Ambient-condition growth of superconducting YBa2Cu4O8 single crystals using KOH flux

YBa₂Cu₄O₈ is a stoichiometric oxide superconductor of T_c80 K. Unlike YBa₂Cu₃O_7−δ, this compound is free from oxygen vacancy or twin formation and does not have any microscopic disorder in the crystal. Doping with Ca raises its T_c to 90 K. The compound is a promising superconductor for technological application. Up to now, single crystals have not been grown without using specialized apparatus with extremely high oxygen pressure up to 3000 bar and at over 1100 °C due to the limited range of reaction kinetics of the compound. This fact has delayed the progress in the study of its physical properties and potential applications. We present here a simple growth method using KOH as flux that acts effectively for obtaining high-quality single crystals in air/oxygen at the temperature as low as 550 °C. As-grown crystals can readily be separated from the flux and exhibit a perfect orthorhombic morphology with sizes up to 0.7×0.4×0.2 mm³. Our results are reproducible and suggest that the crystals can be grown using a conventional flux method under ambient condition.     

Phase diagram of the SrS–Ga2S3 system and its application to the single-crystal growth of SrGa2S4

Ce-doped SrGa₂S₄ compound is expected as a new host material of blue EL devices. However, the basic properties of bulk single crystals have not been fully clarified, since this compound has been mostly synthesized in the form of polycrystals or thin films. Here, we firstly present the pseudo-binary phase diagram of the SrS–Ga₂S₃ system constructed in accordance with our DTA data for single-crystal growth of SrGa₂S₄. It is shown that SrGa₂S₄ compound has a congruent melting point and a eutectic reaction in the side of excess of Ga₂S₃ concentration. On the basis of the phase diagram, single crystals of SrGa₂S₄ are grown using Ga₂S₃ as a self-flux in a horizontal Bridgman furnace. Colorless and transparent crystals having a typical size 2×2×2 mm³ are obtained.     

Growth and properties of Pb[(Zn1/3Nb2/3)0.91Ti0.09]O3 single crystals directly from melt

Pb[(Zn_1/3Nb_2/3)_0.91Ti_0.09]O₃ (PZNT91/9) single crystals were grown by a modified Bridgman method directly from melt using an allomeric Pb[(Mg_1/3Nb_2/3)_0.69Ti_0.31]O₃ (PMNT69/31) single crystal as a seed. X-ray diffraction (XRD) measurement confirmed that the as-grown PZNT91/9 single crystals are of pure perovskite structure. Electrical properties and thermal stabilization of PZNT91/9 crystals grown directly from melt exhibit different characters from those of PZNT91/9 crystals grown from flux, although segregation and the variation of chemical composition are not seriously confirmed by X-ray fluorescence analysis (XPS). The [0 0 1]-oriented PZNT91/9 crystals cut from the middle part of the as-grown crystal boules exhibit broad dielectric-response peaks at around 105 °C, accompanied by apparent frequency dispersion. The values of piezoelectric constant d₃₃, remnant polarization P_r, and induced strain are about 1800–2200 pC/N, 38.8 μC/cm², and 0.3%, respectively, indicating that the quality of PZNT crystals grown directly from melt can be comparable to those of PZNT91/9 single crystals grown from flux. However, further work deserves attention to improve the dielectric properties of PZNT crystals grown directly from melt. Such unusual characterizations of dielectric properties of PZNT crystals grown directly from melt are considered as correlating with defects, microinhomogeneities, and polar regions.     

Viscosity and IR investigations in the Li2O---B2O3 system

The high viscosity in melts of the Li₂O---B₂O₃ system makes it very difficult to grow large crystals of lithium triborate. The viscosity and IR characteristics of molten li₂O---B₂O₃ system are reported in this paper. When the temperature increases the viscosity of li₂O---B₂O₃ system decreases and follows an Arrhenius-type relationship. With an increasing 13203 ratio in Li₂O---B₂O₃ melts, the viscosity rises gradually to a maximum with a composition Li₂O: 3.513203 then it falls rapidly. In order to find active agents to reduce the viscosity, Na₂O, NaCl, LiF, P205, M003, W03 etc oxides were added to Li₂O---B₂O₃ samples respectively and investigated using the orthogonal method. The experimental results show that the addition of acidic oxides can significantly decrease the viscosity in the Li₂O---B₂O₃ system. For Li₂O: 4.513203, an ideal additive agent is 20wt% Li₂O:: 2MoO₃. Near the composition for crystal growth, the percentage reduction of viscosity is 62.2%. The IR spectra of Li₂O---B₂O₃ system revealed that the BO₄⁻/NO₃⁻ ratio is reduced in the melt using Li₂O: 2MoO₃ as an additive. It is proposed that the M003 reduced the concentration of bridging oxygen atoms of BO₄⁻. The change of structure explains the decline in the viscosity. In the crystal structures of lithium triborate, the matrix spaces are so small that larger other cations than Li+ are very difficult to enter the crystal matrix. So the use of additive agents to reduce the viscosity is a possible method if no new phase appears.     

Crystal growth of NdAl3(BO3)4 from K2O/MoO3/Nd2O3/B2O3/KF flux

NdAl₃(BO₃)₄ single crystals were grown by the flux method and the TSSG technique using a K₂O/3MoO₃/B₂O₃/0.5Nd₂O₃/KF flux system. Light-violet clear crystals could be obtained. The effects of fluoride on the growth of NAB crystals were investigated. As the content of KF was gradually increased, the growth form of NAB was changed from the equant to the columnar and the primary crystalline region of NAB was shrinked. At the ratio of KF/K₂O = 0.75, NAB crystals could not be grown.     

Flux growth of PbMg1/3Ta2/3O3 single crystals

Single crystals of PbMg_1/3Ta_2/3O₃ (PMT) were grown by the flux method. The PbO–Pb₃O₄–B₂O₃ system was used as a solvent. Transparent and light yellow PMT single crystals of rectangular shape and dimensions up to 10×6×4 mm³ were obtained. For the applied growth conditions only, the crystals of the perovskite structure were grown. X-ray diffraction tests showed that at room temperature PMT exhibits cubic symmetry with lattice parameter a=4.042(1) Å. Dielectric studies pointed to relaxor properties of PMT. The characteristic broad and frequency-dependent maximum of dielectric permittivity was observed at 179.7 K (1 kHz).     

Preparation and characterization of Ni-incorporated FeS2 single crystals

Nickel-incorporated FeS₂ single crystals with various Ni compositions of Fe_0.99S₂:Ni_0.01, Fe_0.98S₂:Ni_0.02, Fe_0.96S₂:Ni_0.04, and Fe_0.9S₂:Ni_0.1 were grown by chemical vapor transport (CVT) method using ICl₃ as a transport agent. Physical properties of the Ni-incorporated FeS₂ single crystals were characterized using X-ray diffraction, Raman spectroscopy, electrical conductivity, and photoconductivity (PC) measurements. By means of the analyses of the X-ray diffraction patterns, the whole series of Ni-doped FeS₂ single crystals were determined to be single-phase and isostructural. Raman spectroscopy of the Ni-doped FeS₂ crystals was carried out at room temperature. Raman resonant peaks of the Ni-doped FeS₂ crystals demonstrate an energy red-shift behavior with respect to the increase of the dopant densities. Conductivity measurements show the resistivity of the Ni-doped FeS₂ decreased as the doping concentration of Ni is increased. Nickel is an n-type dopant, which behaves like a donor level existed near the conduction band edge of the synthetic FeS₂. On the other hand, dopant effect of nickel on the synthetic FeS₂ also destroys the photoconductive sensitivity in the photoconductivity measurements.     

Influence of oxygen, hydrogen, helium, argon and vacuum on the surface behavior of molten InSb, other semiconductors, and metals on silica

Sessile drop experiments were performed on molten indium antimonide on clean quartz (fused silica) surfaces. A cell was constructed through which argon, helium, oxygen, hydrogen or a mixture of these was flowed at 600 °C. Some of the InSb was doped with 0.1% Ga. The surface tension σ of oxide-free molten InSb was smaller in Ar than in He, may have increased with increasing O₂ in the gas, and was not influenced by Ga or H₂. The contact angle θ on silica was higher in the presence of Ar, was lowered by O₂, and was not influenced by H₂ or Ga. The work of adhesion W and the surface energy σ_sv of the silica were higher in He than in Ar. The surface remained free of solid oxide only in flowing gas containing 0.8 ppm O₂. This behavior is attributed to reaction of O₂ at the surface of the melt to form In₂O gas. When solid oxide formed on Ga-doped material, it was strongly enriched in Ga, with the Ga/In ratio increasing with the concentration of O₂ in the gas.

Examination of published sessile-drop results for liquid metals and semiconductors on silica revealed that W and σ_sv were highest for reactive melts, in which SiO₂ dissolves. For non-reactive melts, W and σ_sv were lower and θ higher in a gas than in a vacuum, regardless of whether the experiments had been carried out in sealed ampoules, a flowing gas, or dynamic vacuum. The implication is that the surface of silica was different in a vacuum than in a gas at 1 bar.     

Crystallization of In2O3 by vapor reaction

Crystallization of In₂O₃ occured in closed porcelain crucibles in air at 960–1200°C by vapor phase reaction of In₂O or In vapor with the oxygen diffusing into the system. The In₂O or In vapors were thermally generated from mixtures such as graphite/In₂O₃, graphite/In, In₂O₃/In and graphite/In₂O₃/In. The graphite/In₂O₃ system at a mole ratio of 30/1 and 1000°C produced yellow, transparent needle crystals with a maximum size of 0.5 X 0.5 X 8 mm and electrical resistivity of 5.5 X 10^-2 ω cm at 25°C.     

Crystal growth of Ce: PrF3 by micro-pulling-down method

Micro-pulling-down (μ-PD) growth apparatus was modified for fluoride crystals. PrF₃ was grown with various concentrations of Ce³⁺ from 0–100%. The crystals were transparent and colorless (CeF₃) or greenish and 3 mm in diameter and 15–50 mm in length. Neither visible inclusions nor cracks were observed. Radioluminescence spectra and decay kinetics were measured for the sample set at room temperature. In comparison to the Czochralski or Bridgman method, the μ-PD method allows to produce single crystalline material in a faster thus more economic way. Once it is established for the fluoride crystals, it is an efficient tool for exploring the field of new functional fluorides.     

Growth and luminescence mechanisms of Ba2ErCl7: a new laser up-conversion crystal

A modified synthesis method for the preparation of Ba₂ErCl₇, a new laser up-conversion material using Er₂O₃, BaCl₂·2H₂O and NH₄Cl, is reported for the first time. Single crystals 5–8 mm in diameter and 10–20 mm in length were grown by both the Czochralski and Bridgman methods. The transmittance spectra for a Ba₂ErCl₇ single crystal was first measured using a HITACHI U-3500 spectrophotometer. There were three intense absorption peaks ⁴I_9/2, ⁴I_11/2 and ⁴I_13/2 in the infrared range which can be excited by 803 and 980 nm and 1.5 μm laser diode (LD), respectively. The cut-off wavelength of the crystal was 230 nm. Intense green luminescence was observed when the crystals were pumped by an 803 nm LD. Up-conversion mechanisms are discussed.     

Investigation of Ni/Au-contacts on p-GaN annealed in different atmospheres

We investigated the effect of different annealing atmospheres on contact behaviour of Ni/Au contacts on moderately doped p-GaN layers. We used the annealing gases N₂, O₂, Ar, and forming gas (N₂/H₂) at varying annealing temperatures from 350°C to 650°C in steps of 50°C. The p-GaN samples were either metalorganic chemical vapor deposition or molecular beam epitaxy grown. Contact characterization was done after each annealing step by using the circular transmission line model. Specific contact resistances were determined to be in the low 10⁻⁴ Ω cm² range for oxidized contacts. Accompanying chemical analysis using depth resolved Auger electron spectroscopy revealed that NiO was formed and Au diffused towards the interface, whereas annealing in forming gas prevented oxidation and did not lead to Ohmic behaviour.     

Growth and spectroscopic properties of Er single doped and Er–Yb co-doped YAl3(BO3)4 crystals

Er³⁺-doped and Er³⁺–Yb³⁺ co-doped yttrium aluminum borate (YAB) single crystals have been grown by the top-seeded solution growth method using a new flux system, namely NaF–MoO₃–B₂O₃. The Er³⁺ concentrations were 1.3 mol% for both single doped and co-doped crystals and the Yb³⁺ concentration in the Er³⁺–Yb³⁺ co-doped crystal was 20.0 mol% in the raw materials. The distribution coefficients of Er³⁺ single doped and Er³⁺–Yb³⁺ co-doped crystals were measured. The polarized absorption and fluorescence spectra of Er³⁺–Yb³⁺ co-doped crystal were recorded and compared with those of Er³⁺ single doped crystal. The results demonstrate that Er³⁺–Yb³⁺ co-doped YAB crystal is a potential candidate for 1.55 μm laser materials.     

Study on phase diagram of Bi2O3---SiO2 system for Bridgman growth of Bi4Si3O12 single crystal

Phase relation of Bi₂O₃---SiO₂ system was evaluated experimentally from DTA and XRD measurements and its stable and metastable phase diagrams were proposed. Although BSO melts near-congruently at 1025°C in the stable phase equilibrium, its melt crystallizes to form metastable phase Bi₂SiO₅ in accordance with the metastable phase diagram while cooling. Therefore, BSO couldn't nucleate and crystallize spontaneously without crystal seed and only Bi₂SiO₅ crystallized at about 850°C with significant supercooling during Bridgman growth. BSO single crystal with 20×20×100mm³ was grown in a vertical Bridgman furnace with a BSO seed according to its phase diagram. The measuring results of scintillation properties of BSO specimen show that its decay constant is 91 ns (about 1/3 of BGO) and light output is 23% of BGO.     

Crystal growth and characterization of the CMR compound La1.2(Sr,Ca)1.8Mn2O7

High-quality centimeter-sized single crystals of La_1.2Sr_1.8−yCa_yMn₂O₇ (0.0y0.2) were successfully grown using a floating zone method associated with an image furnace. We present the growth conditions together with a characterization of the single crystals by means of optical and electron microscopy, EDX and ICPAES analysis, DTA-TGA measurements and redox titration, X-ray powder diffraction, Laue X-ray back-reflection and neutron diffraction. We also stress the main aspects of the complex thermodynamical and kinetic behaviors of these compounds.     

Effects of SiO2 overlayer at initial growth stage of epitaxial Y2O3 film growth

We investigated the dependence of the Y₂O₃ film growth on Si surface at initial growth stage. The reflection high-energy electron diffraction, X-ray scattering, and atomic force microscopy showed that the film crystallinity and morphology strongly depended on whether Si surface contained O or not. In particular, the films grown on oxidized surfaces revealed significant improvement in crystallinity and surface smoothness. A well-ordered atomic structure of Y₂O₃ film was formed on 1.5 nm thick SiO₂ layer with the surface and interfacial roughness markedly enhanced, compared with the film grown on the clean Si surfaces. The epitaxial film on the oxidized Si surface exhibited extremely small mosaic structures at interface, while the film on the clean Si surface displayed an island-like growth with large mosaic structures. The nucleation sites for Y₂O₃ were provided by the reaction between SiO₂ and Y at the initial growth stage. The SiO₂ layer known to hinder crystal growth is found to enhance the nucleation of Y₂O₃, and provides a stable buffer layer against the silicide formation. Thus, the formation of the initial SiO₂ layer is the key to the high-quality epitaxial growth of Y₂O₃ on Si.     

Large-size β-Ga2O3 single crystals and wafers

Large-size single crystals of β-Ga₂O₃ with 1 inc in diameter have been grown by the floating zone technique. The stable growth conditions have been determined by the examination of the crystal structure. Wafers have been cut and fine polished in the (1 0 0), (0 1 0) and (0 0 1) planes. These were highly transparent in the visible and near UV, as well as electrically conductive, indicating the potential use of β-Ga₂O₃ as a substrate for optoelectic devices operating in the visible/near UV and with vertical current flow.     

Synthesis, growth and characterization of a new laser upconversion crystal Ba2ErCl7

A modified method to synthesize the new laser upconversion material Ba₂ErCl₇ using Er₂O₃, BaCl₂ 2H₂O and NH₄CI is reported for the first time in this paper. Single crystals up to 5–8mm in diameter and 10–20 mm in length have been grown by Czochralski method. The transmittance spectra of Ba₂ErCl₇ single crystal has first been measured by using an HITACHI U-3500 spectrophotometer. There are three intense absorption peaks ⁴I_9/2⁴I_11/2 and ⁴I_13/2 in the infrared range which can be excited by 803nm, 980nm and 1.5μm laser diodes (LDs), respectively. The cut-off wavelength of the crystal is 230mn. Intense green luminescence can be observed when the crystal is pumped by a ED at 803nm. The formation of the defects is also discussed.     

氧气对CsPbBr3单晶电学性能的影响

CsPbBr₃兼具高探测效率和较好的稳定性,是当前高性能高能辐射探测器的热门材料。在使用坩埚下降法制备CsPbBr₃单晶的配料阶段,如果无法有效隔绝原料与氧气的接触,氧气会吸附于原料表面难以排出,在原料熔化后会聚集在密封坩埚的上方,导致所得到的单晶颜色沿生长方向逐渐变深,这一颜色变化不会改变CsPbBr₃的禁带宽度。通过对单晶上端切片进行电学性能测试发现,从单晶的中心到外侧,CsPbBr₃单晶的电阻率逐渐下降,陷阱密度和载流子迁移率逐渐增大,但对X射线的响应度基本不变。本文为研究高质量CsPbBr₃单晶的生长提供帮助。     

Crystal growth of Na(V,Ti)2O5

Large single crystals of quasi-one-dimensional antiferromagnetic spin system NaV_2−zTi_zO₅ (0z0.06) have been successfully grown by a flux method. We present growth conditions together with a characterization of the single crystals by means of X-ray powder diffraction, energy dispersive X-ray (EDX) analysis and magnetic susceptibility measurements.