CN101091009A - 制备定向凝固硅锭的方法 - Google Patents

制备定向凝固硅锭的方法 Download PDF

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CN101091009A
CN101091009A CNA2005800450892A CN200580045089A CN101091009A CN 101091009 A CN101091009 A CN 101091009A CN A2005800450892 A CNA2005800450892 A CN A2005800450892A CN 200580045089 A CN200580045089 A CN 200580045089A CN 101091009 A CN101091009 A CN 101091009A
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C·德思洛夫
K·弗里斯塔德
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Norway Solar Energy Co
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Abstract

本发明涉及用于制备定向凝固切克劳斯基、浮区或多晶硅锭或者薄片或者条的方法，它们用于从初始含有0.2ppma至10ppma硼和0.1ppma至10ppma磷的硅原料生产用于太阳能电池的晶片。如果硅原料中的硼含量高于磷含量，那么通过在定向凝固工艺期间向熔融硅添加硼保持熔融硅中的硼含量高于磷含量，以便延伸作为p型材料凝固的定向凝固锭或者薄片或者条的部分。如果在硅原料中磷含量高于硼含量，那么通过在定向凝固工艺期间向熔融硅添加磷保持熔融硅中的磷含量高于硼含量，以便延伸作为n型材料凝固的锭或者薄片或者条的部分。

Description

制备定向凝固硅锭的方法
技术领域
本发明涉及一种用于制备用于生产光电(PV)太阳能电池的定向凝固切克劳斯基、浮区或多晶硅锭，薄硅片或条的方法。
背景技术
近年来，由电子芯片行业中合适的刮屑、切屑、次品所生产的超纯新鲜(virgin)电子级多晶硅(EG-Si)已经用于光电太阳能电池的制备。近来电子行业的低迷导致闲置的多晶硅产能被用来生产适用于生产PV太阳能电池的较低成本等级。这就暂时缓解了太阳能级多晶硅(SoG-Si)供料品质的紧张市场需求。随着电子设备的需求量回到正常水平，预计多晶硅产能中的主要份额将回到电子行业的供应中，而令PV行业供应不足。专供低成本来源的SoG-Si的短缺以及因此而不断扩大的供应缺口现已成为PV行业未来发展最严重的障碍之一。
近年来，已经进行了开发用于SoG-Si的新来源的多次尝试，其独立于电子行业价值链。这些努力不仅包括有效降低现有多晶硅工艺路线成本的新技术，还包括发展冶金学精炼工艺，从而将来源丰富的冶金级硅(MG-Si)纯化到所需的纯度。至今仍然没有人能够在从常规硅进料品质出发生产出符合PV太阳能电池性能要求的预计硅进料纯度的同时成功地显著降低生产成本。
生产PV太阳能电池时，准备SoG-Si供料进料，熔融并定向凝固到专用的铸造用炉内的方形锭中。在熔融之前，含SoG-Si的进料要用硼或磷掺杂，以分别制备p型或n型锭。除了少数例外情况之外，现在的商用太阳能电池通常是基于p型硅锭材料制备的。控制单一掺杂剂(如：硼或磷)的添加，可以使材料获得优选的电阻率，例如在0.5-1.5ohm cm范围。需要p型锭时，相应要添加0.02-0.2ppma硼，并使用特有品质的(掺杂剂含量可以忽略的实际纯净的硅)SoG-Si供料。掺杂工艺假定其他掺杂剂(在该实施例情况下磷)含量可以忽略(P＜1/10B)。
挪威专利申请号20035830填写于2003年12月29号。该申请公开了一种用于制备定向凝固切克劳斯基、浮区或多晶硅锭或薄硅片或条的方法，从而制备基于由冶金级硅通过冶金学精炼工艺所得到的硅原料的晶片。该硅原料中含有0.2ppma到10ppma的硼和0.1-10ppma的磷。由于含有硼和磷，根据挪威专利申请号20035830制备的硅锭将在锭厚度或片或条厚度的40-99％之间的位置具有从p型至n型的特征类型改变，这取决于硼和磷在硅原料中的比率。因此，所制的锭包含了p型和n型硅。
理想的是由同时含硼和磷的硅原料分别制造p型或n型材料，但在挪威专利申请号20035830的实施例中，从p型到n型的变化发生在锭高度的约3/4处。
发明内容
本发明的目的是，提供在同时含硼和磷的硅原料制备的定向凝固硅锭或薄片或条中提高p型或n型材料的数量的方法。
因此，本发明涉及一种用于制备定向凝固切克劳斯基、浮区或多晶硅锭或者薄片或者条的方法，它们用于从初始含有0.2ppma至10ppma硼和0.1ppma至10ppma磷的硅原料生产用于太阳能电池的晶片，所述方法的特征在于，如果硅原料中的硼含量高于磷含量，那么通过在定向凝固工艺期间向熔融硅间歇、连续或者基本连续地添加硼保持熔融硅中的硼含量高于磷含量，以便延伸作为具有预定电阻率或在预定电阻率范围内的p型材料凝固的定向凝固锭或者薄片或者条的部分；或者，如果在硅原料中磷含量高于硼含量，那么通过在定向凝固工艺期间向熔融硅间歇、连续或者基本连续地添加磷保持熔融硅中的磷含量高于硼含量，以便延伸作为具有预定电阻率或在预定电阻率范围内的n型材料凝固的锭或者薄片或者条的部分。
借助本发明的方法，已经发现定向凝固锭或薄片或者条部分在从p型材料转变为n型材料或从n型材料转变为p型材料之前可以被显著延伸。
附图说明
图1是示出根据现有技术制得的定向凝固硅锭的电阻率的图。
图2是示出根据本发明方法制得的定向凝固硅锭的电阻率的图。
发明详述
实施例1(现有技术)
从初始含有0.8ppma硼和3.6ppma磷的硅原料生产定向凝固硅锭。在硅锭中p型材料到n型材料的转变发生在凝固锭的高度的大约60％处。在图1中示出了所制备的硅锭的电阻率，从该图中可以看出从p型材料向n型材料的转变发生在锭高度的约60％处。
实施例2(本发明)
使用实施例1中相同的硅原料制备定向凝固硅锭。当大约50％的锭已经凝固时，向剩余的熔融硅中连续添加硼。如图2可见，从p型材料向n型材料的转变发生在凝固锭高度的大于90％处。加入硅熔体中的硼的量也在图2中示出。
通过比较实施例1和实施例2的结果，可是看出，从p型材料向n型材料的转变从硅锭高度的约60％处移动到硅晶高度的大于90％处。
因此，通过本发明，可以显著增加定向凝固锭的部分(凝固成p型材料或者n型材料)。

Claims (1)

1.一种用于制备定向凝固切克劳斯基、浮区或多晶硅锭或者薄片或者条的方法，它们用于从初始含有0.2ppma至10ppma硼和0.1ppma至10ppma磷的硅原料生产用于太阳能电池的晶片，所述方法的特征在于，如果硅原料中的硼含量高于磷含量，那么通过在定向凝固工艺期间向熔融硅间歇、连续或者基本连续地添加硼保持熔融硅中的硼含量高于磷含量，以便延伸作为p型材料凝固的定向凝固锭或者薄片或者条的部分；或者，如果在硅原料中磷含量高于硼含量，那么通过在定向凝固工艺期间向熔融硅间歇、连续或者基本连续地添加磷保持熔融硅中的磷含量高于硼含量，以便延伸作为n型材料凝固的锭或者薄片或者条的部分。
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NO333319B1 (no) * 2003-12-29 2013-05-06 Elkem As Silisiummateriale for fremstilling av solceller

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CN102005505A (zh) * 2010-10-18 2011-04-06 浙江大学 一种抑制光衰减的掺锡晶体硅太阳电池及其制备方法
CN102560645A (zh) * 2011-09-02 2012-07-11 江苏协鑫硅材料科技发展有限公司 一种在晶体硅形成过程中控制电阻率的方法及其装置
CN102560645B (zh) * 2011-09-02 2016-05-18 江苏协鑫硅材料科技发展有限公司 一种在晶体硅形成过程中控制电阻率的方法及其装置
CN103975097A (zh) * 2011-10-06 2014-08-06 埃尔凯姆太阳能公司 用于生产硅单晶和多晶硅锭的方法

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EP1848843A1 (en) 2007-10-31
CN100567591C (zh) 2009-12-09
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AU2005333767B2 (en) 2010-05-20
US20080029019A1 (en) 2008-02-07
WO2007001184A1 (en) 2007-01-04
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AU2005333767A1 (en) 2007-01-04
JP2008525297A (ja) 2008-07-17

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