A theoretical study of hydrogen adsorption and diffusion on a W(1 1 0) surface

We have used density functional theory to investigate hydrogen adsorption and diffusion on a W(1 1 0) surface. Hydrogen adsorption structures were examined from low coverage to one monolayer, and a threefold hollow site was found to be the most stable site at all coverages. In contrast to previous assertions, the work function decrease is not due to electron transfer from the hydrogen atoms to the W surface, but due to electron depletion at the vacuum region above the hydrogen atoms. Hydrogen atoms can diffuse via short-bridge sites and long-bridge sites at a coverage of θ = 1.0. Although the calculated activation energy for hydrogen diffusion via a short-bridge site is as small as 0.05 eV, field emission microscope experiments have shown that the activation energy for hydrogen diffusion is about 0.20 eV, which agrees fairly well with our calculated value of the activation energy via a long-bridge site. This discrepancy can be related to hydrogen delocalization on the W(1 1 0) surface, which has been suggested by electron energy loss spectroscopy experiments.     

Surface modification of Al-12.6Si alloy by high current pulsed electron beam

The paper investigates the microstructure and property modifications of Al-12.6Si alloy induced by high current pulsed electron beam (HCPEB) treatment. The scanning electron microscope (SEM) results show a fine and equiaxed grain structure of several micrometers is obtained on the top surface of the melted layer. Underneath the top surface, a remelted layer with about 10 μm thickness is obtained and a supersaturated solid solution of Al is formed in the remelted layer. XRD analysis shows that the relative strength of diffraction peaks of Al (1 1 1) and Si (1 1 1) crystal planes is increased after HCPEB treatment. As a result, relative wear resistance of HCPEB-treated sample is significantly improved by a factor of 2.5 due to fine grain strengthening and solid solution strengthening. Therefore, the HCPEB treatment has a good application future in treating Al-Si alloys.     

The influence of hydrogen on the electronic and magnetic structures of TM(0 0 1) (TM=Fe, Co, Ni, and Cu) surfaces and interfaces: Ab-initio calculations

We present ab-initio investigation of the electronic and magnetic structure of TM(0 0 1) surfaces and TM/Cu(0 0 1) systems (TM=Fe, Co, Ni, Cu) with and without hydrogen adsorbed layer. The adsorption energy of hydrogen atom is found to be energetically more stable above the surface layer of Ni(0 0 1) surface than other TM(0 0 1) surfaces. The adsorption energies of hydrogen on TM/Cu(0 0 1) systems are larger than those on TM(0 0 1) surfaces. The relaxed geometries show that hydrogen has a strong influence on the interlayer distance. Furthermore, a marked reduction of Fe, Co, and Ni surface magnetic moments to 2.54, 1.41 and 0.25 μ_B, respectively, is obtained due to the presence of hydrogen.     

Hydrogen desorption kinetics and band bending for 6H-SiC(0 0 0 1) surfaces

The desorption kinetics of hydrogen from polished 6H-SiC(0 0 0 1) surfaces exposed to various sources of hydrogen have been determined using temperature programmed desorption (TPD). For (3 × 3) 6H-SiC(0 0 0 1) surfaces prepared via annealing and cooling in SiH₄, desorption of 0.2 ± 0.05 monolayer of molecular hydrogen was observed to occur at ≈590 °C. This β₁ H₂ desorption peak exhibited second order kinetics with an activation energy of 2.4 ± 0.2 eV. For (3 × 3) 6H-SiC surfaces exposed to atomic hydrogen generated via either a hot rhenium filament or remote hydrogen plasma, low energy electron diffraction patterns showed an eventual conversion back to (1 × 1) symmetry. Spectra acquired using Auger electron and X-ray photoelectron spectroscopies revealed that the atomic hydrogen exposure removed the excess Si. Photoelectron spectroscopy results also showed a 0.5 eV increase in binding energy for the Si2p and C1s core levels after removal of the Si-Si bilayer that is indicative of a decrease in band bending at the SiC surface. TPD from the (3 × 3) 6H-SiC(0 0 0 1) surfaces exposed to atomic hydrogen showed substantially more molecular hydrogen desorption (1-2 ML) through the appearance of a new desorption peak (β_2,3) that started at ≈200 °C. The β_2,3 peak exhibited second order desorption kinetics and a much lower activation energy of 0.6 ± 0.2 eV. A third smaller hydrogen desorption state was also detected in the 650-850 °C range. This last feature could be resolved into two separate desorption peaks (α₁ and α₂) both of which exhibited second order kinetics with activation energies of 4.15 ± 0.15 and 4.3 ± 0.15 eV, respectively. Based on comparisons to hydrogen desorption from Si and diamond surfaces, the β and α desorption peaks were assigned to hydrogen desorption from Si and C sites, respectively.     

Detection of hydrogen with SnO2-coated ZnO nanorods

SnO₂-coated ZnO nanorods on c-plane sapphire substrates were synthesized by pulsed laser deposition. The thickness of the polycrystalline SnO₂ was ∼10 nm, as determined by high-resolution transmission electron microscopy, while the diameter of the ZnO nanorods was ∼30 nm. The sensitivity of the SnO₂/ZnO structures to hydrogen was tested by depositing Ti/Au Ohmic contacts on a random array of the nanorods and measuring the current at fixed voltage. There was no response to 500 ppm H₂ in N₂ at room temperature, but we obtained a sensitivity of ∼70% at 400 °C. The SnO₂/ZnO structures exhibit drift in their recovery characteristics and for sequential detection of hydrogen, as generally reported for SnO₂ thin film sensors.     

Quantum states of hydrogen (H, D, T) atoms on Cu(1 0 0) and (1 1 0) surfaces

We investigate the quantum mechanical behavior of adsorbed hydrogen (H, D, T) on Cu(1 0 0) and (1 1 0) surfaces. We construct potential energy surfaces (PESs) for the motion of the hydrogen H atom on Cu(1 0 0) and (1 1 0) surfaces within the framework of density functional theory. The potential energy takes a minimum value on the hollow site of Cu(1 0 0) and on the short bridge site of Cu(1 1 0). Moreover, we calculate the quantum states of hydrogen atom motion on these calculated PESs. The ground state wave function of the hydrogen atom motion is strongly localized around the hollow site on the Cu(1 0 0) surface. On the other hand, the ground state wave function of the hydrogen atom motion on Cu(1 1 0) is distributed from the short bridge site to two neighboring pseudo-threefold sites. We finally show isotope effects on the quantum states of the motion of hydrogen on both surfaces.     

First-principle study of the hydrogen bonds in a thin film of phthalocyanine molecules

The nature and the strength of intermolecular contacts involved in molecular self-assemblies on a substrate strongly depend on the surrounding functional atoms. Recently, it has been shown that deposition of chlorine-zinc-phthalocyanine (ZnPcCl₈) molecules on Ag(1 1 1) leads to a compact arrangement governed by the activation of a Cl ? H-C bond network. A detailed theoretical study of these contacts based on first-principle density functional calculations and topological analysis of the electron density is reported in this paper. This study reveals that the mechanism of the Cl ? H-C contacts is similar to that of weak hydrogen bonds.     

A green synthetic approach to graphene nanosheets for hydrogen adsorption

A green and facile strategy of preparing graphene by reducing exfoliated graphite oxide (GO) with glucose was developed in this study. The as-prepared samples were characterized by X-ray diffraction (XRD), Raman spectroscopy, Fourier transform infrared spectroscopy (FT-IR), Scanning electron microscopy (SEM), Transmission electron microscopy (TEM) and Atomic force microscopy (AFM). The characterization results indicated that the graphene sheets (GS) were of high quality with smooth surface, rich pore structure and few layer graphene. The samples have a BET specific surface area of 1205.8 m² g⁻¹ measured by N₂ adsorption at 77 K. The hydrogen storage capacity of 2.7 wt.% at 298 K and 25 bar demonstrated that the as-prepared graphene employing glucose as reductant is supposed to be a promising material with outstanding property for hydrogen storage.     

Angle-resolved study of hydrogen abstraction on Si(1 0 0) and Si(1 1 1): Evidence for non-activated pathways

The abstraction of chemisorbed hydrogen on Si(1 0 0) and Si(1 1 1) induced by atomic hydrogen has been investigated by studying with a rotatable mass spectrometer the angle-resolved molecular hydrogen desorption from a Si surface exposed to a chopped beam of atomic hydrogen. The angular distributions of desorbing molecules can be fitted independent of the surface temperature and the surface reconstruction by a cosⁿθ function with n < 1 for Si(1 0 0) and Si(1 1 1). These results are interpreted by non-activated pathways involving site-specific hot-atom abstraction on two adjacent silicon atoms with one having a dangling bond. Possible mechanisms according to the surface reconstructions are discussed.     

Effects of predosed oxygen and hydrogen on CO adsorption on Ni(1 0 0)

We present the results of high-resolution electron energy loss experiments on (CO/O)/Ni(1 0 0) and (CO/H)/Ni(1 0 0) systems. Oxygen and hydrogen interact differently with Ni(1 0 0) surface, nevertheless, both species do not affect to a great extent the vibrational properties of CO. A phase of CO molecules weakly bonded to the surface and unaffected by coadsorbed oxygen and hydrogen, is found. Coverage of 0.5 ML of predosed oxygen chemically passivates the Ni(1 0 0) surface and inhibits any CO adsorption at room temperature. CO sites are unambiguously determined for each predosed Ni(1 0 0) surface.     

Direct observation of surface potential change due to hydrogen termination of CVD diamond surface by metastable-induced electron spectroscopy

Metastable-induced electron spectroscopy (MIES) together with ultraviolet photoemission spectroscopy (UPS) was applied to the analysis of the surface electronic structure of chemical-vapor-deposited diamond films. The films were grown in a microwave plasma, and their surfaces were terminated by hydrogen. The MIES spectrum measured at an as-deposited surface contains peaks due to adsorbates. When this surface was annealed at 400 °C, those peaks were depressed, and the spectrum showed a similar structure to that of UPS. Once the surface was re-hydrogenated, the MIES spectrum rose up at lower energies than the UPS spectrum did for surfaces annealed at lower temperatures. Finally after annealing at 1000 °C, the cutoff energies of MIES and UPS converged at nearly the same values. The result demonstrates that the MIES detects a surface potential which changes locally at the hydrogen-terminated surfaces.     

Construction and timing system of the EPOS beam system

The Forschungszentrum Dresden-Rossendorf provides an intense pulsed 40 MeV electron beam with high brilliance and low emittance (ELBE). The pulse has a length of 1-10 ps and a repetition time of 77 ns, or in slow mode 616 ns. The EPOS system (ELBE Positron Source) generates by pair production on a tungsten converter and a tungsten moderator an intense pulsed beam of mono-energetic positrons. To transport the positrons to the laboratory (12 m) we constructed a magnetic beam guidance system with a longitudinal magnetic field of 75 G. In the laboratory outside the cave, the positron beam is chopped and bunched according to the time structure, because the very sharp bunch structure of the electron pulses is broadened for the positron beam due to transport and moderation.     

Study of reduction processes over cerium oxide surfaces with atomic hydrogen using ultra accelerated quantum chemical molecular dynamics

Ceria plays an important role in catalysis, due to its ability to store and release oxygen depending on the condition present in the catalyst environment. To analyze the role of ceria in catalytic reactions, it is necessary to know the details of the interaction of ceria surface with environmentally sensitive molecules. This study was conducted using ultra accelerated quantum chemical molecular dynamics. Its purpose was to investigate the reduction process of the (1 1 1) and (1 1 0) surfaces of ceria with atomic hydrogen as well as water desorption mechanisms from the surfaces. This simulation demonstrated that when a high-energy colliding hydrogen atoms are adsorbed on the ceria, it pulls up an O atom from the ceria surfaces and results in the formation of a H₂O molecule. This is the first dynamics simulation related to such reduction processes based on quantum chemistry.     

Cleaning of SiC surfaces by low temperature ECR microwave hydrogen plasma

N-type 4H-SiC (0 0 0 1) surfaces were cleaned by low temperature hydrogen plasma in electronic cyclotron resonance (ECR) microware plasma system. The effects of the hydrogen plasma treatment (HPT) on the structure, chemical and electronic properties of surfaces were characterized by in situ reflection high energy electron diffraction (RHEED) and X-ray photoelectron spectroscopy (XPS). The RHEED results indicate that the structures of the films are strongly dependent on the treatment temperature and time. Significant improvements in quality of 4H-SiC films can be obtained with the temperature ranging from 200 °C to 700 °C for an appropriate treatment period. The XPS results show that the surface oxygen is greatly reduced and the carbon contamination is completely removed from the 4H-SiC surfaces. The hydrogenated SiC surfaces exhibit an unprecedented stability against oxidation in the air. The surface Fermi level moves toward the conduction band in 4H-SiC after the treatment indicating an unpinning Fermi level with the density of surfaces states as low as 8.09 × 10¹⁰ cm⁻² eV⁻¹.     

Transient desorption of HD and D2 molecules from the D/Si(1 0 0) surfaces exposed to a modulated H-beam

We have studied the direct and indirect abstraction of D adatoms by H on the Si(1 0 0) surfaces by employing a pulsed H-beam. Desorptions of HD molecules is found to occur promptly as a result of direct abstraction at the beam on-cycles. In contrast, we find that D₂ desorption induced by adsorption of H atoms, i.e., the so-called adsorption-induced desorption (AID), occurs even at the beam off-cycles. The D₂ rate curves measured with the pulsed-H beam are decomposed into four components characterized with the reaction lifetimes of ?0.005, 0.06 ± 0.01, 0.8 ± 0.1, and 30 ± 5 s. We propose that the fastest and the second fastest AID channels are related to the thermodynamical instability of (1 × 1) dihydride domains locally formed on the (3 × 1) monodeuteride/dideuteride domains. The 0.8 s AID channel is attributed to the desorption occurring at the stage when (3 × 1) monodeuteride/dideuteride domains are built up upon H adsorption onto the (2 × 1) monohydride surface. The 30 s AID path is attributed to the thermal desorption accompanied by the shrinkage of the (3 × 1) domains which were excessively formed during the beam on-cycles on the (2 × 1) monohydride surface. Atomistic mechanisms are proposed for these three AID pathways.     

Interaction of hydrogen with InN thin films elaborated on InP(1 0 0)

III-V semiconductor compound structures are widely applied in technology of advanced microelectronics, optoelectronics, and gas sensors. In this paper, we report on the use of XPS to characterize in situ the interaction of thermally activated hydrogen atoms and hydrogen molecules with InP(1 0 0) surfaces covered by thin InN overlayers. XPS spectra were taken with an ESCALAB-210 spectrometer after repeated hydrogenation cycles at temperatures up to 350 °C. The evolution of the In 3d, In 4d, P 2p, N 1s, O 1s and C 1s photoelectron spectra was carefully monitored. The XPS spectra of the hydrogen exposed surface revealed significant differences compared to those from the non-hydrogenated surface. InN films were found to be weakly reactive to hydrogen under experimental conditions explored. The behavior of P atoms at the hydrogenated surface was dependent on the parameters characterizing each hydrogenation (exposure, hydrogen species used, annealing temperature). Moreover, the heavily hydrogenated surface exhibited a phosphorus enrichment.     

The dynamics of hydrogen adsorption on polycrystalline uranium

The dynamics of dissociative hydrogen adsorption on clean polycrystalline uranium has been studied using temperature programmed desorption and supersonic molecular beams. The initial sticking probability was measured as a function of incident kinetic energy between 3 and 255 meV. Two adsorption channels were observed; a non-activated direct channel was shown to be active over the entire energy range studied and a low energy indirect channel that was characterised by a decrease in sticking probability with increasing beam energy, and an insensitivity to both surface temperature and a range of hydrogen coverages. Together these results suggest the existence of an unaccommodated molecular precursor that has sufficient lifetime and mobility to locate favourable sites and dissociatively adsorb.     

Electrical characterization of deep levels in n-type GaAs after hydrogen plasma treatment

Deep level transient spectroscopy (DLTS) and Laplace-DLTS (L-DLTS) have been used to investigate defects in an n-type GaAs before and after exposure to a dc hydrogen plasma (hydrogenation). DLTS revealed the presence of three prominent electron traps in the material in the temperature range 20-300 K. However, L-DLTS with its higher resolution enabled the splitting of two narrowly spaced emission rates. Consequently four electron traps at, E_C—0.33 eV, E_C—0.36 eV, E_C—0.38 eV and E_C—0.56 eV were observed in the control sample. Following hydrogenation, all these traps were passivated with a new complex (presumably the M3), emerging at E_C—0.58 eV. Isochronal annealing of the passivated material between 50 and 300 °C, revealed the emergence of a secondary defect, not previously observed, at E_C—0.37 eV. Finally, the effect of hydrogen passivation is completely reversed upon annealing at 300 °C, as all the defects originally observed in the reference sample were recovered.     

Effects of substrate temperature on the efficiency of hydrogen incorporation on the properties of Al-doped ZnO films

Al-doped ZnO (AZO) transparent conducting films were successfully prepared on glass substrates by RF magnetron sputtering at different substrate temperatures in Ar and H₂ + Ar sputtering ambient. The effects of substrate temperature on the effectiveness of hydrogen incorporation in Al-doped ZnO films were investigated. The microstructural, electrical and optical properties of AZO films were systematically analyzed by surface profiler, X-ray diffractometry, scanning electron microscope, four-point probe measurement and UV/vis spectrophotometer. The XRD patterns and SEM pictures indicate that the crystallinity of AZO thin films was markedly improved with hydrogen incorporation at low substrate temperature, while the improvement of crystallinity was not an obvious change at high substrate temperature. The results also indicate that hydrogen incorporation has the stronger effectiveness on the transparent conductive properties of AZO films with the substrate temperature decreasing. The resistivity of the films decreases, especially for lower substrate temperatures, due to the incorporation of hydrogen atoms. These results suggest that substrate temperature should be controlled to the lower level to effectively reduce resistivity without detriment to transmittance of AZO thin films when hydrogen is incorporated.     

Variable temperature FT-IR studies on hydrogen adsorption on the zeolite (Mg,Na)-Y

Variable-temperature infrared spectroscopy was used for the thermodynamic studies on the adsorption of hydrogen on the zeolite (Mg,Na)-Y. Adsorption renders the HH stretching mode infrared active, and simultaneous measurement of IR absorbance and hydrogen equilibrium pressure, over a range of temperature, allowed adsorption enthalpy and entropy to be determined. The standard adsorption enthalpy and entropy resulted to be ΔH° = −18.2(±0.8) kJ mol⁻¹ and ΔS° = −136(±10) J mol⁻¹ K⁻¹, respectively. The adsorption enthalpy is substantially higher than the hydrogen liquefaction heat, which suggests that magnesium-containing porous materials are potential candidates in the search for suitable adsorbents for reversible hydrogen storage.