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The chemical and electronic structure of the interface between a sputter-deposited Zn(O,S) buffer layer and an industrial Cu(In,Ga)(S,Se)2 (CIGSSe) absorber for thin-film solar cells is investigated with X-ray and UV photoelectron spectroscopy, inverse photoemission spectroscopy, and X-ray emission spectroscopy. We find a CIGSSe absorber surface band gap of 1.61 (±0.14) eV, which is significantly increased as compared to the minimal value derived with bulk-sensitive methods (≈1.1 eV). We find no indication for diffusion of absorber elements into the buffer layer. Surface- and bulk-sensitive measurements of the buffer layer suggest the presence of S-Zn and S-O bonds in the Zn(O,S) layer. We find that the naturally existing downward band bending toward the CIGSSe absorber surface is increased by the formation of the interface, likely enhancing carrier separation under illumination. We also derive a flat conduction band alignment, in line with the reported high conversion efficiencies of corresponding large-area solar cells.

The sulfur L2,3 X-ray emission spectra of the alkaline earth metal sulfides BeS, MgS, CaS, SrS, and BaS are investigated and compared with spectra calculations based on density functional theory. Very distinct spectral shapes are found for the different compounds. With decreasing electronegativity of the cation, that is, increasing ionic bonding character, the upper valence band width and its relative spectral intensity decrease. These general trends are qualitatively reproduced by the spectra calculations, which give quite an accurate description of the spectral shapes in the upper valence band region. On the low energy side of the sulfur 3s → 2p transition dominating the spectra, we find strong satellites caused by "semi-Auger" decays involving configuration interaction. These satellites, previously believed to be energetically forbidden for sulfur L2,3 emission and only observed for the L2,3 emission of Cl to Cr, increase in intensity as the bonding character becomes more ionic and dominate the spectra for SrS and BaS. The intensities, energies, and widths of the satellites vary strongly between the investigated compounds, giving a very specific spectral fingerprint that can be used for speciation analysis.

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.

2D/3D perovskite heterostructures have emerged as a promising material composition to reduce nonradiative recombination in perovskite-based LEDs and solar cells. Such heterostructures can be created by a surface treatment with large organic cations, for example, n-butylammonium bromide (BABr). To understand the impact of the BABr surface treatment on the double-cation (Cs0.17FA0.83Pb(I0.6Br0.4)3) (FA = formamidinium) perovskite thin film and further optimize the corresponding structures, an in-depth understanding of the chemical and electronic properties of the involved surfaces, interfaces, and bulk is required. Hence, we study the impact of the BABr treatment with a combination of surface-sensitive X-ray photoelectron spectroscopy and bulk-sensitive resonant inelastic soft X-ray scattering (RIXS). A quantitative analysis of the BABr-treated perovskite thin film shows a modified chemical perovskite surface environment of carbon, nitrogen, bromine, iodine, and lead, indicating that the treatment leads to a perovskite surface with a modified composition and bonding structure. With K-edge RIXS, the local environment at the nitrogen and carbon atoms is probed, allowing us to identify the presence of BABr in the perovskite bulk albeit with a modified bonding environment. This, in turn, identifies a "hidden parameter" for the optimization of the BABr treatment and overall performance of 2D/3D perovskite solar cell absorbers.

The chemical and electronic structures of 15 different sulfates are studied using S L2,3 soft X-ray emission spectroscopy (XES). Sulfur L2,3 XES spectra of sulfates are distinctively different from those of other sulfur compounds, which makes XES a powerful technique for sulfate detection. Furthermore, subtle but distinct differences between the spectra of sulfates with different cations are observed, which allow a further differentiation of the specific compound. Most prominently, the position and width of the emission from "S 3s" derived bands systematically vary for different compounds, which can be understood with electronic structure and spectral calculations based on density functional theory.

Isotopically modulated silicon and germanium multilayers are analyzed by means of femtosecond spectroscopy and pulsed X-ray scattering for determining thermal conductivity and phonon modes. Isotopic modulation decreases thermal conductivity stronger than expected from a band bending model in the coherent phonon transport regime, in particular for silicon. Femtosecond spectroscopy and X-ray scattering resolve zone-folded vibration modes, which are located at the edge of the new, smaller Brillouin zone due to the multilayer periodicity. These modes can contribute to the reduction of thermal conductivity by Umklapp processes within the zone-folded mini-bands. Color-coded increase in ultrafast X-ray scattering in vicinity to the mini-zone boundary of a germanium multilayer.

The chemical and electronic structure of the interface between a sputter‐deposited Zn(O,S) buffer layer and an industrial Cu(In,Ga)(S,Se)2 (CIGSSe) absorber for thin‐film solar cells is investigated with X‐ray and UV photoelectron spectroscopy, inverse photoemission spectroscopy, and X‐ray emission spectroscopy. We find a CIGSSe absorber surface band gap of 1.61 (±0.14) eV, which is significantly increased as compared to the minimal value derived with bulk‐sensitive methods (≈1.1 eV). We find no indication for diffusion of absorber elements into the buffer layer. Surface‐ and bulk‐sensitive measurements of the buffer layer suggest the presence of S‐Zn and S‐O bonds in the Zn(O,S) layer. We find that the naturally existing downward band bending toward the CIGSSe absorber surface is increased by the formation of the interface, likely enhancing carrier separation under illumination. We also derive a flat conduction band alignment, in line with the reported high conversion efficiencies of corresponding large‐area solar cells. [ABSTRACT FROM AUTHOR]

The inelastic background of hard x-ray photoelectron spectroscopy data is analyzed to paint a depth-resolved picture of the CdS/Cu(In,Ga)Se2 (CdS/CIGSe) layer structure. The CdS/CIGSe interface is the central component in next-generation chalcopyrite thin-film photovoltaic devices. By analyzing both, the (unscattered) core-level peaks and the inelastic background, and by varying the excitation photon energy from 2.1 up to 14 keV, we can derive photoemission information over a broad range of electron kinetic energies and, hence, sampling depths. With this complementary information, the CdS film thickness of a CdS/CIGSe interface can be accurately determined as a function of the CdS deposition time. For the thinner CdS films, the film thickness can be shown to vary laterally. Furthermore, small amounts of Se and process-related Rb can be detected in a thin (∼2 nm) surface layer of all investigated CdS films. [ABSTRACT FROM AUTHOR]