CN101495681A - 用于生产半导体级硅的装置和方法 - Google Patents
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Abstract
本发明涉及用于生产半导体级硅锭块、包括太阳能级硅锭块的装置和方法，其中通过在熔融和结晶工艺的热区中使用没有氧化物的材料充分减少或除去了热区中氧的存在。所述方法可以用于任何现有工艺中，包括用于半导体级硅锭块、包括太阳能级硅锭块结晶的工艺，比如布里奇曼工艺、块浇铸工艺和用于生长单晶硅晶体的CZ工艺。本发明还涉及用于实施该熔融和结晶工艺的装置，其中所述热区的材料中没有氧化物。
Description
本发明涉及用于生产半导体级硅锭块、包括太阳能级硅锭块的装置和方法。
背景技术
在接下来的数十年中，预期世界上的石油供应将逐渐耗尽。这意味着必须在数十年内替换我们在上个世纪的主要能源，既要覆盖目前的能量消耗又要覆盖将来全球能源需求的增加。
此外，化石能源的使用将地球的温室效应增加至可能变得危险的程度，引起了许多关注。因此，为了我们的气候和环境，目前化石燃料的消耗应该优选被可再生的和可持续的能源/载体代替。
这些能源的一种是太阳光，其以比目前日消耗(包括任何可预见的人类能耗)大许多的能量辐照地球。然而，太阳能电池电力迄今为止仍过于昂贵而不能与核能、热能等相竞争。如果要实现太阳能电池电力的巨大潜力，这需要改变。
来自太阳能板的电力的成本是能量转换效率与该太阳能板生产成本的函数值。因此，用于降低太阳能电池电力成本的一个策略是增加能量转换效率。
现有技术
在当今的光伏(PV)工业中，从锭块切割用于PV应用的多晶晶片，该锭块基于布里奇曼(Bridgman)法通过定向凝固(DS)在熔炉中铸造。这些工艺中主要的挑战是保持硅原料的纯度。两个引起污染问题的元素是氧和碳。
根据“Handbook of Photovoltaic Science and Engineering(光伏科学和工程手册)”，John Wiley & Sons，2003，存在的问题是，氧化物或含氧化物的材料与熔融金属接触(包括通过隔离涂层的迁移)将氧引入熔融金属中。氧导致从熔体蒸发的SiO气体的形成，并且SiO气体随后将与热区中的石墨反应形成CO气体。CO气体进入硅熔体并因此将碳引入固体硅中。也就是说，在热区中使用氧化物或含氧化物的材料会引起一系列的反应，导致将碳和氧均引入固体硅中。与布里奇曼法相关的典型数值是2～6×1017/cm2的间隙氧水平和2～6×1017/cm2的取代碳。
硅金属中碳的增加会导致形成针状SiC晶体，特别是在锭块的最高区域中。这些针状SiC晶体已知为半导体电池中的短路pn结，导致电池效率剧烈降低。间隙氧的增加可能在形成的硅金属退火后导致氧沉淀和/或再结合活性氧络合物。
发明目的
本发明的主要目的在于提供高纯度半导体级硅锭块的生产方法，该方法充分减少/消除了硅金属的碳和氧的污染问题。
本发明的另一目的是提供用于实施本发明方法的装置。
本发明的目的可以通过以下本发明说明书中和/或附随的权利要求中阐明的特征来实现。
发明概述
本发明基于以下实现，即硅的碳和/或氧污染的问题与熔炉中的热还原环境中氧化物或含氧化物材料的存在有关，且目前在热区中使用的材料，诸如电绝缘、坩埚、承载构建元件和热绝缘可以用不含氧化物的材料代替。
因此，本发明的第一方面提供了用于生产半导体级硅锭块的方法，其中通过以下步骤充分减少或消除了热区中氧的存在：
-在由氮化硅、碳化硅或这些的复合物制成的坩埚中，结晶半导体级硅锭块，任选还包括进料硅材料的熔融，该坩埚任选用无氧化物的隔离涂层涂覆，
-在硅锭块结晶期间，将坩埚容纳在具有惰性气氛的密封热区中，任选还包括进料硅材料的熔融，
-至少在热区中使用包括热绝缘元件的承载构建元件，该构建元件由碳和/或石墨材料制成，并且
-至少在热区中使用电绝缘元件，该电绝缘元件由氮化硅Si3N4制成。
根据本发明第一方面的方法可以用于任何已知的工艺，包括用于半导体级硅锭块、包括太阳能级硅锭块的结晶，诸如布里奇曼法或相关的定向凝固方法、块浇铸方法和用于硅单晶生长的CZ法。
本发明的第二方面提供了用于制造单晶或多晶的半导体级硅锭块的装置，其包括具有惰性气氛的密封热区，其中
-至少在热区中包括热绝缘元件的该装置的所有承载构建元件由碳和/或石墨材料制成，
-至少在热区中的电绝缘由氮化硅Si3N4制成，和
-坩埚由氮化硅(Si3N4)、碳化硅(SiC)或者这些的复合物制成，任选用无氧化物的隔离涂层涂覆。
本文使用的术语“惰性气氛”意思是，与热区中硅金属和该装置的材料相接触的气氛，对于该装置的材料和硅金属相，不管是固态还是液态，基本上都是化学惰性的。本文使用的术语包括任何气压的惰性气氛，包括真空。
该装置可以是任何已知的用于半导体级硅锭块、包括太阳能级硅锭块结晶的装置，诸如用于执行布里奇曼方法或相关定向凝固方法的熔炉、用于完成块浇铸方法的结晶罐、用于完成单晶硅晶体CZ生长的CZ拉晶器。通过在太阳能级硅的熔融和结晶期间在热区中使用非氧化物的材料，消除/充分减少了硅金属相的碳和氧污染的问题。这将充分减少金属相中碳化硅晶体的形成，提升由晶片制成的PV电池的高太阳能转换效率。另一个导致较高转换效率的因素是间隙重组活性氧络合物的减少/避免。降低的污染水平还将带来的优点是，由于不存在硬且易碎的内含物(如碳化物和氧化物)，简化了硅金属加工为太阳能晶片的后续工艺。
附图说明
图1是用于半导体级锭块定向凝固的现有技术熔炉示意图。
本发明实施方式的实施例
通过用于生产多晶硅锭块的装置实施方式的实施例，对本发明进行进一步详细说明。该实施例决不应解释为对通过在热区中避免使用含氧材料来避免碳和氧污染这一总的发明构思的限制。本发明思想可以用于任何已知的制造半导体级硅的热区中。
该选定的实施例是用于执行多晶硅定向凝固的典型熔炉，如图1所示，该熔炉是本申请人的国际专利申请WO 2006/082085图1的复制。该熔炉包括通过图中标示为2的绝缘壁限定的气密性结晶室。内室由具有框11的底板9、壁10和盖5限定。提供用于维持内室中惰性气氛的抽吸出口24和注射喷枪12。坩埚1容纳有金属13，并且金属13首先被熔融，然后通过调节加热元件8和21以及冷却回路4，15，16，17，19，20，22和23的运行经历定向凝固。
当使用该熔炉时，通过使用氮化硅、碳化硅或这些的复合物制成、且任选用无氧化物的隔离涂层涂覆的坩埚1，可以完成本发明的目的。适合的氮化硅坩埚的实例在NO 317080中公开，其教导这样的氮化硅不能润湿液态硅，使得坩锅易于滑动固化的金属，该氮化硅总开孔率在40体积％与60体积％之间且其中表面上至少50％的孔大于Si3N4粒子的平均直径。然而，可以使用任何仅由氮化硅制成的并且不会润湿液态硅的坩埚。纯氮化硅坩埚不包含或包含可忽略量的氧/氧化物。因此消除了氧从该坩埚到液态金属的迁移，使得充分减少或消除了固态金属中的间隙氧的水平和SiO的形成。为了消除热区中所有的氧源，根据本发明DS熔炉的实施例，使用碳制成的壁10、具有框11的底板9、盖5和喷枪24和12。因此不存在限定结晶室内部密封区域的含氧元件，使得实际上消除了氧迁移到熔体中以及与熔体接触得到的CO气体的形成。
Claims (9)
1.用于生产半导体级硅锭块的方法，其中通过以下步骤充分减少或消除了热区中氧的存在：
-在由氮化硅、碳化硅或这些的复合物制成的坩埚中，结晶半导体级硅锭块，任选还包括进料硅材料的熔融，
-在硅锭块结晶期间，将所述坩埚容纳在具有惰性气氛的密封热区中，任选还包括进料硅材料的熔融，
-在热区中使用包括热绝缘元件的承载构建元件，该承载构建元件由碳和/或石墨材料制成，和
-在热区中使用由氮化硅Si3N4制成的电绝缘元件。
2.根据权利要求1所述的方法，其中所述坩埚用无氧化物的隔离涂层涂覆。
3.根据权利要求1所述的方法，其中所述半导体级结晶方法是布里奇曼法或相关的定向凝固法、块浇铸法、或者用于单晶硅晶体生长的CZ法。
4.根据权利要求1～3中任一项所述的方法，其中形成的硅锭块是太阳能级硅锭块。
5.用于制造半导体级硅锭块的装置，其包括具有惰性气氛的热区，其中
-在热区中包括热绝缘元件的所述装置的所有承载构建元件由碳和/或石墨材料制成，
-在热区中的所述电绝缘元件由氮化硅Si3N4制成，和
-坩埚由氮化硅Si3N4、或者碳化硅SiC或者这些的复合物制成。
6.根据权利要求5所述的装置，其中用无氧化物的隔离涂层涂覆所述坩埚。
7.浇铸用于光伏应用的多晶晶片生产用锭块的结晶炉，其特征在于在热区中的所有承载和功能元件由非氧化物的材料制成。
8.根据权利要求5或7所述的熔炉，其中所述浇铸坩埚由氮化硅Si3N4、碳化硅SiC或者这些的复合物制成。
9.根据权利要求5或7所述的熔炉，其中所述电绝缘元件由Si3N4制成。
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| CN101812729A (zh) * | 2010-04-28 | 2010-08-25 | 江西赛维Ldk太阳能高科技有限公司 | 一种低碳含量的多晶硅锭以及制备方法 |
| CN102781832A (zh) * | 2010-03-26 | 2012-11-14 | 三菱综合材料株式会社 | 多晶硅锭的制造方法及多晶硅锭 |
| CN102859049A (zh) * | 2010-03-30 | 2013-01-02 | Rec沃佛普特有限公司 | 制造半导体级硅晶锭的方法、可再使用的坩埚及其制造方法 |
| CN107723798A (zh) * | 2017-10-30 | 2018-02-23 | 中国电子科技集团公司第四十六研究所 | 一种高效率制备高纯半绝缘碳化硅单晶生长装置及方法 |
| CN110878430A (zh) * | 2013-09-06 | 2020-03-13 | Gtat公司 | 用来生产大块硅碳化物的器具 |
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| US8317920B2 (en) | 2008-09-19 | 2012-11-27 | Memc Singapore Pte. Ltd. | Directional solidification furnace for reducing melt contamination and reducing wafer contamination |
| WO2011009062A2 (en) | 2009-07-16 | 2011-01-20 | Memc Singapore Pte, Ltd. | Coated crucibles and methods for preparing and use thereof |
| KR101391021B1 (ko) * | 2009-10-19 | 2014-04-30 | 제이엑스 닛코 닛세키 킨조쿠 가부시키가이샤 | 실리콘 또는 실리콘 합금 용해로 |
| DE102009044390B4 (de) * | 2009-11-02 | 2014-06-26 | Hanwha Q.CELLS GmbH | Herstellungsverfahren und Herstellungsvorrichtung zur Herstellung eines Halbleiterkristallkörpers |
| US20110180229A1 (en) * | 2010-01-28 | 2011-07-28 | Memc Singapore Pte. Ltd. (Uen200614794D) | Crucible For Use In A Directional Solidification Furnace |
| JP4815003B2 (ja) * | 2010-03-09 | 2011-11-16 | 佑吉 堀岡 | シリコン結晶成長用ルツボ、シリコン結晶成長用ルツボ製造方法、及びシリコン結晶成長方法 |
| US20120248286A1 (en) | 2011-03-31 | 2012-10-04 | Memc Singapore Pte. Ltd. (Uen200614794D) | Systems For Insulating Directional Solidification Furnaces |
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| CN111912811B (zh) * | 2020-08-05 | 2023-07-25 | 西安奕斯伟材料科技有限公司 | 测量单晶硅中元素含量的方法及装置 |
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- 2007-06-20 WO PCT/NO2007/000219 patent/WO2007148985A1/en active Application Filing
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| CN102781832A (zh) * | 2010-03-26 | 2012-11-14 | 三菱综合材料株式会社 | 多晶硅锭的制造方法及多晶硅锭 |
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| CN102859049B (zh) * | 2010-03-30 | 2016-01-20 | 瑞科斯太阳能源私人有限公司 | 制造半导体级硅晶锭的方法、可再使用的坩埚及其制造方法 |
| CN101812729A (zh) * | 2010-04-28 | 2010-08-25 | 江西赛维Ldk太阳能高科技有限公司 | 一种低碳含量的多晶硅锭以及制备方法 |
| CN110878430A (zh) * | 2013-09-06 | 2020-03-13 | Gtat公司 | 用来生产大块硅碳化物的器具 |
| CN110878430B (zh) * | 2013-09-06 | 2021-10-22 | Gtat公司 | 用来生产大块硅碳化物的器具 |
| CN107723798A (zh) * | 2017-10-30 | 2018-02-23 | 中国电子科技集团公司第四十六研究所 | 一种高效率制备高纯半绝缘碳化硅单晶生长装置及方法 |
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| EP2035604A1 (en) | 2009-03-18 |
| KR20090024802A (ko) | 2009-03-09 |
| TW200806827A (en) | 2008-02-01 |
| JP2009541193A (ja) | 2009-11-26 |
| WO2007148985A1 (en) | 2007-12-27 |
| US20090314198A1 (en) | 2009-12-24 |
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