Structural,vibrational study and superprotonic behavior of a new mixed dipotassium hydrogenselenate dihydrogenphosphate K2(HSeO4)1.5(H2PO4)0.5

Ongoing studies of the KHSeO₄–KH₂PO₄ system aiming at developing novel proton conducting solids resulted in the new compound K₂(HSeO₄)_1.5(H₂PO₄)_0.5 (dipotassium hydrogenselenate dihydrogenphosphate). The crystals were prepared by a slow evaporation of an aqueous solution at room temperature. The structural properties of the crystals were characterized by single-crystal X-ray analysis: K₂(HSeO₄)_1.5(H₂PO₄)_0.5 (denoted KHSeP) crystallizes in the space group P 1¯ with the lattice parameters: a = 7.417(3) Å, b = 7.668(2) Å, c = 7.744(5) Å, α = 71.59(3)°, β = 87.71(4)° and γ = 86.04(6)°. This structure is characterized by HSeO₄⁻ and disordered (H_xSe/P)O₄⁻ tetrahedra connected to dimers via hydrogen bridges. These dimers are linked and stabilized by additional hydrogen bonds (O–H–O) and hydrogen bridges (O–H…O) to build chains of dimers which are parallel to the [0, 1, 0] direction at the position x = 0.5.The differential scanning calorimetry diagram showed two anomalies at 493 and 563 K. These transitions were also characterized by optical birefringence, impedance and modulus spectroscopy techniques. The conductivity relaxation parameters of the proton conductors in this compound were determined in a wide temperature range. The transport properties in this material are assumed to be due to H⁺ protons hopping mechanism.     

3C-SiC(001)-3 × 2 reconstructed surface analyzed by high-resolution medium energy ion scattering

The atomic structure of the 3C-SiC(001)-3 × 2 reconstructed surface was analyzed precisely by high-resolution medium energy ion scattering (MEIS). The present MEIS analysis unambiguously shows that the (3 × 2) surface consists of Si adatoms (1/3 ML, 1 ML = 1.05 × 10¹⁵ atoms/cm²) on top and underlying Si adlayer (2/3 ML) on the bulk truncated Si plane. As the result, the most probable structure is focused on the Two Adlayer Asymmetric Dimer Model predicted by ab initio calculations and the modified versions with alternating long and short dimers in the 2nd adlayer proposed by photoelectron diffraction (PED) and by grazing incidence X-ray diffraction (GIXRD) analyses. Observed MEIS spectra are well reproduced by the structure relatively close to that determined by PED rather than GIXRD. Interestingly, the first principle calculations using VASP (Vienna ab initio simulation package) prefer symmetric dimers in the second Si adlayer and non-relaxed interplanar distance between the top Si and 2nd C plane of the bulk-truncated surface, which are, however, unable to reproduce the observed MEIS spectra. The distorted 2nd adlayer (asymmetric dimers) may correlate with the compressed interplanar distance between the underlying Si and C planes.     

Thermodynamics and kinetics of CO and benzene adsorption on Pt(111) studied with pulsed molecular beams and microcalorimetry

The adsorption and desorption of the system CO/Pt(111) and C₆H₆/Pt(111) at 300 K has been investigated with a pulsed molecular beam method in combination with a microcalorimeter. For benzene the sticking probability has been measured in dependence of the coverage θ. For coverages θ > 0.8 transient adsorption is observed. From an analysis of the time-dependence of the molecular beam pulses the rate constant for desorption is determined to be 5.6 s^? 1. With a precursor-mediated kinetic adsorption model this allows to obtain also the hopping rate constant of 95.5 s^? 1. The measured adsorption enthalpies could be best described by (199 ? 77θ ? 51θ²) kJ/mol, in good agreement with the literature values. For CO on Pt(111) also transient adsorption has been observed for θ > 0.95 at 300 K. The kinetic analysis yields rate constants for desorption and hopping of 20 s^?1 and 51 s^?1, respectively. The heats of adsorption show a linear dependence on coverage (131 ? 38θ) kJ/mol between 0 ≤ θ ≤ 0.3, which is consistent with the desorption data from the literature. For higher coverage (up to θ = 0.9ML) a slope of ?63 kJ/mol describes the decrease of the differential heat of adsorption best. This result is only compatible with desorption experiments, if the pre-exponential factor decreases strongly at higher coverage. We found good agreement with recent quantum chemical calculations made for (θ = 0.5ML).     

Mechanoluminescence characterisation of γ-irradiated (KNa)Br:Ce3+ phosphor

The mechanoluminescence (ML) of γ-irradiated coloured powder of (KNa)Br:Ce(0.1–10 mol%) phosphor is reported in this paper. The samples are prepared by wet chemical method. The ML intensities are found to be dependent on concentrations of Ce³⁺ ion and γ-rays radiation dose. The variation of peak ML intensity of (KNa)Br:Ce(0.5 mol%) with different γ-rays dose is found as linear up to 2.5 kGy high dose from 0.08 kGy, whereas for the KBr:Ce(0.5 mol%) and NaBr:Ce(0.5 mol%) samples the ML intensities increases sublinearly. The prepared sample shows minimum fading in ML intensity. The ML characterisation shows the good linearity, less fading and simple ML glow curve structure, thus the prepared material may be useful for radiation dosimetry.     

Magnetic anisotropy of epitaxial Fe layers grown on Si(0 0 1)

The magnetic properties of epitaxial iron films up to 80 monolayers (ML) thickness grown on Si(0 0 1) by using a template technique were investigated by means of superconducting quantum interference device and magneto-optic Kerr effect techniques. The thinnest films investigated (∼3 ML) exhibit a composition close to Fe₃Si with a Curie temperature below room temperature (RT) and strong out-of-plane remanent magnetization that reflects the presence of a dominant second order surface anisotropy term. Thicker films (⩾4 ML) are ferromagnetic at RT with remanent magnetization in film-plane and a composition closer to pure Fe with typically 8–10% silicon content. When deposited at normal incidence such films show simple in-plane fourfold anisotropy without uniaxial contribution. The relevant fourth-order effective anisotropy constant K₄^eff was measured versus film thickness and found to change its sign near 18 ML. The origin of this remarkable behavior is investigated by means of a Néel model and mainly traced back to fourth-order surface anisotropy and magneto-elastic effects related to the large biaxial in-plane compressive strain up to 3.5% in the thinnest (⩽25 ML) films.     

Diffusion-promoted-desorption mechanism for D2 desorption from Si(100) surfaces

Temperature-programmed-desorption (TPD) spectra and isothermal desorption rates of D₂ molecules from a Si(100) surface have been calculated to reproduce experimental β_1, A-TPD spectra and isothermal desorption rate curves. In the diffusion-promoted-desorption (DPD) mechanism, hydrogen desorption from the Si(100) (2 × 1) surfaces takes place via D atom diffusion from doubly-occupied Si dimers (DODs) to their adjacent unoccupied Si dimers (UODs). Taking a clustering interaction among DODs into consideration, coverages θ_DU of desorption sites consisting of a pair of a DOD and UOD are evaluated by a Monte Carlo (MC) method. The TPD spectra for the β_1, A peak are obtained by numerically integrating the desorption rate equation R = ν_A exp(? E_d, A / k_BT)θ_DU, where ν_A is the pre-exponential factor and E_d, A is the desorption barrier. The TPD spectra calculated for E_d, A = 1. 6 eV and ν_A = 2.7 × 10⁹ /s are found to be in good agreement with the experimental TPD data for a wide coverage range from 0.01 to 0.74 ML. Namely, the deviation from first-order kinetics observed in the coverage dependent TPD spectra as well as in the isothermal desorption rate curves can be reproduced by the model simulations. This success in reproducing both the experimental TPD data and the very low desorption barrier validates the proposed DPD mechanism.     

Deposition of device quality amorphous silicon and solar cell from argon dilution of silane

In our present study hydrogenated amorphous silicon (a-Si:H) thin films and solar cells have been prepared in a conventional single chamber rf-PECVD unit from silane–argon mixture by varying radio frequency (rf) power densities from 6 mW/cm² to 50 mW/cm². By optimizing the properties of the intrinsic material we have chosen a material which is deposited at 6 mW/cm² rf power density, 0.2 Torr pressure, 175 ^oC substrate temperature and by 97% argon dilution. For this material minority carriers (holes) diffusion length (L_d) measured in the as deposited state is 180 nm and it degrades by 15% after light soaking. This high L_d value indicates that the material is of device quality. We have fabricated a single junction solar cell having the structure p-a-SiC:H/i-a-Si:H/n-a-Si:H without optimizing the doped layers. This set exhibits a mean open circuit voltage of 0.8 V and conversion efficiency of 7.7%. After light soaking conversion efficiency decreases by 15% which demonstrates that it is possible to deposit device grade material and solar cells from silane–argon mixture.     

Ga-induced restructuring of Si(5 5 12) − 2 × 1 reconstructed surface at room temperature

Motivated by the need to form 1D-nanostructured dopants on silicon surfaces, we have attempted to grow Ga on the high index Si(5 5 12) surface which has a highly trenched (1D) morphology. The evolution of the interface with Ga adsorption in the monolayer regime has been probed by in situ AES, LEED and EELS. Controlling the kinetics by changing the Ga flux rates shows an interesting difference in the 1.0 to 1.5 ML region. The low flux rate (0.03 ML/minute) results in a Frank van der Merwe (layer by layer) growth mode up to 2 ML, while the higher flux rate (0.1 ML/minute) shows a transient island formation after the completion of 1 ML. The low rate shows the formation of 2 × (3 3 7) and (2 2 5) superstructures, while only the 2 × (3 3 7) is observed in a wide coverage range for the higher rate. The results demonstrate the ability to kinetically control the surface phases with different electronic properties of this technologically important interface.     

Coverage-dependent molecular tilt of carbon monoxide chemisorbed on Pt{110}: A combined LEED and DFT structural analysis

The adsorption of carbon monoxide on the Pt{110} surface at coverages of 0.5 ML and 1.0 ML was investigated using quantitative low-energy electron diffraction (LEED IV) and density-functional theory (DFT). At 0.5 ML CO lifts the reconstruction of the clean surface but does not form an ordered overlayer. At the saturation coverage, 1.0 ML, a well-ordered p(2 × 1) superstructure with glide line symmetry is formed. It was confirmed that the CO molecules adsorb on top of the Pt atoms in the top-most substrate layer with the molecular axes tilted by ± 22° with respect to the surface normal in alternating directions away from the close packed rows of Pt atoms. This is accompanied by significant lateral shifts of 0.55 Å away from the atop sites in the same direction as the tilt. The top-most substrate layer relaxes inwards by ? 4% with respect to the bulk-terminated atom positions, while the consecutive layers only show minor relaxations. Despite the lack of long-range order in the 0.5 ML CO layer it was possible to determine key structural parameters by LEED IV using only the intensities of the integer-order spots. At this coverage CO also adsorbs on atop sites with the molecular axis closer to the surface normal (< 10°). The average substrate relaxations in each layer are similar for both coverages and consistent with DFT calculations performed for a variety of ordered structures with coverages of 1.0 ML and 0.5 ML.     

Synthesis of oligomeric poly[(1, 2-propanediamine)-alt-(oxalic acid)] and anomalous proton conductivities of the thin films

New proton-conductive polyamide oligomers, oligomeric poly[(1, 2-propanediamine)-alt-(oxalic acid)], were synthesized to investigate the proton transport properties of bulk and thin films. The obtained oligomers were characterized by the X-ray diffraction, FT-IR spectra, ¹H NMR, Matrix Assisted Laser Desorption/Ionization Time of Flight (MALDI-TOF) mass spectrum, and electrical conductivity measurements. The bulk proton conductivity is 3.0 × 10^? 4 S cm^? 1 at the relative humidity (RH) of 80%. The proton conductivity of thin film is relatively higher than that of bulk sample. Thickness dependence of the proton conductivity was observed in these thin films. The maximum proton conductivity of the thin film is 4.0 × 10^? 3 S cm^? 1 at the relative humidity (RH) of 80%, which is higher one order magnitude than that of the bulk sample. The activation energies of bulk and 200 nm thick film are 1.0 and 0.69 eV at the RH of 60%, respectively.     

Single crystalline graphene synthesized by thermal annealing of humic acid over copper foils

Production of graphene by thermal annealing on copper foil substrates has been studied with different sources of carbon. The three carbon sources include humic acid derived from leonardite, graphenol, and activated charcoal. Hexagonal single crystalline graphene has been synthesized over the copper foil substrates by thermal annealing of humic acid, derived from leonardite, in argon and hydrogen atmosphere (Ar/H₂=20). The annealing temperature was varied between 1050 °C and 1100 °C at atmospheric pressure. Samples have been investigated using scanning electron microscope (SEM) and Raman spectroscopy. At lower temperatures the thermal annealing of the three carbon sources used in this study produces pristine graphene nanosheets which cover almost the whole substrate. However when the annealing temperature has been increased up to 1100 °C, hexagonal single crystalline graphene have been observed only in the case of the humic acid. Raman analysis showed the existence of 2D band around 2690 cm⁻¹.     

Structural,XPS and impedance analysis of LixCoVO4 (x = 0.8, 1.0, 1.2)

Lithium cobalt vanadate Li_xCoVO₄ (x = 0.8; 1.0; 1.2) has been prepared by a solid state reaction method. The XRD analysis confirms the formation of the sample. A new peak has been observed for Li_1.0CoVO₄ and for Li_1.2CoVO₄ indicating the formation of a new phase. The XPS analysis indicates the reduction in the oxidation of vanadium and oxygen with the addition of Li in Li_xCoVO₄ (x = 0.8, 1.0, 1.2). The impedance analysis gives the conductivity value as 2.46 × 10^− 5, 6.16 × 10^− 5, 9 × 10^− 5 Ω^− 1 cm^− 1 for Li_xCoVO₄ (x = 0.8; 1.0; 1.2), all at 623 K. The similarity in the bulk activation energy (E_a) and the activation enthalpy for migration of ions (E_ω) indicate that the conduction in Li_1.2CoVO₄ has been due to hopping mechanism.     

1H NMR study of proton dynamics in (NH4)3H(SO4)2

Proton dynamics in (NH₄)₃H(SO₄)₂ has been studied by means of ¹H solid-state NMR. The ¹H magic-angle-spinning (MAS) NMR spectra were traced at room temperature (RT) and at Larmor frequency of 400.13 MHz. ¹H static NMR spectra were measured at 200.13 MHz in the range of 135–490 K. ¹H spin-lattice relaxation times, T₁, were measured at 200.13 and 19.65 MHz in the ranges of 135–490 and 153–456 K, respectively. The ¹H chemical shift for the acidic proton (14.7 ppm) indicates strong hydrogen bonds. In phase III, NH₄⁺ reorientation takes place; one type of NH₄⁺ ions reorients with an activation energy (E_a) of 14 kJ mol^− 1 and the inverse of a frequency factor (τ₀) of 0.85 × 10^− 14 s. In phase II, a very fast local and anisotropic motion of the acidic protons takes place. NH₄⁺ ions start to diffuse translationally, and no proton exchange is observed between NH₄⁺ ions and the acidic protons. In phase I, both NH₄⁺ ions and the acidic protons diffuse translationally. The acidic protons diffuse with parameters of E_a = 27 kJ mol^− 1 and τ₀ = 4.2 × 10^− 13 s. The translational diffusion of the acidic protons is responsible for the macroscopic proton conductivity, as the NH₄⁺ translational diffusion is slow and proton exchange between NH₄⁺ ions and the acidic protons is negligible.     

Highly sensitive hydrogen detection by medium energy Ne+ impact

Hydrogen atoms on solid surfaces were measured directly by elastic recoil detection analysis (ERDA) using medium energy (100–150 keV) Ne⁺ ions with an excellent sensitivity of (～ 1 × 10¹² H/cm²) without any absorber foils and time-of-flight techniques. An electrostatic toroidal analyzer acquired H⁺ ions with energy around 11 keV recoiled from Si(111)-1 × 1-H surfaces. The H⁺ fraction strongly depends upon emerging angle and takes a value more than 50% at the angle below 70° and a saturated value of 17% at the angle above 80° with respect to surface normal. We detected H atoms on the reduced TiO₂(110) exposed to water molecules at room temperature (2 L) and estimated the absolute amount of H to be ～ 2.0 × 10¹⁴ H/cm² corresponding to ～ 38% (～ 0.38 ML) of the bridging oxygen atoms.     

Growth protocols and characterization of epitaxial graphene on SiC elaborated in a graphite enclosure

The epitaxial growth of graphene by the sublimation of Si-terminated silicon carbide (SiC) is studied inside a graphite enclosure in a radio-frequency furnace by comparing different in situ processes involving hydrogen etching or not and different growth conditions. For the growth under vacuum, even with the surface preparation of hydrogen etching, the morphology of the synthesized graphene is found full of voids and defects in the form of a multilayer graphene film. For the growth under Ar, the hydrogen etching plays a vital role to improve the graphene quality in terms of surface roughness, the number of graphene layers and the domain size. For the graphene samples grown with the proposed protocol, the original combination of micro-probe Raman spectroscopy and simultaneous optical transmission and reflection measurements reveals a detailed spatially resolved image of the graphene domains with monolayer domain size of ~5×5 µm² on about 2/3 of the total sample surface. The magnetotransport data yield charge-carrier mobilities up to 2900 cm²/Vs as found for high quality graphene on the Si-face of SiC. The observed magnetoquantum oscillations in the magnetoresistance confirm the expected behavior of single-layer graphene.     

In situ magneto-optical Kerr effect study of uncovered Fe films on ZnSe(0 0 1)

The magnetic properties of uncovered Fe/ZnSe/GaAs(1 0 0) ultrathin films have been determined in situ by magneto-optical Kerr effect (MOKE). Fe films up to 10 monolayers (ML) thick were deposited on c(2×2) Zn-rich ZnSe/GaAs(0 0 1) surfaces at 180 °C. We have studied the thickness dependence of the in-plane lattice parameter of the Fe films and of the MOKE hysteresis loops in the longitudinal geometry, at 150 K, under magnetic fields up to 0.1 T applied along the [1 1 0] and [1-1 0] directions of the ZnSe(0 0 1). Reflection high energy electron diffraction show that in the low thickness regime the Fe films present an in-plane structural anisotropy characterized by an expansion along the [1 1 0] direction. Hysteretic loops were obtained only starting from ∼5 ML Fe. We found the onset of an uniaxial magnetic anisotropy with [1 1 0] magnetic easy axis at 7 ML Fe.     

Mechanoluminescence,thermoluminescence and photoluminescence studies on Al2O3:Tb phosphors

Terbium activated Al₂O₃ phosphors were synthesized by combustion technique using hydrazine as a reductive non-carbonaceous fuel. X-ray diffraction (XRD) patterns of the samples were recorded to confirm the formation of the sample. Scanning electron microscope (SEM) images were taken to study the surface morphology of the sample. The photoluminescence (PL), thermoluminescence (TL) and mechanoluminescence (ML) properties of the γ-ray irradiated samples were studied. ML was excited impulsively by dropping a piston on the sample. In ML glow curves one peak with a shoulder was observed. ML intensity increases with activator concentration. Optimum ML was observed for the sample having 0.5 mol% of Tb ions. In the TL glow curve two distinct peaks, one around 222 °C and another around 280 °C, were observed for the samples having 0.5 mol% of activator concentration. In the PL spectra the ⁵D₄→⁷F₅ line at 544 nm in the green region is observed, which is the strongest in Al₂O₃ system. It is suggested that de-trapping of trapped charge carriers followed by recombination is responsible for ML and TL in this system.     

Iterative reconstruction of radially-sampled 31P bSSFP data using prior information from 1H MRI

The purpose of this study is to improve direct phosphorus (³¹P) MR imaging. Therefore, 3D density-adapted radially-sampled balanced steady-state free precession (bSSFP) sequences were developed and an iterative approach exploiting additional anatomical information from hydrogen (¹H) data was evaluated. Three healthy volunteers were examined at B₀ = 7 T in order to obtain the spatial distribution of the phosphocreatine (PCr) intensities in the human calf muscle with a nominal isotropic resolution of 10 mm in an acquisition time of 10 min. Three different bSSFP gradient schemes were investigated. The highest signal-to-noise ratio (SNR) was obtained for a scheme with two point-reflected density-adapted gradients. Furthermore, the conventional reconstruction based on a gridding algorithm was compared to an iterative method using an ¹H MRI constraint in terms of a segmented binary mask, which comprises prior knowledge. The parameters of the iterative approach were optimized and evaluated by simulations featuring ³¹P MRI parameters. Thereby, partial volume effects as well as Gibbs ringing artifacts could be reduced. In conclusion, the iterative reconstruction of ³¹P bSSFP data using an ¹H MRI constraint is appropriate for investigating regions where sharp tissue boundaries occur and leads to images that represent the real PCr distributions better than conventionally reconstructed images.     

Metastable helium atom scattering from Ni(1 1 0) surface

The survival probability (SP) of metastable helium atoms (He¹) during scattering from the clean, alkalated and oxygen-adsorbed Ni(1 1 0) surfaces has been examined in the kinetic energy range of 50–400 meV. The measurements were carried out using a time-of-flight technique and a pulsed-discharge type metastable helium atom source. The SP is nearly constant for a kinetic energy (E_kin) of 50–100 meV and decreases exponentially with the increase in E_kin at 100–400 meV. It has been shown that the SP at E_kin=100–400 meV depends on the repulsive part of the He¹-surface interaction potential.     

Ab initio determination of atomic structure and energy of surface states of bare and hydrogen covered GaN (0001) surface — Existence of the Surface States Stark Effect (SSSE)

Density Functional Theory (DFT) calculations indicate that energetically stable structure of clean GaN(0001) surface posses (2 × 1) reconstruction, having every second row of Ga located near plane of N atoms, that gives rise to Ga-related dispersionless surface electronic state, already identified by angle resolved photoelectron spectroscopy (ARPES) measurements [S.S. Dhesi et al. Phys. Rev. B 56 (1997) 10271, L. Plucinski et al. Surf. Sci 507-10 (2002) 223, S. M. Widstrand et al. Surf. Sci. 584 (2005) 169]. The energy reduction in reconstruction proceeds via change of the hybridization of the occupied Ga surface states from sp³ to sp², transforming the empty states to p_z type. It is also shown that the electric subsurface field, modeled in new slab model which allows to simulate electric fields at the semiconductor surfaces [P. Kempisty et al., J. Appl. Phys. 106 (2009) 054901], strongly affects the energy of electronic states of GaN(0001) surfaces. The change of the field may shift the energy of surface states of bare and hydrogen covered GaN(0001) surface, by several eV with respect to the band states. The phenomenon, denoted as Surface States Stark Effect (SSSE), explains various band bending values, measured at differently doped n-type GaN(0001) surfaces. It is shown also that, for the adsorbate density up to one H atom for each Ga surface atom i.e. 1 monolayer coverage (1 ML), the hydrogen adatoms are located at the on-top positions, i.e. directly above Ga atoms. For these adsorbate densities, the H-related quantum surface state is located slightly below the valence band maximum (VBM) in the case of p-type GaN surface. For n-type GaN, the H-related surface state is located deeply in the valence band, about 2 eV below VBM. For higher, 1.25 ML hydrogen coverage, the two H adatoms create either surface attached H₂ ad-molecule (energetically stable) or triple bridge configuration is created (metastable). The H₂ ad-molecule is weekly attached to the surface, having the desorption energy barrier equal to 0.16 eV. For 1.25 ML coverage the DFT results were obtained for p-type GaN only. They show that in the ad-molecule case, a new surface electronic state arises which is located about 6.7 eV below VBM. In the case of the bridge configuration, the bridge related surface state is located closely to the conduction band minimum (CBM).