Band structure symmetry effects in Gd multilayers grown on W(1 1 2)

We present evidence of coverage-dependent band structure symmetry effects in scanning tunneling microscopy. We find that the symmetry of the Gd induced band located at about 2 eV below the Fermi energy, at the surface Brillouin zone center, appears to be strongly dependent on the atomic structure in the bilayer regime for Gd on W(1 1 2). Light polarization dependent photoemission from this band indicates more d_z² symmetry character for rectangular Gd structures and rather more d_xzd_yz character for the quasi hexagonal bilayer structure. Band symmetry changes accompanying the structural phase transition from rectangular to quasi-hexagonal Gd bilayer structures are consistent with arguments used to explain the apparent STM corrugation observed for Gd on W(1 1 2) (Surf Sci 520(2002)43).     

Refractory metal reactivity towards oxide surface: W/TiO2(1 1 0) case

Reactivity of deposited tungsten towards TiO₂(1 1 0) surface was studied using synchrotron radiation photoemission spectroscopy (both core levels, valence band and resonant photoemission) on Materials Science Beamline at ELETTRA. W depositions carried out at room temperature on TiO₂(1 1 0) surface give rise to an interfacial reaction which leads to a metastable situation due to kinetic limitations. Annealing induces chemical changes which are function of the initial coverage; for fractional coverage, annealing induces completion of oxidation of deposit whereas reduction to metallic tungsten occurs for highest coverage. These results demonstrate that interaction of W with TiO₂(1 1 0) surface is, as the one of molybdenum, driven by a balance between W-O interactions and W-W depending on tungsten atoms density on TiO₂ surface.     

Characterization of ultra-thin TiO2 films grown on Mo(112)

Ultra-thin TiO₂ films were grown on a Mo(112) substrate by stepwise vapor depositing of Ti onto the sample surface followed by oxidation at 850 K. X-ray photoelectron spectroscopy showed that the Ti 2p peak position shifts from lower to higher binding energy with an increase in the Ti coverage from sub- to multilayer. The Ti 2p peak of a TiO₂ film with more than a monolayer coverage can be resolved into two peaks, one at 458.1 eV corresponding to the first layer, where Ti atoms bind to the substrate Mo atoms through Ti-O-Mo linkages, and a second feature at 458.8 eV corresponding to multilayer TiO₂ where the Ti atoms are connected via Ti-O-Ti linkages. Based on these assignments, the single Ti 2p_3/2 peak at 455.75 eV observed for the Mo(112)-(8 × 2)-TiO_x monolayer film can be assigned to Ti³⁺, consistent with our previous results obtained with high-resolution electron energy loss spectroscopy.     

Modification of Shockley surface state by long-chain n-alkane: Photoemission study on tetratetracontane/Au(111) interface

Modification of quasi two-dimensional surface electron system on Au(111) with adsorption of long-chain n-alkane molecule n-CH₃(CH₂)₄₂CH₃ (tetratetracontane: TTC) was investigated by angle-resolved photoemission spectroscopy. Significant modification of the energy band structure of the Shockley surface state was induced by the adsorption of TTC monolayer with “flat-on” structure. The energy shift of the Shockley surface state toward the Fermi level reaches about 160 meV at Γ? point (k = 0 Å^− 1). The possible origin of the stabilization of the surface electron system with TTC monolayer is discussed.     

Magnetic and electrical properties of Ba2CrMo1 − xWxO6 double perovskite

Effects of the partial substitution of W^5+,6+ for Mo^5+,6+ on the structural and physical properties of Ba₂CrMoO₆ have been investigated. Polycrystalline Ba₂CrMo_1 − xW_xO₆samples have been prepared by sol-gel method in a stream of 5% Ar/H₂ gas at various sintering temperatures. Rietveld analysis of X-ray diffraction patterns shows a partial disorder of Mo/W and Cr on the B sites of the double perovskite, which plays a dominant role in the structural and magnetic properties of these compounds. The symmetry is cubic (Fm3?m) for all samples, and no phase transition was detected for Ba₂CrMo_1 − xW_xO₆. The Curie temperature T_C has been analyzed by two methods: a linear extrapolation of M(T) to zero magnetization and the thermodynamic model. The experimental results indicate that T_C decrease from 335 K (x = 0) to 285 K (x = 0.5) with increasing W substitution independently of the method used to obtain T_C. A systematic decrease in saturation magnetization, M_s with increasing W substitution has been observed in this solid solution series. This decrease of magnetization arises from the disorder at the Cr and Mo/W sites. Electrical properties change as well strongly along the series.     

Orientational ordering of 4-pentyl-4′-cyanobiphenyl molecules evaporated on multi-layered polyimide film

Using optical second-harmonic (SH) generation and polarized absorption (PA) measurements, the orientational ordering process of 4-pentyl-4′-cyanobiphenyl (5CB) was studied during evaporation onto the alignment layer of polyimide (PI) Langmuir-Blodgett films. The intensity of SH signal increased in the beginning of the deposition, but it saturated after the first 5CB monolayer was formed. The PA measurement suggested that a layer-by-layer growth was induced after the formation of 5CB monolayer with accompanying the orientational ordering. The orientational order of the first 5CB monolayer was studied in terms of the orientational order parameters, S₁ = 〈cosθ〉 and S₂ = 〈(3cos²θ − 1)/2〉, using the SHG and PA measurements. It was found that S₁ decreased as the thickness of PI alignment layer increased from 0.4 to 4.4 nm, while S₂ was nearly constant. These results indicate that the Coulomb interaction between the permanent dipole of 5CB and its image dipole makes a significant contribution to the orientational ordering of deposited 5CBs.     

Surface morphology and growth mechanisms for sputtered amorphous silicon nitride thin films

Evolution of surface of sputter-deposited amorphous Si₃N₄ films growth on Si (100) substrates was investigated using atomic force microscopy (AFM). The scaling behaviors of the AFM topographical profiles were analyzed using the one-dimensional power spectral density. The results of root-mean-square surface height variation showed that there is a power law relationship between the surface roughness and deposition time. It is interesting to note that the growth exponent can be divided into one region and two regions, respectively, when Si₃N₄ films are deposited at different working pressures. A very low growth exponent of β = 0.07 ± 0.01 was found when Si₃N₄ films were deposited at a working pressure of 1.6 × 10^− 1 Pa. However, the growth exponent β can be divided into two regions, which is β₁ = 0.09 ± 0.01, β₂ = 0.24 ± 0.03 and β₁ = 0.09 ± 0.01, β₂ = 0.33 ± 0.04, when the films were deposited at a working pressure of 2.1 × 10^− 1 Pa and 2.7 × 10^− 1 Pa, respectively. The mechanisms of anomalous dynamic scaling exponents of Si₃N₄ films deposited at different working pressures were discussed.     

Analysis of surface states and series resistance in Au/n-Si Schottky diodes with insulator layer using current-voltage and admittance-voltage characteristics

In order to good interpret the experimentally observed Au/n-Si (metal-semiconductor) Schottky diodes with thin insulator layer (18 Å) parameters such as the zero-bias barrier height (Φ_bo), ideality factor (n), series resistance (R_s) and surface states have been investigated using current-voltage (I-V), capacitance-frequency (C-f) and conductance-frequency (G-f) techniques. The forward and reverse bias I-V characteristics of Au/n-Si (MS) Schottky diode were measured at room temperature. In addition, C-f and G-f characteristics were measured in the frequency range of 1 kHz-1 MHz. The higher values of C and G at low frequencies were attributed to the insulator layer and surface states. Under intermediate forward bias, the semi-logarithmic Ln (I)-V plot shows a good linear region. From this region, the slope and the intercept of this plot on the current axis allow to determine the ideality factor (n), the zero-barrier height (Φ_bo) and the saturation current (I_S) evaluated to 2.878, 0.652 and 3.61 × 10⁻⁷ A, respectively. The diode shows non-ideal I-V behavior with ideality factor greater than unity. This behavior can be attributed to the interfacial insulator layer, the surface states, series resistance and the formation barrier inhomogeneity at metal-semiconductor interface. From the C-f and G-f characteristics, the energy distribution of surface states (N_ss) and their relaxation time (τ) have been determined in the energy range of (E_c − 0.493E_v)-(E_c − 0.610) eV taking into account the forward bias I-V data. The values of N_ss and τ change from 9.35 × 10¹³ eV⁻¹ cm⁻² to 2.73 × 10¹³ eV⁻¹ cm⁻² and 1.75 × 10⁻⁵ s to 4.50 × 10⁻⁴ s, respectively.     

Structure and electrochemical reactivity of 3-[tris(2-methoxyethoxy)silyl]-propanethiol adsorbed on silver surface

A novel stable self-assembled chemisorbed layers, providing protection of metal surface against electrooxidation capable of blocking propylene carbonate (PC) electroreduction and Li electrodeposition, were produced from 3-[tris-(2-methoxyethoxy)silyl]-propanethiol (SIS2) on silver. Reflection-absorption infrared spectroscopy (RAIRS) indicated cleavage of the S-H bond upon adsorption of SIS1 [3-(trimethoxysilyl)-propanethiol] and SIS2 species with the formation of S-Ag bonds on the metal surface. By cyclic voltammetry it was found that the primary adsorbate formed on a Ag electrode at E_ad (between − 0.2 and − 1.2 V vs. SCE) underwent reductive desorption at E < − 1.3 V vs. SCE. From the charge involved in this process, the saturation surface coverage was estimated as 4.2 10^− 10 mol cm^− 2. A compact SIS2 layer after long-time aging (hydrolysis and condensation) was electroinactive and thus non-desorbable from the electrode surface during the potential cycling. The structures of SIS2 and its complexes with Li⁺ cations on the Ag surface were calculated and visualized by the AM1d semi-empirical method.     

Microporous titanosilicate AM-2: Rb-exchange and thermal behaviour

Rb-exchange and thermal stability of the microporous titanosilicate AM-2 were analysed by powder X-ray diffraction, thermo-gravimetric analysis, and chemical analysis of the mother liquid after exchange. The dehydration and thermal stability of the exchanged structure were monitored with in situ high temperature powder X-ray diffraction. Crystal structures were refined with Rietveld methods at 25 and 400 °C. The AM-2 structure was found to incorporate Rb⁺ by replacing K⁺. After four exchange cycles and 166 h reaction time at 90 °C, the chemical composition was refined to K_0.18Rb_1.82TiSi₃O₉·H₂O. Extrapolation suggests that higher exchange ratios may be obtained after further cycles. H₂O was expelled by heating, leading to a dehydrated structure at 360 °C. Dehydration was associated with a change of space group symmetry from orthorhombic P2₁2₁2₁ to monoclinic P2₁, which proved to be reversible after rehydration. This change of symmetry leaves the AM-2 characteristic structural topology uninfluenced and causes only minor distortions. The monoclinic AM-2 structure breaks down above 600 °C to become X-ray amorphous, and at 750 °C a wadeite-type phase (K_xRb_2−xTiSi₃O₉) crystallises. This transformation is irreversible and leads to immobilisation of Rb⁺.     

Freezing transition of Langmuir-Gibbs alkane films on water

We show that adding CTAB (CTAB, hexadecyltrimethylammonium bromide) in sub-millimolar bulk concentrations to water reduces its surface tension (ST) to a level where spontaneous surface spreading of a monolayer of medium-sized alkane (C_nH_2n+2, 12 ≤ n ≤ 17) occurs. ST and X-ray reflectivity (XR) measurements are used to show that the quasi two-dimensional (2D) liquid monolayer can be driven through a reversible surface freezing phase transition upon cooling. Grazing incidence diffraction (GID) shows that the frozen monolayer is crystalline, hexagonally packed, with surface-normal molecules, and a crystalline coherence length of at least a few hundred Å, very similar to the structure of surface-frozen (SF) monolayers at the surface of similar-length alkane melts.     

In-situ monitoring of the time evolution of the effective thermal conductivity of snow

We report on a 3-month long time series of in-situ measurements of the effective thermal conductivity (k_eff) of snow at 6 heights in an Alpine snowpack in the Mont-Blanc mountain range, France, at an altitude of 2400 m. Measurements were carried out automatically every 2 days using heated-needle probes embedded in the snowpack. The experimental procedure used is presented in detail and demonstrates the applicability of single heated-needle probes for the evaluation of k_eff in snow, both for long-term measurements within the snowpack and occasional use in the field. Results based on 139 automatically collected data show k_eff values ranging between 0.04 and 0.35 W m^− 1 K^− 1, and a consistent pattern of effective thermal conductivity increase throughout the measurements campaign. The temporal rate of change of k_eff varies up to 0.01 W m⁻¹ K^− 1day^− 1, with maximum values just after snowfall.     

Fabrication of (K, Na)NbO3 glass-ceramics and crystal line patterning on glass surface

Crystallization behavior of (30−x)K₂O-xNa₂O-25Nb₂O₅-45SiO₂ (KNNS; x = 0, 5, 10, 20 and 30) (mol%) glasses was clarified and perovskite-type nonlinear optical (K, Na)NbO₃ (KNN) crystals were synthesized by using a conventional glass-ceramics method. It was found that Na₂O amounts over around x = 10 mol% were necessary to form perovskite-type KNN crystals showing second-harmonic generations. The substitution of K⁺ and Na⁺ ions was confirmed from X-ray diffraction (XRD) analysis. A continues-wave of Yb:YVO₄ fiber laser (wavelength: 1080 nm) was irradiated onto CuO doped KNNS; x = 10 (Cu-KNNS) surface. The absorption coefficient of this Cu-KNNS glass was determined to be α = 5.0 cm⁻¹. Perovskite-type KNN crystals were patterned in the condition of the laser power of >1.20 W and the laser scanning speed of S = 7 μm/s, and their structure was determined by Raman scattering spectra and XRD analysis.     

Low power CW optical limiting properties of bis(2-aminopyridinium)-succinate-succinic acid (2APS) single crystal

The increase in the usage of low power CW lasers in various applications needs for the design of optical limiters with low thresholds. The optical limiting properties and nonlinear refractive index (n₂ = −2.4189 × 10⁻⁸ cm²/W) of transparent organic crystal bis(2-aminopyridinium)-succinate-succinic acid (2APS) single crystal using continuous wave He-Ne laser excitation following Z-scan method have been evaluated. The sample exhibited negative (defocusing) nonlinearity. This thermally induced defocusing nature of 2APS crystal can be used to design the low power optical limiters. As the origin for this nonlinearity is thermal, a complete thermal transport properties such as thermal diffusivity (α_s = 5.97 ± 0.03 × 10⁻³ cm²/s), thermal effusivity (e_s = 1.94 ± 0.02 × 10⁻² J/cm²-K-s^1/2), thermal conductivity (k_s = (4. 66 ± 0.04) × 10⁻³ W/cm-K)) and specific heat capacity (C_ps = (5.61 ± 0.05) × 10⁻¹ J/g-K) of the material were studied following the photopyro electric (PPE) technique.     

Highly (100)-oriented Ce1 − xFexO2 − δ solid solution films prepared by laser chemical vapor deposition

Ce_1 − xFe_xO_2 − δ solid solution films were prepared on amorphous silica substrates by laser chemical vapor deposition using metal dipivaloylmethanate precursors and a semiconductor InGaAlAs (808 nm in wavelength) laser. X-ray diffraction revealed the formation of single Ce_1 − xFe_xO_2 − δ phase at x ≤ 0.15, while CeO₂ and Fe₂O₃ phases were found for higher Fe content. Highly (100)-oriented Ce_1 − xFe_xO_2 − δ (x = 0.02) films were obtained at laser power, P_L = 50-200 W and deposition temperature, T_dep = 800-1063 K. Lotgering factor (200) was calculated to be above 0.8 for films prepared at P_L = 50-150 W. X-ray photoelectron spectroscopy revealed the presence of Fe³⁺, Ce⁴⁺ and Ce³⁺ on solid solution films. Cross-sectional transmission electron microscope images disclosed a film columnar feather-like structure with a large number of nano-scale interspaces. Deposition rates were 2 or 3 orders of magnitude higher than those reported for conventional metal organic chemical vapor deposition of CeO₂.     

Novel transparent conducting oxide: Anatase Ti1−xNbxO2

Single-crystalline Ti_1−xNb_xO₂ (x = 0.2) films of 40 nm thickness were deposited on SrTiO₃ (100) substrates by the pulsed laser deposition (PLD) technique. X-ray diffraction measurement confirmed epitaxial growth of anatase (001) film. The resistivity of Ti_1−xNb_xO₂ films with x ≥ 0.03 is 2-3 × 10^− 4 Ω cm at room temperature. The carrier density of Ti_1−xNb_xO₂, which is almost proportional to the Nb concentration, can be controlled in a range of 1 × 10¹⁹ to 2 × 10²¹ cm^− 3. Optical measurements revealed that internal transmittance in the visible and near-infrared region for films with x = 0.03 was more than 97%. These results demonstrate that the presently developed anatase Ti_1−xNb_xO₂ is one of the promising candidates for the practical TCOs.     

Pyroelectric Ta-modified LiNbO3 thin films and devices for thermal infrared detection

High-performance pyroelectric infrared (IR) detectors have been fabricated using tantalate-doped lithium niobate LiNb_1 − xTa_xO₃ (abbreviated as LNT, with x = 0-1.0) thin films deposited on Pt(111)/Ti/SiO₂/Si(100) substrates by diol-based sol-gel processing, in which, tantalate (Ta) is adopted as dopant in lithium niobate. The randomly oriented LNT thin film exhibits a relatively small dielectric constant and a large pyroelectric coefficient. The pyroelectric characteristics of detectors with various tantalate contents, as a function of modulation frequency, were investigated. It was found that LiNb_0.8Ta_0.2O₃ had the largest voltage responsivity of 7020 (V/W) at 70 Hz, and a specific detectivity (D^?) of 7.76 × 10⁷ cm Hz^1/2/W at 200 Hz. These results indicate that the LNT thin film with x = 0.20 is most suitable for application as high-performance pyroelectric thin-film detectors.     

Investigation of inhibition effect of rhodanine-N-acetic acid on mild steel corrosion in HCl solution

Corrosion inhibition effect of rhodanine-N-acetic acid (R-NA) on mild steel (MS) corrosion in 0.1 M HCl solution was investigated. For this purpose, potentiodynamic polarization, electrochemical impedance spectroscopy (EIS), linear polarization resistance (LPR) as well as hydrogen gas evolution (VH₂−t) and the change of open circuit potential as a function of immersion time (E_ocp − t) were used. The MS surfaces exposed to 0.1 M HCl solution in the absence and presence of inhibitor were examined by scanning electron microscopy (SEM). The thermodynamic parameters of adsorption were calculated and discussed. In order to gain more information about the adsorption mechanism, the EIS technique was used to evaluate the potential of zero charge (PZC) and a mechanism of adsorption process was proposed. It was found that, R-NA is a good corrosion inhibitor for the MS corrosion in 0.1 M HCl solution. The inhibition efficiency increased with increasing inhibitor concentration and reached 98% at 1.0 × 10⁻² M R-NA. The high inhibition efficiency was related to adsorption of R-NA on steel surface. Surface SEM images showed a good surface coverage of inhibitor on the metal surface.     

Chemically deposited lead sulfide and bismuth sulfide thin films and Bi2S3/PbS solar cells

Solar cells with a short-circuit current density (J_sc) of 6 mA/cm², an open circuit voltage (V_oc) of 280 mV and a conversion efficiency of 0.5% under a 1000 W/m² solar radiation were prepared by sequential chemical deposition of Bi₂S₂ (160 nm) and PbS (400 nm) thin films. The optical band gap (E_g) of Bi₂S₃ (160 nm) decreased from 1.67 to 1.61 eV upon heating the as-deposited film at 250 °C in air for 15 min to make it crystalline, but also reduced its thickness to 100 nm. Photoconductivity of this film is 0.003 (Ω cm)^− 1. The E_g of PbS film (200 nm) deposited at 25 °C (24 h) is 0.57 eV, and is 0.49 eV for the film deposited at 40 °C. The electrical conductivity of the latter is 0.48 (Ω cm)^− 1. The photo-generated current density for a Bi₂S₃(100 nm)/PbS(300 nm) absorber stack is above 40 mA/cm² under AM 1.5 G (1000 W/m²) solar radiation. However, the optical losses in the cell structure reduces the J_sc. Spectral sensitivity of the external quantum efficiency of the cell establishes the contribution of Bi₂S₃ and PbS to J_sc. The energy level diagram of the cell structure suggests a built-in potential of 470 mV for the present case. Six series-connected cells gave the V_oc of 1.4 V and J_sc of 5 mA/cm².     

Synthesis and electrical properties of cubic NaxWO3 thin films across the metal-insulator transition

Highly oriented (1 0 0) Na_xWO₃ thin films were fabricated in the composition range 0.1 ≤ x ≤ 0.46 by pulsed laser deposition technique. The films showed transition from metallic to insulating behaviour at a critical composition between x = 0.15 and 0.2. The pseudo-cubic symmetry of Na_xWO₃ thin films across the transition region is desirable for understanding the composition controlled metal-insulator transition in the absence of any structural phase transformation. The electrical transport properties exhibited by these films across the transition regime were investigated. While the resistivity varied as T² at low temperatures in the metallic regime, a variable range hopping conduction was observed for the insulating samples. For metallic compositions, a non-linear dependence of resistivity in temperature was also observed from 300 to 7 K, whose exponent varied with the composition of the film.