Research Progress on Impurity Characteristics and Deep Chemical Purification Technology in High-purity Quartz
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摘要:
随着战略性新兴产业的快速发展，高纯石英成为诸多尖端领域的关键性基础原料之一。高纯石英的战略地位日益凸显，而我国高端高纯石英砂对外依存度仍居高不下，加快推进我国高纯石英砂制备关键技术的发展迫在眉睫。在概述国内外高纯石英资源的基础上，从杂质的存在形式和杂质对产品质量的影响两个方面分析了高纯石英中的杂质特征，并系统总结了高纯石英深度提纯酸处理法和热处理法两个关键技术进展情况，提出现阶段我国高纯石英提纯存在的问题及建议，以期为我国高纯石英提纯技术的发展提供参考。
Abstract:With the rapid development of strategic emerging industries, high purity quartz has become one of the key basic raw materials for many cutting-edge fields. The strategic position of high-purity quartz is becoming more and more prominent, and the dependence of China's high-end high-purity quartz sand on foreign countries is still high, so it is urgent to accelerate the key technology of high-purity quartz sand preparation in China. Based on the overview of high purity quartz resources at home and abroad, the impurity characteristics in high purity quartz were analyzed from two aspects: the existence of impurities and the influence of impurities on product quality, and the progress of two key technologies for deep purification of high purity quartz, acid treatment method and heat treatment method, were systematically summarized.
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Key words:
- high purity quartz /
- purification /
- impurity elements /
- chemical leaching /
- chlorination roasting
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表 1 石英杂质元素的赋存状态和存在形式
Table 1. Occurrence state and existent form of impurity elements in quartz
元素 赋存状态及存在形式 元素 赋存状态及存在形式 Al 黏土类矿物；类质同象 Li 电荷补偿杂质；包裹体 Fe 赤、黄铁矿等独立矿物；类质同象；亚微米包裹体 Na 钠长石、云母等独立矿物；电荷补偿杂质；包裹体 Ca 方解石、萤石等独立矿物；包裹体 Ti 金红石；类质同象 Mg 白云石、云母等独立矿物；包裹体 B 类质同象 K 钾长石、黏土矿等独立矿物；电荷补偿杂质；包裹体 H 电荷补偿杂质；包裹体中的水、有机质 
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表 2 硅氧键Si-O和常见Me-O键键能[23] /(kJ·mol-1)
Table 2. Siloxane bond energy and common Me-O bond energy
化学元素 Si4+ Ti4+ Fe3+ Mg2+ Mn2+ Cu2+ Ca2+ 键能 10 312~13 146 12 058 3 845 3 816 3 745 3 598 3 510 化学元素 Al3+ Pb2+ Ba2+ Zn2+ Li+ Na+ K+ 键能 7 201~7 858 3 469 3 213 3 037 1 469 1 347 1 251
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表 3 杂质元素对产品质量的影响
Table 3. Effect of impurity elements on product quality
杂质元素 对产品质量的影响 碱金属元素Li、K、Na 降低石英玻璃的使用温度和机械强度，在高温下对石英玻璃的析晶起催化作用，导致石英玻璃出现失透、高温变形等现象。降低碱金属元素的含量有利于提高高纯石英坩埚的软化点，增强石英坩埚的抗变形性，提高单晶的成品率。IOTA标准砂要求碱金属元素总和低于2.4×10-6，用于工艺管、硅片处理、石英块、提单晶硅用的半导体坩埚所需高纯石英要求其总和 < 1.4×10-6，CZ型坩埚要求其总和 < 0.5×10-6，而用于12英寸或更大尺寸硅片所需超高纯石英砂要求其总和 < 0.08×10-6 过渡金属元素Cr、Cu、Fe 使石英玻璃产生色斑或引起石英玻璃的高温变色，影响光透过率，降低仪器的可靠性和稳定性能，在光纤应用中，会引起微观不均匀、增加光纤损耗，甚至导致信号失真，但在半导体应用中，产品中微小含量的过渡金属元素可以促进结晶生长 Al和P 进入石英晶格，会产生较强的化学键，影响石英制品的导电性，同时，增强了石英玻璃的析晶作用，降低了使用寿命。少量的Al不会影响到高纯石英产品的质量，IOTA标准砂要求Al元素含量(12~18) ×10-6，但光导纤维中微量的Al便会降低石英玻璃的光传导。P元素的存在会严重影响单晶硅的拉制，故高纯石英坩埚对P要求高，要求P元素含量 < 0.04×10-6
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