Resolving buried interfaces with Low Energy Ion Scattering

We investigate the use of Low Energy Ion Scattering (LEIS) to characterize buried interfaces of ultra-thin films. LEIS spectra contain depth-resolved information in the so-called sub-surface signal. However, the exact correlation between the sub-surface signal and the depth composition is still unknown. For this reason, LEIS spectra so far only provided qualitative information about buried interfaces. In this study, we investigate nm-thin films of Si-on-W and Si-on-Mo, where we compare simulated data to LEIS spectra. We present a method to extract depth-sensitive compositional changes -- resolving buried interfaces -- from LEIS spectra for the first few nanometers of a thin film sample. In the case of Si-on-Mo, the simulation of the LEIS sub-surface signal allows obtaining a quantitative measurement of the interface profile that matches the value determined using the LEIS layer growth profile method with an accuracy of 0.1 nm. These results pave the way to further extend the use of LEIS for the characterization of features buried inside the first few nanometers of a sample.Comment: 25 pages, 11 figure

Control of YH₃ formation and stability via hydrogen surface adsorption and desorption

Yttrium is known to form two hydrides: YH2, a metal, and YH3, which is dielectric. However, the stability of YH3 is not fully understood, especially in the context of thin films, where the yttrium layer must be coated to protect it from oxidation. In this work, we show that the stability of a YH3 thin film depends on the capping layer material. Our investigation reveals that YH3 appears to be stabilized by hydrogen that is adsorbed to the capping layer surface. This is evidenced by the YH3-YH2 transition temperature, which was found to be correlated with the desorption temperature of hydrogen from the surface. We posit that surface-adsorbed hydrogen prevents hydrogen from diffusing out of the thin film, which limits YH3 dissociation to the solubility of hydrogen in the YH2/YH3 thin film

Role of Excess Bi on the Properties and Performance of BiFeO₃ Thin-Film Photocathodes

BiFeO3 (BFO) has recently been identified as a promising photocathode material for photoelectrochemical (PEC) water splitting due to its light absorption and photoelectrochemical properties. The performance-limiting factors, in particular the impact of stoichiometry on the performance, still need to be understood. The effect of the ratio of Bi/Fe in the precursor solution for sol-gel synthesis on the properties and performance of BFO thin films is investigated in this study. Thin films with a stoichiometric Bi/Fe ratio and with a 10% excess of Bi are prepared on fluorine-doped tin-oxide substrates. While bulk characterization techniques show the formation of phase-pure BFO, surface characterization techniques indicate Bi enrichment on the surface. Light absorption and band gap do not change with excess Bi, whereas the current density is two times higher for Bi excess films compared to stoichiometric films at 0.6 V vs RHE. Electrochemical impedance spectroscopy attributes this improved performance of excess Bi thin films to a lower recombination rate and a lower charge transfer resistance. The lower recombination rate is attributed to fewer Bi and O vacancies, which can act as recombination centers. Therefore, adjusting the Bi/Fe ratio is an effective strategy to enhance the PEC performance of BFO photocathodes.</p

Changes to the Fossil Record of Insects through Fifteen Years of Discovery

The first and last occurrences of hexapod families in the fossil record are compiled from publications up to end-2009. The major features of these data are compared with those of previous datasets (1993 and 1994). About a third of families (>400) are new to the fossil record since 1994, over half of the earlier, existing families have experienced changes in their known stratigraphic range and only about ten percent have unchanged ranges. Despite these significant additions to knowledge, the broad pattern of described richness through time remains similar, with described richness increasing steadily through geological history and a shift in dominant taxa, from Palaeoptera and Polyneoptera to Paraneoptera and Holometabola, after the Palaeozoic. However, after detrending, described richness is not well correlated with the earlier datasets, indicating significant changes in shorter-term patterns. There is reduced Palaeozoic richness, peaking at a different time, and a less pronounced Permian decline. A pronounced Triassic peak and decline is shown, and the plateau from the mid Early Cretaceous to the end of the period remains, albeit at substantially higher richness compared to earlier datasets. Origination and extinction rates are broadly similar to before, with a broad decline in both through time but episodic peaks, including end-Permian turnover. Origination more consistently exceeds extinction compared to previous datasets and exceptions are mainly in the Palaeozoic. These changes suggest that some inferences about causal mechanisms in insect macroevolution are likely to differ as well

Sputtering and nitridation of transition metal surfaces under low energy, steady state nitrogen ion bombardment

Transition metal surfaces exposed to low-energy reactive ions undergo dynamic changes in composition and density due to implantation and compound formation. We report measurements of nitrogen ion induced sputter yields for transition metals relevant to fusion and optics applications. Thin films of molybdenum, ruthenium, palladium and tungsten are bombarded by nitrogen ions of kinetic energies in the range of 50–500 eV at steady state fluences (1 × 1018ions/cm2). Measured sputter yields are explained through energy and momentum transfer under the binary collision approximation using the Monte Carlo code TRIDYN. X-ray Photoelectron spectroscopy (XPS) studies showed the nitrogen content in the films at the end of ion exposure is independent of incoming ion energy. This occurs due to competing implantation and preferential surface nitrogen sputtering processes within the XPS probing depth. All metals investigated showed evidence of a nitride formed due to energetic nitrogen impact. The combination of XPS and TRIDYN simulations were applied to extract effective reaction cross-sections for each metal

Nb Texture Evolution and Interdiffusion in Nb/Si-Layered Systems

In this paper, we present a detailed study on the microstructure evolution and interdiffusion in Nb/Si-layered systems. Interlayer formation during the early stages of growth in sputter-deposited Nb-on-Si and Si-on-Nb bilayer systems is studied in vacuo using a high-sensitivity low-energy ion-scattering technique. An asymmetric intermixing behavior is observed, where the Si-on-Nb interface is ∼2× thinner than the Nb-on-Si interface, and it is explained by the surface-energy difference between Nb and Si. During Nb-on-Si growth, the crystallization of the Nb layer occurs around 2.1 nm as-deposited Nb thickness with a strong Nb(110)-preferred orientation, which is maintained up to 3.3 nm as-deposited Nb thickness. A further increase in the Nb layer thickness above 3.3 nm results in a polycrystalline microstructure with a reduced degree of texture. High-resolution cross-sectional transmission electron microscopy imaging is performed on Nb/Si multilayers to study the effect of the Nb layer texture on interdiffusion during low-temperature annealing. Nb/Si multilayers with amorphous 2 nm Nb layers and strongly textured 3 nm thick Nb layers, with limited grain-boundary pathways for diffusion, show no observable interdiffusion during annealing at 200 °C for 8 h, whereas in a Nb/Si multilayer with polycrystalline 4 nm thick Nb layers, a ∼1 nm amorphous Nb/Si interlayer is formed at the Si-on-Nb interface during annealing