Growth of SiGe bulk crystals with uniform composition by utilizing feedback control system of the crystal–melt interface position for precise control of the growth temperature

We developed an automatic feedback control system of the crystal–melt interface position to keep the temperature at the interface constant during growth, and demonstrate its successful application to grow Ge-rich SiGe bulk crystals with uniform composition. In this system, the position of the crystal–melt interface was automatically detected by analyzing the images captured using in situ monitoring system based on charge-coupled-devices camera, and the pulling rate of the crucible was corrected at every 1 min. The system was found to be effective to keep the crystal–melt interface position during growth even when the variation of the growth rate is quite large. Especially, the interface position was kept for 470 h during growth of Ge-rich SiGe bulk crystal when we started with a long growth melt of 80 mm. As a result, a 23 mm-long Si_0.22Ge_0.78 bulk crystal with uniform composition was obtained thanks to the constancy of the growth temperature during growth through the control of the interface position. Our technique opens a possibility to put multicomponent bulk crystal in a practical use.     

ø300 mm直拉硅单晶生长过程中的变晶现象及其影响因素

直拉法生长直径300 mm硅单晶过程中,直径均匀是获得高品质硅单晶的关键。在生产实践中发现,当硅晶体进入等径生长阶段,过高的提拉速度会引起晶体发生扭晶现象,导致晶线断裂随即变晶,对等径生长不利。本文采用数值模拟和理论相结合的方法分析了ø300 mm硅单晶生长过程中扭晶现象的成因,建立了不同提拉速度下晶体直径与熔体温度分布的关系,分析了晶体发生扭晶的影响因素。结果表明,随着提拉速度的增加,熔体自由表面产生过冷区且该过冷区随提拉速度的增加不断扩大,过冷区的产生是导致晶体发生扭晶的主要原因。提出了一种基于有限元热场数值模拟的最大稳定提拉速度的判别方法,并给出了通过改变晶体旋转速度来改善熔体自由表面温度分布的工艺措施建议,从而避免晶体扭晶现象的发生。研究结果对设计大尺寸硅单晶生长热场具有一定的指导作用。     

Process design for the shape control of crystals grown by Kyropoulos or SAPMAC method

A mathematical model has been proposed to design the process for growing a shaped crystals by Kyropoulos method or SAPMAC method. Crystal shape evolution behaviours under various processes were analysed. The results show that the crystal would go through a transitory shoulder‐expanding stage after which the crystal diameter rapidly decreases under a constant pulling rate and a constant heater temperature. Reducing pulling rate and heater temperature could depress the decrease of crystal diameter after the shoulder‐expanding stage so that enhance the length of crystal. However, the crystal diameter is more sensitive to pulling rate than to heater temperature, and an equal‐diameter crystal can not be grown in non‐undercooled melt by soley reducing the heater temperature. That means that adjusting the pulling rate is the most effective and convenient approach for controlling crystal diameter evolution and simultaneously decreasing both the pulling rate and the heater temperature is the optimal process for growing an equal‐diameter crystal. Moreover, a numerical approach for quantifactional designing crystal shape and corresponding growth processes was proposed according to the model, an example of crystal shape design was given out. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Automated growing of large single crystals controlled by melt level sensor

The process of single crystal pulling is considered with simultaneous starting material make-up into the melt and heater temperature control in response to a signal generated by the electronic contact melt level sensor, viz.: (i) conditions ensuring the radial broadening steadiness; (ii) effect of melt level displacement, melt temperature changes, changes of solid/liquid interface shape, melt evaporation on the growing crystal diameter; (iii) conditions of crystal purification from impurities and uniform distribution of dopant.     

Evaporation induced diameter control in fiber crystal growth by micro‐pulling‐down technique: Bi4Ge3O12

Diameter self‐control was established in Bi₄Ge₃O₁₂ fiber crystal growth by micro‐pulling‐down technique. In accordance with Bi₂O₃‐GeO₂ phase diagram, the diameter was controlled due to compensation of solidification with evaporation of volatile Bi₂O₃ self‐flux charged into the crucible with excess. The crucibles had capillary channels of 310 or 650 μm in outer diameter. The crystals up to 400 mm long and 50‐300 μm in diameter were grown at pulling‐down rates of 0.04‐1.00 mm/min. The melt composition and the pulling rate were generally only two parameters determining solidification rate. As a result, crystals with uniform (± 10%) diameter and aspect ratio up to 10⁴ were produced without automation of the process. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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.     

On the Iso‐Diameter Growth of β ‐BaB2O4 (BBO) Crystals by Flux Pulling Method

The iso‐diameter growth of β ‐BaB₂O₄ (BBO) crystals by the flux pulling method have been studied based on the phase equilibrium diagram in the BaB₂O₄‐Na₂O pseudo‐binary system and from the interface stability. The mathematical expressions for the cooling rate in the growth of the crystals with constant diameter under stable growth conditions are derived, the experimental phenomena such as diameter contraction and difficulty to grow a lengthy crystal by the flux pulling method are explained, the prerequisite for iso‐diameter BBO crystal growth from the flux is suggested; a new continuous charging flux pulling method is introduced to grow large‐sized high quality crystals with a relative high growth rate.     

Ce∶LuAG闪烁晶体的生长研究

Ce∶LuAG晶体是一种性能优良的闪烁材料,但采用提拉法生长Ce∶LuAG时,经常出现开裂和包裹物缺陷。本文通过理论与实践相结合的方式分析了温度梯度、提拉速度、晶体旋转速度和热应变等因素对晶体产生缺陷的影响,并提出了解决办法,给出了适合生长优质Ce∶LuAG晶体的工艺参数:熔体上方温度梯度在5 ℃/mm左右,放肩角度在30°~60°,提拉速度1.0~1.5 mm/h,晶体旋转速度15~25 r/min。最后成功生长出直径30 mm、等径长50 mm质量较为完好的Ce∶LuAG单晶,晶体内核心面积小。     

Crystal pulling with a floating nonwetted shaper

In crystal growth by pulling from the melt, the crystal cross-section can be controlled with the help of a shaper, which in the case of semiconductor and metal single crystals is usually lighter than and not wetted by the melt. In order to better control the crystal cross-section, we controlled the temperature near the aperture of the shaper during crystal growth. Graphite was used as a floating shaper and in order to allow close observation of crystal growth, a low melting-point material, i.e., Sn, was chosen as the melt. Single crystals were grown with excellent control over the cross-sectional shape and size. Single crystals were also grown under two other conditions, i.e., no temperature control and crucible temperature control. The control over the crystal cross-section in these two cases, however, was inferior to that in the case of shaper (aperture) temperature control. This difference was explained with the help of knowledge of the shaper (aperture) temperature, which was measured in each of the three cases.     

Analyses of Crystal Shape Monitoring of LEC-Grown InP Crystals by using a Disc Approximation Approach

This paper analyzes crystal shape monitoring for automatic diameter control (ADC) during the liquid encapsulated Czochralski (LEC) growth of InP crystals. The crystal diameter (shape) is monitored numerically (diagrammatically) by using a disc approximation approach based on precise weight and pulling length measurements. The error in the diameter calculation based on the approximation is estimated to be sufficiently small for practical use. The monitoring accuracy was investigated for crystal bodies with nearly flat growth interfaces, and for their shoulder portions with largely convex growth interfaces. For the straight body portions, the accuracy depended on diameter, d, and improved from ±15% for d=10 mm to ±3% for d=50mm. For the shoulder portions, the diameter was monitored with nearly the same accuracy. This method has therefore made it possible to monitor the growing crystal visually in real time, and was applied to the growth of <111> InP crystals with a cone angle of less than 39° and a smooth appearance to avoid twinning.     

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.     

Effect of the growth rate on thermal conditions during the growth of single crystals with melt feeding

An attempt is made to establish a correlation between the radial and axial growth rates and the change in the conditions of heat transfer from a growing crystal to the atmosphere of the water-cooled vacuum furnace for the growth of large alkali halide single crystals. It is found experimentally that an increase in the growth rate leads to an increase in the automatic compensation of the melt temperature by the main heater. In this case, the thickness of the layer of melt condensate on the end face and the lateral surface of the crystal decreases. It is revealed that the possibility of growing infinitely long ingots in the presence of intense melt evaporation is restricted by the possibilities of the heat transport through the boundary between the furnace atmosphere and the cooled furnace walls, onto which melt condensate deposits.     

Influence of growth conditions on microstructure and properties of GaSe crystals

GaSe crystals have been grown from melt. There are several reasons why it is difficult to meet ideal demands for nonlinear optic material, GaSe single crystal. First, these crystals have a tendency towards lamination because of great difference in a and c crystal lattice parameters and very weak Vander der Waals forces in c direction. Next, there is a great difference in saturation vapor pressure of the components, which can cause nonstoichiometry of a melt-grown crystal composition. Another obstacle in the growth of perfect GaSe crystals is dendrite formation caused by instability of the growth front. To overcome this obstacle we used Bridgman technique and have found the temperature and pressure conditions, and growth velocity which provide growth of perfect bulk single crystals of about 100 mm in length and 20 mm in diameter. Sharp Laue patterns and a rocking curve confirm perfect structure of the grown crystals. Electron-probe X-ray microanalysis shows stoichiometric composition of GaSe crystals and X-ray phase analysis reveals presence of single-phased hexagonal structure.     

Growth of the organic nonlinear optical material mnba-Et (4′-nitrobenzylidene-3-ethylcarbonylamino-4-methoxyaniline) crystals by the czochralski method

For the first time melt growth of the nonlinear optical organic material 4′-nitrobenzylidene-3-ethylcarbonylamino-4-methoxyaniline (MNBA-Et) by the Czochralski (CZ) method has been carried out to achieve single crystals with large diameter. [100] oriented boules having a diameter of 15 mm and maximum height of 15 mm have been prepared. The structural quality of the CZ crystals is comparable to those from solution growth. The colour of the melt and the grown crystal changes from transparent to opaque as a result of using the same melt for multiple growing cycles deteriorating considerably the optical transmittance.     

Pulling CsI(Na) single crystals from melt by continuous method without plastic deformation

It is established that bromine impurity in CsI(Na) crystals not only facilitates the homogeneous incorporation of an activator into the lattice and prevents complex activator clusters from forming, but it also significantly hinders (at certain concentrations) the action of the primary and secondary dislocation slip systems. It is shown that the automatic pulling of large CsI-based crystals can be provided by the introduction of a single Br impurity into the charge; this impurity, to a large extent, strengthens only the top part of the crystal. The absence of plastic deformation in CsI-CsBr(Na) crystals with a diameter Ø300 mm and height h = 600 mm (grown by the continuous method) and Ø500 mm and h = 200 mm (grown by the automatic Kiropulos method) has been experimentally confirmed.     

Improved growth of PbI2 single crystals

The phase equilibrium and the crystallization process of lead iodide (PbI₂) melt have been primarily investigated according to the lead–iodine phase diagram. It is found that the iodine evaporation and the segregated lead deposition are the two important factors that affect the PbI₂ crystal quality. The new method of Pulling U-type quartz growth ampoule has been made to impede the decomposition of PbI₂ and the vaporization and condensation of iodine. An orange and translucent PbI₂ single crystal of large size was obtained by the improved growth method, i.e. U-type ampoule pulling. Resistivity of the as-grown crystal is up to 4×10¹¹ Ω cm, and IR transmission is up to 45% in the region from 7800 to 450 cm⁻¹. Therefore, the improved growth method is a promising convenient new method for the growth of high quality PbI₂ crystals.     

Growth and Optical Properties of Doped LiTaO3 Single Crystals

Single crystals of lithium tantalate (LiTaO₃) doped with Pr, Nd + Yb and Tm were grown by the Czochralski method. A thermal system with 50 mm diameter iridium crucible and two different afterheaters (active and passive) was checked with respect to temperature distribution in a pulling region. The obtained crystals were up to 20 mm in diameter and up 50 mm in length. Crystals were poled, and the Curie temperature was determined for specimens cut of from different parts of single crystals. The polarized absorption spectra, time resolved emission spectra and emission lifetime of Pr³⁺ doped LiTaO₃ crystals were measured. An intense emission from the ³P₀ level was observed. Optical properties of the Yb³⁺ ions excited by energy transfer from Nd3+ ions have been researched for LiTaO₃:Nd, Yb crystals.     

A new optical medium—Cd<Subscript>0.75</Subscript>Sr<Subscript>0.25</Subscript>F<Subscript>2</Subscript> single crystals

For the first time, single crystals of the Cd_0.75Sr_0.25F₂ solid solution with the fluorite structure are grown from melt by the Bridgman-Stockbarger method. The composition of these single crystals corresponds to the composition congruently melting at the minimum point on the phase diagram. The maximum diameter of the crystal is 50 mm; the maximum height is 30 mm. The vickers microhardness of the semitransparent crystals equals 191 ± 43 kg/mm². The transmission cutoff in the IR range is ～10 μm.     

Growth of Tb3Ga5O12 fiber and bulk crystals using micro-pulling-down apparatus

A micro-pulling-down process, using Ir crucibles and RF heating, has been used to grow single-crystal fiber and bulk crystals of Tb₃Ga₅O₁₂ garnet (TGG). Single crystals ranging up to 450 mm in length have been produced. The crystals were 1–4 mm in diameter and were seeded-grown in the direction close to 1 1 1. The maximal crystal diameter achieved was 10 mm. Dependence of behavior of the solid–liquid interface on the growth parameters (temperature and pulling-rate) is discussed in detail.     

Comparison of Ba(B1-xAlx)2O4 Single Crystals on their Diameters

Small diameter crystals of Ba(B_1-xAl_x)₂O₄ were grown by Floating zone pulling down method and Micro-pulling down method to be compared with large diameter crystals grown by Czochralski method. While the Czochralski grown crystal was opaque, the crystal transparency was actually improved with the decrease of crystal diameter, i.e., the decrease of constitutional supercooling. The reason was the increase of temperature gradient caused by down-sizing of the crystal diameter deduced by down-sizing of the growth furnace. The adequate diameter for transparent crystal was determined depending on the Al content.