Chemisorbed hydrogen on tungsten materials: atomic scale analysis using low energy ion beams
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Engineering topics
Publications and source records attributed to Whaley, Josh A..
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In situ analysis of surfaces during high-flux plasma exposure represents a long-standing challenge in the study of plasma–material interactions. While post-mortem microscopy can provide a detailed picture of structural and compositional changes, in situ techniques can capture the dynamic evolution of the surface. In this study, we demonstrate how spectroscopic ellipsometry can be applied to the real-time characterization of W nanostructure (also known as “fuzz”) growth during exposure to low temperature, high-flux He plasmas. Strikingly, over a wide range of sample temperatures and helium fluences, the measured ellipsometric parameters (Ψ,Δ) collapse onto a single curve that can be directly correlated with surface morphologies characterized by ex situ helium ion microscopy. The initial variation in the (Ψ,Δ) parameters appears to be governed by small changes in surface roughness (<50 nm) produced by helium bubble nucleation and growth, followed by the emergence of 50 nm diameter W tendrils. This basic behavior appears to be reproducible over a wide parameter space, indicating that the spectroscopic ellipsometry may be of general practical use as a diagnostic to study surface morphologies produced by high-flux He implantation in refractory metals. An advantage of the methods outlined here is that they are applicable at low incident ion energies, even below the sputtering threshold. As an example of this application, we apply in situ ellipsometry to examine how W fuzz growth is affected both by varying ion energy and the temperature of the surface.
Understanding hydrogen incorporation into palladium requires detailed knowledge of surface and subsurface structure and atomic interactions as surface hydrogen is being embedded. Using density functional theory (DFT), we examine the energies of hydrogen layers of varying coverage adsorbed on Pd(111). Here we find that H–H and H–Pd interactions promote the formation of the well-known ($\sqrt{3}$ x $\sqrt{3}$) phases but also favor an unreported (3 × 3) phase at high H coverages for which we present experimental evidence. We relate the stability of isolated H vacancies of the (3 × 3) phase to the need of H 2 molecules to access bare Pd before they can dissociate. Following higher hydrogen dosage, we observe initial steps of hydride formation, starting with small clusters of subsurface hydrogen. The interaction between H and Pd is complicated by the persistent presence of carbon at the surface. X-ray photoelectron spectroscopy experiments show that trace amounts of carbon, emerging from the Pd bulk despite many surface cleaning cycles, become mobile enough to repopulate the C-depleted surface at temperatures above 200 K. When exposed to hydrogen, these surface carbon atoms react to form benzene, as evidenced by scanning tunneling microscopy observations interpreted with DFT.
The passivation of polycrystalline nickel surfaces against hydrogen uptake by oxygen is investigated experimentally with low energy ion scattering (LEIS), direct recoil spectroscopy (DRS), and thermal desorption spectroscopy (TDS). These techniques are highly sensitive to surface hydrogen, allowing the change in hydrogen adsorption in response to varying amounts of oxygen exposure to be measured. The chemical composition of a nickel surface during a mixed oxygen and hydrogen exposure was characterized with LEIS and DRS, while the uptake and activation energies of hydrogen on a nickel surface with preadsorbed oxygen were quantified with TDS. By and large, these measurements of how the oxygen and hydrogen surface coverage varied in response to oxygen exposure were found to be consistent with predictions of a simple site-blocking model. This finding suggests that, despite the complexities that arise due to polycrystallinity, the oxygen-induced passivation of a polycrystalline nickel surface against hydrogen uptake can be approximated by a simple site-blocking model.
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The effect of nitrogen on the surfaces of polycrystalline ITER-grade tungsten and a tungsten single crystal were studied with low energy ion scattering (LEIS) and direct recoil spectroscopy (DRS). LEIS and DRS measurements on both tungsten surfaces were performed in an ultra-high vacuum system as various quantities of N 2 were introduced into the chamber through a variable leak valve. The obtained ion energy spectra reveal that nitrogen was readily adsorbed onto the surface, in turn limiting the amount of hydrogen that could be adsorbed onto the surface. These results not only provide insight into how the presence of nitrogen on tungsten surfaces may play a role in hydrogen adsorption and retention, but also serve to benchmark models being developed to describe the H-N-W system.