In situ XPS study of the surface chemistry of MAPI solar cells under operating conditions in vacuum.

The most limiting factor for the commercialization of perovskite solar cells is the lack of long-term stability under operating conditions. To examine the intrinsic stability of the perovskite film, we investigated the chemical and electronic properties of methylammonium lead triiodide (CH3NH3PbI3) perovskite by in situ X-ray photoelectron spectroscopy (XPS). In particular, XPS data were collected under dark conditions, at applied voltage, under illumination, at open circuit, and under operating conditions. In addition, operation in ambient air atmosphere was analysed by XPS. It was observed that the chemical properties of methylammonium lead triiodide change upon illumination under open-circuit condition by formation of metallic lead species and then by conversion into PbI2 due to evaporation of the organic compounds. These changes, however, can be restricted by applying an extraction voltage to the device contacts that will extract the photogenerated charges from the absorber. As these results were obtained in vacuum, i.e., in an inert atmosphere, experiments prove that the photogenerated charge carriers intrinsically induce changes in chemical and electronic properties if they are not extracted from the absorber. By illuminating CH3NH3PbI3 in ambient air, the metallic lead species react with oxygen and form lead oxides and lead complexes, which passivate the film and remove the in-gap states.

Band alignment investigations of heterostructure NiO/TiO2 nanomaterials used as efficient heterojunction earth-abundant metal oxide photocatalysts for hydrogen production.

Earth-abundant NiO/anatase TiO2 heteronanostructures were prepared by a straightforward one-pot sol-gel synthetic route followed by a suitable thermal post-treatment. The resulting 0.1-4 wt% NiO-decorated anatase TiO2 nanoparticles were characterized by X-ray diffraction, electron microscopy, Raman and UV-visible spectroscopy and N2 sorption analysis, and showed both nanocrystallinity and mesoporosity. The careful determination of the energy band alignment diagram by a suitable combination of XPS/UPS and absorption spectroscopy data revealed significant band bending at the interface of the p-n NiO/anatase TiO2 heterojunction nanoparticles. Furthermore, these heterojunction photocatalysts exhibited an improved photocatalytic activity in H2 production by methanol photoreforming compared to pure anatase TiO2 and commercial P25. Thus, an average H2 production rate of 2693 µmol h-1 g-1 was obtained for the heterojunction of a 1 wt% NiO/anatase photocatalyst, which is one of the most efficient NiO/anatase TiO2 systems ever reported. An enhanced dissociation efficiency of the photogenerated electron-hole pairs resulting from an internal electric field developed at the interface of the NiO/anatase TiO2 p-n heterojunctions is suggested to be the reason of this enhanced photocatalytic activity.

Dissociative adsorption of H2O on LiCoO2 (00l) surfaces: Co reduction induced by electron transfer from intrinsic defects.

Understanding the mechanism of the interaction of lithium ion conductors with water is crucial for both fundamental and technological points of view. Despite the generally accepted fact that water is one of main sources of the degradation of Li-ion recharge batteries, the physicochemical processes occurring at the water-lithium ion conductor interface are not fully understood. By using synchrotron X-ray photoelectron spectroscopy (SXPS) and O K- and Co L- X-ray absorption near edge structure (XANES), we evidence that H2O is dissociatively adsorbed on LiCoO2 thin film at room temperature resulting in the formation of OH groups and the accumulation of the negative charge at the surface accompanied by electron transfer to the initial empty Co3d (eg (*)) state. By considering the experimentally obtained energy diagram of the ionic conductor and water, direct charge transfer is not favorable due to a high difference in the chemical potential of the ionic conductor and electronic levels of the molecule. Here, we develop the model for the dissociative water adsorption which explains the electron transfer to LiCoO2 by using the atomistic approach. The model takes into account the intrinsic defects found on the surface (<2 nm depth) by using the depth resolved photoemission experiments and can be explored to other layered transition metal oxides to interpret the interaction of water with the surface of ionic conductors.

Investigation of sodium insertion into tetracyanoquinodimethane (TCNQ): results for a TCNQ thin film obtained by a surface science approach.

In this contribution, we investigate the insertion of sodium into tetracyanoquinodimethane (TCNQ) and its effect on the electronic structure by means of a surface science experiment. We exposed a TCNQ thin film stepwise to sodium vapour and monitored the electronic structure by X-ray photoelectron spectroscopy (XPS) and ultra-violet photoelectron spectroscopy (UPS). During the insertion experiment three stages were observed, which can be related to three different phases, predominantly consisting of TCNQ(0), TCNQ(1-) and TCNQ(2-). With increasing sodium content the Fermi level shifts upwards and new electronic states appear in the band gap. For phases with high sodium content the sodium diffusion seems to be inhibited which we attribute to closed diffusion pathways in the molecular structure of TCNQ(1-).

Silicon based tandem cells: novel photocathodes for hydrogen production.

A photovoltaic tandem cell made of amorphous silicon (a-Si) and microcrystalline silicon (µc-Si) was investigated as a photocathode for hydrogen evolution in a photoelectrochemical device. The electronic and electrochemical properties of the samples were characterized using X-ray photoemission spectroscopy (XPS) and cyclic voltammetry (CV), whereas the morphology of the surface in contact with the electrolyte was investigated by scanning electron microscopy (SEM). The electric efficiency of the tandem cell was determined to be 5.2% in a photoelectrochemical (PEC) setup in acidic solution which is only about half of the photovoltaic efficiency of the tandem cell. A significant improvement in efficiency was achieved with platinum as a catalyst which was deposited by physical vapour deposition (PVD) under ultra-high vacuum (UHV) conditions.

Developments in nanostructured LiMPO4 (M = Fe, Co, Ni, Mn) composites based on three dimensional carbon architecture.

Nanostructured materials lie at the heart of fundamental advances in efficient energy storage and/or conversion, in which surface processes and transport kinetics play determining roles. This review describes recent developments in the synthesis and characterization of composites which consist of lithium metal phosphates (LiMPO(4), M = Fe, Co, Ni, Mn) coated on nanostructured carbon architectures (unordered and ordered carbon nanotubes, amorphous carbon, carbon foams). The major goal of this review is to highlight new progress in using different three dimensional nanostructured carbon architectures as support for the phosphate based cathode materials (e.g.: LiFePO(4), LiCoPO(4)) of high electronic conductivity to develop lithium batteries with high energy density, high rate capability and excellent cycling stability resulting from their huge surface area and short distance for mass and charge transport.

Deposition of tetracene on GaSe passivated Si(111).

The growth of tetracene on GaSe half-sheet passivated Si(111) is investigated under ultrahigh vacuum (UHV) using low-energy electron diffraction (LEED) and photoelectron spectroscopy (PS). A highly ordered thin-film growth was observed in the initial stages of the deposition process. All proposed structures form a coincidence lattice with the underlying substrate, due to the influence of the molecule-substrate interactions and are built up by either flat lying tetracene molecules at low coverage or tilted molecules at higher coverages. Photoelectron spectroscopy (XPS/UPS) shows that the deposited tetracene molecules induce band bending in the silicon substrate. No band bending was observed in the tetracene film, and an interface dipole potential of 0.45 eV was measured between the GaSe passivated Si(111) surface and the tetracene film.

Synchrotron-induced photoemission of GaAs electrodes after electrochemical treatment in aqueous electrolytes.

Electrochemically-induced oxidation and reduction reactions of UHV-cleaved GaAs(110) surfaces have been studied after emersion under potential control using high resolution synchrotron-induced photoelectron spectroscopy. High quality spectra of the As and Ga core 3d lines and the valence band region have been obtained. The spectra of the anodic oxide show strong emission of bulk-like Ga(2)O(3) and some As(2)O(3) with the admixture of suboxides and hydroxides. Ga(2)O(3) and As(2)O(3) are cathodically reduced leaving the GaAs surface covered mostly with elemental As, some As-H and remnants of Ga-suboxides and -hydroxides.