Photoionization of the M-shell of Kr Well Above Threshold: Experiment and Theory

Photoionization cross sections and asymmetry (β) parameters for Kr 3s, 3p, and 3d subshells have been measured and calculated in the 300–1300-eV photon energy range. Good agreement between experiment and theory is found for both cross-section branching ratios and β parameters. Interchannel coupling among the channels arising from 3s, 3p, and 3d subshells is found to be necessary for quantitative accuracy of the theory. This shows that the interchannel coupling phenomenology far above threshold, found previously for outer shells of Ne and Ar, is also operative for inner atomic shells