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

IRAS04496-6958: A luminous carbon star with silicate dust in the Large Magellanic Cloud

We describe ISO observations of the obscured Asymptotic Giant Branch (AGB) star IRAS04496-6958 in the Large Magellanic Cloud (LMC). This star has been classified as a carbon star. Our new ISOCAM CVF spectra show that it is the first carbon star with silicate dust known outside of the Milky Way. The existence of this object, and the fact that it is one of the highest luminosity AGB stars in the LMC, provide important information for theoretical models of AGB evolution and understanding the origin of silicate carbon stars.Comment: 4 pages, 3 figures, accepted for publication in A&A Letter

Summer Precipitation Predicts Spatial Distributions of Semiaquatic Mammals

Citation: Ahlers, A. A., Cotner, L. A., Wolff, P. J., Mitchell, M. A., Heske, E. J., & Schooley, R. L. (2015). Summer Precipitation Predicts Spatial Distributions of Semiaquatic Mammals. Plos One, 10(8), 14. doi:10.1371/journal.pone.0135036Climate change is predicted to increase the frequency of droughts and intensity of seasonal precipitation in many regions. Semiaquatic mammals should be vulnerable to this increased variability in precipitation, especially in human-modified landscapes where dispersal to suitable habitat or temporary refugia may be limited. Using six years of presence-absence data (2007-2012) spanning years of record-breaking drought and flood conditions, we evaluated regional occupancy dynamics of American mink (Neovison vison) and muskrats (Ondatra zibethicus) in a highly altered agroecosystem in Illinois, USA. We used noninvasive sign surveys and a multiseason occupancy modeling approach to estimate annual occupancy rates for both species and related these rates to summer precipitation. We also tracked radiomarked individuals to assess mortality risk for both species when moving in terrestrial areas. Annual model-averaged estimates of occupancy for mink and muskrat were correlated positively to summer precipitation. Mink and muskrats were widespread during a year (2008) with above-average precipitation. However, estimates of site occupancy declined substantially for mink (0.56) and especially muskrats (0.09) during the severe drought of 2012. Mink are generalist predators that probably use terrestrial habitat during droughts. However, mink had substantially greater risk of mortality away from streams. In comparison, muskrats are more restricted to aquatic habitats and likely suffered high mortality during the drought. Our patterns are striking, but a more mechanistic understanding is needed of how semiaquatic species in human-modified ecosystems will respond ecologically in situ to extreme weather events predicted by climate-change models

ISO observations of obscured Asymptotic Giant Branch stars in the Large Magellanic Cloud

We present ISO photometric and spectroscopic observations of a sample of 57 bright Asymptotic Giant Branch stars and red supergiants in the Large Magellanic Cloud, selected on the basis of IRAS colours indicative of high mass-loss rates. PHOT-P and PHOT-C photometry at 12, 25 and 60 $\mu$m and CAM photometry at 12 $\mu$m are used in combination with quasi-simultaneous ground-based near-IR photometry to construct colour-colour diagrams for all stars in our sample. PHOT-S and CAM-CVF spectra in the 3 to 14 $\mu$m region are presented for 23 stars. From the colour-colour diagrams and the spectra, we establish the chemical types of the dust around 49 stars in this sample. Many stars have carbon-rich dust. The most luminous carbon star in the Magellanic Clouds has also a (minor) oxygen-rich component. OH/IR stars have silicate absorption with emission wings. The unique dataset presented here allows a detailed study of a representative sample of thermal-pulsing AGB stars with well-determined luminosities.Comment: 19 pages, 10 figures. Accepted for publication in Astronomy and Astrophysics Main Journa