Catalytic water splitting to hydrogen and oxygen is considered as one of the convenient routes for the sustainable energy conversion. Bifunctional catalysts for the electrocatalytic oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) are pivotal for the energy conversion and storage, and alternatively, the photochemical water oxidation in biomimetic fashion is also considered as the most useful way to convert solar energy into chemical energy. Here we present a facile solvothermal route to control the synthesis of amorphous and crystalline cobalt iron oxides by controlling the crystallinity of the materials with changing solvent and reaction time and further utilize these materials as multifunctional catalysts for the unification of photochemical and electrochemical water oxidation as well as for the oxygen reduction reaction. Notably, the amorphous cobalt iron oxide produces superior catalytic activity over the crystalline one under photochemical and electrochemical water oxidation and oxygen reduction conditions.

Room temperature partial oxidation (corrosion) of cubic CoO led to the formation of mixed valence CoOx with better electrochemical water oxidation activities in alkaline pH. Activation of both octahedral Co3+ and Co2+ to layered oxohydroxide–hydroxide during alkaline electrochemical water oxidation has been demonstrated.

The surface chemistry and the interface formation during the initial stages of the atomic layer deposition (ALD) of Al2O3 from trimethylaluminum (TMA) and H2O on InP(100) were studied by synchrotron radiation photoemission spectroscopy and scanning tunneling microscopy. The effect of the ex situ surface cleaning by either H2SO4 or (NH4)2S was examined. It is shown that the native oxide on the InP surface consisted mainly of indium hydrogen phosphates with a P enrichment at the interface with InP. After a (NH4)2S treatment, S was present on the surface as a sulfide in both surface and subsurface sites. Exposure to TMA led to the formation of a thin AlPO4 layer, irrespective of the surface cleaning. The surface Fermi level of p-type InP was found to be pinned close to midgap after H2SO4 cleaning and moved only slightly further toward the conduction band edge upon TMA exposure, indicating that the AlPO4/InP interface was rather defective. (NH4)2S passivation led to a Fermi level position of p-type InP close to the conduction band edge. Hence, the InP surface was weakly inverted, which can be attributed to surface doping by S donors. TMA exposure was found to remove surface S, which was accompanied by a shift of the Fermi level to midgap, consistent with the removal of (part of) the S donors in combination with a defective AlPO4/InP interface. Further TMA/H2O ALD did not lead to any detectable changes of the AlPO4/InP interface and suggested simple overgrowth with Al2O3.

SummaryWe report on results on the preparation of thin (<100 nm) aluminum oxide (Al2O3) films on silicon substrates using thermal atomic layer deposition (T-ALD) and plasma enhanced atomic layer deposition (PE-ALD) in the SENTECH SI ALD LL system. The T-ALD Al2O3 layers were deposited at 200 °C, for the PE-ALD films we varied the substrate temperature range between room temperature (rt) and 200 °C. We show data from spectroscopic ellipsometry (thickness, refractive index, growth rate) over 4” wafers and correlate them to X-ray photoelectron spectroscopy (XPS) results. The 200 °C T-ALD and PE-ALD processes yield films with similar refractive indices and with oxygen to aluminum elemental ratios very close to the stoichiometric value of 1.5. However, in both also fragments of the precursor are integrated into the film. The PE-ALD films show an increased growth rate and lower carbon contaminations. Reducing the deposition temperature down to rt leads to a higher content of carbon and CH-species. We also find a decrease of the refractive index and of the oxygen to aluminum elemental ratio as well as an increase of the growth rate whereas the homogeneity of the film growth is not influenced significantly. Initial state energy shifts in all PE-ALD samples are observed which we attribute to a net negative charge within the films.

The electronic and structural properties of thin epitaxial Mn films on Si(111)-(7 × 7) and their silicide reaction are studied by means of low-energy electron diffraction, scanning tunnelling microscopy (STM) and photoemission spectroscopy (PES). The deposition of Mn at room temperature initially results in the growth of islands. The metal–silicon reaction already occurs at this temperature, which is further enhanced by annealing up to 400°C, leading to the formation of manganese silicide and turning islands into nearly closed films at higher coverage. A pseudo-(1 × 1) phase develops for Mn films of up to 1 monolayer (ML) thickness. For films of higher thicknesses of up to 5 ML, a ( )R30° phase is observed. STM images show that then the silicide film is almost closed and exhibits a strain relief network reflecting an incommensurate interface structure. PES reveals that the (1 × 1) phase is semiconducting while the ( )R30° phase is metallic. For both phases, Si 2p core level photoemission data indicate that the surface is probably terminated by Si atoms.

The removal of the native oxides from NH4OH-cleaned p-GaAs (100) by exposure to trimethyl-aluminum (TMA) was studied by in situ photoelectron spectroscopy using synchrotron radiation. The reduction of high-valence As- and Ga-oxides occurred through different routes: while As3+ was reduced to As(1±Δ)+ suboxides (with 0 ≤ Δ ≤ 1), Ga3+ was directly removed. The surface Fermi level was shifted by about 100 meV towards the valence band edge upon TMA exposure. This indicates that removing the native oxide of GaAs by TMA is insufficient to create interfaces between GaAs and Al2O3 with defects densities below the 1012 cm−2 range.

Electron confinement in thin films of Pb on Cu(111) leads to the formation of quantum well states, formed out of the upper valence band of Pb. Their evolution as a function of film thickness is characterized in angle-resolved photoemission and can be interpreted in terms of a straightforward quantum well model. This permits an identification of film growth mode at low temperatures. Bringing the films into thermal equilibrium by annealing induces strong changes in the spectra. Their interpretation demonstrates that specific "magic" layers are preferred because of total energy minimization induced by the arrangement of quantum well states with respect to the Fermi level.

A detailed study of the atomic layer deposition of Al 2 O 3 on Ru film surfaces by means of in situ photoelectron spectroscopy has been carried out. We discuss how the atomic layer deposition reaction between trimethylaluminum (TMA) and H 2 O is affected by the Ru substrate. We found that RuO 2 , when present on the substrate surface, participates in the reaction with TMA and the substrate reduces to Ru. The reduction of oxygencontaining substrates to Ru is solely due to the direct reaction of the Al precursor with the substrate through adsorption on active sites. The final Al 2 O 3 /Ru structures have an interface depleted from oxygen and show different band offsets depending on the initial chemistry.