CN1013910B - 半导体器件及其制造方法 - Google Patents

半导体器件及其制造方法

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CN1013910B
CN1013910B CN87102619A CN87102619A CN1013910B CN 1013910 B CN1013910 B CN 1013910B CN 87102619 A CN87102619 A CN 87102619A CN 87102619 A CN87102619 A CN 87102619A CN 1013910 B CN1013910 B CN 1013910B
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山岸英雄
山口美则
浅冈圭三
宏江昭彦
近藤正隆
津下和永
太和田善久
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Kanegafuchi Chemical Industry Co Ltd
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Abstract

一种具有多结的非晶形或微晶形半导体的光电器件，其中包含高浓度杂质的一或多层被插入在p型导电层和n型导电层之间。被插入的层形成一隧道结以提高光电转换率。

Description

本发明涉及非晶形硅或非晶形合金多结太阳能产生电池。
在先有技术中的多结太阳能产生电池中，其在第一层半导体材料中光所产生的载流子会与存在于第一层和第二层半导体材料间p-n面的电子和空穴复合，因而在各层之间产生一电流。然而，这种器件中的缺点在于，某些从第一层移来的载流子在p-n界面未能找到电子或空穴，而是透入到第二层中。此外，在第二层中的许多载流子移过p-n结界面而进入第一层，从而导致降低器件的总效率。故需要免除在先有技术中的半导体器件所存在的上述问题。
本发明的一个目的就是要提供一种其效率较常用的同类型电池高的非晶形硅多结太阳能产生电池。
因此，本发明涉及的是一种非晶形和/或微晶形（下文称为“非晶形”）结构的半导体器件，其分层的p-i-n或n-i-p型光电元件配置有高杂质浓度层，其中的杂质浓度已经提高到足以促进在该器件的n-p或p-n结界面上的载流子的复合。
本发明的其它目的、特点和特性，该结构的有关元件的制造和运作方法和功能，以及对复合的部分和经济的制造法，等等，在参考附图，研究下列叙述和所附权项后，就可以明白过来，所有上述所提到的都构成本说明书的一部分，其中相同的编号表示各图中的相应部分。
单独的附图描述本发明的最佳实施例。
如图所示，所提供的一种非晶形半导体器件可以用作光电池。该半导体器件在说明的实施例中由下列部分构成：一对外部电极11，一层毗 邻电极10的p型层6，一层毗邻p型层6的本征型i型层7和一层毗邻该i型层7的n型层2。另一附加的n型层9配置在第二电极11的邻近，一层界面i型层8则配置在n型层9的邻近。一层p型层3配置在i型层8的邻近并与n型层2形成一p-n界面。各层是由已知的材料，例如硅、碳化硅、氮化硅、锗硅、硅锡或它们的混合物构成的，各层的厚度约为那些在光电元件中常见的厚度。
本发明其中一个新颖和有利的特点在于，在多结光电元件的n-p或p-n界面部分有高的杂质浓度层（4，5），如附图所示。这些层中的杂质已经提高到足以促进自由电子和靠近界面处的电子空穴复合。
n型层2和p型层3间的界面1可以是该两层的边界，如附图所示，或者是n-p或p-n界面的p型层和n型层间新提供的层。如果该界面是一新提供的层，它最好包含N、O、Fe、Cu和Ge金属或其组合而不含p型或n型掺杂剂。
p型层3和n型层2间的n-p或p-n界面部分的最佳厚度根据这些层中的杂质和它们的浓度确定，但鉴于本薄膜形成技术，厚度最好应大于10埃。p型层或n型层的厚度最好约为70-700埃。当该p型层备有杂质浓度层时，最好使用一种如硼的p型掺杂剂，以构成厚度约在10-300埃范围内的薄层。而当n型层备有杂质浓度层时，最好使用一种如磷的n型掺杂剂，以构成厚度约在10-500埃范围内的薄层。高杂质浓度层愈厚，光吸收的损失就愈大。
另一方面，在加有附加p-n界面层的实施例中，该界面层厚度应约为10-300埃，最好为30-150埃。
在提高的杂质浓度足以促进载流子的复合时，由投射到第一半导体层上的光所产生的电子会更有效地和p-i-n型光电元件中的p-n界面上的第二半导体层处所产生的空穴复合。换句话说，n-p或p-n界面上的I-V（电流-电压）曲线应做得尽可能的直。
最佳的杂质浓度视引进的杂质类型和高杂质浓度层的厚度而定，因此，其范围不能无条件地定下来。当将-p型或n型掺杂剂用作杂质时，掺杂剂的浓度应大于其在毗邻i型层7、8的p型或n型层中的浓度的二倍，最好是3-10倍。此时，该浓度应为0.01-3atm%，最好为0.05-2atm%。
当p型和n型层间有高杂质浓度层，例如掺有Cu、Fe、O、N或Ge的层时，除p型或n型掺杂剂外的杂质浓度，对于Cu和Fe而言约为0.01至3atm%，而对于O-N和Ge而言约为1至10atm%。
n-p或p-n结界面部分上的高杂质浓度层的供应将带隙中的能级（局部能级浓度）提高超过一个数量级，因而促进载流子的复合和改进光的转换率。
现参考实例以叙述根据本发明制造得的半导体器件。
实例1
用一个具有平行板电容的耦合辉光放电仪将半导体层制进太阳电池中。该电池有一个1.0厘米2有效面积的玻璃基板/SnO2电极/p型层（厚度为150埃）;一层厚度为600埃的i型层;一层厚度为300埃的n型层;一层厚度为100埃的n型高杂质浓度层;一层厚度为100埃的p型高杂质浓度层;一层厚度为150埃的p型层;一层5000埃的i型层;一层500埃的n型层和一个铝电极。一个100毫瓦/厘米2的AM-1太阳模拟装置被用来鉴定性能。所得结果是η＝8.5%，Voc＝1.75伏，Jsc＝6.84毫安/厘米2，FF＝71%。
该层具有下列条件：
p型层：SiH420sccm，B2H6（以H2稀释至1000ppm）50sccm，10毫瓦/厘米2，1.0托。
i型层：SiH430sccm，10毫瓦/厘米2，0.5托。
n型层：SiH420sccm，PH3（以H2稀释至1000ppm），10毫瓦/厘米2， 0.5托。
p型高杂质浓度层：SiH420sccm，B2H6（以H2稀释至1000ppm）100sccm，10毫瓦/厘米2，1.0托。
n型高杂质浓度层：SiH420sccm，PH3（以H2稀释至1000ppm）300sccm，10毫瓦/厘米2，0.5托。
实例2
和例1的做法一样将半导体层制进一太阳电池，该电池有一个1.0厘米2有效面积的玻璃基板/SnO2电极/p型层（厚度为150埃）;一层厚度为600埃的i型层;一层厚度为300埃的n型层;一层厚度为100埃的n型高度杂质浓度层;一层厚度为100埃的p型高杂质浓度层;一层厚度为150埃的p型层;一层厚度为5000埃的i型层和一层厚度为500模并有一铝电极附于其上的n型层。一个100毫瓦/厘米2的AM-1太阳埃拟装置被用来鉴定性能。所得结果是：η＝7.0%，Voc＝1.59伏，Jsc＝7.22毫安/厘米2，FF＝61%。
高杂质浓度层是在与形成例1的p型层相同的条件下加进500sccm的N2制得的。
对比例1
除了不提供例1中的n型和p型高杂质浓度外，按例1相同的方法将半导体层制进太阳电池，并用与例1相同的方法鉴定性能。所得结果是：η＝6.2%，Voc＝1.49伏，Jsc＝7.17毫安/厘米2FF＝58%。
从上述的例子可知，用Jsc、Voc和FF表示的太阳电池性能显然可以根据本发明在p-n或n-p结界面上的用高杂质浓度层提供一多结太阳电池的做法加以改进。
在本发明与目前被认为是最实用和最佳的实施例一起叙述的情况下，不言而喻，本发明不受限于该被公开的实施例，相反，本发明的目的是要将所附权利要求的精神和范围中所包括的各种修改和等效装置覆盖在内。

Claims (16)

1、一种基本上由非晶材料组成并有多结结构的半导体器件，该器件有被设置在一对电极之间的多个串联的P-I-N光电单元，每一单元由P-I-N层组成，其特征在于，至少有一个促进电子空穴复合的高杂质部分，每一个所说高杂质部分的杂质浓度都比多个所说各层的杂质浓度高，而且每一个所说高杂质部分被设置在由所说多个串联光电单元中的两相邻光电单元所限定的界面处。
2、根据权利要求1的器件，其特征在于，该器件包括两个串联的所说P-I-N光电单元，以及一个设置在两个光电单元之间的高杂质部分。
3、根据权利要求2的器件，其特征在于，所说的一个高杂质部分具有选自氮、氧、铁、铜和锗的组合中的杂质。
4、根据权利要求3的器件，其特征在于，所说一个高杂质部分具有范围为10-300
Figure 87102619_IMG2
的厚度。
5、根据权利要求1的器件，其特征在于，该器件包括两个串联的所说P-I-N光电单元和一个高杂质部分，后者形成在所说两相邻光电单元之一的一部分中。
6、根据权利要求5的器件，其特征在于，所说的一个高杂质部分掺以基本上由P型掺杂剂组成的掺杂剂。
7、根据权利要求6的器件，其特征在于，所说的一个高杂质部分具有一个范围在10-300 之内的厚度。
8、根据权利要求5的器件，其特征在于，所说的一个高杂质部分掺以基本上由n型掺杂剂组成的掺杂剂。
9、根据权利要求8的器件，其特征在于，所说的一个高杂部分具有范围为10-500
Figure 87102619_IMG4
的厚度。
10、根据权利要求1的器件，其特征在于，所说器件包括第一和第二P-I-N光电单元及由两层组成的一个高杂质部分，这两层中一层掺以由n型掺杂剂组成的掺杂剂而且是所说第一光电单元的所说n型层的一部分，而另一层则掺以由p型掺杂剂组成的掺杂剂而且是所说第二光电单元的p型层的一部分。
11、根据权利要求1的器件，其特征在于，所说器件包括三个串联的所说P-I-N光电单元及两个高杂质部分，每一部分设置在由所说三个串联P-I-N所限定的界面中之一的对应处。
12、根据权利要求1的器件，其特征在于，所说器件包括四个串联的所说P-I-N光电单元及三个高杂质部分，每一部分设置在由所说四个串联P-I-N光电单元所界定的界面之一对应处。
13、一种如权利要求1所规定的半导体器件的制造方法，包括
（a）形成一对电极;
（b）形成一p型层，层中有p型掺杂杂质的第一浓度;
（c）形成一本征层;以及
（d）形成一n型层，层中有n型掺杂杂质的第二浓度;
其特征在于，还包括：
（e）在由所说p型层和所说n型层所限定的界面处形成一杂质层，所说杂质层具有第三浓度，此浓度较所说第一和第二浓度都高，促进电子-空穴复合在所说杂质层中的复合;需要时重复步骤（b）-（e）。
14、根据权利要求13的方法，其特征在于，所说杂质层在所说p型层中形成。
15、根据权利要求13的方法，其特征在于，所说杂质层在所说n型层中形成。
16、根据权利要求13的方法，其特征在于，所说杂质层是一插置在所说p型层和所说n型层之间的边界层。
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EP0241226A3 (en) 1988-09-07
US4926230A (en) 1990-05-15
AU7102687A (en) 1987-10-08
EP0241226A2 (en) 1987-10-14
CN87102619A (zh) 1987-11-11
AU604234B2 (en) 1990-12-13
CA1295401C (en) 1992-02-04
JPS62234379A (ja) 1987-10-14

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