elopment Status of Germanium Single Crystal Materials
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摘要: 锗因其资源稀缺、优异的光学和物理性能，广泛应用于光纤系统、红外光学系统、电子和太阳能应用、探测器等高科技领域，是战略性产业所需的重要功能材料和结构材料。简单介绍了目前国内锗单晶生长的两种主要方法：直拉法（Czochralski，CZ）和垂直梯度凝固法（vertical gradient freeze，VGF）。对国内和国外知名锗材料生产企业的锗单晶生长方法、直径、电阻率等相关技术参数，进行了统计和比较。针对不同的单晶材料性能，分析了红外光学用锗单晶、太阳能电池用锗单晶和高纯锗单晶的应用领域和发展现状。Abstract: Owing to its scarce resources and excellent optical and physical properties, germanium is widely used in fiber-optic systems, infrared optical systems, electronic and solar energy applications, detectors, and other high-technology fields. It is an important functional and structural material which is needed in strategic industries. Two main methods of single crystal growth in germanium, Czochralski method(CZ)and vertical gradient freeze method(VGF), were briefly introduced. Technical parameters such as the method of germanium crystal growth, diameter and resistivity of germanium in popular germanium material-producing enterprises at home and abroad were analyzed and compared. Based on the properties of different single-crystal materials, the application fields and development status of germanium single crystals for infrared optics, germanium single crystal for solar cells, and high-purity germanium single crystal were analyzed.
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图 1 预计2020年红外用锗量（单位：吨）
Figure 1. Estimated infrared germanium consumption in 2020(unit: ton)
图 2 生长炉方案（1-晶座；2-石英防护罩；3-锥形防护罩；4-副加热器；5-内坩埚；6-主坩埚；7-基座；8-主加热器；9-石墨毡。）
Figure 2. The scheme of growth furnace(1-crystal holder; 2-quartz shield; 3-cone shield; 4-additional heater; 5-inner crucible; 6-main crucible; 7-pedestal; 8-main heater; 9-graphite felt)
图 3 预计2020年光伏用锗量（单位：吨）
Figure 3. Estimated germanium amount for photovoltaic in 2020 (unit: ton)
图 4 高纯锗晶体生长与探测器制作流程图
Figure 4. Flow chart of HPGe crystal growth and detector fabrication
表 1 2019年全球锗金属产量
Table 1. Global germanium metal production in 2019
China Russia Other countries 65% 5% 30% Other countries: Includes Belgium, Canada, Germany, Japan, and Ukraine 
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表 2 2015~2018年美国锗金属进口来源
Table 2. USA germanium metal import sources from 2015 to 2018
China Belgium Germany Russia Other countries 59% 22% 9% 7% 3% Notes: Import sources are based on gross weight of wrought and unwrought germanium metal and germanium metal powders
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表 3 锗单晶参数指标统计
Table 3. Germanium single crystal parameter statistics
Company Growthmethod Conductivitytype Size
（upon request）Larger sizes Resistivity
（upon request）Yunnan Lincang Xinyuan Germanium Co., Ltd CZ N 10-350 mm 380 mm 5-40 Ω·cm VGF P 4、6 inch 8 inch 0.001-0.04 Ω·cm China Germanium Co., Ltd. CZ N ≤105 mm ＞105 mm 5-40 Ω·cm P 4、6 inch 6 inch 0.001-0.04 Ω·cm GRINM Electro-optic Materials Co., Ltd. CZ N 5-350 mm 350 mm 5-40 Ω·cm Yunnan KIRO-CH Photonics Co. Ltd. CZ N 10-300 mm 300 mm 5-40 Ω·cm Vital Materials Co., Ltd. CZ N 3-310 mm 310 mm 5-40 Ω·cm VGF P 4、6 inch 6 inch 0.001-0.04 Ω·cm Umicore CZ N 10-350 mm 350 mm 5-40 Ω·cm P 0.001-0.04 Ω·cm AXT VGF P 4、6 inch 6 inch 0.001-0.04 Ω·cm Photonic Sense CZ N 10-330 mm 450 mm 5-40 Ω·cm P - 0.001-0.04 Ω·cm Germanium and Applications Ltd. CZ N 8-300 mm 300 mm 5-40 Ω·cm P 4、6 inch 6 inch 0.01-0.05 Ω·cm
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表 4 全球军民用红外市场规模及预测
Table 4. Global military and civilian infrared market size andforecastMillion Dollars
Year 2017 2018 2019 2020E 2023E Military market 8546 8886 9251 9566 10795 Civil market 4125 4573 5041 5601 7465
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表 5 高纯锗探测器能量分辨率的优势
Table 5. Advantages of high purity germanium detector energy resolution
Detector Ray energy/keV FWHM(full width at half maxima)/keV HPGe 1330 1.75 HgI2 1330 22 CdTe 1330 25 GaAs 1330 22
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