Thermal stress relaxation phenomenon through forming the interstitial region in CZ silicon pulled with rapid and slow cooling heat shields

This review article aims to clarify a mechanism of point defects formation in a CZ Si crystal through an experimental arrangement using the two kinds of heat shields with different slow-pulling periods. Point defects in a melt grown silicon crystal have been studied for a long time. The author and his co-researchers have reported about “Mechanism for generating interstitial atoms by thermal stress during silicon crystal growth” [in Progress in Crystal Growth and Characterization of Materials, 66 (2019) 36-46]. The experimental arrangement includes constant growing, changing pulling rate and finally detaching crystals from the melt. The two types of heat shields were used to change the cooling history of the grown crystals, for changing a temperature gradient at a bulk part in the grown crystal, G_b. In order to prove that the formation of an interstitial region or a boundary of vacancies (Vs)/interstitials (Is) in a silicon crystal is a phenomenon of relaxing thermal stress, the author explains that a G_b in a crystal forms thermal stress and causes some silicon atoms at lattice positions to move to the closest interstitial sites to relax the stress. The author defines a new term of metastable interstitial atom, I’, or I's as the plural of I’. The I’ coexists with the metastable vacancy V’ from where the I’ is displaced. The plural of V’ is defined to be V's. The author defines the above state to be a complex (I’+ V’), or (I ’+ V’)s as the plural of (I’+ V’), and explains that the (I’+ V’) s convert to Is and form the Is region. The (I’+ V’) is considered as the Frenkel pair-like complex.The crystals were firstly pulled with a high pulling rate, and the pulling rate was consequently decreased to a slow one. Then the crystals were pulled with the slow constant pulling rate for different periods making different cooling processes. Finally, the grown crystals were detached from the melt and cooled rapidly. Characterization of defects, such as Vs, Is, and defect-free (D-F) regions were identified in X-ray topographs (XAOP(s)). Wafer lifetime mapping (WLTM(s)) allows confirming dislocation loop (DL) regions. The results show that the Is are generated depending on the pulling period of the slow pulling and the shapes of the heat shields. The Is and DL regions are formed in a region at temperatures near the melting point. The Is form an Is region through a defect-free (D-F) region, forming the Vs/Is boundary. When the thermal stress weakens, the DL region changes to the Is region; the Is region changes to the D-F region; and the D-F region changes to the Vs region. Temperature gradient distribution is induced toward various directions at different parts of the growing crystal depending on the different slow-pulling periods. The temperature gradient, G_b, includes a temperature gradient from the cooled region shaded by the heat shield to the growth interface and a temperature gradient from the upper surface cooled during the long-time growth to the growth interface. The G_b exceeding a certain threshold at near the melting point forms thermal stress, generating Is to relax the stress.     

声光晶体TeO2的生长及缺陷研究

本文研究了直接ＴeO２晶体中的主要晶体缺陷形成机理,讨论分析了Ｔ eO2单晶生长的工艺参数对晶体缺陷的影响,结果表明：晶体裂缝的主要与温度梯度有关,温度梯度大于２０－２５℃/cm及出现界面翻转时,易造成晶全的开裂,位错密度增加,晶体中的包裹体主要为气态包裹全,它的形成主要与籽晶的转速和晶体的提拉速率有关,转速１５－１８r/min,拉速０.55mm/h,固液界面微凹,可以减少晶体中的气态包裹体,晶体台阶由晶体生长过程中温度和生长速度的引起伏引起,当台阶间距较宽时,易形成包裹体。     

CZ法生长参数对TeO2晶体质量的影响

本文主要讨论CZ法生长TeO2晶体中温度梯度、拉速、转速等工艺参数对晶体质量的影响,分析了晶体开裂、包裹物等宏观缺陷以及位错等微观缺陷的形成机理.从晶体形态、包裹体和位错密度变化等方面探讨了晶体生长参数与晶体缺陷之间的内在关系.     

Synthesis of chalcogenide and pnictide crystals in salt melts using a steady-state temperature gradient

Some examples of growing crystals of metals, alloys, chalcogenides, and pnictides in melts of halides of alkali metals and aluminum at a steady-state temperature gradient are described. Transport media are chosen to be salt melts of eutectic composition with the participation of LiCl, NaCl, KCl, RbCl, CsCl, AlCl₃, AlBr₃, KBr, and KI in a temperature range of 850–150°C. Some crystals have been synthesized only using a conducting contour. This technique of crystal growth is similar to the electrochemical method. In some cases, to exclude mutual influence, some elements have been isolated and forced to migrate to the crystal growth region through independent channels. As a result, crystals of desired quality have been obtained using no special equipment and with sizes sufficient for study under laboratory conditions.     

Bridgman growth and properties of potassium lithium niobate single crystals

Transparent KLN crystals 10mm in diameter and 25 to 45mm in length have been grown by the modified vertical Bridgman technique from different melts in the range of 3035mol% K₂O, 1723mol% Li₂O and 4350mol% Nb₂O₅. The growth conditions are a growth rate of less than 0.25 mm/hr, temperature gradient in solid-liquid interface of 23 °C/mm and growth direction of <110>. As-grown KLN crystals have tetragonal tungsten bronze structure. Most of the as-grown crystals do not crack when cooling through the paraelectric/ferroelectric phase transition. 180° domain structures are observed after the KLN crystal was etched in boiling 2HNO₃:Hf. Dielectric properties and transmission spectrum of the as-grown KLN crystals are measured.     

Crystal growth of β-Phthalocyanines from the vapour phase in closed ampoules

An influence of temperature gradient, inert gas pressure and pulling rate on the growth parameters of β-phthalocyanine single crystals grown in the closed ampoules is investigated. The morphology and structure — sensitive properties of β-CuPc crystals grown under different conditions are compared.     

General principles of the synthesis of chalcogenides and pnictides in salt melts using a steady-state temperature gradient

The possibilities of growing crystals of metals, alloys, chalcogenides, and pnictides in halide melts using a steady-state temperature gradient are analyzed. Halides of alkali metals and aluminum can be used as transport media. The choice is determined by the melting temperature of salt mixtures. A conducting contour can also be applied to increase transport efficiency. This technique of crystal growth is similar to the electrochemical method. To eliminate interference during migration, some elements can be isolated and forced to migrate through independent channels to the crystal formation region. The technique considered here makes it possible to grow crystals of necessary quality without special equipment; the small crystal sizes are sufficient for laboratory study.     

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.     

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.     

Étude expérimentale des paramètres thermiques qui conditionnent la pureté de monocristaux de gallium obtenus par tirage

Crystal shape, temperature gradient at the interface and efficiency of solute rejection are studied as a function of the initial melt temperature for gallium single crystals grown by the pulling technique. In an alloy containing about 100 ppm Ag, the critical temperature gradient where a constitutional supercooling occurs, is found to be close to 8.8°C cm⁻¹.     

大尺寸电阻加热式碳化硅晶体生长热场设计与优化

大尺寸低缺陷碳化硅(SiC)单晶体是功率器件和射频(RF)器件的重要基础材料,物理气相传输(physical vapor transport, PVT)法是目前生长大尺寸SiC单晶体的主要方法。获得大尺寸高品质晶体的核心是通过调节组分、温度、压力实现气相组分在晶体生长界面均匀定向结晶,同时尽可能减小晶体的热应力。本文对电阻加热式8英寸(1英寸=2.54 cm)碳化硅大尺寸晶体生长系统展开热场设计研究。首先建立描述碳化硅原料受热分解热质输运及其多孔结构演变、系统热输运的物理和数学模型,进而使用数值模拟方法研究加热器位置、加热器功率和辐射孔径对温度分布的影响及其规律,并优化热场结构。数值模拟结果显示,通过优化散热孔形状、保温棉的结构等设计参数,电阻加热式大尺寸晶体生长系统在晶锭厚度变化、多孔介质原料消耗的情况下均能达到较低的晶体横向温度梯度和较高的纵向温度梯度。     

φ200mm蓝宝石晶体生长工艺研究

采用单晶提拉炉成功生长出φ200mm ×180mm大尺寸Al2O3晶体.探讨了晶体生长工艺参数和晶体开裂之间的关系,并讨论了晶体中的热应力、热应变、温度梯度、提拉速度之间的关系,分析了影响晶体质量主要是晶体开裂的原因,设计出生长大尺寸Al2O3晶体的最佳工艺条件.     

碲锌镉垂直布里奇曼法晶体生长过程固液界面的演化

计算模拟了半导体材料碲锌镉垂直布里奇曼法单晶体生长过程,以等温线图展示了固液界面形状的演化,分析了温度梯度和坩埚移动速率对固液界面形状以及晶体内组分偏析的影响.计算结果表明在凝固的初始段,固液界面的凹陷深度较大,随后有较大幅度的减小.整个凝固过程中固液界面的凹陷深度值有一定的波动性.提高温度梯度、降低坩埚移动速率均能有效地减小固液界面的凹陷,改善晶体的径向组分偏析.     

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.     

半导体单晶生长过程中的位错研究

阐述了现有的半导体单晶位错模型,即临界切应力模型和粘塑性模型的基本理论及应用状况.分析了熔体法单晶生长过程中影响位错产生、增殖的各种因素,以及抑制位错增殖的措施.与熔体不润湿、与晶体热膨胀系数相近的坩埚材料,低位错密度的籽晶可有效地抑制生长晶体的位错密度;固液界面的形状及晶体内的温度梯度是降低位错密度的关键控制因素,而两因素又受到炉膛温度梯度、长晶速率、气体和熔体对流等晶体生长工艺参数的影响.最后,对熔体单晶生长过程的位错研究进行了展望.     

On the void distribution and size in shaped sapphire crystals

Ribbon and rod sapphire pulling has been performed in three different crystal growth equipments in order to study the effect of the installation, of the atmosphere, of the die shape, of the feed material and of the pulling rate on the distribution, number and diameter of the characteristic voids (micro‐bubbles) in the crystals. The location of the bubbles in the crystals depends on the die geometry; however, in most cases they are essentially located close to the crystal periphery and then can be efficiently removed by lapping. After statistical analysis of the results, it is demonstrated that the number of gas moles incorporated in the crystals, inside the voids, is totally independent of any growth parameter. It is also shown that the bubble diameter depends only on the pulling rate. Consequently, for a given pulling rate, the number of bubbles auto‐adjusts in order to satisfy the constant molar gas incorporation. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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.     

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)     

Compositional Effects on Solidification of Congruently Melting InSb

In vertical Bridgman and Czochralski growth of stoichiometric electronic materials such as InSb, GaSb, and GaAs, growth from stoichiometric melts is commonly desired to achieve high quality. Off-stoichiometric growth is considered significant in the quest to understand transport phenomena leading to the observed sporadic inclusions. Here we apply radiographic interface visualization and calibrated interface temperature measurements to study growth of InSb from off-stoichiometric melts. The crystals are analyzed for structure and chemical segregation. Results indicate concentration boundary layer formation in the melt ahead of the interface. Evidence is presented for heterogeneous nucleation sites within αInSb. Analysis indicates that these nucleation sites develop ahead of the interface in the off-stoichiometric melt phase as the melt temperature at the interface drops below the congruent melting temperature of αInSb.     

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...