Atomic force microscopy of Au deposition from aqueous HF onto Si(111)

Non-contact atomic force microscopy (AFM) was employed following emersion to examine Au nanoclusters deposited from aqueous mixtures of HF and 10⁻⁴ M KAu(CN)₂ onto Si(111). As the HF concentration is increased, the growth rates both parallel and perpendicular to the substrate of the approximately oblate Au hemispheroids increase. AFM images were obtained for times at which previously reported in situ second harmonic generation signals from the interface reach a maximum. At the time when the second harmonic enhancement is maximized during deposition from 0.500 (5.00) M HF, the Au nanoclusters have an average diameter of 94 (109) nm and an average height of 3.6 (9.5) nm. These cluster diameters can be understood qualitatively by the shift of the plasmon resonance due to depolarization as the cluster size increases, causing the resonant second harmonic enhancement at 532 nm to pass through a maximum at cluster diameters in the range 90–110 nm.     

Optical second-harmonic investigations of the isothermal desorption of SiO from the Si(100) and Si(111) surfaces

The isothermal desorption of SiO from the Si(100) and Si(111) surfaces was investigated by means of optical second-harmonic generation (SHG). Due to the high adsorbate sensitivity of this method, desorption rates could be measured over a wide range from 10⁻¹ to 10⁻⁶ ML s⁻¹. From their temperature dependence between 780 and 1000 K, activation energies of E_A=3.4±0.2 eV and E_A=4.0±0.3 eV and pre-exponential factors of ν₀=10^16±1 s⁻¹ and ν₀=10^20±1 s⁻¹ for SiO desorption were obtained for Si(100) and Si(111), respectively. In the case of the Si(100) surface, a pronounced decrease of the first-order rate constants was observed upon increasing the initial coverage from 0.02 to 0.6 ML. The results are interpreted in terms of coverage-dependent oxygen-binding configurations, which influence the stability of the oxide layer.     

Conductance studies of NaBPh4, NBu4I, NaI, NaCl, NaBr, NaClO4 and the limiting ionic conductance in water + propan-1-ol mixtures at 298.15 K

The electrical conductivities of NaBPh₄, NBu₄I, NaI, NaCl, NaBr and NaClO₄ have been studied in the mixtures of propan-1-ol with water. The obtained results were analysed using the Fuoss–Justice equation. The individual limiting ionic conductivities of Na⁺, NBu₄⁺, BPh₄⁻, I⁻, Cl⁻, Br⁻, ClO₄⁻ ions have been determined using the Fuoss–Hirsch assumption. The dependencies of the limiting molar conductances Λ_o and Walden products Λ_oη versus mixed solvent composition have been discussed.     

Solid-phase epitaxy of CaSi2 on Si(1 1 1) and the Schottky-barrier height of CaSi2/Si(1 1 1)

Thin Ca films were evaporated on Si(1 1 1) under UHV conditions and subsequently annealed in the temperature range 200–650 °C. The interdiffusion of Ca and Si was examined by ex situ Auger depth profiling. In situ monitoring of the Si 2p core-level shift by X-ray photoemission spectroscopy (XPS) was employed to study the silicide formation process. The formation temperature of CaSi₂ films on Si(1 1 1) was found to be about 350 °C. Epitaxial growth takes place at T≥400 °C. The morphology of the films, measured by atomic force microscopy (AFM), was correlated with their crystallinity as analyzed by X-ray diffraction (XRD). According to measurements of temperature-dependent I–V characteristics and internal photoemission the Schottky-barrier height of CaSi₂ on Si(1 1 1) amounts to qΦ_Bn=0.25 eV on n-type and to qΦ_Bp=0.82 eV on p-type silicon.     

Phase transitions and electrical properties of CsH(SO4)0.76(SeO4)0.24 mixed crystals

The study by X-ray diffraction, calorimetry, vibrational and impedance spectroscopy of CsH(SO₄)_0.76(SeO₄)_0.24 new solid solution is presented. Crystals of this composition undergo two phase transitions at T = 333 and 408 K. The last one at 408 K is a superionic-protonic transition (SPT) related to a rapid [HS(Se)O₄⁻] reorientation and fast H⁺ diffusion. A sudden jump in the conductivity plot confirms the presence of this transition. Above 408 K, this high temperature phase is characterized by high electrical conductivity (7 × 10^t-3 Ω⁻ cm⁻¹) and low activation energy (E_a < 0.3 eV).     

Direct decomposition of nitrogen monoxide over a K-deposited Co(0 0 0 1) surface: Comparison to K-doped cobalt oxide catalysts

The influence of deposited potassium on the oxidation and NO reactivity of a Co(0 0 0 1) surface was studied using X-ray photoelectron spectroscopy. The formation of surface CoO was observed when the clean Co(0 0 0 1) surface was exposed to O₂ at 500 K. In contrast, the Co atoms on the K-deposited Co(0 0 0 1) surface remained at a lower oxidation state, CoO_x (0 < x < 1). No adsorption or dissociation of NO occurred on the CoO/Co(0 0 0 1) surface at 320 K, whereas a NO₂⁻ species formed on the oxidized K/Co(0 0 0 1) surface. This species is considered to be an intermediate in NO decomposition. It was concluded that the role of potassium was (i) to form the NO₂⁻ intermediate, and (ii) to keep the Co surface partially oxidized (CoO_x) as the active site for the dissociation of the NO₂⁻ species.     

Structural and electrical properties of crystalline (1−x)Ta2O5−xTiO2 thin films fabricated by metalorganic decomposition

Polycrystalline (1−x)Ta₂O₅−xTiO₂ thin films were formed on Si by metalorganic decomposition (MOD) and annealed at various temperatures. As-deposited films were in the amorphous state and were completely transformed to crystalline after annealing above 600 °C. During crystallization, a thin interfacial SiO₂ layer was formed at the (1−x)Ta₂O₅−xTiO₂/Si interface. Thin films with 0.92Ta₂O₅–0.08TiO₂ composition exhibited superior insulating properties. The measured dielectric constant and dissipation factor at 1 MHz were 9 and 0.015, respectively, for films annealed at 900 °C. The interface trap density was 2.5×10¹¹ cm⁻² eV⁻¹, and flatband voltage was −0.38 V. A charge storage density of 22.8 fC/μm² was obtained at an applied electric field of 3 MV/cm. The leakage current density was lower than 4×10⁻⁹ A/cm² up to an applied electric field of 6 MV/cm.     

Impedance studies on polyacrylonitrile–CuX2–DMSO (X=Cl, Br, CF3SO3) solid polymer electrolyte

A series of polyacrylonitrile–dimethylsulfoxide–CuX₂ (X=CF₃SO₃⁻, Cl⁻, Br⁻), films (foils) were prepared by means of the solution cast technique. The thickness of the foils was between 0.04 and 0.09 cm and they contained 70–80 wt.% of the solvent. Conductivities of the solid electrolytes were obtained from impedance measurements. The conductivity increases with the increase of the salt content up to 8 wt.%; at higher concentrations (>8 wt.%) the conductivity is more or less stable, and reaches, in the case of Cu(CF₃SO₃)₂ and CuCl₂, the level of ca. 10⁻³ Ω⁻¹ cm⁻¹ at room temperature. The foils based on the CuBr₂ show even higher conductivity, close to 10⁻² Ω⁻¹ cm⁻¹ at room temperature, a value comparable to that characteristic for liquid solutions. The temperature variation of the conductivity for all the systems studied is of the Arrhenius type. The activation energy, determined from linear plots lnσ=f(T⁻¹), is of the order ca. 14 kJ mol⁻¹ for the PAN/CuBr₂/DMSO and of ca. 21 kJ mol⁻¹ for the PAN/CuCl₂/DMSO and the PAN/Cu(CF₃SO₃)₂/DMSO systems.     

Theoretical study of HOCl adsorption on ice surface

Adsorption of HOCl on ice surface was studied using the ab initio molecular orbtial theory. We applied Hartree–Fock (HF) self-consistent field and the second-order Møller–Plesset (MP2) level of theory to cluster models of the (0001) surface ice Ih to optimize adsorption structures and binding energies. In all stable binding configurations, HOCl acts as a proton donor in a hydrogen bond. The presence of neighboring water molecules can strengthen the interaction of HOCl with ice. In the HOCl·(H₂O)₄ system, interaction hydrogen bond length is about 1.85 Å, and binding energies are −10.063−11.149 kcal mol⁻¹. We also calculated the vibrational frequencies of HOCl affected by the ice surface.     

Defect versus nanocrystal luminescence emitted from room temperature and hot-implanted SiO2 layers

Silicon nanocrystals have been synthesized in SiO₂ matrix using Si ion implantation. Si ions were implanted into 300-nm-thick SiO₂ films grown on crystalline Si at energies of 30–55 keV, and with doses of 5×10¹⁵, 3×10¹⁶, and 1×10¹⁷ cm⁻². Implanted samples were subsequently annealed in an N₂ ambient at 500–1100°C during various periods. Photoluminescence spectra for the sample implanted with 1×10¹⁷ cm⁻² at 55 keV show that red luminescence (750 nm) related to Si-nanocrystals clearly increases with annealing temperature and time in intensity, and that weak orange luminescence (600 nm) is observed after annealing at low temperatures of 500°C and 800°C. The luminescence around 600 nm becomes very intense when a thin SiO₂ sample is implanted at a substrate temperature of 400°C with an energy of 30 keV and a low dose of 5×10¹⁵ cm⁻². It vanishes after annealing at 800°C for 30 min. We conclude that this luminescence observed around 600 nm is caused by some radiative defects formed in Si-implanted SiO₂.     

Observation of triangular terraces and triangular craters of CaF2 film on Si(1 1 1) substrate

We have investigated the growth mode and surface morphology of CaF₂ film on Si(1 1 1)7×7 substrate by reflection high-energy electron diffraction (RHEED) using very weak electron beam and atomic force microscopy (AFM). It was found by RHEED intensity oscillation measurements and AFM observations that three-dimensional (3D) islands grow at RT; however, rather flat surface appears with two-dimensional (2D) islands around 300 °C. Especially, at high temperature of 700 °C, characteristic equilateral triangular terraces (or islands) with flat and wide shape grow with the tops directed toward [1 1 −2] of substrate Si(1 1 1). On the other hand, the desorption process of the CaF₂ film due to electron stimulated desorption (ESD) was also examined. It was found that the ESD process at 300 °C forms characteristic equilateral triangular craters on the film surface with the tops (or corners) directed toward [−1 −1 2] of substrate Si(1 1 1), provided that the film was grown at 700 °C.     

Thickness-dependent coercivity of ultrathin Co films on a rough substrate: Cu-buffered Si(111)

The hysteresis loops, of Co films with thicknesses ranging from 12- to 80-monolayer-equivalent (MLE) coverages grown by thermal evaporation on a Cu-covered Si(111) surface, were measured in situ by the surface magneto-optic Kerr effect (SMOKE) technique. The hysteresis loops were measured as a function of Co coverage under an external sinusoidal magnetic field at fixed driving frequency. The coercivity H_c of the Co film versus thickness t followed a power law t⁻ⁿ with n=0.4±0.1 between 12 and 44 MLE, and stabilized after 44 MLE, up to the 80 MLE studied. The surface morphology of the 80-MLE Co film was imaged ex situ by atomic force microscopy (AFM) and scanning tunneling microscopy (STM), revealing cauliflower-like islands that were rough both in the short and long range. Analysis of the height–height correlation function for the largest image gave measurements of the effective roughness exponent (0.8), the vertical interface width w(2500 Å), and the lateral correlation length ξ(10 000 Å). We suggest that the coercivity changed in part due to changes in roughness of the Co films, deposited on a rough substrate; the spatial roughness would create an additional surface anisotropy, contributing to a fluctuation in the domain wall energy, resulting in a roughness-dependent coercivity.     

Effects of cation- or oxide ion-defect on conductivities of apatite-type La–Ge–O system ceramics

A series of apatite-type La–Ge–O ceramics were prepared and their cation-defect at the 4f+6h sites and oxide ion-defect at 2a site were investigated. In La_xGe₆O_12+1.5x ceramics of x=6–12, the higher conductivities were obtained in the region of apatite composition, La_x(GeO₄)₆O_1.5x−12 (x=8–9.33), and the highest conductivity was achieved for La₉(GeO₄)₆O_1.5 (x=9), where the number of cation (La³⁺) occupying the 4f+6h sites is 9 and the number of oxide ion occupying the 2a site is 1.5. The ceramics with cation- and oxide ion-defects were La_9−0.66xSr_x(GeO₄)₆O_1.5 (x=0–1), La_9−1.33xZr_x(GeO₄)₆O_1.5 (x=0–1), La_9−xSr_x(GeO₄)₆O_1.5−0.5x (x=0–3), La_9−xZr_x(GeO₄)₆O_1.5+0.5x (x=0–1), La_x(GeO₄)_3x−21(AsO₄)_27−3xO_1.5 (x=0–3), La_x(GeO₄)_33−3x(AlO₄)_3x−27O_1.5 (x=0–3), La₉(GeO₄)_6−x (AlO₄)_xO_1.5−0.5x (x=0–3), La₉(GeO₄)_6−x(AsO₄)_xO_1.5+0.5x (x=0–1), La_9.33−xSr_x(GeO₄)₆O_2−0.5x (x=0–1.2) and La_x(GeO₄)_4.5(AlO₄)_1.5O_1.5x−12.75 (x=8.8–9.83), which were prepared by the partial substitution of La³⁺and GeO₄⁴⁻of the basic apatite La₉(GeO₄)₆O_1.5 with Sr²⁺ or Zr⁴⁺ and AlO₄⁵⁻ or AsO₄³⁻. Such substitutions lowered the conductivity of La₉(GeO₄)₆O_1.5. These results were discussed by the electrostatic interaction between Sr²⁺, Zr⁴⁺, AlO₄⁵⁻ or AsO₄³⁻ and oxide ion as a conductive species.     

The S-wave pion–nucleon scattering lengths from pionic atoms using effective field theory

The pion–deuteron scattering length is computed to next-to-next-to-leading order in baryon chiral perturbation theory. A modified power-counting is then formulated which properly accounts for infrared enhancements engendered by the large size of the deuteron, as compared to the pion Compton wavelength. We use the precise experimental value of the real part of the pion–deuteron scattering length determined from the decay of pionic deuterium, together with constraints on pion–nucleon scattering lengths from the decay of pionic hydrogen, to extract the isovector and isoscalar S-wave pion–nucleon scattering lengths, a⁻ and a⁺, respectively. We find a⁻=[0.0936(±0.0011)]M_π⁻¹ and a⁺=[−0.0029(±0.0009)]M_π⁻¹.     

NIR-FT-SERS of 4″-trimethylsilylethylsulfanyl-4,4′-di(phenyleneethynylene)benzenethiol on Au nanospheres

Oligo(phenyleneethynylene) (OPE) compounds have been identified as promising molecular electronic bridges. Self-assembled monolayers of 4″-trimethylsilylethylsulfanyl-4,4′-phenyleneethynylenebenzene thiol (OPE′) on Au were characterized by surface-enhanced Raman scattering (SERS). The FT-Raman spectrum of OPE′ shows three C–S bands at 834, 1086, and 1131 cm⁻¹. From the FT-Raman to the SERS spectra, the 1086 cm⁻¹ band exhibits a 9 cm⁻¹ red shift. Chemisorption of OPE′ to the gold surface occurs via oxidative cleavage of the disulfide bond and the formation of the Au–S bond. The Au–S vibration is visible in the SERS spectra at 257 cm⁻¹. Peaks due to the S–S and S–H stretch are observed at 544 and 2519 cm⁻¹, respectively, in the FT spectrum, but are unobserved in the surface-enhanced spectra. The C–H stretching region (2700–3350 cm⁻¹) in the spectrum of neat OPE′ shows three distinct bands, whereas the SERS spectra show a single broad band. Assignments of vibrational bands were based on DFT calculations performed at the B3LYP level with good agreement between theoretical and experimental values. An average percent difference of 2.52 was obtained for the non-CH stretching frequencies.     

One- and two-dimensional solid-state magic angle spinning NMR studies on the hydration process of layered sodium disilicate SKS-6

Three different kinds of silanols, which include isolated silanol, silanol I (with the hydroxyl proton bonded to an oxygen atom in the adjacent layer) and silanol II (with the hydroxyl proton bonded to the non-bridging oxygen at the same silicon atom), are generated during the hydration process of SKS-6 (δ-Na₂Si₂O₅). ¹H–¹H nuclear Overhauser enhancement spectroscopy reveals that the proton of silanol I has an effective chemical exchange or spin diffusion with the proton of hydrogen-bonded water, while the proton of silanol II is likely far away from the other proton-containing species. ²⁹Si magic angle spinning, ¹H→²⁹Si CP/MAS NMR and ¹H–²⁹Si phase-modulated Lee–Goldburg decoupled correlation experiments demonstrate that the local environments of the silicon sites in the final hydrated sample are mainly composed of Q² [(SiO)₂Si(OH)O⁻Na⁺], Q³ [(SiO)₃Si(OH) and (SiO)₃SiO⁻Na⁺] and Q⁴ [Si(OSi)₄] groups.     

Effect of annealing temperature on the structural and electrical properties of SrBi2Ta2O9 thin films for memory-based applications

Ferroelectric SrBi₂Ta₂O₉ (SBT) thin films were grown on p-type (1 0 0) Si substrates by radio frequency sputtering technique. The crystallinity of the films was studied using grazing incidence X-ray diffraction pattern. The spectra showed the films were polycrystalline with dominant orientation along (1 1 5) plane. The surface morphology was investigated by atomic force microscope. The chemical composition was studied by Rutherford back-scattering, which yielded a near stoichiometric composition of SBT. The capacitance–voltage characteristics of Al/SBT/Si capacitors measured at 100 kHz showed a hysteresis nature with a clockwise rotation and the memory window of the hysteresis loop was 0.88 V with the gate voltage ±5 V. The interface trap density was calculated by using Hills method at room temperature and a value in the order of 10¹¹–10¹² eV⁻¹ cm⁻² was found depending on the crystallization temperature at midgap region.     

Study of the ferroelectric–paraelectric phase transition of NaH3(SeO3)2 single crystals by H and Na NMR

The ¹H and ²³Na spin–lattice and spin–spin relaxation times of NaH₃(SeO₃)₂ single crystals grown using the slow-evaporation method were measured as functions of temperature and frequency in the ferroelectric and paraelectric phases. The changes in the symmetry of the (SeO₃)²⁻ dimers as a result of the ferroelectric–paraelectric phase transition are associated with large changes in the spin–lattice and spin–spin relaxation times, and in the number of resonance lines. The large changes in the relaxation times at 195 K indicate that the H and Na ions are significantly affected by this transition. The change in the number of resonance lines for the ¹H and ²³Na nuclei means that the orientations of the (SeO₃)²⁻ dimers and the environments of the Na ions change at T_C. Therefore, the orientations of the (SeO₃)²⁻ dimers and the environments of the Na ions play important roles in the phase transitions. In conclusion, the ferroelectric–paraelectric phase transition of NaH₃(SeO₃)₂ is accompanied by changes in hydrogen-bond structure and distortions of the (SeO₃)²⁻ and Na⁺ ion lattices, which form a slightly distorted octahedron.     

Crystal growth and characterisation of new organic nonlinear optical materials: 6-cyano and 6-nitro-2,2-dimethyl-3,4-epoxychroman

Two chiral organic nonlinear optical materials, (3S,4S)-(−)-6-cyano-2,2-dimethyl-3,4-epoxychroman (1) and (3R,4R)-(+)-6-nitro-2,2-dimethyl-3,4-epoxychroman (2), have been grown into single crystals of cm³-size. Although both compounds crystallise in the orthorhombic P2₁2₁2₁ space group, they are not isomorphous and their crystal packings are quite different. Angle tuned type II phase-matched second harmonic generation between 0.8 and 1.064 μm has been evidenced, with effective nonlinear coefficients d_eff of 1 and 5 pm/V at 0.96 μm for 1 and 2, respectively. These values are in agreement with those estimated in the oriented gas model approximation using EFISH first order hyperpolarisability values (β₀=2.6 and 4.0×10⁻³⁰ esu for 1 and 2, respectively).     

Coverage dependent promoter action: K coadsorption and reactions with CO and CO2 on Pd{1 1 0}

The adsorption of CO and CO₂ on K-predosed Pd{1 1 0} at room temperature has been examined via reflection–absorption infrared spectroscopy (RAIRS). CO₂ adsorbs on 0.37 ML K-predosed Pd{1 1 0} with high sticking probability and a reactive chemisorbed intermediate, CO₂⁻, is detected in RAIRS at room temperature. Reaction of this species ultimately yields carbonate. The same high K precoverage induces dissociation of CO at low CO exposure. Carbonate is detected at higher CO exposure and is probably produced via stepwise oxidation of molecularly adsorbed CO. In contrast at low K precoverage (0.11 ML), CO remains intact but the C–O bond is considerably weakened with respect to CO chemisorbed on clean Pd{1 1 0}. These findings illustrate a dual promoter mechanism of K in the adsorption and reaction of CO or CO₂ at high K coverage. The alkali metal induces dissociation of these molecules and directly participates in the formation of a surface compound, K₂CO₃.