Quantum state-resolved gas/surface reaction dynamics probed by reflection absorption infrared spectroscopy

International audienceWe report the design and characterization of a new molecular-beam/surface-science apparatus for quantum state-resolved studies of gas/surface reaction dynamics combining optical state-specific reactant preparation in a molecular beam by rapid adiabatic passage with detection of surface-bound reaction products by reflection absorption infrared spectroscopy (RAIRS). RAIRS is a non-invasive infrared spectroscopic detection technique that enables online monitoring of the buildup of reaction products on the target surface during reactant deposition by a molecular beam. The product uptake rate obtained by calibrated RAIRS detection yields the coverage dependent state-resolved reaction probability S(θ). Furthermore, the infrared absorption spectra of the adsorbed products obtained by the RAIRS technique provide structural information, which help to identify nascent reaction products, investigate reaction pathways, and determine branching ratios for different pathways of a chemisorption reaction. Measurements of the dissociative chemisorption of methane on Pt(111) with this new apparatus are presented to illustrate the utility of RAIRS detection for highly detailed studies of chemical reactions at the gas/surface interface

Methods for nitrogen activation by reduction and oxidation

The industrial Haber-Bosch process to produce ammonia (NH3) from dinitrogen (N2) is crucial for modern society. However, N2 activation is inherently challenging and the Haber-Bosch process has significant drawbacks, as it is highly energy intensive, not sustainable due to substantial CO2 emissions primarily from the generation of H2 and requires large-centralized facilities. New strategies of sustainable N2 activation, such as low-temperature thermochemical catalysis and (photo)electrocatalysis, have been pursued, but progress has been hindered by the lack of rigor and reproducibility in the collection and analysis of results. In this Primer, we provide a holistic step-by-step protocol, applicable to all nitrogen-transformation reactions, focused on verifying genuine N2 activation by accounting for all contamination sources. We compare state-of-the-art results from different catalytic reactions following the protocol’s framework, and discuss necessary reporting metrics and ways to interpret both experimental and density functional theory results. This Primer covers various common pitfalls in the field, best practices to improve reproducibility and cost-efficient methods to carry out rigorous experimentation. The future of nitrogen catalysis will require an increase in rigorous experimentation and standardization to prevent false positives from appearing in the literature, which can enable advancing towards practical technologies for the activation of N2

Experimental and First-Principles Spectroscopy of Cu₂SrSnS₄ and Cu₂BaSnS₄ Photoabsorbers

Cu2BaSnS4 (CBTS) and Cu2SrSnS4 (CSTS) semiconductors have been recently proposed as potential wide band gap photovoltaic absorbers. Although several measurements indicate that they are less affected by band tailing than their parent compound Cu2ZnSnS4, their photovoltaic efficiencies are still low. To identify possible issues, we characterize CBTS and CSTS in parallel by a variety of spectroscopic methods complemented by first-principles calculations. Two main problems are identified in both materials. The first is the existence of deep defect transitions in low-temperature photoluminescence, pointing to a high density of bulk recombination centers. The second is their low electron affinity, which emphasizes the need for an alternative heterojunction partner and electron contact. We also find a tendency for downward band bending at the surface of both materials. In CBTS, this effect is sufficiently large to cause carrier-type inversion, which may enhance carrier separation and mitigate interface recombination. Optical absorption at room temperature is exciton-enhanced in both CBTS and CSTS. Deconvolution of excitonic effects yields band gaps that are about 100 meV higher than previous estimates based on Tauc plots. Although the two investigated materials are remarkably similar in an idealized, defect-free picture, the present work points to CBTS as a more promising absorber than CSTS for tandem photovoltaics

Understanding adhesion at as-deposited interfaces from ab initio thermodynamics of deposition growth: thin-film alumina on titanium carbide

We investigate the chemical composition and adhesion of chemical vapour deposited thin-film alumina on TiC using and extending a recently proposed nonequilibrium method of ab initio thermodynamics of deposition growth (AIT-DG) [Rohrer J and Hyldgaard P 2010 Phys. Rev. B 82 045415]. A previous study of this system [Rohrer J, Ruberto C and Hyldgaard P 2010 J. Phys.: Condens. Matter 22 015004] found that use of equilibrium thermodynamics leads to predictions of a non-binding TiC/alumina interface, despite the industrial use as a wear-resistant coating. This discrepancy between equilibrium theory and experiment is resolved by the AIT-DG method which predicts interfaces with strong adhesion. The AIT-DG method combines density functional theory calculations, rate-equation modelling of the pressure evolution of the deposition environment and thermochemical data. The AIT-DG method was previously used to predict prevalent terminations of growing or as-deposited surfaces of binary materials. Here we extent the method to predict surface and interface compositions of growing or as-deposited thin films on a substrate and find that inclusion of the nonequilibrium deposition environment has important implications for the nature of buried interfaces.Comment: 8 pages, 6 figures, submitted to J. Phys.: Condens. Matte