CN87102619A - 半导体器件及其制造方法 - Google Patents

半导体器件及其制造方法 Download PDF

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CN87102619A
CN87102619A CN87102619.8A CN87102619A CN87102619A CN 87102619 A CN87102619 A CN 87102619A CN 87102619 A CN87102619 A CN 87102619A CN 87102619 A CN87102619 A CN 87102619A
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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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    • H01L31/0376—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including amorphous semiconductors
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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结界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结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发明书的一部分，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结界面。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结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结界面的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结界面层的实施例中，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结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结界面上的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0.01-3    atm%，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：SiH430 sccm，10毫瓦/厘米2，0.5托。
n型层：SiH420 sccm，PH3（以H2稀释至1000ppm），10毫瓦/厘米2， 0.5托。
p型高杂质浓度层：SiH420 sccm，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：SiH420 sccm，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。
与例1相比
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 (11)

1、一种实质上由非晶形和/或微晶形材料组成的半导体器件，其特征在于，它的多结结层包括一或多层掺以n型掺杂剂的n型层，一或多层掺以p型掺杂剂的p型层，以及至少一层包括一个高浓度的杂质并被插入所说p型和所说n型层间的薄层，从而促进载流子的复合。
2、根据权利要求1的半导体器件，其特征在于，所说被插入的薄层位于所说p型层之上，并且比其余p型层具有较高的杂质浓度。
3、根据权利要求2的半导体器件，其特征在于，所说被插入的薄层具有在10-300埃范围内的厚庹。
4、根据权利要求2的半导体器件，其特征在于，所说杂质主要包括p型掺杂剂。
5、根据权利要求1的半导体器件，其特征在于，所说被插入的薄层位于所说n型层之上，并且比其余n型层具有较高的杂质浓度。
6、根据权利要求5的半导体器件，其特征在于，所说杂质主要包括n型掺杂剂。
7、根据权利要求5的半导体器件，其特征在于，所说较高浓度层具有在10-700埃范围内的厚度。
8、根据权利要求1的半导体器件，其特征在于，所说被插入薄层至少包括两层较薄的层。
9、一种为具有非晶形结构类型的光电电池用的半导体器件，其特征在于，它包括：
一层n型层;
一层p型层;以及
一层在所说p型层和所说n型层间的边界层，所说边界层的杂质来自由氮、氧、铁、铜和锗组成的组合，其杂质浓度大于在所说n型和所说p型层中杂质的总浓度。
10、一种在半导体器件中的p-n或n-p结界面上促进电子-电子空穴复合的方法，其特征在于，该方法包括：
（a）形成一层具有掺进p型杂质的第一浓度的p型层，
（b）形成一层具有掺进p型杂质的第二浓度的n型层;以及
（c）在毗邻所说界面的所说p型层或n型层上形成一浓度层，如该层配置在所说p型上，其浓度大于所说第一浓度，如该层配置在所说n型层上，则其浓度大于所说第二浓度。
11、一种在半导体器件中的p-n或n-p结界上促进电子-电子空穴复合的方法，其特征在于，该方法包括：
（a）形成一层具有掺进p型杂质的第一浓度的p型层;
（b）形成一层具有掺进n型杂质的第二浓度的n型层;以及
（c）在所说界面上形成一层边界层，该边界层的杂质来自由氮、氧、铁、铜和锗组成的组合，而且其浓度大于所说n型层和p型层中杂质的总浓度。
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CN1035644C (zh) * 1993-03-15 1997-08-13 杨永清 太阳电池
CN101752445B (zh) * 2008-11-28 2013-05-29 瀚宇彩晶股份有限公司 光传感器、感光二极管、二极管层及其制造方法
CN103137778A (zh) * 2011-11-25 2013-06-05 吉富新能源科技(上海)有限公司 内部光二次散射之高效率双结薄膜太阳能电池技术
CN105359279A (zh) * 2013-06-18 2016-02-24 原子能和替代能源委员会 多结太阳能电池
CN105359279B (zh) * 2013-06-18 2017-05-24 原子能和替代能源委员会 多结太阳能电池

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US4926230A (en) 1990-05-15
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AU7102687A (en) 1987-10-08
EP0241226A2 (en) 1987-10-14
AU604234B2 (en) 1990-12-13
CA1295401C (en) 1992-02-04
JPS62234379A (ja) 1987-10-14

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