Tetrairon Ethanedithiolate Complex with Intermolecularly Bridging bis(diphenylphosphino)acetylene

In this article, a tetrairon ethanedithiolate complex [(µ-SCH₂CH₂S-µ)Fe₂(CO)₅]₂(Ph₂PC≡CPPh₂) was reported. The title complex could be easily prepared by ligand exchange reaction of the starting material (µ-SCH₂CH₂S-µ)Fe₂(CO)₆ with Ph₂PC≡CPPh₂ and Me₃NO·2H₂O in CH₂Cl₂/MeCN solutions at ambient temperature. The title complex was new and structurally characterized by NMR spectroscopy and X-ray diffraction analysis. Its molecular structure reveals that it consists of two butterfly diiron ethanedithiolate units linked together through Ph₂PC≡CPPh₂. In addition, intermolecular C-H…O hydrogen bonds and π-π stacking interactions stabilize the solid state in the crystal packing diagram.     

Development of Personal UV Biodosimeter Based on Vitamin D Photosynthesis

Abstract

A new approach to monitoring of vitamin D synthetic capacity of UV solar/artificial radiation is described. Nematic liquid crystal (LC) was converted into cholesteric phase by chiral dopant of 7-dehydrocholesterol (provitamin D₃), and the effects of UV irradiation were studied using spectral and polarized observations. Significant changes in optical characteristics of the LC films depending on UV exposure were observed as a result of UV initiated photoisomerization that changed helical twisting power of dopant molecules.     

Effects of the Substrate Crystals upon the Structure of Thermal Oxide Layers on Si

Comparisons of Bragg reflections from thermal oxide thin films on Si wafers were made for five sets of samples with various kinds of substrates. The intensities of the reflections for the samples with the substrate of better quality were stronger than those of poor one, indicating that the structures of the crystalline SiO₂ in the oxide layer were related with the quality of the Si substrates. It is also shown that no diffraction peaks were observed from the oxide layers grown on Si substrates by chemical vapor deposition.     

An X-ray Study of KBrxI1−x Mixed Crystals

KBr_xI_1−x mixed crystals have been prepared by melting and their X-ray patterns have been recorded with a powder diffractometer. From measurements of the Bragg reflections, the lattice constants, grain size, lattice straian and mean Deby-Waller factor have been determined. In the composition region × < 0.2 and × > 0.7, the lattice constant follows Vegard's law. However, in the region 0.2 < × < 0.7 where a miscibility gap has been reported, single phase mixed crystals are formed but the lattice constants have values larger than those expected from Vegard's law, indicating a strained lattice. The lattice strain directly determined from the half-widths of the Bragg reflections also shows larger values in the same composition region. The mean Debye-Waller factor shows a decrease with the degree of mixing, assuming a minimum value in the equimolar region.     

Photocatalytic properties of TiO2/ZnO thin film

ABSTRACT

TiO₂, ZnO and ZnO/TiO₂ thin films have been prepared by radio frequency magnetron sputtering method under different temperatures. Their photo catalytic activities have been investigated. The structural of the thin films were characterized by X-ray diffraction and Raman spectroscopy. The photo catalytic activities of TiO₂ and ZnO/TiO₂ samples were evaluated by the photo decomposition of methylene blue. We note that the structural proprieties of the thin films showed a perfect crystallization along the (002) for ZnO, Rutile (110) for TiO₂ and Anatase (101) for TiO₂. The experimental results show that the bilayer ZnO/TiO₂ were the most efficient photo catalysts compared to the layer of TiO₂. This increased catalytic effect can attributed to the interface between the ZnO layer and the TiO₂ one, which modify significantly the chemical potential of the bilayer.     

Development of multifunctional photoactive self-cleaning glasses

Glasses for architecture must have many functions in addition to their transparency. For example, the glasses with the functions, of self-cleaning, light control, UV reduction, anti-bacterial, energy conversion, and so on, will be used in buildings in the near future. This paper reviews some results on multifunctional photoactive glasses based on multi-layer coatings containing TiO₂ film and other functional coatings developed by us recently. The self-cleaning of glasses can be realized by coating the photoinduced super-hydrophilic nanoporous thin films based on TiO₂ photocatalysts via sol–gel route. A new method to enhance the photocatalytic activity of TiO₂ thin films direct coated on soda-lime glass was developed by treating the films in acidic solutions. The films also have good photoinduced anti-bacterial properties. The doping of a small amount of silver into the TiO₂ porous film can enhance its anti-bacteria effect without UV light irradiation. The TiO₂ thin films by appropriate heat-treatment can operate as self-cleaning glass in the visible light region. The UV reduction self-cleaning glasses are prepared by magnetron sputtering two layers of TiO₂–CeO₂ and TiO₂ thin films on soda-lime glasses. The TiO₂–CeO₂ thin films can cut all of UV light through adjusting the ratio of TiO₂ and CeO₂. The TiO₂/TiN/TiO₂ type multi-layer coated on glass substrate can act as low-E self-cleaning glass. The potential water-repellent coating based on TiO₂ is discussed finally.     

Effect of N2/CH4 flow ratio on microstructure and composition of hydrogenated carbon nitride films prepared by a dual DC-RF plasma system

Hydrogenated carbon nitride (a-CN:H) films were deposited on n-type (1 0 0) silicon substrates making use of direct current radio frequency plasma enhanced chemical vapor deposition (DC-RF-PECVD), using a gas mixture of CH₄ and N₂ as the source gas in range of N₂/CH₄ flow ratio from 1/3 to 3/1 (sccm). The deposition rate, composition and bonding structure of the a-CN:H films were characterized by means of X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared spectrometry (FTIR). The mechanical properties of the deposited films were evaluated using nano-indentation test. It was found that the parameter for the DC-RF-PECVD process had significant effects on the growth rate, structure and properties of the deposited films. The deposition rate of the films decreased clearly, while the N/C ratio in the films increased with increasing N₂/CH₄ flow ratio. CN radicals were remarkably formed in the deposited films at different N₂/CH₄ flow ratio, and their contents are related to the nitrogen concentrations in the deposited films. Moreover, the hardness and Young’s modulus of the a-CN:H films sharply increased at first with increasing N₂/CH₄ flow ratio, then dramatically decreased with further increase of the N₂/CH₄ flow ratio, and the a-CN:H film deposited at 1/1 had the maximum hardness and Young’s modulus. In addition, the structural transformation from sp³-like to sp²-like carbon-nitrogen network in the deposited films also was revealed.     

Discovery of difference in the diffuse scattering from nonstoichiometric Ca0.87La0.13F2.13 and Ca0.92Er0.08F2.08 crystals with different types of clusters of structural defects

A new approach to application of diffuse scattering (DS) for studying the defect structure of crystals on laboratory radiation sources is implemented. The basic principles of this approach are as follows: (i) choice of crystals with a high concentration of structural defects (highly nonstoichiometric Ca_{1 ? x} R _x F_{2 + x} phases), (ii) application of intermeasurement minimization method (experimental comparison) to select a weak desired DS signal from a superposition of signals of different nature, and (iii) choice of the basic model proceeding from the reliable information provided by accurate analysis of the contribution of structural defects to Bragg reflections. Significantly different DS diffraction patterns have been recorded for Ca_0.87La_0.13F_2.13 and Ca_0.92Er_0.08F_2.08 crystals, characterized by different types of structural-defect clusters, determined from the Bragg diffraction data. Experiments performed at 90–100 K proved that DS is caused by clusters with stable atomic configurations rather than cooperative thermal atomic vibrations. A set of methods is proposed which can efficiently be used in diagnostics of nanomaterials.     

Studies on a possible growth mechanism of silver nanoparticles loaded on TiO2 thin films by photoinduced deposition method

The TiO₂ thin films loaded with silver nanoparticles were prepared on soda-lime glass substrates by a photoinduced deposition method. The TiO₂ films immersed in AgNO₃ solution were vertically irradiated by UV light with center wavelength of 365 nm for 60 h. The as-produced films were characterized by X-ray diffraction (XRD), UV–Vis spectroscopy, X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The studies show that the film after UV excitation is composed of anatase phase TiO₂ and metallic silver with face centered cubic structure. A possible growth mechanism of silver nanoparticles on TiO₂ thin films under UV irradiation was proposed. The charge carriers of TiO₂ semiconductor are generated by photoexcitation. Owing to the conduction band position of TiO₂ which is above the standard potential of Ag⁺/Ag, the generated electrons could transfer from the conduction band to Ag⁺ adsorbed on the surface of the TiO₂ films. Therefore, the Ag⁺ was finally reduced into a Ag atom, which could preferentially localize in the grain boundaries of TiO₂ particles due to high surface free energy there. With the irradiation time extended, silver nanoparticles were shaped into certain morphologies on the surface of the TiO₂ films.     

Zr(IV) and Hf(IV) β-diketonate complexes as precursors for the photochemical deposition of ZrO2 and HfO2 thin films

In this paper amorphous ZrO₂ and HfO₂ thin films were obtained by direct UV irradiation of Zr(IV) and Hf(IV) β-diketonate precursor complexes on Si(1 0 0) and fused silica substrates. The precursors, Zr(CH₃COCHCOCH₃)₄ and Hf(C₆H₅COCHCOCH₃)₄ were deposited as amorphous thin films by spin coating. The photochemistry of these films was monitored by FT-IR spectroscopy. The photolysis with 254 nm light led to the loss of the ligands from the coordination complexes, and the production of metallic oxides. The thin films products were characterized by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). These analyses revealed that as-deposited films are amorphous and that the presence of carbon is thought to arise from the ligands. However, post-annealing of the photodeposited films favors the stoichiometric and optical properties of ZrO₂ and HfO₂ thin films.     

On the anharmonic vibrations in crystalline silicon

Using a total of 1052 Bragg reflections of silicon, an X-ray investigation has been carried out to deduce the anharmonic thermal parameter β, apart from the estimation of the harmonic contribution of the thermal vibration at room temperature. Reflections of type h + k + l = 4n, and 4n ± 1 were used to estimate these parameters using MoK α radiation and a Nonius CAD-4 X-ray diffractometer. We obtain B_si, = 0.451(0.008) Ų and β_si = 0.279(2.630) eV Å⁻³ with R = 3.12%. The present B and β values are in very good agreement with the earlier studies.     

Influence of silver concentration in Agx(Sb0.33S0.67)100−x thin amorphous films on photoinduced crystallization

One of the recent applications of thin chalcogenide films is in rewritable optical data recording. This technology is based on reversible phase transition between crystalline and amorphous state. Currently, the primary materials for rewritable optical are Ge–Sb–Te and Ag–In–Sb–Te alloys, but materials research still continues due to the need for increased storage capacity and data recording rates. (Ag)–Sb–S thin films were prepared by thermal evaporation of Sb₃₃S₆₇ bulk and optically induced diffusion and dissolution of thermally evaporated Ag films. Prepared samples were characterized by electron microprobe (SEM-EDX), differential scanning calorimetry (DSC) and by UV–Vis–NIR and Raman spectroscopy. The phase-change recording processes in (Ag)–Sb–S films were carried out by photocrystallization experiments done by Ar⁺ ion laser. The laser exposed dots were studied by scanning electron microscopy (SEM) and transmission optical microscopy. Micro X-ray diffraction (μ-XRD) was used for the exposed dots crystallinity study. Photocrystallization kinetic curves (showing the dependence of optical transmission on laser exposure time) were also established. Crystallization mechanism of Ag_x(Sb_0.33S_0.67)_100−x samples was discussed.     

Electric‐field‐induced internal deformation in piezoelectric BiB3O6 crystals

For the first time electric‐field‐induced atomic displacements (internal strains) in non‐ferroelectric polar BiB₃O₆ single crystal plates (point symmetry 2) were investigated using X‐ray diffraction technique. The intensity variations of selected Bragg reflections were collected for three different orientations of the applied external electric field vector with respect to the crystal lattice and used for calculating the microscopic structural response of BiB₃O₆. Due to the limited number of the reflections providing measurable changes in Bragg intensities we restricted ourselves in analyzing the shift of the B₃O₆ sublattice relative to the Bi one. In addition, we considered the deformation of the Bi‐O, B(1)‐O and B(2)‐O bond lengths and identified the [B(2)O₃] group as the most sensitive structural unit to an external electric perturbation. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Spray pyrolysis deposition and characterization of highly (100) oriented magnesium oxide thin films

Transparent dielectric thin films of MgO has been deposited on quartz substrates at different temperatures between 400 and 600°C by a pneumatic spray pyrolysis technique using Mg(CH₃COO)₂·4H₂O as a single molecular precursor. The thermal behavior of the precursor magnesium acetate is described in the results of thermogravimetry analysis (TGA) and differential thermal analysis (DTA). The prepared films are reproducible, adherent to the substrate, pinhole free and uniform. Amongst the different spray process parameters, the substrate temperature effect has been optimized for obtaining single crystalline and transparent MgO thin films. The films crystallize in a cubic structure and X‐ray diffraction measurements have shown that the polycrystalline MgO films prepared at 500°C with (100) and (110) orientations are changed to (100) preferred orientation at 600°C. The MgO phase formation was also confirmed with the recorded Fourier Transform Infrared (FTIR) results. The films deposited at 600°C exhibited highest optical transmittivity (>80%) and the direct band gap energy was found to vary from 4.50 to 5.25 eV with a rise in substrate temperature from 500 to 600°C. The measured sheet resistance and the resistivity of the film prepared at 600°C were respectively 10¹³Ω/□ and 2.06x10⁷Ω cm. The surface morphology of the prepared MgO thin films was examined by atomic force microscopy. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Photoluminescence and radiation damage in W,Mg, Ca doped Bi4Ge3O12 crystals

Spectral properties and radiation damage in W, Mg and Ca doped Bi₄Ge₃O₁₂ (W:BGO, Mg:BGO, Ca:BGO) crystals before and after thermal treatment and gamma‐ray (γ‐) or ultraviolet (UV) radiation were studied. The absorption and the photoluminescence (PL) spectra of doped BGO crystals in visible region were measured. Before γ or UV radiation, the emission intensity of W:BGO crystal is stronger than that of pure BGO at about 500 nm. After γ radiation (10k Gy), the emission intensities of doped BGO are all weaker than pure BGO under identically condition. However, the emission intensity of W:BGO is stronger than that of pure BGO after UV exposure (10k Gy). Thermal treated (annealed in N₂ at 550 °C for 6 h) W:BGO has shown a much stronger emission intensity than others. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of pressure on photo-induced expansion of As0.2Se0.8 layer

The effect of hydrostatic pressure on photo-induced surface expansion in As_0.2Se_0.8 thin films has been studied in the pressure range of 0–0.5 GPa. The development of the surface relief was investigated at different intensities and exposure of laser irradiation. We have observed that the applied pressure suppressed the rate of the surface relief formation, therefore the pressure dependent components of the structural transformations in glasses should be included to the model of this phenomenon.     

Refinement of the atomic structure of specimens cut out from different growth pyramids of a K(H0.052D0.948)2 PO4 single crystal

The structures of two crystalline specimens cut out from the pyramidal and prismatic growth sectors of a K(H_0.052D_0.948)₂PO₄ single crystal have been studied by diffuse neutron scattering and precision diffuse X-ray scattering. Diffuse scattering is concentrated in the vicinity of the Bragg reflections and is practically the same in specimens cut out from different growth sectors of a single crystal. X-ray diffraction analysis using the extinction parameters provided the establishment of a higher perfection of the specimen cut out from the prismatic growth sector. The precision X-ray studies revealed different configurations of hydrogen bonds in the specimens.     

Low temperature polycrystalline silicon film formation by metal induced crystallization with nickel salt derived by ultrasonic spray pyrolysis

Solution‐based nickel induced crystallization of amorphous silicon (a‐Si) films was performed. The nickel solution was prepared by dissolving (CH₃CO₂)₂Ni in deionized water and applied uniformly on a‐Si films by low‐cost ultrasonic spray pyrolysis method. Crystallization could be realized for a‐Si films coated with a 0.2 M nickel solution and annealed at 500 °C. The effect of substrate temperature during nickel solution deposition was analyzed. Micro‐Raman and x‐ray diffraction measurement show that a‐Si is fully crystallized at 550 °C for 7 h with a nickel concentration of 0.8 M. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal structure of tetramethylammoniuml-histidinatobis (thiocyanato) vanadyl (IV) monohydrate

The title compound, [(CH₃)₄N] [VO(l-His)(NCS)₂]·H₂O, has been prepared by the reaction of [(CH₃)₄N]₄[VO(NCS)₄]₂·H₂O with histidine in aqueous solution. The crystal is orthorhombic, space groupP2₁2₁2₁ witha=9.839(6),b=11.835(5),c=17.366(6) Å,Z=4. The structure was solved by direct methods and refined by full-matrix least-squares to anR of 0.073 for 1067 reflections. In the complex anion VO²⁺ was coordinated by two thiocyanate groups and al-histidine which functions as a tridentate chelate.