Preparation of Φ420 mm Ultra Large Diameter Infrared Germanium Single Crystals AITranslate

［1］（左建坤， 潘美妍， 段辉高， 贾红辉， 胡跃强. 新型红外隐身结构材料研究综述 ［J］.光电工程， 2023， 50（5）： 7.）

J K Zuo， M Y Pan， H G Duan， H H Jia， Y Q Hu. A review of new infrared stealth structural materials ［J］. Photoelectric Engineering， 2023， 50（5）： 7.

［2］（黄宇飞， 徐嘉， 白绍竣， 高冀， 李昂， 高洪涛. 卫星红外遥感术及其在防灾救灾中的应用研究 ［J］. 航天返回与遥感， 2020， 41（5）： 118.）

Y F Huang， J Xu， S J Bai， Y Gao， A Li， H T Gao. Satellite infrared remote sensing technology and its application in disaster prevention and relief ［J］.Space Return and Remote Sensing， 2020， 41（5）： 118.

［3］（董汝昆， 吴绍华， 王柯， 尹国良， 史娜娜， 姚杨， 郭晨宇. 锗单晶材料的发展现状 ［J］.红外技术， 2021， 43（5）： 510.）

R K Dong， S H Wu， K Wang， G L Yin， N N Shi， Y Yao， C Y Guo. Development status of germanium single crystal materials ［J］.Infrared Technology， 2021， 43（5）： 510.

［4］（马奎， 洛桑才仁， 陈超， 张万益， 王丰翔. 全球锗资源分布、供需及消费趋势研究 ［J］.矿产保护与利用， 2019， 39（5）： 16.）

K Ma， C R Luosang， C Chen， W Y Zhang， F X Wang. Global Distribution， supply， demand and consumption of germanium resources ［J］.Mineral Protection and Utilization， 2019， 39（5）： 16.

［6］（李宝学， 赵燕， 罗玉萍， 孙吉单. 大直径锗单晶制备工艺研究及其指标分析 ［J］.云南冶金， 2016， 45（6）： 50.）

B X Li， Y Zhao， Y P Luo， J D Sun. Study on the preparation of large-diameter germanium single crystal and its index analysis ［J］.Yunnan Metallurgical， 2016， 45（6）： 50.

［7］（陈安萌， 梁德印， 聂云松， 李昊谦， 韩波. “资源一号”02E星红外相机探测器成像验证方法研究 ［J］.航天返回与遥感， 2021， 42（4）： 37.）

A M Chen， D Y Liang， Y S Nie， H Q Li， B Han. Study on the imaging verification method of “ZY-1” 02E infrared camera detector ［J］.Space Return and Remote Sensing， 2021， 42（4）： 37.

［8］（葛桓宇， 肖正航， 王跃. 基于热变形补偿的双材料低温镜头支撑结构研究 ［J］.航天返回与遥感， 2022， 43（3） ： 69.）

H Y Ge， Z H Xiao， Y Wang. Study on bi-material cryogenic lens support structure based on thermal deformation compensation ［J］.Space Return and Remote Sensing， 2022， 43（3）： 69.

［9］（马绍芳， 裴玉兰， 冯德伸， 解红霞. 大直径红外光学锗单晶 ［J］.广东微量元素， 1998， 5（2）： 64.）

S F Ma， Y L Pei， D S Feng， H X Xie. Large diameter infrared optical germanium single crystal ［J］.Guangdong Micronutrient， 1998， 5（2）： 64.

［10］（潘朝猛， 康丽珠， 罗敏， 陶亮， 陈树刚， 陈波， 白忠宏， 崔海， 徐参军， 赵劲松. 空间红外相机技术发展现状及应用 ［J］.红外技术， 2022， 44（11）： 1186.）

C M Pan， L Z Kang， M Luo， L Tao， S G Chen， B Chen， Z H Bai， H Cui， C J Xu， J S Zhao. Development and application of space infrared camera technology ［J］. Infrared Technology， 2022， 44（11）： 1186.

［11］（张红勇， 姚婕. 锗单晶直拉生长法的自动等径控制方法［P］. 中国， CN 102758250A， 2012.）

H Y Zhang， J Yao. An automatic equal diameter control method for Czochralski growth of germanium single crystal［P］. China， CN 102758250A， 2012.

［12］（高欢欢， 黎建明， 冯德伸， 王霈文， 李葳. <100>p型4英寸无位错锗单晶的研制 ［J］.稀有金属， 2018， 42（3） ： 285.）

H H Gao， J M Li， D S Feng， P W Wang， W Li. Preparation of p-type 4-inch dislocation-free germanium single crystals ［J］.Chinese Journal of Rare Metals， 2018， 42（3）： 285.

［13］（丁国强， 苏小平， 张峰燚， 黎建明， 冯德伸. VGF法生长6英寸Ge单晶中热应力的数值模拟优化 ［J］.稀有金属， 2011， 35（2）： 244.）

G Q Ding， X P Su， F Y Zhang， J M Li， D S Feng. Numerical simulation optimization of thermal stress in 6-inch GE single crystal grown by VGF method ［J］. Chinese Journal of Rare Metals， 2011， 35（2）： 244.

［14］（肖祥江， 惠峰， 董汝昆， 吕春富. 用VGF法生长6英寸锗单晶中籽晶熔接工艺研究 ［J］.半导体技术， 2017， 42（11）： 860.）

X J Xiao， F Hui， R K Dong， C F Lv. Research on fusion technology of 6-inch germanium single crystal by VGF method ［J］. Semiconductor Technology， 2017， 42（11）： 860.

［15］（陈燕. 直拉法生长锗单晶的水平放肩工艺实践 ［J］. 云南冶金， 2002， 31（6）： 36.）

Y Chen. The practice of horizontal shoulder-laying process for the growth of germanium single crystals by Czochralski method ［J］.Yunnan Metallurgy， 2002， 31（6）： 36.

［16］（原洛渭， 高利强. 双段式加热锗单晶生长设备的结构设计 ［J］.电子工业专用设备， 2008， 157（2）： 11.）

L W Yuan， L Q Gao. Structure design of double-stage heating equipment for germanium single crystal growth ［J］.Special Equipment for Electronic industry， 2008， 157（2）： 11.

［17］（冯德伸， 苏小平， 闵振东， 尹士平. Φ300 mm红外锗单晶生长及性能测试 ［J］.稀有金属， 2006， 30（5）： 694.）

D S Feng， X P Su， Z D Min， S P Yin. Growth and properties of Φ300 mm infrared germanium single crystal ［J］. Chinese Journal of Rare Metals， 2006， 30（5）： 694.

［18］（陈晨， 赵堃， 韩焕鹏. 6英寸低位错锗单晶生长热场设计 ［J］.人工晶体学报， 2021， 50（6）： 979.）

C Chen， K Zhan， H P Han. Thermal field design of 6-inch low dislocation germanium single crystal growth ［J］. Journal of Intraocular Lenses， 2021， 50（6）： 979.

［19］（闫洪. Φ6.5 mm×8.9 mm半导体锗单晶圆片电阻率的测定 ［J］.电子质量， 2007， （10）： 50.）

H Yan. Determination of resistivity of Φ6.5 mm×8.9 mm semiconductor germanium single crystal wafer ［J］. Electronic Mass， 2007， （10）： 50.

［20］（单志远， 秦瑞锋， 宁永铎， 李洋， 张果虎. 水平超导磁场直拉法硅单晶熔体过热现象 ［J］.稀有金属， 2023， 47（7）： 1050.）

Z Y Shan， R F Qin， Y D Ning， Y Li， G H Zhang. Phenomenon of melt superheating during Czchralski silicon crystal growth under horizontal superconducting magnetic field ［J］.Chinese Journal of Rare Metals， 2023， 47（7）： 1050.

［21］（左建龙， 冯德伸， 李楠. 锗单晶中位错密度的影响因素 ［J］.稀有金属， 2010， 34（5）： 726.）

J L Zuo， D S Feng， N Li. The influence factors of dislocation density in germanium single crystal ［J］. Chinese Journal of Rare Metals， 2010， 34（5）： 726.

［22］（穆宏赫， 王鹏飞， 施宇峰， 张中晗， 武安华， 苏良碧. 热交换坩埚下降法制备大直径氟化铈晶体的热场设计与优化 ［J］.无机材料学报， 2023， 38（3）： 288.）

H H Mu， P F Wang， Y F Shi， Z H Zhang， A H Wu， L B Su. Design and optimization of thermal field of large-size cerium fluoride crystal prepared by heat exchange crucible descent method ［J］.Journal of Inorganic Materials， 2023， 38（3）： 288.

Basic Information:

DOI：10.13373/j.cnki.cjrm.XY24010026

Chinese Library Classification Number:TN362

Citation Information:

Germanium is a typical sparse metal with good infrared transmittance, high refractive index, low dispersion and good chemical stability. It is widely used in infrared detection and laser technology and is currently the most ideal infrared optical material. One of them is the preferred material for thermal imager optical systems (8~12 μm band）. In the military field, infrared technology has been widely used in various military services such as land, sea and air. Among them, infrared imaging precision guidance is one of the mainstream directions of infrared technology application in various countries, realizing infrared imaging search, infrared terminal guidance, and infrared photoelectric fire control. In the civil field, infrared temperature measurement and infrared imaging through infrared detectors have been widely used in civil fields such as industry, transportation, electric power, petrochemicals, agriculture, medicine, remote sensing, security monitoring and prevention, and scientific research, and have become automatic control, online monitoring, non-contact measurement, equipment fault diagnosis, resource exploration, remote sensing measurement, environmental pollution monitoring and analysis, human medical imaging examination and other important methods. In recent years, in order to obtain a larger observation field of view and higher sensitivity and resolution, space infrared optical remote sensing loads have put forward increasingly higher requirements for the diameter and uniformity of infrared lenses. Ultra-large diameter infrared (diamete ≥420 mm) germanium single crystal is one of the preferred materials for large field of view and high-quality space-based infrared photoelectric imaging systems. However, the actual preparation process still faces difficulties in crystallization and poor optical and resistivity uniformity. Therefore, it is necessary to conduct research on the preparation of large-diameter germanium single crystal materials. Germanium and silicon both belong to the first generation of semiconductor materials, so their preparation technology is similar, the technical process is basically the same, the technical principles are basically the same, and the hardware equipment is basically similar. On the basis of these common points, the preparation technology of the two types of materials is due to the characteristics of the materials themselves. There is a difference. The physical properties of germanium are quite different from those of silicon materials. The main reason is that germanium has low thermal conductivity, so its crystallization control is slightly different from that of silicon. It is relatively difficult to form a suitable temperature gradient when drawing larger diameters. During the drawing process, the thermal field design plays a decisive role in the crystallization of single crystals. The thermal field is the core of growing single crystals. Only a thermal field with a suitable temperature gradient can grow a large-diameter germanium single crystal. Therefore, how to obtain a suitable temperature Gradient thermal field is the primary research content of single crystal growth. Czochralski method is used to grow single crystals. There is only one set of heater systems in the Czochralski single crystal furnace, and the thermal field temperature gradient is completely determined by the thermal field structure. The growth of large-diameter single crystals requires a large temperature gradient to release the latent heat of crystallization released during the growth of the single crystal. However, a large temperature gradient will lead to large residual stress in the single crystal. The existence of residual stress seriously affects the processing performance and optics of the crystal. Therefore, it is necessary to study the influence of thermal fields of different structures on the temperature gradient to obtain a suitable temperature gradient, which can ensure the crystallization of single crystals and minimize the residual stress of single crystals. The selection of crystal pulling process technology and crystal pulling parameters plays a key role in controlling the impurity distribution and resistivity uniformity of single crystal, while single crystal annealing also plays an important role in eliminating residual stress and improving the process ability of the crystal. This paper proposed a new dual-thermal heater structure. Combined with CGSim simulation software, a large-scale combined thermal field theoretical model was established. By using numerical simulation, the thermal field temperature distribution and bottom heater in the dual-heater system were analyzed. The influence of power on the shape of crystal solid-liquid interface was analyzed, and it was determined that the bottom heater can have a greater impact on the radial temperature gradient distribution of the melt. Within a suitable range, the higher the bottom heating power, the smaller the radial temperature, and the more effective it was. It was beneficial to the crystallization of Φ420 mm germanium single crystal；the bottom heater power affected the radial temperature of the melt and indirectly affected the shape of the solid-liquid interface of the crystal. Within a certain range, as the bottom heater power increases, the protrusion of the solid-liquid interface increased. The interface protrusion of large-diameter germanium single crystal directly affected the radial resistivity distribution of the crystal. The double heater structure could adjust the shape of the solid-liquid interface of the crystal, thereby adjusting the radial resistivity. Under the conditions of bottom heater power of 20 kW and feed volume of 350 kg, a 420 mm ultra-large diameter germanium single crystal was finally prepared. The test results showed that the optical uniformity of Φ420 mm germanium single crystal obtained by using this thermal field structure reached 6.52×10⁻⁵, and the resistivity uniformity reached 19%, both of which were better than the usage index requirements. The research results could provide a better reference for the preparation of similar types of large-diameter single crystal materials.