K2(Rb2,Cs2,Tl2)TeBr6(I6) and Rb3(Cs3)Sb2(Bi2)Br9(I9) perovskite compounds

We systematize available experimental data on the crystal structure of the ternary halides K₂(Rb₂,Cs₂,Tl₂)TeBr₆(I₆) and Rb₃(Cs₃)Sb₂(Bi₂)Br₉(I₉), analyze the general trends in the properties of their single crystals, and examine the key features of the physicochemical interaction in related systems.     

Al2O3/SiO2 and HfO2/SiO2 dichroic mirrors for UV solid-state lasers

HfO₂/SiO₂ and Al₂O₃/SiO₂ multilayers to be employed as high reflectance end mirrors in Cerium-doped fluoride solid-state lasers were produced by radio frequency sputtering. The components were designed to have high transmittance at the pumping wavelength and high reflectance in a wavelength band corresponding to the active medium emission. A photoacoustic beam deflection technique and inspection of the irradiated area under a microscope were used to measure the laser induced damage threshold of the mirrors at the pumping wavelength. These coatings were tested in a laser cavity.     

Natural and persistent superhydrophilicity of SiO2/TiO2 and TiO2/SiO2 bi-layer films

Sol-gel SiO₂/TiO₂ and TiO₂/SiO₂ bi-layer films have been deposited from a polymeric SiO₂ solution and either a polymeric TiO₂ mother solution (MS) or a derived TiO₂ crystalline suspension (CS). The chemical and structural properties of MS and CS bi-layer films heat-treated at 500 °C have been investigated by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and transmission electron microscospy. Water contact angle measurements show that MS SiO₂/TiO₂ and CS TiO₂/SiO₂ bi-layer films exhibit a natural superhydrophilicity, but cannot maintain a zero contact angle for a long time over film aging. In contrast, CS SiO₂/TiO₂ bi-layer films exhibit a natural, persistent, and regenerable superhydrophilicity without the need of UV light. Superhydrophilic properties of bi-layer films are discussed with respect to the nature of the TiO₂ single-layer component and arrangement of the bi-layer structure, i.e. TiO₂ underlayer or overlayer.     

Crystal Structure of (H3O)2[(UO2)2(SeO4)3(H2O)2](H2O)3.5

Crystals of (H₃O)₂[(UO₂)₂(SeO₄)₃(H₂O)₂](H₂O)_3.5 were prepared from aqueous solutions by evaporation. The crystal structure [monoclinic system, space group P2₁/m, a = 11.9402(11), b = 13.6452(14), c = 13.7271(12) Å, β = 109.436(7)°, V = 2109.1(3) ų] was solved by the direct method and refined to R ₁ = 0. 048 (wR ₂ = 0. 082) for 3677 reflections with |F _hkl |F _hkl |. The structure consists of [(UO₂)₂(SeO₄)₃(H₂O)₂]₂₋ layers arranged parallel to the (010) plane. The layers are formed by uranium and selenium coordination polyhedra sharing common vertices and are linked with each other by hydrogen bonds through the H₂O and H₃O⁺ groups arranged between the layers. __________ Translated from Radiokhimiya, Vol. 47, No. 5, 2005, pp. 412–414. Original Russian Text Copyright ? 2005 by Krivovichev, Kahlenberg.     

The role of TiO2 and ZrO2 in Na2OMO2SiO2 glasses

The glass transition temperatures of $\text{(1?x)}\text{Na}{}_2\text{O}\text{·}\text{1}\text{2}\text{x}\text{MO}{}_2\text{·2}\text{SiO}{}_2$ and Na₂O·xMO₂·(2 ?x)SiO₂ glasses, with M = Ti or Zr, have been related to the structural role and coordination of Ti and Zr. The role of network-former, intermediate or modifier of a cation has been fundamentally linked to ionic field strength; T_g values depend on ionic field strength and coordination. Titanium behaves like an intermediate oxide; its coordination ranges between four and six, depending on $\text{Ti}\text{Si}$ ratio. The role of zirconium changes according to the degree of substitution for Na or Si and progressively approaches that of a modifier ion.     

Syntheses and structures of Ta2(WO2)0.87H0.26(PO4)4 and Ta2(MoO2)(PO4)4

Tantalum hydrogen phosphate, β-TaH(PO₄)₂, has a three-dimensional structure that is stable to remarkably high temperature (∼600 °C) presumably due to the presence of strong hydrogen bonds. Impedance measurements indicate a low conductivity, 2.0 × 10⁻⁶ S/cm at 200 °C in 5% H₂. In further studies aimed at enhancing the conductivity by aliovalent doping, we have investigated systematically the synthesis of compounds in the TaH(PO₄)₂-W₂P₂O₁₁ system at 380 °C. As a result, a new phase, Ta₂(WO₂)_0.87H_0.26(PO₄)₄, was identified and subsequently the molybdenum analog Ta₂(MoO₂)(PO₄)₄ was also prepared. The structures were determined by single crystal X-ray diffraction techniques. The structures of Ta₂(WO₂)_0.87H_0.26(PO₄)₄ and Ta₂(MoO₂)(PO₄)₄ can be formally derived from the structure of β-TaH(PO₄)₂ by the replacement of two P-OH protons with an MO₂²⁺ (M = Mo and W) group together with a change in the orientation of some phosphate tetrahedra.     

超临界流体干燥法制备TiO2/ Fe2O3 和TiO2/ Fe2O3/ SiO2 复合纳米粒子及光催化性能

以TiCl₄ 、Fe (NO₃ )₃·9H₂O 和Na₂SiO₃19H₂O 为原料, 采用溶胶凝胶法结合超临界流体干燥法(SCFD)制备了纳米级TiO₂/ Fe₂O₃ 和TiO₂/ Fe₂O₃/ SiO₂ 复合光催化剂。以光催化降解苯酚对所得催化剂的催化活性进行了评价。结果表明, 纳米TiO₂/ Fe₂O₃ 复合粒子与单组分TiO₂ 比较, 复合粒子光催化活性高于单组分的TiO₂, 6h 苯酚降解率高达95.9 %。SiO₂ 的加入可以抑制纳米粒子粒径的长大和晶相的转变, 增强TiO₂ 纳米粒子的热稳定性。复合光催化剂中Fe₂O₃ 最佳掺入量为0.06 %, SiO₂ 最佳掺入量为10 %(摩尔分数) 。并用XRD、TEM 和FTIR 等手段进行了表征。TiO₂ 以锐钛矿型形式存在, SiO₂ 以无定性形式存在。比较了不同制备方法制得的TiO₂/ Fe₂O₃ 复合光催化剂, 得出超临界干燥法制备的光催化剂具有粒径小、比表面积大、分散性好、光催化活性高等特点。采用超临界流体干燥可直接得锐钛型纳米复合光催化剂。     

Hydrothermal Crystallization in the Systems La2(CO3)3 ? 6H2O-CaCO3(BaCO3)-R-H2O (R = Na2CO3, K2CO3, NaHCO3, KHCO3, NaCl, NH4Cl, CO(NH2)2)

Crystallization in the systems La₂(CO₃)₃ ⋅ 6H₂O-CaCO₃(BaCO₃)-R-H₂O (R = Na₂CO₃, K₂CO₃, NaHCO₃, KHCO₃, NaCl, NH₄Cl, CO(NH₂)₂) was studied under hydrothermal conditions (400–450°C). The solid reaction products were found to contain LaOHCO₃ and NaLa(CO₃)₂. Detailed thermal decomposition schemes were proposed for these phases, and their lattice parameters were refined. __________ Translated from Neorganicheskie Materialy, Vol. 41, No. 11, 2005, pp. 1366–1372. Original Russian Text Copyright ? 2005 by Nikol'skaya, Dem'yanets.     

Microstructure control for sputter-deposited ZrO2, ZrO2·CaO and ZrO2·Y2O3

The microstructure of pure and oxide-stabilized cubic ZrO₂ has been determined as a function of the principal deposition conditions for coatings prepared by r.f. diode reactive sputtering. Broad control of crystal structure, phase composition, grain size and crystallographic orientation is obtained by appropriate selection of the target composition, substrate bias and substrate temperature. The crystal structure and phase composition obtained for coatings are compared with predictions based on the equilibrium phase diagrams. The microstructural control demonstrated in this work should make possible rapid, efficient and systematic optimization of ZrO₂ coatings for future engineering applications.     

Reactivity of the H2O2/TiO2 system

The reactivity of the H₂O₂/TiO₂ system for samples treated at atmospheric pressure is studied by means of Auger Electron Spectroscopy. The most significant changes on the TiO₂ ‘final’ state are: (i) The I(O)/I(Ti) peak-to-peak ratio is diminished by 15%. (ii) The LMV transition suffers an energy shift of +2 eV, whereas the peak-to-peak width diminishes 1.5 eV. (iii) Its structure changes with respect to that of the TiO₂ ‘initial’ state although it is not identified with any one of the known stoichiometric oxides. (iv) When the samples that represent the ‘final’ state are heated up to 650 K, the AES spectrum matches quite well that of the TiO₂ ‘initial’ state.     

Investigation on solar photocatalytic activity of TiO2 loaded composite: TiO2/Eggshell, TiO2/Clamshell and TiO2/CaCO3

The TiO₂/Eggshell, TiO₂/Clamshell and TiO₂/CaCO₃ loaded composites were prepared by sol-gel method and characterized by XRD and SEM. Their photocatalytic activities were measured through the degradation of Acid Red B under solar light irradiation. The influences of TiO₂ loaded content, heat-treated temperature and time on the photocatalytic activities were reviewed. The effects of irradiation time and dye initial concentration on the photocatalytic degradation were also investigated. The results showed that the photocatalytic activity can be greatly enhanced by appropriate TiO₂ loaded content.     

Homogene,abschreckbare hochdruckphasen in den systemen AgSbSe2 - AgInSe2 und AgBiSe2 - AgInSe2

Quenchable, homogenous high pressure phases in the systems AgSbSe₂ - AgInSe₂ and AgBiSe₂ - AgInSe₂ could be synthesized from appropriate mixtures of the ternary compounds in a belt-type high-pressure apparatus. The phases AgSb_1?xIn_xSe₂ crystallize with the rocksalt structure at the Sb-rich side and with the α-NaFeO₂ structure at the In-rich side of the phase diagram. All AgBi_1?xIn_xSe₂ samples have α-NaFeO₂-structure. The high temperature B1-type modification of AgBiSe₂ is quenchable to room temperature at high pressures. Annealing of the high pressure phases at 1 bar and 300°C yielded the starting mixtures of AgInSe₂ with chalcopyrite structure and AgSbSe₂ or AgBiSe₂, rsp. At 1 bar, 25°C the high pressure phases could be stored for at least 8 months.     

Flux growth of single magnetic sublattice antiferromagnetic garnets Ca3 Fe2 Ge3 O12 and Ca3 Mn2 Ge3 O12

Magnetic single crystals garnets Ca₃ X₂ Ge₃ O₁₂ with X = Mn³⁺ or Fe³⁺ containing Ca²⁺ and Ge⁴⁺ are of great interest due to the rise of an antifer-romagnetic order in one definite octahedral site. The optimal conditions for obtaining single magnetic-sublattice garnets of large size (1 cm in diameter) have been analyzed. Two groups of solvents have been tested: Bi₂ O₃ or PbO based flux. The best results were obtained with PbO flux and starting composition : % Moles 44 PbO 1b 35 GeO₂ 1b 15 CaO 1b 6 X₂ O₃.     

Comparison of the Electronic Structures of La2CuO4, Sr2CuO2Cl2, and Sr2CuO2F2

First-principles cluster calculations are reported of the local electronic structure of the three compounds: La₂CuO₄, Sr₂CuO₂Cl₂, and Sr₂CuO₂F₂. The copper and the planar oxygen 2p atomic orbitals exhibit a similar degree of covalency. The out-of-plane orbitals, however, are quite different with the atomic orbital lowered significantly in energy for chlorine and fluorine apical positions.     

纳米-Al2O3/SiO2加入量对MgO-Al2O3-SiO2复相陶瓷烧结机理的影响

为了探究纳米-Al₂O₃/SiO₂加入量对MgO-Al₂O₃-SiO₂复相陶瓷烧结行为的作用机理。以微米级MgO、纳米级Al₂O₃和SiO₂为主要原料制备陶瓷基复合材料。通过XRD和 SEM等检测手段对烧后试样的物相组成和微观结构进行测试与表征,重点研究Al₂O₃/SiO₂的加入对复相陶瓷物相组成、微观结构及烧结性能的影响。结果表明:随着Al₂O₃/SiO₂加入量的增大,试样烧后相对密度和烧后线变化率呈先增大后减小再增大的趋势,加入15%Al₂O₃/SiO₂(质量分数)的试样经1 500 ℃烧结后,其相对密度可以达到94%。引入的Al₂O₃/SiO₂与基体中的MgO生成镁铝尖晶石与镁橄榄石相,原位反应伴随的体积膨胀,抵消部分烧结过程中的体积收缩。Al₂O₃/SiO₂加入量为75%(质量分数)的试样经1 400 ℃烧结后,基体中有大量堇青石相生成,随着煅烧温度提高到1 500 ℃,堇青石分解所产生的高温液相促进了试样的烧结收缩。     

Effect of doping with Co2O3, TiO2, Fe2O3, and Mn2O3 on the properties of Ce0.8Gd0.2O2?δ

The effects of Co, Fe, Mn, and Ti oxide additions on the sinterability and crystal-chemical, thermal, and electrical properties of Ce_0.8Gd_0.2O_2−δ have been studied. The results indicate that these oxides enhance the sinterability of the mixed oxide, regardless of whether they were introduced before or after synthesis. The most effective sintering aid is Co₂O₃. The lattice parameters of Ce_0.8Gd_0.2O_2−δ samples containing different metal oxide additions (1 mol %) are refined in space group Fm3m. The temperature-dependent thermal expansion data are used to determine the linear thermal expansion coefficients of the samples. Manganese oxide additions reduce the electrical conductivity of Ce_0.8Gd_0.2O_2−δ, whereas the other dopants increase it in the order Ti < Fe < Co. The activation energy for conduction increases in the order Co < Ti < Fe < Mn. Original Russian Text ? E.Yu. Pikalova, A.N. Demina, A.K. Demin, A.A. Murashkina, V.E. Sopemikov, N.O. Esina, 2007, published in Neorganicheskie Material, 2007, Vol. 43, No. 7, pp. 830–837.     

Les phases SrLa2Al2O7 et SrGd2Al2O7

SrLa₂Al₂O₇ and SrGd₂Al₂O₇ belong to the structural type Sr₃Ti₂O₇. In SrGd₂Al₂O₇ strontium and gadolinium occupy respectively the 12 and 9 coordinated sites, whereas in SrLa₂Al₂O₇ the homologous cations are statistically distributed. The fluorescence spectra of both phases activated by Eu³⁺ ions show that the only possible position of Eu³⁺ is the 9 coordinated site.     

Photoconductivity effects in CuInS2, CuInSe2 and CuInTe2 thin films

Photoconductivity response spectra for CuInS₂, CuInSe₂ and CuInTe₂ thin films are reported. The temperature dependences of the spectra are utilized to determine the bandgap energies as functions of temperature. Photoconductive response times are measured for these I–III–VI₂ ternary semiconductors and are discussed in terms of deposition parameters and post-deposition treatments. The photoconductive decay times are in the range 10^-3 – 10¹ ms.     

Dielectric properties of Pb3 (PO4)2 | Pb3 (AsO4)2

The dielectric constants of Pb₃ (PO₄)₂ | Pb₃ (AsO₄)₂ at room temperature are intrinsic and fulfill the Lyddane - Teller - Sachs relation. At higher temperatures the specific conductivity increases with an activation energy of 0.56 eV leading to Maxwell - Wagner polarization effects thereby increasing the effective dielectric constant. Corresponding peaks in ∈' (T) are extrinsic and not attributed to structural phase transformations.     

Comparison between SiO2 films deposited by atomic layer deposition with SiH2[N(CH3)2]2 and SiH[N(CH3)2]3 precursors

Thin SiO₂ layers were deposited by atomic layer deposition (ALD) using either Bis-dimethylamino-silane (BDMAS: SiH₂(N(CH₃)₂)₂) or Tris-dimethylamino-silane (TDMAS: SiH(N(CH₃)₂)₃) precursors. The purpose of this study is to evaluate these precursors for their suitability for ALD of hafnium (Hf)-silicate gate dielectrics. The advantages of these precursors are that the melting points and vapor pressures are moderate. The thickness of SiO₂ deposited using ALD process is controlled by the number of growth cycles and the growth rate was different for each precursor, that for BDMAS being 1.5 times that for TDMAS at the same reactor pressure. The carbon impurity in the SiO₂ film deposited using BDMAS was about half an order of magnitude less than that using for TDMAS. Furthermore, the carbon impurity was reduced to about the detection limit of secondary ion mass spectrometry after high temperature annealing at 1000 °C during 5 s.