电子级多晶硅原料中痕量硼磷杂质的脱除研究进展

doi:10.11949/0438-1157.20230668

摘要/Abstract

摘要：

三氯氢硅和氢气中痕量硼磷杂质的含量是影响多晶硅品质的主要因素。提高硼磷杂质的脱除效率有利于电子级多晶硅的大规模生产，实现我国能源信息产业升级。综述了三氯氢硅和氢气中硼磷杂质脱除方法的研究进展，重点介绍了各类提纯方法的特点。其中，反应-吸附-精馏耦合技术集合了精馏法和化学提纯法的优点，是三氯氢硅精制过程中最具有发展前景的方法；吸附法凭借其负载的活性物质对硼磷杂质的高选择性，成为氢气精制最常使用的工艺。最后，系统探讨了吸附剂结构特点及与吸附性能的构效关系，在此基础上总结并展望了多晶硅原料中硼磷杂质脱除面临的挑战和发展方向。

关键词: 硼磷杂质, 吸附, 蒸馏, 反应精馏, 三氯氢硅, 氢

Abstract:

The content of trace boron and phosphorus impurities in trichlorosilane and hydrogen is the main factor affecting the quality of polysilicon. Improving the removal efficiency of boron and phosphorus impurities is crucial for the large-scale production of electronic-grade polysilicon, which is essential for advancing China’s energy and information industries. This paper provides a summary of the research progress on removing boron and phosphorus impurities in SiHCl₃ and H₂, and highlights the characteristics of various purification methods. The coupled reaction-adsorption-rectification technology, which combines the advantages of rectification and chemical purification, is the most promising method for purifying SiHCl₃. The adsorption method, known for its high sensitivity to boron and phosphorus impurities, is the most commonly used method for purifying H₂. Finally, the thesis systematically discusses the structural characteristics of adsorbents and their relationship with adsorption performance. It also summarizes the challenges and development direction of removing boron and phosphorus impurities from polysilicon raw materials.

Key words: boron and phosphorus impurities, adsorption, distillation, reactive rectification, trichlorosilane, hydrogen

中图分类号:

TQ 128

闫可欣, 姜洪涛, 高维群, 郭晓晖, 孙伟振, 赵玲. 电子级多晶硅原料中痕量硼磷杂质的脱除研究进展[J]. 化工学报, 2024, 75(1): 83-94.

Kexin YAN, Hongtao JIANG, Weiqun GAO, Xiaohui GUO, Weizhen SUN, Ling ZHAO. Recent advances in the removal of trace boron and phosphorus impurities from electronic grade silicon raw materials[J]. CIESC Journal, 2024, 75(1): 83-94.

图/表 5

图1 三氯氢硅精制方法

Fig.1 Refining method of trichlorosilane

图2 隔板塔-精馏塔相结合的精馏工艺流程[12]

Fig.2 The combined rectification process of dividing wall column and rectifying column[12]

图3 使用水平隔板塔的精制流程[14]A1—吸附器1; A2—吸附器2; B—高沸点杂质; C—冷凝器; D—低沸点杂质; F—原料液; G—循环蒸汽; H—蒸发器; K1—精馏塔1; K2—精馏塔2; K3—水平隔板塔; L12—精馏塔K1塔顶的液相流股 (L代表液相流股, 1代表精馏塔K1, 2代表塔顶流股);V21—精馏塔塔底的气相流股 (V代表气相流股, 2代表精馏塔K2, 1代表塔底流股); P—产品流股; R—塔顶循环流股

Fig.3 The refining process with column using horizontal dividing wall[14]

图4 反应提纯法机理

Fig.4 Mechanism of reaction purification method

图5 螯合作用反应式[52]

Fig.5 The process of chelation reaction[52]

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