CN101501863A - 带有镧系元素以改变光谱的硅太阳能电池及其制造方法 - Google Patents
带有镧系元素以改变光谱的硅太阳能电池及其制造方法 Download PDFInfo
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Abstract
为了改善太阳能电池的能量利用率,用一种或者多种不同的镧系元素掺杂硅材料,使得该材料进入约600nm深的层中。由此可以通过激励和复合所述镧系元素的不成对的4f电子,使得具有至少高于硅的能带间隙(1.12eV)两倍的能量的光子转换成两个或者更多至少高于硅的能带间隙范围中的能量的或者与之相等的能量的光子。由此对电子空穴对形成提供带有一种近于硅的能带间隙的附加光子。
Description
应用领域和现有技术
本发明涉及一种针对太阳能电池的硅材料掺杂方法,以及用相应方法掺杂的硅材料,还有涉及用这样的硅材料制成的太阳能电池。
由于硅作为“间接半导体”的特性,其在室温下只有弱的发光特性。只有在约20K的温度处才能够检测到强的电致发光。与之相对地在400-1200nm的波长范围中硅的良好吸收特性使之成为特别适用作光电过程的原材料的基础。
用硼和磷元素掺杂的硅具有一种特有的光吸收。镧系元素(Lanthanide)的典型特性是由外层电子从周围的晶体场几乎完全地屏蔽的4f轨道的不成对电子。从而不成对电子的受激状态的能级与所述晶体场无关,在很大程度上是恒定不变的。尽管与所述晶体场有很少的相互作用,然而占据该能级的跃迁概率非常强烈地受所述晶体场的影响,并且在发射带的不同量子效能中表现出取决于所述晶体结构。镧系元素在完全不同技术领域中公知为天然的和技术的发光物质中的发光活化物。
任务和解决方案
本发明的基本任务是提供一种本文开头所述的方法、一种硅材料以及太阳能电池,用之可以避免现有技术的问题并且改善尤其是成品太阳能电池的能量利用率。
所述任务通过一种有权利要求1的特征的方法、一种有权利要求23的特征的硅材料以及一种有权利要求27的特征的、用这样的硅材料制造的太阳能电池解决。本发明的有利的和优选的实施方式是其它权利要求的主题并且在下文中详细地说明。某些下述特征只说明一次。然而与之无关地,这些特征应当能够适用于所述方法、所述硅材料以及所述成品太阳能电池。权利要求书的内容通过表达上的参考成为本说明书的内容。
如所公知的那样,要掺杂的硅材料以平的形式、即作为晶片或类似物而存在。根据本发明在所述硅材料的、小于1μm的最上层或者最上部区域中掺杂入镧系元素,以便由此改变所述硅材料的吸收特性。这既可以适用于单晶的太阳能电池也可以适用于多晶的太阳能电池。
通过在所述硅结构中或者所述太阳能电池的其它结构以及这些结构组成的混合相(Mischphasen)中掺入镧系元素可以达到有效地利用太阳光的UV和近UV的射线。这应当以这样的形式发生:通过激励和复合(Rekombination)所述镧系元素的不成对的4f电子,由具有至少高于硅的能带间隙(1.12eV)两倍的能量的光子构成两个或者更多具有仅仅少量地高于或者相等于硅的能带间隙(1.12eV)两倍的能量的光子。硅的主发射线在低于1.12eV的范围中。于是该非本征的光致发光可以对产生电能做贡献,则其方式是对于形成电子-空穴对提供具有近于硅能带间隙的能量的附加光子。通过镧系元素电子的激励和复合而出现的光子应当会直接对p-硅或者n-硅中的电子-空穴对的形成做贡献。
有利的是,在硅材料的最上层或者硅材料的表面上施加所述镧系元素或者相应的掺杂材料。这在一方面具有所述施加方法简单的优点。另外可以把本文开头所述的、所述硅材料的最上层中的光子的转化特别良好地用于以后的电能产生。就这方面而言,掺杂所述硅材料或者太阳能电池的最上层是特别有利的。
在本发明的扩展方案中可以在所述硅材料上的一个层中或者仅部分地由硅构成的硅材料的层中引入所述镧系元素。一个可能性是抗反射层或者由Si3N4制成的层。另一个可能性是由TCO制成的层,也就是说用透光的导电氧化物材料例如ZnO或者TiO。另一个可能的层是由碳纳米管(CNT)制成的层,所述纳米管制成的层同样也可以施加在太阳能电池的本来的硅中。再一另个可能的层是由非晶硅(a-硅)制成的层,在某些情况下还可以与SiOx或者SiO2结合。在这种上面提到的、引入仅部分地由硅构成的层中的情况下,还可以在带有氧配位场(Sauerstoff-Ligandenfeld)的矿物相中嵌入镧系元素。
在本发明的另一个扩展中,所述镧系元素的掺入可以在所述硅材料的pn结的区域中进行。在此,在从带有高得多的能量的光子中产生在硅的能带间隙附近的光子情况下,也可以有良好的效果。
在本发明的另一个扩展中,可以在所述硅材料的后表面区即背侧的区域中,掺入镧系元素。
在本发明的再一个扩展中,可以在基本上由SiO2构成的硅材料层中掺入所述镧系元素。
在当前Si太阳能电池制造中使用的、具有高温下的游离的氧和氮存在的扩散工艺中,也可以在硅材料中或者在对硅的界面中或者上构成下列结构或者相,如:
1.镧系元素-氧簇(Lanthanid-Sauerstoff-Cluster)
2.Si-B-P-O-镧系元素相
3.镧系元素-Si-O-N相或者其混合相
在严格意义上不被称为纯的Si-镧系元素化合物的区域也可以通过上文所述的、与镧系元素联系的形成电子空穴对的工艺而对提高效率做贡献。一个目标还是:通过所述扩散方法在硅占优势的结构中产生尤其是与镧系元素结合的氧簇,并且从而能够实现具有在可见光谱范围(400-800nm)中的辐射的、对于许多镧系元素公知的光致发光。
在太阳能电池表面附近的pn结中引入镧系元素的扩散可以有目的地用于构成p优势的O-镧系元素结构或者簇。一个可能性是,将镧系元素扩散到硅材料中。另一个可能性在于,用溅射方法施加所述镧系元素。为此可以使用基本上通常的溅射源和施加装置。
在本发明的另一个扩展中可以进行用镧系元素的掺杂,其方式是,所述镧系元素被含在含水的溶液中或者凝胶(Gel)中,所述含水的溶液或凝胶被施加在所述硅材料上。在此,接着有利地对扩散进行退火。
在本发明的再另一个扩展中可以通过气相工艺或者CVD工艺施加所述镧系元素。
在本发明的另一个扩展中,可以通过等离子工艺将所述镧系元素施加到所述硅材料上以及扩散到其中。
在本发明的又一个扩散中可以通过冷凝、也就是说通过从类气相中的沉积来施加所述镧系元素。这可以没有退火(Temperung)地进行,然而这对于所述镧系元素的扩散可以看作是有利的。
在本发明的另一个扩展中,可以通过固体接触、也就是通过直接施加镧系元素材料来施加所述镧系元素。
在本发明的又一个扩展中,可以通过离子注入用镧系元素掺杂所述硅材料。
在本发明的另一个扩展中,可以从在所述硅材料上的用镧系元素掺杂的层中把镧系元素扩散到所述硅材料中去,有利的是在热作用下或者通过退火进行。
在如此地施加镧系元素以后,可以一个另外的步骤中进行所述硅材料或者所述表面的退火。这可以起改善扩散进所述掺杂材料的作用。但是该步骤不是一定必需的。
在所述使用材料方面可以采用不同的镧系元素,然而或者也可以只用一种单一的镧系材料。然而还可以,将不同镧系元素的组合用于掺杂,然后这些镧系元素共同地存在。作为镧系元素尤其适合的是那些主发射线在光的可见范围中的、也就是在大约1.2eV以下的镧系元素。它们是La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb和Lu。然而,有利的是,在本发明的范畴内将Er排除在所采用的镧系元素之外。用镧系元素掺杂也可以与用例如Mn2+那样的、另外的掺杂元素联合进行。首先,可以通过主发射线在光的可见范围中改善光在硅材料中在UV和近UV范围内的吸收,确切地说,不仅在硅材本身中而且还在p掺杂以及n掺杂的硅中、在硅氧簇中、在SiO(x)中和在Si3N4中。同样地可以改善硅材料的不同矿物相中的光吸收。
在本发明的另一个扩展中,所述镧系元素的扩散以小于1μm的深度进行,例如仅仅500nm至600nm。由此可以使得扩散工艺保持得较简单。此外,更小深度的扩散也可以认为是足够的。
可能的是,在硅材料中有通过掺杂镧系元素而形成的层,其中在此所述层还可以构成为一个自己的层。有利的是,如前所述,该层在硅材料中或者成品太阳能电池中处于相对很上部。
如本发明所述的硅材料同样可以通过具有上述可能性的方法根据本发明来制造。用这样的硅材料然后可以构成如本发明所述的太阳能电池。
这些特征和其它特征,可以从权利要求书中以及从说明书中得出,其中不论是单个的特征本身或者多个特征的子组合的形式,都可以在本发明的实施方式中实施或者实施于其它的领域中,并且可以有利地形成本文所要求保护的可受保护的实施方式。把本申请划分成各个段以及小标题并不在其普遍性限制本文所作的论述。
Claims (27)
1.掺杂太阳能电池的硅材料的方法,其中所述硅材料以平的形式作为晶片或类似物存在,其特征在于,将镧系元素掺杂到小于1μm的最上层或者最上部区域中,以改变所述硅材料的吸收特性。
2.如权利要求1所述的方法,其特征在于,所述镧系元素或者所述掺杂材料被施加在最上层或者表面上。
3.如权利要求1或2所述的方法,其特征在于,将所述镧系元素引入太阳能电池的硅上的、主要由Si3N4构成的层中。
4.如权利要求1或2所述的方法,其特征在于,
将所述镧系元素引入太阳能电池的硅上的TCO层中。
5.如权利要求1或2所述的方法,其特征在于,将所述镧系元素引入太阳能电池的硅上的、透明的碳纳米管层中。
6.如权利要求1或2所述的方法,其特征在于,将所述镧系元素引入太阳能电池的非晶硅上的层中,其中所述层优选基本上由Si3N4构成。
7.如以上权利要求中任一项所述的方法,其特征在于,将所述镧系元素引入太阳能电池的硅的pn结的区域中。
8.如以上权利要求中任一项所述的方法,其特征在于,将所述镧系元素引入太阳能电池的硅的下表面区的区域中。
9.如以上权利要求中任一项所述的方法,其特征在于,将所述镧系元素引入太阳能电池的硅上的、主要由SiO2构成的层中。
10.如以上权利要求中任一项所述的方法,其特征在于,将所述镧系元素扩散到所述硅材料中去。
11.如以上权利要求中任一项所述的方法,其特征在于,通过溅射方法施加所述镧系元素或者将所述镧系元素引入所述硅材料中。
12.如以上权利要求中任一项所述的方法,其特征在于,将所述镧系元素作为含水的溶液或凝胶来施加或者引入所述硅材料中。
13.如以上权利要求中任一项所述的方法,其特征在于,通过气相工艺来施加或者向所述硅材料中引入所述镧系元素。
14.如以上权利要求中任一项所述的方法,其特征在于,通过等离子工艺来施加或者向所述硅材料中引入所述镧系元素。
15.如以上权利要求中任一项所述的方法,其特征在于,通过冷凝来施加或者向所述硅材料中引入所述镧系元素。
16.如以上权利要求中任一项所述的方法,其特征在于,通过固体接触来施加或者向所述硅材料中引入所述镧系元素。
17.如以上权利要求中任一项所述的方法,其特征在于,通过离子注入来施加或者向所述硅材料中引入所述镧系元素。
18.如以上权利要求中任一项所述的方法,其特征在于,经过用镧系元素掺杂的层和接着的、镧系元素向所述硅材料中的扩散,来施加或者向所述硅材料中引入所述镧系元素。
19.如以上权利要求中任一项所述的方法,其特征在于,在将所述镧系元素施加到所述硅材料上或者所述硅材料中以后,接着进行退火。
20.如以上权利要求中任一项所述的方法,其特征在于,在所采用的镧系元素中排除铒。
21.如以上权利要求中任一项所述的方法,其特征在于,将所述镧系元素扩散到所述硅材料中的深度小于1000nm,优选在500nm至600nm的深度。
22.如以上权利要求中任一项所述的方法,其特征在于,用镧系元素掺杂的层在所述硅材料的层内,优选构成为一个自己的层。
23.用于制造太阳能电池的、晶片或类似形式的硅材料,其特征在于,所述硅材料通过如以上权利要求中任一项所述的方法用镧系元素掺杂。
24.如权利要求23所述的硅材料,其特征在于,在所采用的镧系元素中排除铒。
25.如权利要求23或24所述的硅材料,其特征在于,所述镧系元素向所述硅材料中扩散的深度小于1000nm,优选在500nm至600nm深度。
26.如权利要求23至25中任一项所述的硅材料,其特征在于,用镧系元素掺杂的层在所述硅材料的层内,其中它优选构成一个自己的层。
27.太阳能电池,所述太阳能电池具有如权利要求23至26中任一项所述硅材料或者由其制造。
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DE102006031300A DE102006031300A1 (de) | 2006-06-29 | 2006-06-29 | Verfahren zur Dotierung von Siliziummaterial für Solarzellen, entsprechend dotiertes Siliziummaterial und Solarzelle |
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EP (1) | EP2038935A1 (zh) |
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KR (1) | KR20090042905A (zh) |
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AU (1) | AU2007264127A1 (zh) |
DE (1) | DE102006031300A1 (zh) |
NO (1) | NO20090454L (zh) |
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Cited By (3)
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CN105552170A (zh) * | 2016-01-29 | 2016-05-04 | 佛山市聚成生化技术研发有限公司 | 一种太阳能电池的制备方法及由该方法制备的太阳能电池 |
CN105839182A (zh) * | 2016-04-11 | 2016-08-10 | 西安隆基硅材料股份有限公司 | 晶体硅及其制备方法 |
CN106169512A (zh) * | 2016-08-24 | 2016-11-30 | 晶科能源有限公司 | 一种稀土掺杂的晶体硅、其制备方法及太阳能电池 |
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ES2311431B2 (es) * | 2008-06-06 | 2009-07-21 | Universidad Politecnica De Madrid | Procedimiento de fabricacion de dispositivos optoelectronicos de banda intermedia basados en tecnologia de lamina delgada. |
CN102828242B (zh) * | 2012-09-06 | 2015-05-27 | 西安隆基硅材料股份有限公司 | 含有下转换发光量子点的晶体硅及其制备方法 |
WO2016055669A1 (es) * | 2014-10-08 | 2016-04-14 | Universidad De La Laguna | Colector fotovoltaico |
CN105762206A (zh) * | 2016-04-11 | 2016-07-13 | 西安隆基硅材料股份有限公司 | 晶体硅及其制备方法 |
KR102040516B1 (ko) * | 2018-02-01 | 2019-12-05 | 성균관대학교산학협력단 | 단일 밴드 상향 변환 발광체 및 이의 제조 방법 |
CN110577209A (zh) * | 2019-09-19 | 2019-12-17 | 天津大学 | 原位合成碳纳米管表面负载氧化铜纳米颗粒的制备方法 |
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Cited By (3)
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CN105552170A (zh) * | 2016-01-29 | 2016-05-04 | 佛山市聚成生化技术研发有限公司 | 一种太阳能电池的制备方法及由该方法制备的太阳能电池 |
CN105839182A (zh) * | 2016-04-11 | 2016-08-10 | 西安隆基硅材料股份有限公司 | 晶体硅及其制备方法 |
CN106169512A (zh) * | 2016-08-24 | 2016-11-30 | 晶科能源有限公司 | 一种稀土掺杂的晶体硅、其制备方法及太阳能电池 |
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JP2009542018A (ja) | 2009-11-26 |
NO20090454L (no) | 2009-03-11 |
WO2008000332A1 (de) | 2008-01-03 |
US20090199902A1 (en) | 2009-08-13 |
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