Surface evolution during crystalline silicon film growth by low-temperature hot-wire chemical vapor deposition on silicon substrates

We investigate the low-temperature growth of crystalline thin silicon films: epitaxial, twinned, and polycrystalline, by hot-wire chemical vapor deposition (HWCVD). Using Raman spectroscopy, spectroscopic ellipsometry, and atomic force microscopy, we find the relationship between surface roughness evolution and (i) the substrate temperature (230–350 °C) and (ii) the hydrogen dilution ratio (H2/SiH4=0–480). The absolute silicon film thickness for fully crystalline films is found to be the most important parameter in determining surface roughness, hydrogen being the second most important. Higher hydrogen dilution increases the surface roughness as expected. However, surface roughness increases with increasing substrate-temperature, in contrast to previous studies of crystalline Si growth. We suggest that the temperature-dependent roughness evolution is due to the role of hydrogen during the HWCVD process, which in this high hydrogen dilution regime allows for epitaxial growth on the rms roughest films through a kinetic growth regime of shadow-dominated etch and desorption and redeposition of growth species

Combining phosphate species and stainless steel cathode to enhance hydrogen evolution in microbial electrolysis cell (MEC)

Microbial electrolysis cells (MEC) must work around neutral pH because of microbial catalysis at the anode. To develop a hydrogen evolution cathode that can work at neutral pH remains a major challenge in MEC technology. Voltammetry performed at pH 8.0 on rotating disk electrodes showed that the presence of phosphate species straightforwardly multiplied the current density of hydrogen evolution, through the so-called cathodic deprotonation reaction. The mechanism was stable on stainless steel cathodes whereas it rapidly vanished on platinum. The phosphate/stainless steel system implemented in a 25 L MEC with a marine microbial anode led to hydrogen evolution rates of up to 4.9 L/h/m2 under 0.8 V voltage, which were of the same order than the best performance values reported so far. Keywords: Hydrogen; Microbial electrolysis cell (MEC); Stainless steel; Phosphat

Reduced complexity models for water management and anode purge scheduling in DEA operation of PEMFCs

In this work, the dynamic behavior of Fuel Cell operation under Dead-Ended Anode conditions is shown. A DEA can be fed with dry hydrogen, since water crossing through the membrane is sufficient to humidify the fuel. The reduced requirements for inlet humidification yield a system with lower cost and weight compared to FCs with flow-through or recirculated anodes. The accumulation of water and nitrogen in the anode channel is first observed near the outlet. A stratified pattern develops in the channel where a hydrogen-rich area sits above a depleted region and is stabilized by the effect of gravity. A model is presented which describes the dynamic evolution of a blanketing N2 front in the anode channel and a hydrogen starved region. Understanding, modeling, and predicting the front evolution can reduce the H2 wasted during purges, avoid over drying the membrane, and mitigate degradation associated with hydrogen starved areas

Trapping of hydrogen atoms in X-irradiated salts at room temperature and the decay kinetics

The salts (hypophosphites, formates, a phosphite, a phosphate, and an oxalate) were X-irradiated, whereby hydrogen formed chemically by a radiolytic process becomes trapped in the solid. By room temperature vacuum extraction, the kinetics for the evolution of this trapped hydrogen was studied mass spectrometrically. All salts except two exhibited second-order kinetics. The two exceptions (NaH2PO2(H2O) and K2HPO4) showed first-order kinetics. Based on experimental results, the escape of hydrogen involves three steps: the diffusion of hydrogen atoms from the bulk to the surface, association of these atoms on the surface (rate controlling step for second-order hydrogen evolution), and the desorption of molecular hydrogen from the surface. The hydrogen does not escape if the irradiated salt is stored in air, apparently because adsorbed air molecules occupy surface sites required in the escape mechanism

The direct hydrothermal deposition of cobalt-doped MoS2 onto fluorine-doped SnO2 substrates for catalysis of the electrochemical hydrogen evolution reaction

Metal chalcogenides, and doped molybdenum sulfides in particular, have considerable potential as earth-abundant electrocatalysts for the hydrogen evolution reaction. This is especially true in the case of solar-to-hydrogen devices, where an ability to deposit these materials on transparent substrates is therefore desirable. Hydrothermal methods are perhaps the most common route by which metal chalcogenide materials suitable for the hydrogen evolution reaction are produced. Such methods are simple and scalable, but the direct hydrothermal deposition of metal chalcogenides on transparent oxide electrodes has hitherto never been reported. Such an advance would greatly facilitate the expansion of the field by removing the requirement for separate hydrothermal-synthesis and catalyst-deposition steps. In this paper, we show that the ternary chalcogenide Co2Mo9S26 can be synthesised on a fluorine-doped tin oxide substrate by hydrothermal methods directly from solutions of the simple metal salts. These films display good activity for the hydrogen evolution reaction from acid solution, achieving current densities of 10 mA cm−2 at 260 mV overpotential with a Tafel slope of 64 mV per decade. Moreover, the resulting films can be made to be translucent, a very useful property which would allow light to be transmitted through the catalyst to an underlying light-harvesting array in any solar-to-hydrogen device employing this material at the cathode

Helium Atmospheres on Warm Neptune- and Sub-Neptune-Sized Exoplanets and Applications to GJ 436 b

Warm Neptune- and sub-Neptune-sized exoplanets in orbits smaller than Mercury's are thought to have experienced extensive atmospheric evolution. Here we propose that a potential outcome of this atmospheric evolution is the formation of helium-dominated atmospheres. The hydrodynamic escape rates of Neptune- and sub-Neptune-sized exoplanets are comparable to the diffusion-limited escape rate of hydrogen, and therefore the escape is heavily affected by diffusive separation between hydrogen and helium. A helium atmosphere can thus be formed -- from a primordial hydrogen-helium atmosphere -- via atmospheric hydrodynamic escape from the planet. The helium atmosphere has very different abundances of major carbon and oxygen species from those of a hydrogen atmosphere, leading to distinctive transmission and thermal emission spectral features. In particular, the hypothesis of a helium-dominated atmosphere can explain the thermal emission spectrum of GJ 436 b, a warm Neptune-sized exoplanet, while also consistent with the transmission spectrum. This model atmosphere contains trace amounts of hydrogen, carbon, and oxygen, with the predominance of CO over CH4 as the main form of carbon. With our atmospheric evolution model, we find that if the mass of the initial atmosphere envelope is 1E-3 planetary mass, hydrodynamic escape can reduce the hydrogen abundance in the atmosphere by several orders of magnitude in ~10 billion years. Observations of exoplanet transits may thus detect signatures of helium atmospheres and probe the evolutionary history of small exoplanets.Comment: ApJ, accepte

The ionisation parameter of star-forming galaxies evolves with the specific star formation rate

We investigate the evolution of the ionisation parameter of star-forming galaxies using a high-redshift ($z\sim 1.5$) sample from the FMOS-COSMOS survey and matched low-redshift samples from the Sloan Digital Sky Survey. By constructing samples of low-redshift galaxies for which the stellar mass ($\mathrm{M}_{*}$), star formation rate (SFR) and specific star formation rate (sSFR) are matched to the high-redshift sample we remove the effects of an evolution in these properties. We also account for the effect of metallicity by jointly constraining the metallicity and ionisation parameter of each sample. We find an evolution in the ionisation parameter for main-sequence, star-forming galaxies and show that this evolution is driven by the evolution of sSFR. By analysing the matched samples as well as a larger sample of $z<0.3$, star-forming galaxies we show that high ionisation parameters are directly linked to high sSFRs and are not simply the byproduct of an evolution in metallicity. Our results are physically consistent with the definition of the ionisation parameter, a measure of the hydrogen ionising photon flux relative to the number density of hydrogen atoms

Hydrogen production by electrolysis of a phosphate solution on a stainless steel cathode

The catalytic properties of phosphate species, already shown on the reduction reaction in anaerobic corrosion of steels, are exploited here for hydrogen production. Phosphate species work as a homogeneous catalyst that enhances the cathodic current at mild pH values. A voltammetric study of the hydrogen evolution reaction is performed using phosphate solutions at different concentrations on 316L stainless steel and platinum rotating disk electrodes. Then, hydrogen is produced in an electrolytic cell using a phosphate solution as the catholyte. Results show that 316L stainless steel electrodes have a stable behaviour as cathodes in the electrolysis of phosphate solutions. Phosphate (1 M,pH 4.0/5.0) as the catholyte can equal the performance of a KOH 25%w solution with the advantage of working at mild pH values. The use of phosphate and other weak acids as catalysts of the hydrogen evolution reaction could be a promising technology in the development of electrolysis units that work at mild pH values with low-cost electrodes and construction materials