Hydrothermal crystal growth of the potassium niobate and potassium tantalate family of crystals

Single crystals of KNbO₃ (KN), KTaO₃ (KT), and KTa_1−xNb_xO₃ (x=0.44, KTN) have been prepared by hydrothermal synthesis in highly concentrated KOH mineralizer solutions. The traditional problems of inhomogeneity, non-stoichiometry, crystal striations and crystal cracking resulting from phase transitions associated with this family compounds are minimized by the hydrothermal crystal growth technique. Crystals of good optical quality with only minor amounts of metal ion reduction can be grown this way. Reactions were also designed to provide homogeneous distribution of tantalum and niobium metal centers throughout the KTN crystal lattice to maximize its electro-optic properties. Synthesis was performed at relatively low (500-660 °C) temperatures in comparison to the flux and Czochralski techniques. This work represents the largest crystals of this family of compounds grown by hydrothermal methods to date.     

Ein neuartiges Polyoxocobaltat(II)‐Anion in Rb2Co2O3

A New Polyoxocobaltate(II) Anion in Rb₂Co₂O₃ Rb₂Co₂O₃ was prepared via the azide/nitrate route. Mixtures of the precursors Co₃O₄, RbN₃ and RbNO₃ in the molar ratios 6:17:1 were heated in a special regime up to 450 °C and annealed at this temperature for 50 h in silver crucibles. Single crystals have been grown by subsequent annealing of prepared powder at 450 °C for 500 h in silver crucibles, which were sealed in glass ampoules under dried Ar. According to the X‐ray analysis of the crystal structure (Pnma, Z = 8, 11.729(2), 6.058 (1), 8.004(1) Å) cobalt is trigonal planar coordinated by oxygen atoms. The CoO₃‐units share through all corners and build up an infinite two‐dimensional Co₂O₃‐network.     

Synthesis and Crystal Structure of CsCu3O2, Containing a New Type of Oxocuprate(I) Polyanion

CsCu₃O₂ was prepared via the azide route. Stoichiometric mixtures of the precursors (CsN₃, Cu₂O and CuO) were heated in a special regime up to 450 °C and annealed at this temperature for 50 h in silver crucibles. Single crystals have been grown by subsequent annealing of as prepared powders at 450 °C for 2000 h in silver crucibles, which were sealed in glass ampoules under dried Ar. According to the X‐ray analysis of the crystal structure (P3¯m1, Z = 1, a = 5.250(1), c = 5.442(1)Å, γ = 120°) copper is linearly coordinated by oxygen atoms. The CuO₂‐dumb‐bells are connected to an infinite two‐dimensional Cu₃O₂‐network. CsCu₃O₂ is isostructural with CsCu₃S₂, CsAu₃S₂, CsAu₃Se₂ and RbAu₃Se₂.     

Flux growth and magnetic properties of FeVO4 single crystals

FeVO₄ (I) single crystals are grown by the flux method using V₂O₅ as the self-flux. The grown crystals exhibit a characteristic morphology with natural facets. The quality of the crystals is confirmed by X-ray diffraction and EPMA techniques. Magnetic properties are investigated by means of magnetic susceptibility, magnetization, and heat capacity measurements. Two magnetic phase transitions are observed at ∼13 and ∼20 K. Such unusual magnetic behaviors are suggested to originate from two different Fe ligand environments of octahedral FeO₆ and trigonal bipyramidal FeO₅ in a six-column doubly bent chain.     

Synthesis and Properties of Rb6Mn2O6

Rb₆Mn₂O₆ was prepared via the azide/nitrate route. Stoichiometric mixtures of the precursors (Mn₃O₄, RbN₃ and RbNO₃) were heated in a special regime up to 500 °C and annealed at this temperature for 75 h in silver crucibles. Single crystals have been grown by annealing a mixture with a slight excess of rubidium components at 450 °C for 500 h. According to the single crystal structure analysis, Rb₆Mn₂O₆ is isotypic to K₆Mn₂O₆, and crystallizes in the monoclinic space group P2₁/c with a = 6.924(1) Å, b = 11.765(2) Å, c = 7.066(1) Å, β = 99.21(3)°, 2296 independent reflections, R₁ = 5.23 % (all data). Manganese is tetrahedrally coordinated and two tetrahedra are linked by sharing a common edge, forming a dimer [Mn₂O₆]⁶⁻. The magnetic behavior has been investigated.     

Radiofrequency spark source mass spectrometric analysis of oxygen in undoped silicon crystals and of carbon in undoped and carbon doped gallium arsenide crystals

Radiofrequency spark source mass spectrometry is a reliable and precise analytical method to measure the amount of oxygen in silicon grown by the Czochralski technique from SiO₂ crucibles in the common range from 2ppm(atomic) to 20ppm(atomic) and in silicon grown by the floating zone technique below 0.1ppm(atomic). The technique is also excellent for the measurement of the amount of carbon in semi-insulating gallium arsenide grown under low and high pressure N₂ ambient gas by the B₂O₃ encapsulated Czochralski technique from pyrolytic BN crucibles in the common range from 0.02ppm(atomic) to 0.4ppm(atomic). The results are in rather good agreement with concentrations measured by charged particle activation analysis and consistent with those obtained using other methods.     

Latest developments of bulk crystals and thin films of rare-earth doped CaF2 for laser applications

Several CaF₂ single crystals doped with trivalent rare-earth ions have been grown in the recent years in the form of bulk crystals by using the Bridgman method and in the form of thin films by using the MBE and LPE techniques. The spectroscopic, gain and laser properties of these crystals doped with Pr³⁺, on the one hand, and with Yb³⁺, Tm³⁺ or Er³⁺ ions, on the other hand, have been studied and are reviewed here for their laser potentials in the red and in the infrared spectral domains, respectively.     

Growth of germanium dioxide single crystals with α-quartz structure and investigation of their crystal structure,optical, elastic,piezoelectric, dielectric and mechanical properties

The optimal growing conditions for α-GeO₂ single crystals and Si-substituted α-GeO₂ crystals have been found. The quality and sizes of the grown crystals of α-GeO₂ have allowed studying their morphology, internal constitution and measuring their piezoelectric, dielectric, elastic and other physical properties.     

Micro-sized Sb2O3 octahedra fabricated via a PEG-1000 polymer-assisted hydrothermal route

The micro-sized Sb₂O₃ octahedra can be synthesized on a large scale via a simple PEG-1000 polymer-assisted hydrothermal route (PAHR) in the temperature range of 160-180 °C for 10-14 h. The structures, compositions, and morphologies of the as-synthesized products are derived from X-ray power diffraction pattern, X-ray photoelectron spectra, and field emission scanning electronic microscope. Meanwhile, the optical properties of the micro-sized Sb₂O₃ octahedra are studied by their photoluminescene spectroscopy and Raman spectrum. Furthermore, the possible growth mechanism of the micro-metered Sb₂O₃ octahedra is discussed on the basis of a series of supplementary experiments. And it has been found that PEG-1000, sodium tartrate, the reaction temperature, and the reaction time have considerable effects on the final morphology of Sb₂O₃, while the pH value has an influence on the formation of the Sb₂O₃ crystals.     

氧化铝载体和氧化钡助剂对钌基氨合成催化剂结构和性能的影响

采用不同来源γ-Al2O3(市售Al2O3-1,合成Al2O3-2)作为钌基氨合成催化剂载体,利用浸渍法制备了一系列添加不同BaO助剂含量的Ba-Ru/Al2O3催化剂.通过X射线衍射(XRD)、N2-低温物理吸附、X射线荧光光谱(XRF)、透射电镜(TEM)、H2程序升温还原(H2-TPR)、NH3程序升温脱附(NH3-TPD)和X射线光电子能谱(XPS)等方法研究了不同来源的Al2O3以及BaO助剂含量对负载型钌基催化剂的物相结构、织构性质、微观形貌、表面性质和催化剂的氨合成活性等方面的影响.结果表明,载体的物理化学性质对制备的钌基氨合成催化剂的结构以及活性有较大影响.BaO助剂对催化剂的影响主要表现在两个方面:添加量不同导致BaO与γ-Al2O3的作用力不同,从而进一步影响催化体系的比表面积和孔结构性质;BaO助剂会对体系的Ru物种还原性质以及催化剂表面酸碱性质进行调节,适量BaO的加入能够极大提高反应活性,而这种最佳量与载体性质密切相关.     

Magnetic properties of Co2V2O7 single crystals grown by flux method

Based on the phase diagram of CoO–V₂O₅ system, single crystals of Co₂V₂O₇ are grown using V₂O₅ as self-flux at a slow cooling rate. The quality of grown crystals is analyzed by X-ray powder diffraction and electron probe microanalysis techniques. Magnetic properties are investigated by means of susceptibility, magnetization, and heat capacity measurements. Our experimental results suggest that Co₂V₂O₇ is a three-dimensional antiferromagnet, in which two magnetic transitions may occur at low temperature and a spin-flop-like transition may occur at the applied field along the b-axis. By contrast to Ni₂V₂O₇, it is suggested that similar and different magnetic properties may arise from their similar crystal structures and different magnetic ions, respectively.     

Functionalizing Single Crystals: Incorporation of Nanoparticles Inside Gel‐Grown Calcite Crystals

Synthetic single crystals are usually homogeneous solids. Biogenic single crystals, however, can incorporate biomacromolecules and become inhomogeneous solids so that their properties are also extrinsically regulated by the incorporated materials. The discrepancy between the properties of synthetic and biogenic single crystals leads to the idea to modify the internal structure of synthetic crystals to achieve nonintrinsic properties by incorporation of foreign material. Intrinsically colorless and diamagnetic calcite single crystals are turned into colored and paramagnetic solids, through incorporation of Au and Fe₃O₄ nanoparticles without significantly disrupting the crystalline lattice of calcite. The crystals incorporate the nanoparticles and gel fibers when grown in agarose gel media containing the nanoparticles, whereas the solution‐grown crystals do not. As such, our work extends the long‐history gel method for crystallization into a platform to functionalize single‐crystalline materials.     

Crystal growth of a novel oxygen-deficient layered perovskite: Ba7Li3Ru4O20

Single crystals of both Ba₇Li₃Ru₄O₂₀ and Ba₄NaRu₃O₁₂ were grown from reactive molten hydroxide fluxes. Ba₇Li₃Ru₄O₂₀ is a 7L-layer perovskite-related phase resulting from the stacking of six [AO₃] layers and one oxygen deficient [AO₂] layer, thereby creating LiO₄ tetrahedra in addition to the LiO₆ octahedra and face-sharing Ru₂O₉ bi-octahedra formed from the [AO₃] layers. The compound crystallizes in the space group with a=5.7927(1) Å and c=50.336(2) Å, Z=3. Ba₄NaRu₃O₁₂ crystallizes in the space group P6₃mc with lattice parameters of a=5.8014(2) Å and c=19.2050(9) Å, Z=2. Ba₄NaRu₃O₁₂ is identical to a previously reported neutron refinement structure. The magnetic properties of Ba₇Li₃Ru₄O₂₀ are also reported.     

Synthesis and Crystal Structure of Na7Cu3O8, Containing a New Type of Oxocuprate(III) Oligoanion

Na₇Cu₃O₈ was prepared through oxidation of a Na₃CuO₂/NaCuO mixture (2:1) in dried oxygen at 450 °C. Single crystals have been grown by annealing of Na₇Cu₃O₈, in the presence of Na₂O₂, at 450 °C for 2000 h in silver crucibles, which were sealed in glass ampoules under dried Ar. According to the X-ray analysis of the crystal structure ( , Z = 1, a = 5.5891(2), b = 6.0945(2), c = 7.8890(3) Å, α = 110.059(2), β = 108.669(2), γ = 90.237(2)°) a new Cu₃O₈^7- oxocuprate anion, consisting of three edge sharing CuO₄ squares, is the prominent structural feature. These anions are aligned parallel to the space diagonal of the unit cell and can be regarded as infinite chains from which every fourth copper atom has been removed. This new representative of an oxocuprate(III) anion gives support to the expectation that the gap between dimeric and infinite edge sharing units of square planar cuprate anions can be closed, in principle.     

The Crystal Structure of Sr2TiSi2O8

Sr₂TiSi₂O₈ single crystals were grown by Czochralski pulling and from a high-temperature solution. X-ray diffractometry revealed the modulated crystal structure of Sr₂TiSi₂O₈ to belong to the 5D superspace group P4bm (−α, α, 1/2; α, α, 1/2) with α=0.3. Atomic positions, anisotropic displacement factors and positional modulation parameters for Sr₂TiSi₂O₈ are determined and discussed. The positional modulation is further investigated by electron diffraction and high-resolution transmission electron microscopy. In the latter experiments, the 2D modulation appears to be superimposed by some 1D modulation waves. This effect is discussed in terms of growth conditions.     

Single crystal growth and structure of La4Cu3MoO12

We report the synthesis and structure determination of single crystals of La₄Cu₃MoO₁₂ grown from a CuO/KCl flux. This material, whose structure had previously been reported based solely on polycrystalline diffraction data, shows frustrated magnetic behavior and an anti-ferromagnetic ordering of spin-1/2 triangles at low temperatures. The structural and atomic parameters determined from the single crystal data are in very good agreement with those reported previously. However, HREM data showed evidence for disorder in the stacking of the Cu₃MoO₄ planes, and thus a twinned structural refinement in space group P2₁/m was replaced by an equivalent disordered structural model in space group Pm. This development of a synthetic route to single crystals of La₄Cu₃MoO₁₂ will allow a more detailed investigation of its complex electronic and magnetic properties.     

Production of reactive oxygen species induced by a new [60]fullerene derivative bearing a tetrazole unit and its possible biological applications

The wide range of physical and chemical properties of modified fullerenes has drawn increasing attention in the past few years. As part of this research, this paper describes the preparation, characterization, and photophysical properties of a new fullerene derivative chemically modified with a tetrazole. The photophysical properties were studied by EPR radical spin-trapping technique and showed that reactive oxygen species (ROS) can be produced through UVA photosensitization. EPR spin-trapping experiments with singlet oxygen (¹O₂) and superoxide (O₂⁻) inhibitors (β-carotene and superoxide dismutase, respectively) revealed also that: (i) the main ROS produced is ¹O₂ and (ii) ¹O₂ is being partially dismutated to O₂⁻. The results suggest that this derivative can be used in biological applications, as for example, in topic photodynamic therapy (PDT) as a photosensitizer.     

Single-crystal synthesis, structure analysis, and physical properties of the calcium ferrite-type NaxTi2O4 with 0.558<x<1

Single crystals of calcium ferrite CaFe₂O₄-type NaTi₂O₄ having millimeter-sized needle shapes were synthesized by a reaction of Na metal and TiO₂ in a sealed iron vessel at 1473 K. Sodium-deficient Na_xTi₂O₄ single crystals with 0.558<x<1 were successfully synthesized by a topotactic oxidation reaction using NaTi₂O₄ single crystals as parent materials. The crystal structures of Na_xTi₂O₄ with x=0.970, 0.912, 0.799, 0.751, 0.717, 0.686, 0.611, and 0.558 were determined by the single-crystal X-ray diffraction method. The basic framework constructed by the Ti1O₆ and Ti2O₆ double rutile chains was maintained in these Na_xTi₂O₄ compounds. Based on the results of bond valence analysis, we speculated that the Ti1 sites are preferentially occupied by Ti³⁺ cations over the compositional range of 0.8<x<1, while both the Ti1 and Ti2 sites are randomly occupied by Ti³⁺ and Ti⁴⁺ cations at x=0.558. Magnetic susceptibility data indicated that the broad maximum around 40 K observed in as-grown NaTi₂O₄ is suppressed by an Na deficiency and vanishes in Na_0.717Ti₂O₄. The electrical resistivity increased with the Na deficiency; however, it was still semiconductive in Na_0.799Ti₂O₄.     

Synthesis and nonlinear optical properties of BaTi(BO3)2 and Ba3Ti3O6(BO3)2 crystals in glasses with high TiO2 contents

The ternary BaO-TiO₂-B₂O₃ glasses containing a large amount of TiO₂ (20-40 mol%) are prepared, and their optical basicities (Λ), the formation, structural features and second-order optical nonlinearities of BaTi(BO₃)₂ and Ba₃Ti₃O₆(BO₃)₂ crystals are examined to develop new nonlinear optical materials. It is found that the glasses with high TiO₂ contents of 30-40 mol% show large optical basicities of Λ=0.81-0.87, suggesting the high polarizabity of TiO_n polyhedra (n=4-6) in the glasses. BaTi(BO₃)₂ and Ba₃Ti₃O₆(BO₃)₂ crystals are found to be formed as main crystalline phases in the glasses. It is found that BaTi(BO₃)₂ crystals tend to orient at the surface of crystallized glasses. The new XRD pattern for the Ba₃Ti₃O₆(BO₃)₂ phase is proposed through Rietvelt analysis. The second harmonic intensities of crystallized glasses were found to be 0.8 times as large as α-quartz powders, i.e., I^2ω(sample)/I^2ω(α-quartz)=0.8, for the sample with BaTi(BO₃)₂ crystals and to be I^2ω(sample)/I^2ω(α-quartz)=68 for the sample with Ba₃Ti₃O₆(BO₃)₂ crystals. The Raman scattering spectra for these two crystalline phases are measured for the first time and their structural features are discussed.     

Synthesis and Crystal Structure of Rb3AgO2

Rb₃AgO₂ was prepared via the azide/nitrate route. Stoichiometric mixtures of the precursors (Ag₂O, RbN₃ and RbNO₃) were heated in a special regime up to 450 °C and annealed at this temperature for 50 h in silver crucibles. Single crystals have been grown by subsequent annealing of the as prepared powder at 450 °C for 500 h in silver crucibles, which were sealed in glass ampoules under dried Ar. According to the X‐ray analysis of the crystal structure (P2₁2₁2₁, Z = 16, a = 12.800(1), b = 12.848(1), c = 14.329(1)Å, 6566 independent reflections, R(all) = 0.0795, R_w(all) = 0.0218), Rb₃AgO₂ is isostructural with K₃AgO₂. The structure can be derived from the fluorite structure type. Silver is linearly coordinated by oxygen atoms, while Rb has pseudo‐tetrahedral coordination. The crystal under investigation was composed of four twin individuals.