Behavior of phosphorus impurities during Czochralski growth of high‐purity germanium single crystals

The effect of evaporation of phosphorus impurities from the melt is investigated as well as the contaminating effect of quartz glass crucibles on residual content and distribution of this impurities by length of high‐purity germanium single crystals. The residual content of phosphorus impurities is mainly influenced by the contaminating effect of crucible material and its distribution by length of crystals is described by the model accounting for the impurities income from crucible material. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

硒化镉多晶原料的提纯

采用改进的垂直无籽晶气相法生长大尺寸高质量的CdSe单晶体要求原料的纯度高。本文根据差热(DIA)和热失重(TG)测试结果，设计出连续抽空区域升华提纯CdSe原料的新方法，用该方法提纯的原料生长出大尺寸、高质量的GtSe单晶体。等离子体质谱仪(ICP-MS)分析结果表明，新方法对CdSe的提纯是有效的，纯化后的原料可以生长出大尺寸高质量的CdSe单晶体。     

Growth of ultra‐high purity PbI2 single crystal: (1) Preparation of high purity PbI2

In order to prepare high purity lead iodide (PbI₂) single crystals, the starting material‐iodine (I) has been purified by the sublimation method, and the PbI₂ polycrystalline by the normal freezing method. The purification effect of these methods has been confirmed by evaluating the impurity concentration in ingot by glow discharge mass spectrometry (GDMS) analysis. By comparing the purity of three different starting materials, non‐purified iodine+6N‐Pb, purified iodine+6N‐Pb and commercial 6N‐PbI₂, PbI₂ synthesized by purified iodine in the present experiment has the highest purity. This indicates that these purification methods are suitable. The present research results are expected to prepare high‐resistivity PbI₂ used in radiation detector. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Singular ring‐shaped distribution of Nd in NdxY1‐xVO4 crystals grown by floating zone method

A singular ring‐shaped distribution of high Nd concentration was observed in Nd‐doped YVO₄ single crystals grown by the floating zone (FZ) method. The ring‐shaped distribution appeared 500‐1000 μm inside from the rim of the crystals. Results of growth experiments by the anisotropic heating floating zone (AHFZ) method showed that the Nd concentration was high at the high‐temperature side of the grown crystals. We found a small concave projection at a part of the convex solid‐liquid interface by quenching the molten zone during growth. The cause of the singular ring‐shaped distribution of the Nd‐rich area was discussed in relation with the concave projection at the interface and the convection in the molten zone. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Simulation of dopant zone-leveling in a solid ingot

Simple simulation procedure permitting to perform accurate calculations of the dopant distribution in an ingot after desired number of passes of the molten zone is presented. The results obtained for various distribution coefficients and various widths of the molten zone are discussed. It is shown that the number of passes indispensable for the dopant concentration leveling drastically decreases with the width of the molten zone even for the most disadvantageous range of the distribution coefficients.     

Radial and axial impurity distribution in high-purity germanium crystals

To grow high purity germanium (HPGe) crystals in an underground environment for ultra-low background experiments is being studied. In the present work, HPGe crystals along 〈100〉 direction have been grown by the Czochralski method. In order to investigate the distribution of the impurities as a function of length for a grown crystal, i.e. the axial direction, we fabricated a system to measure the resistivity along the axial direction at both room temperature and liquid nitrogen temperature. The distribution of the impurities along the radial direction was measured with a Hall Effect System. The results show that the carrier concentration in some crystals grown in a hydrogen atmosphere has an impurity level of about 10¹⁰/cm³, which meets the requirements of detector-grade crystals.     

Preparation of Oriented Single Crystals of Iron and Dilute Iron-Silicon Alloys by the Strain Anneal Technique

Single crystals with demanded crystallographic orientation of the crystal axis, of iron and iron alloyed with some 0.5 and 0.9 wt % silicon were prepared by the strainanneal method. The raw materials used in this study were powder carbonyl iron and pure silicon. Attempts to grow single crystals from vacuum melted iron containing about 1200 ppm oxygen were unsuccessful. The large pinning of grain boundaries by second phase particles is assumed to be the main factor influencing grain boundary mobility. From materials zone refined in hydrogen atmosphere single crystals of Fe, Fe−0.5 and 0.9 wt % Si were readily prepared and the yield of 90% of oriented single crystal was obtained. It was found that the number of twin grains on the crystal surfaces was rapidly lowered on increasing the silicon content.     

熔盐法制备三元层状MAX相陶瓷的研究进展

MAX相是一种兼具金属和陶瓷性能的新型三元层状过渡金属碳氮化物。传统合成MAX相的方法都有一定的局限性,如反应温度较高、合成时间过长、合成样品较少,且大部分无法直接一步制备所需MAX相。近些年来,采用熔盐法合成MAX相的报道越来越多,并且工艺持续改进。本文从传统熔盐法合成MAX相出发,分析并阐述了新熔盐法合成MAX相的研究进展。传统熔盐法利用较低熔点的熔盐作为反应溶剂,提高了反应效率;熔盐屏蔽法以熔盐作为反应溶剂的同时还可防止氧化,使得反应可以在空气中进行;路易斯酸盐法则是将熔盐作为反应原料来合成MAX新相;熔盐电化学法以电脱氧的方式,将合成原料由纯金属改为金属氧化物,降低了生产成本。熔盐法所合成MAX相产物较传统方法所合成产物的产量及纯度更高,所需要的温度、能耗以及成本更低。因此,熔盐合成法是未来大批量合成MAX相以及MAX新相合成的一个重要方法。     

The Properties of Undoped InP and GaP Bulk Crystals Prepared by Floating Zone Melting

Undoped GaP and InP crystals which are produced by floating zone melting without a crucible were investigated. The background concentration was 10¹⁵cm⁻³ after several passages of the molten zone. The fundamental residual impurities are carbon and silicon penetrating into the crystals during the crystallization process. After purification, the electron mobility of GaP was 200 cm²/V. s, and for InP – 4000 cm²/Vs. The compensation decreased to 20%. A very effective purification was observed with respect to the carbon atoms, but for silicon this result is observed only after several passages of the molten zone. GaP and InP are basic materials for optoelectronic devices and it is important to investigate the possibility for production of pure bulk crystals. A proper method for this aim is the floating zone melting, where the crucible effect is removed and the influence of residual impurities is observed. In this work the influence of the number of floating zone passages on the electrical and luminescence properties of InP and GAP bulk crystals has been investigated.     

Effect of Annealing on the Luminescene Property of PbWO4 Crystals Grown by the Czochralski Method

PWO Crystals grown by the Czochralski method were annealed under different conditions. The transmittance of PWO crystal was decreased when it was annealed in anoxygen‐rich environment; where as it was in creased when the crystal was annealed in vacuum. A mechanism on the transmittance change was proposed. The main peaks of X‐ra y exite demission spectra showed that both as‐grown and vacuum‐annealed crystals fit into blue light region with the latter one showing higher intensity. The oxygen‐rich annealed crystals hifted to longer wave length of green light region at lower intensity. The faster components in the light yield of crystals annealed in vacuum were higher correspondence to its higher intensity of the blue light.     

Purification and crystal growth of TlBr for application as a radiation detector

Thallium bromide is a semiconductor compound with high atomic number and density. It has a CsCl‐type simple cubic crystal structure and it is non‐hygroscopics. The TlBr crystals are relatively soft with a knoop hardness number of 12. In this work, the TlBr commercial powder was purified by zone refining and the purest material section was used for crystal growth by Bridgman method. Efforts have been concentrated on the purification of the TlBr. The purification efficiency has been evaluated (NAA and ICP‐MS) by impurities reduction results after zone refining passes. The crystalline quality was evaluated by X‐ray diffraction. The characterized TlBr crystal as a detector has shown good response to gamma radiation. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

红外LED用GaAs单晶的垂直梯度凝固制备研究

GaAs单晶是当前光电子器件的主要衬底材料之一,在红外LED中有着重要应用。但杂质浓度高、迁移率低等缺点会严重影响红外LED器件性能。为生产出低杂质浓度、高迁移率、载流子分布均匀、高利用率的红外LED用掺硅垂直梯度凝固(VGF)法GaAs单晶,本文研究了热场分布、合成舟和炉膛材质、工艺参数对单晶的成晶质量、杂质浓度、迁移率、载流子分布的影响。利用CGSim软件对单晶生长热场系统进行数值模拟研究,温区一至温区六长度比例为8∶12∶9∶5∶5∶7时,恒温区达到最长,位错密度达到1 000 cm^-2以下,成晶率达到85%。采用打毛石英合成舟进行GaAs合成,用莫来石炉膛替代石英炉膛,可以获得迁移率整体高于3 000 cm²/(V·s)的GaAs单晶,满足红外LED使用要求。对单晶生长工艺参数展开研究,采用提高头部生长速度、降低尾部生长速度的方式提高单晶轴向载流子浓度均匀性,头尾部载流子浓度差降低33%,尾部迁移率从2 900 cm²/(V·s)提高到3 560 cm²/(V·s)。单晶有效利用长度提高33...     

Vapour growth and morphology of PbBr2 crystals

In this paper, the vapour transport of PbBr₂ under vacuum during vacuum distillation refining and its condensation on the wall of the vessel were described. The macro‐ and micro morphologies of PbBr₂ crystals grown in the vessel (glass tube) were studied. The crystal shape changed dramatically depending on the positions of condensation in the vessel, i.e., the crystal shape varied from an isometric polyhedron to columnar crystals with facets, and to a massive crystal without facets with a rise in the wall temperature. These results were interpreted in terms of the concentration gradient of the molecules in the vessel, surface roughening and/or surface melting of the crystals. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

ZnGeAs2多晶合成与表征

ZnGeAs2是黄铜矿结构的三元化合物半导体材料,在红外非线性光学方面有重要应用前景.本文探讨了ZnGeAs2多晶的形成途径和合成机理,报道了一种ZnGeAs2多晶合成方法.以高纯(6N)Zn、Ge、As单质为原料,按化学计量比,富Zn1‰和As2‰配料,采用双温区合成方法,辅以机械、温度振荡和梯度降温的合成工艺,合成出均匀致密的单相ZnGeAs2多晶.经XRD和EDS分析表明:合成产物为黄铜矿结构的单相ZnGeAs2多晶,晶胞常数为a=b=0.56745 nm,c=1.11580 nm,与标准PDF卡片(No.730397)一致;各组成元素的原子比Zn∶Ge∶AS=1.00∶0.98∶1.95,接近理想化学计量比.上述分析结果表明,合成产物可用于ZnGeAs2单晶生长,为进一步研究ZnGeAs2晶体的非线性光学性能和应用奠定了较好的基础.     

Production of high purity TeO2 single crystals for the study of neutrinoless double beta decay

High purity TeO₂ crystals are produced to be used for the search for the neutrinoless double beta decay of ¹³⁰Te. Dedicated production lines for raw material synthesis, crystal growth, and surface processing were built compliant with radio-purity constraints specific to rare event physics experiments. High sensitivity measurements of radio-isotope concentrations in raw materials, reactants, consumables, ancillaries, and intermediary products used for TeO₂ crystals production are reported. Indications are given on the crystals perfection and how it is achieved and maintained in a large scale production process. Production and certification protocols are presented and resulting ready-to-use TeO₂ crystals are described.     

Floating zone growth of high-quality SrTiO3 single crystals

Strontium titanate single crystals 15–20 mm in diameter and 40–80 mm in length were grown by a floating zone method with radiation heating. Additional crystal heating just below the molten zone by an in-growth annealing furnace was applied in order to lower the temperature gradients and to achieve slower cooling of the grown crystal. The crystal perfection was studied with X-ray topography and double-crystal diffractometry. The most perfect crystals were grown in [0 0 1] direction with single grain rocking curve widths of about 30″ and subgrain misorientations of 1′–3′ over 10×10 mm² areas of the boule cross-section for both (0 0 1)-, (1 1 0)- and (1 1 1)-oriented slices. Such high-quality crystal can be grown reproducibly with starting materials of 4N grade quality.     

基于迁移学习的大尺寸铸锭晶体硅热场设计

不同尺寸的铸锭晶体硅生长过程具有相似性,小尺寸晶体的生长规律可以迁移至大尺寸。本文采用迁移学习(TL)对G8型铸锭炉进行热场设计,设计对象为侧、顶加热器位置及体积、侧隔热笼分区块高度,主要设计目标为减少晶体内部的位错缺陷、抑制硅锭边缘多晶且使晶体生长界面微凸。首先使用神经网络对已有的G7铸锭炉建立热场几何参数与热场评价参数间的映射模型,然后将该模型迁移至G8铸锭炉,对比不同模型结构对迁移过程的影响,采用Dropout分析模型是否存在过拟合,并使用遗传算法(GA)结合聚类算法(CA)对热场几何参数进行优化,以上为G8热场设计过程。最后对优化结果采用数值模拟方法研究其在晶体生长过程中的温度分布、固液界面形状等,最终选定的优化方案能够实现较高质量的长晶。将该方案同时应用于G7和G8热场并进行对比,结果表明G8在硅熔体和硅晶体中的轴向温度梯度均小于G7,在晶体生长界面沿径向的温度梯度也小于G7,这有利于减小晶体内部的热应力。     

Connection of the Thermocapillary Flow Characteristics and the Impurity Distribution Pattern in Floating Zone Molten Molybdenum Single Crystals

The results of the impurity distribution in W-doped Molybdenum single crystals grown by electron beam floating zone melting are related to the characteristics of computed steady thermocapillary flow and impurity distribution within the molten zone. Particularly the influence of the number and the strength of eddies in the molten zone on the impurity distribution pattern in the grown crystal for different aspect ratios is considered.     

Simplified version of calculation of the composition distribution along a single crystal of a binary solid solution obtained by pulling from a feeding melt

The possibility of obtaining single crystals of binary solid solutions exhibiting strong segregation upon crystallization by pulling from a feeding melt with the use of a crucible shaped as a truncated cone and a feeding ingot of complex shape is shown. The composition distribution along the crystal length is found by solving the continuity equation for the second component flux under certain initial and boundary conditions. It is shown that single crystals can be obtained in which the second-component concentration in the stationary mode exceeds the corresponding value in the feeding ingot. The method developed is applied to Ge-Si solid solutions.     

Numerical study of influences of buoyancy and solutal Marangoni convection on flow structures in a germanium‐silicon floating zone

This paper presents a numerical study of Marangoni flows in a floating zone of germanium‐silicon crystals, which was performed by using a commercial finite element program FIDAD^TM. The numerical results point out that for fluids with a small Pr number the influence of buoyancy forces cannot be ignored in the numerical model. Furthermore, the competition between the thermocapillary (TC) and solutocapillary (SC) flows in the floating zones was qualitatively examined. If the TC flow is as strong as that in the Si‐rich floating zone, the SC flow may be restricted to the bottom area near the free surface. Otherwise, the SC flow may overcome the TC flow and induce a surface transfer of species. The numerical predictions agree well with the previous experiment results. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)