Organic-inorganic lead perovskites have shown great promise as photovoltaic materials, and within this class of materials (CH3NH3)PbI3-xClx is of particular interest. Herein we use soft X-ray spectroscopy and density functional theory calculations to demonstrate that the methylammonium cations in a typical photovoltaic layer may dissociate into a metastable arrangement of CH3I-Pb2 defects and trapped NH3. The possibility that other metastable configurations of the organic components in (CH3NH3)PbI3-xClx is rarely considered but adds an entirely new dimension in understanding the charge trapping, ionic transport, and structural degradation mechanisms in these materials. Understanding the influence of these other configurations is of critical importance for further improving the performance of these photovoltaics.

A quinone/catechol redox platform replaces Cl2 or HCl for processing germanium metal or germanium dioxide to germanes.

Cooperative performance of mixed-valent Eu(2+) /Eu(3+) in single-compound phosphors offers significant advantages in color rendering and luminescence efficiency, but their synthesis is challenging because of Eu(2+) oxidation. Using the tunable nature of the metal-ion nodes in metal-organic frameworks (MOFs), we present an in situ reduction and crystallization route for preparing MOFs and doping Eu(2+) /Eu(3+) with a controlled ratio. These materials exhibit rich photoluminescence, including intrinsic- and sensitized-emissions of Eu(2+) and Eu(3+) , and long-lived luminescence from charge transfer. Color rendering can be easily achieved by fine-tuning the valence states of Eu. A linear relation between temperature and the intensity ratio of Eu(2+) /Eu(3+) emissions provides outstanding properties for applications as self-calibrated luminescent thermometers with a wide working temperature range. Further incorporation of Tb(3+) into the MOFs results in white light, utilizing all Eu(2+) ,Tb(3+) , and Eu(3+) emissions in a single crystalline lattice.

The electronic structures of a series of gallium complexes are examined using X-ray absorption spectroscopy (XAS) in combination with ab initio calculations. The chemical states of Ga are strongly affected by the ligands and the bonding environment. For complexes containing multiple gallium sites, we demonstrate that XAS can identify the chemical state of each unique gallium center. A reliable understanding of the chemical nature of the core element in a coordination complex with strong core-ligand interaction can be obtained only when both experimental and theoretical approaches are combined.

A nominal GeOx (x ≤ 2) compound contains mixtures of Ge, Ge suboxides, and GeO2, but the detailed composition and crystallinity could vary from material to material. In this study, we synthesize GeOx nanoparticles by chemical reduction of GeO2, and comparatively investigate the freshly prepared sample and the sample exposed to ambient conditions. Although both compounds are nominally GeOx, they exhibit different X-ray diffraction patterns. X-ray absorption fine structure (XAFS) is utilized to analyse the detailed structure of GeOx. We find that the two initial GeOx compounds have entirely different compositions: the fresh GeOx contains large amorphous Ge clusters connected by GeOx, while after air exposure; the Ge clusters are replaced by a GeO2-GeOx composite. In addition, the two GeOx products undergo different structural rearrangement under H2 annealing, producing different intermediate phases before ultimately turning into metallic Ge. In the fresh GeOx, the amorphous Ge remains stable, with the GeOx being gradually reduced to Ge, leading to a final structure of crystalline Ge grains connected by GeOx. The air-exposed GeOx on the other hand, undergoes a GeO2→GeOx→Ge transition, in which H2 induces the creation of oxygen vacancies at intermediate stage. A complete removal of oxides occurs at high temperature.