Microtube-Czochralski (μT-CZ) growth of bulk benzophenone single crystal for nonlinear optical applications

Microtube-Czochralski technique was employed to grow large size benzophenone single crystal for the first time. In conventional Czochralski pulling technique, the growth of bulk single crystal will be initiated by a pre-grown seed, whereas in microtube-Czochralski technique a microtube that is made out of a metal such as stainless steel (8 μm ID) can be used to grow bulk single crystal. A specially designed furnace having inert gas atmosphere, condensation free enclosure and in situ annealing facility was employed. Benzophenone crystal having cubic facet (15 mm) with high optical quality was grown when the following vital growth parameters are set to the corresponding optimized values such as pulling rate: 1–2 mm/h, seed rotation rate: 5–10 rpm and the axial thermal gradient: 8 °C/cm. The grown crystals were cut and polished. Thin plate like polished samples were used to justify the optical quality of the grown samples by UV–VIS–NIR spectroscopy. Powder SHG measurement shows that the grown samples exhibit three times higher second harmonic generation than potassium dihydrogen phosphate (KDP).     

Effect of the titanium doping of the Fe—Co—C solvent on the nitrogen content of diamond single crystals grown at high pressures and temperatures

Diamond single crystals have been grown experimentally in Fe—Co-based alloys—solvents for carbon with a titanium content varying from 1 to 2 wt %. Average growth rates and morphological features of the grown crystals have been defined; the defect-and-impurity states and characteristics of macroinclusions have been analyzed. It has been found that an increase of titanium content of the Fe—Co—C solvent from 1 to 2 wt % brings about a change of the single crystal type from Ib to IIa. The use of the solvent having 1.5 wt % of titanium allows growing diamond single crystals of mixed Ib + IIb types.     

Special features of growing diamond single crystals in the Fe-Co-Zr-C system

The results have been considered of the investigations into the effect of various concentrations of zirconium addition to the Fe-Co alloy solvent on the growth rate and habit of a diamond single crystal grown by the temperature gradient method in the diamond thermodynamic stability region. The dependence of the defect and impurity state of grown crystals on the percentage of the zirconium addition has been established. The maximum zirconium content and temperature of the alloy solvent, which provide the growth of structurally perfect type IIa diamond single crystals, have been defined.     

Homogeneous Si0.5Ge0.5 bulk crystal growth as substrates for strained Ge thin films by the traveling liquidus-zone method

Compositionally uniform Si_0.5Ge_0.5 bulk crystals were grown by the traveling liquidus-zone method which we developed for alloy crystal growth. Grown crystals were characterized as substrates for compressive-strained Ge thin films for high mobility p-channels of complementary metal oxide semiconductor transistors. Compositional uniformity was excellent and crystallinity was also excellent for 10 mm diameter crystals. However, crystallinity was degraded for 30 mm diameter crystals although compositional uniformity was excellent. Transmission electron microscope (TEM) observation showed high dislocation density at the interface between a Si seed and a grown crystal due to lattice mismatch. However, the dislocation density decreased as crystal growth proceeded. High quality 30 mm diameter crystals will be grown when the single crystal length is extended judging from TEM results. In this paper, we report on the growth and characterization of Si_0.5Ge_0.5 crystals as substrates for strained Ge thin films.     

The formation and characterization of diamond crystallites by microwave plasma enhanced chemical vapor deposition – a comparison of gaseous and solid carbon sources as precursors

Commercial diamond powders are in irregular shapes and have been used as seeds for growing well crystallized fine diamond grits in this study. The surfaces of irregular diamond particles would serve as the seed for the subsequent growth of the diamond crystallites using microwave enhanced chemical vapor deposition (MPECVD). Both gaseous and solid carbon sources were used to transform the irregular shaped diamond seeds with sharp edges and corners along with the increase in size to the final equilibrium form of diamond crystallites. In case of gaseous carbon source, the effect of increasing methane content and applying negative dc bias voltage on the formation of diamond crystallites was significant. While in case of solid carbon source, well-faceted diamond crystallites can he extracted from the molten metal-carbon-hydrogen (M-C-H) system. Surface etch pits are numerous; especially noticeable after long exposure in hydrogen plasma. Both growth rates of diamond crystallite irrespective of the carbon sources tend to be parabolic at the later stage of growth. Electronic Publication     

Fe+Ni+C体系合成粗颗粒金刚石单晶的生长特征

在配备有高精密化控制系统SPD6×1670T型国产六面顶压机上,采用Fe80Ni20粉末触媒和高纯石墨开展粗颗粒金刚石单晶的生长特征研究。在粉末触媒技术合成金刚石的基础上,引入旁热式组装,以及采用优选粒度的触媒,特别是通过优化合成工艺严格地控制了合成腔体内晶体的成核量及生长速度。最终,在高温高压条件下(约5.4GPa、1435℃)成功合成出尺寸达到0.95mm(18/20目)的优质的粗颗粒金刚石单晶,分析了粗颗粒金刚石的生长特征和晶体缺陷,期待研究的结果有助于我国高品级粗颗粒金刚石的发展。     

Surface structures of synthetic diamonds

Diamond crystals of about 2 mm in size were grown by the temperature gradient method using Ni, Ni-Fe alloy and Fe as solvent metals. Several characteristic patterns were seen on the surfaces of the grown diamonds and were found to correspond to the texture of the quenched solvent metals. A vague vein-like pattern appeared when Ni was used. The surface patterns became finer with the increase of the content of Fe in Ni-Fe alloy, and when 70 wt% Fe-30 wt% Ni alloy was used, very fine dendritic patterns were seen on all of the faces of diamond in accordance with the symmetries of the lattice. The patterns are formed by the precipitation of carbon atoms in the space of the dendrites of the solvent metals during the quenching process. Lamellar patterns and etch pits were seen when Fe was used. The patterns are formed when Fe dissolves the diamond surfaces to produce Fe₃C during the quenching process.     

High Resolution Synchrotron X-Radiation Diffraction Imaging of Crystals Grown in Microgravity and Closely Related Terrestrial Crystals

Irregularities in three crystals grown in space and in four terrestrial crystals grown under otherwise comparable conditions have been observed in high resolution diffraction imaging. The images provide important new clues to the nature and origins of irregularities in each crystal. For two of the materials, mercuric iodide and lead tin telluride, more than one phase (an array of non diffracting inclusions) was observed in terrestrial samples; but the formation of these multiple phases appears to have been suppressed in directly comparable crystals grown in microgravity. The terrestrial seed crystal of triglycine sulfate displayed an unexpected layered structure, which propagated during directly comparable space growth. Terrestrial Bridgman regrowth of gallium arsenide revealed a mesoscopic structure substantially different from that of the original Czochralski material. A directly comparable crystal is to be grown shortly in space.     

Defect-and-impurity state of type Ib diamond single crystals of cubic habit

Type Ib diamond single crystals of size to 5–6 mm and to 2.4 carats in weight have been grown at high pressures and temperatures. The defect-and-impurity state and dislocation structures of these crystals have been studied using the IR and optical microscopies as well as the method of the selective etching. To produce type Ib crystals of cubic habit has been made possible by the minimization of the growing temperature. Defect regions in the form of a cone with the basis 0.2–1.8 mm in diameter and 0.5–2.5 mm in height are contained by these crystals. The study of the cone-shaped defect regions using the selective etching showed that at the exposure on the faces the etching pits are of the tetragonal shape and the dislocation density in them exceeds the density of dislocations in crystals that were grown under the usual conditions by 70 to 100 times. The observed defect regions are formed in the course of the diamond crystals growth as the temperature decreases by ~ 30–35°C at the crystallization front because of the increasing heat sink in the direction of a seed crystal.     

Suppression of inhomogeneous segregation in graphene growth on epitaxial metal films

Large-scale uniform graphene growth was achieved by suppressing inhomogeneous carbon segregation using a single domain Ru film epitaxially grown on a sapphire substrate. An investigation of how the metal thickness affected growth and a comparative study on metals with different crystal structures have revealed that locally enhanced carbon segregation at stacking domain boundaries of metal is the origin of inhomogeneous graphene growth. Single domain Ru film has no stacking domain boundary, and the graphene growth on it is mainly caused not by segregation but by a surface catalytic reaction. Suppression of local segregation is essential for uniform graphene growth on epitaxial metal films.     

Special features of the formation of a microrelief on the surface of diamond single crystals when grown in solvent based on an iron-cobalt-zirconium alloy

It has been shown that when growing diamond single crystals in the diamond thermodynamic stability region using solvents based on iron-cobalt-zirconium alloys virtually all crystal faces exhibit microrelieves, which represent the combination of valleys and peaks, whose depth and height do not exceed several micrometers. The origin of the microrelief has been caused by the features of the solvent crystallization and phase transformations in it as the temperature decreases. A liquid solvent is crystallized as a mixture of elongated grains of composition (Fe, Co)₃C with interlayers of α-solid solution of eutectic composition between them, which results in the formation of valleys and peaks on the crystal surface. Cooling the solvent leads also to the formation of microscopic diamond single crystals and precipitation of excess graphite from the α-solid solution of composition (Fe, Co)₃C. The relief observed on faces of the grown crystals is of the surface nature only.     

CIGS thin films, solar cells, and submodules fabricated using a rf-plasma cracked Se-radical beam source

Coevaporated Cu(In,Ga)Se₂ (CIGS) film growth using a rf-plasma cracked Se-radical beam (R-Se) source leads to a significant reduction in the amount of raw Se source material wasted during growth and exhibits unique film properties such as highly dense, smooth surfaces and large grain size. R-Se grown CIGS solar cells also show concomitant unique properties different from conventional evaporative Se (E-Se) source grown CIGS cells. In the present work, the impact of modified surfaces, interfaces, and bulk crystal properties of R-Se grown CIGS films on the solar cell performance was studied. When a R-Se source was used, Na diffusion into CIGS layers was enhanced while a remarkable diffusion of elemental Ga and Se into Mo back contact layers was observed. Improvements in the bulk crystal quality as manifested by large grain size and increased Na concentration with the use of a R-Se source is expected to be effective to improve photovoltaic performance. Using a R-Se source for the growth of CIGS absorber layers at a relatively low growth temperature, we have successfully demonstrated a monolithically integrated submodule efficiency of 15.0% (17 cells, aperture area of 76.5 cm²) on 0.25-mm thick soda-lime glass substrates.     

悬浮区域熔炼法制备REB6（LaB6、CeB6）单晶体及其表征

采用区域熔炼法成功制备出了高质量、高纯度、大尺寸的LaB6、CeB6单晶体。系统分析了制备过程中每个参数对晶体生长的影响,确定了晶体成长最佳工艺:(1)LaB6:转速为30r/min,生长速度为8～10mm/h,两次区熔;(2)CeB6:转速为30r/min,生长速度15～20mm/h,一次区熔。然后对晶体进行表征,主要方法有单晶衍射、断面扫描、拉曼衍射、摇摆曲线。由此可知悬浮区域熔炼法是制备高质量、高纯度、大尺寸REB6的最佳方法。     

Necking and seed growth of Bi2Sr2CaCu2Ox superconducting single crystals

Single crystals of Bi₂Sr₂CaCu₂O_x were grown using a travelling solvent floating zone technique in an infrared radiation furnace with seed crystals. The purpose of the process was to obtain large single crystals. The use of seed crystals was found to be quite effective for increasing the thickness of the crystal in the c-axis direction. Characterization of the single crystal was investigated using a polarized optical micrograph, EPMA, TEM, RBS and a high resolution X-ray diffractometer.     

Fabrication of heterostructures of halogen-bridged quasi-one-dimensional mixed-valence transition metal complexes

Single-heterostructure crystals of a series of halogen-bridged quasi-one- dimensional mixed-valence transition metal complexes (HMMCs) were fabricated by selective coordination epitaxial growth (SCE growth). The overgrowth crystals of the HMMC were grown on the columnar crystals of the substrate HMMC in solution. The single-heterostructure crystals were epitaxially grown only when the two HMMCs had similar crystal structures. If their crystal structures were different, no heterostructure crystal was grown. This result suggests that the degree of mismatch between the crystal structures of the substrate and the overgrowth is the predominant factor which determines the SCE growth of the HMMCs.     

大尺寸优质金刚石单晶的生长

由于基本解决了晶种法生长金刚石大单晶的若干技术问题,在我国首次生长出尺寸达3.2mm、重40mg 的优质金刚石单晶。     

锥头籽晶对DKDP晶体生长和损伤阈值的影响

籽晶是影响DKDP晶体生长和光损伤阈值的一个重要因素。采用传统降温法,分别利用Z片和锥头作为籽晶,从氘化程度为85%的溶液生长了DKDP晶体,并选取部分样品进行3倍频光损伤阈值测试。实验证明,DKDP晶体可以在不同籽晶下基本实现稳定生长,锥头籽晶所得DKDP晶体对晶体损伤阈值提高有积极作用且能有效缩短生长周期。     

Growth of the non-linear optical crystals of lithium triborate and beta barium borate

LiB₃O₅ single crystals were grown from B₂O₃ self flux solution without N₂ gas flow. The effects of seed orientations and rotation rate on crystal quality and crystal size were investigated. β-BaB₂O₄ crystals were grown by the TSSG technique using NaF as well as Na₂O as the flux. The dimensional variation of grown crystal depending on the flux system was investigated.     

Crucibleless crystal growth and Radioluminescence study of calcium tungstate single crystal fiber

In this article, single phase and high optical quality scheelite calcium tungstate single crystal fibers were grown by using the crucibleless laser heated pedestal growth technique. The as-synthesized calcium tungstate powders used for shaping seed and feed rods were investigated by X-ray diffraction technique. As-grown crystals were studied by Raman spectroscopy and Radioluminescence measurements. The results indicate that in both two cases, calcined powder and single crystal fiber, only the expected scheelite CaWO₄ phase was observed. It was verified large homogeneity in the crystal composition, without the presence of secondary phases. The Radioluminescence spectra of the as-grown single crystal fibers are in agreement with that present in Literature for bulk single crystals, presented a single emission band centered at 420 nm when irradiated with β-rays.     

直流热阴极CVD金刚石薄膜生长特性研究

为了获得高质量的金刚石薄膜,采用直流热阴极化学气相沉积系统分别在不同基片温度和不同碳源气体含量条件下生长金刚石薄膜,利用Raman光谱、SEM和XRD检测方法研究了基片温度和碳源气体含量对金刚石薄膜生长特性的影响.结果表明,金刚石薄膜与基片Mo之间有Mo2C的过渡层存在;1000℃的温度能够促进金刚石晶体的生长,抑制其他碳杂质的形成,CH4体积分数为2%适于快速生长高纯度的金刚石薄膜.