CN102201464A - 包括柔性或硬性基板的光电装置及其制造方法 - Google Patents

包括柔性或硬性基板的光电装置及其制造方法 Download PDF

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CN102201464A
CN102201464A CN2011100702886A CN201110070288A CN102201464A CN 102201464 A CN102201464 A CN 102201464A CN 2011100702886 A CN2011100702886 A CN 2011100702886A CN 201110070288 A CN201110070288 A CN 201110070288A CN 102201464 A CN102201464 A CN 102201464A
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明承烨
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NEO LAB CONVERGENCE Inc
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Abstract

本发明提供光电装置及其制造方法，该光电装置包括，基板；第一电极，位于上述基板上；第二电极，位于上述第一电极的对面，从中光被入射；第一单元电池，位于上述第一电极和上述第二电极之间，并包括纯半导体层，该纯半导体层包括在上述第二电极一侧的表面上形成凹凸的晶硅晶粒；第二单元电池，位于上述第一单元电池和上述第二电极之间。

Description

包括柔性或硬性基板的光电装置及其制造方法
技术领域
本发明涉及包括硬性或柔性基板的光电装置及其制造方法。
背景技术
近年来，由于CO2的过度排放所导致的气候变暖和高油价，在未来能源逐渐变成左右人类生存的最重要的问题。虽然存在风力、生物燃料、氢/燃料电池等很多新的可再生能源技术，但是作为所有能源基础的太阳能是无限的清洁能源，因此利用太阳光的光电装置备受瞩目。
入射到地球表面的太阳光相当于120,000TW，因此，在理论上由光电转换效率(conversion efficiency)为10％的光电装置，只要覆盖地球陆地面积的0.16％，可以产生两倍于全球一年消耗能源的20TW电力。
实际上，在过去的十年，全球的太阳光市场每年以40％的速度高速增长。目前，光电装置市场的90％由单晶硅(single-crystalline)或多晶硅(multi-crystalline or poly-crystalline)等块(bulk)型硅光电装置占有。但是，由于太阳能级硅片(Solar-grade silicon wafer)的生产满足不了爆发性的需求，因此在全球范围内发生缺货现象，这成为降低生产成本的一大障碍。
与此相反，使用氢化非晶硅(a-Si:H)吸光层的薄膜(thin-film)硅光电装置相对于块型硅光电装置能够使其厚度减少至百分之一以下，且能够大面积低价生产。
另一方面，由于单一接合(Single-junction)薄膜硅光电装置具有性能极限，因此开发多个单元电池层压的双重接合薄膜硅光电装置或三重接合薄膜硅光电装置，以达到高稳定效率(Stabilized efficiency)。
以双重接合或三重接合薄膜硅光电装置的情况，为了通过光散射来提高效率，进行着对电极表面的凹凸的研究。
发明内容
本发明的光电装置及其制造方法，其目的在于在光电装置的电极表面上形成凹凸。
本发明所要解决的技术课题，不局限于上述的技术课题，本发明所属技术领域的具有一般知识的人可以根据下面的叙述能够清楚地理解其它的技术课题。
根据本发明的光电装置包括，基板；第一电极，位于上述基板上；第二电极，位于上述第一电极的对面，从中光被入射；第一单元电池，位于上述第一电极和上述第二电极之间，并包括纯半导体层，该纯半导体层包括在上述第二电极一侧的表面上形成凹凸的晶硅晶粒；第二单元电池，位于上述第一单元电池和上述第二电极之间。
根据本发明的光电装置的制造方法包括，形成上述第一单元电池的n型半导体层的步骤；在上述n型半导体层上形成包括围住晶硅晶粒的非晶硅物质的上述第一单元电池的纯半导体层的步骤；对上述纯半导体层的表面进行蚀刻的步骤；上述纯半导体层上形成上述第一单元电池的p型半导体层的步骤。
根据本发明的光电装置及其制造方法，可以在电极表面上通过单元电池的晶硅晶粒形成充分的凹凸。
附图说明
图1a和图1b表示根据本发明实施例的光电装置；
图2a至图2h表示根据本发明实施例的光电装置的制造方法。
附图标号说明
100：基板
110：第一电极
120：第二电极
130：第一单元电池
131：n型半导体层
133：纯半导体层
133a：氢化非晶硅物质
133b：晶硅晶粒
135：p型半导体层
140：第二单元电池
141：n型半导体层
143：纯半导体层
145：p型半导体层
150：中间反射膜
具体实施方式
下面参照附图详细说明根据本发明实施例的光电装置。
图1表示根据本发明实施例的光电装置。如图1所示，根据本发明实施例的光电装置包括，基板100；第一电极110；第二电极120；第一单元电池130；第二单元电池140。
基板100可以为柔性基板或硬性基板。柔性基板可以是不锈钢(stainlesssteel)、铝箔等金属基板，也可以是聚邻苯二甲酸酯(PEN，PolyethyleneNaphthalate)或聚对苯二甲酸乙二醇酯(PET，Poly Ethylene Terephthalate)等塑料基板。基板为金属基板的情况下，为了使其与基板上形成的电极绝缘，在基板表面上可以形成绝缘膜。硬性基板可以是玻璃基板。
第一电极110位于基板100上。以n-i-p型光电装置的情况，光通过第二单元电池140入射，因此邻接于基板100的第一电极110可以具有透光性，也可以不具有透光性。因此，第一电极110可以由金属构成，也可以由例如透明导电氧化物(TCO，Transparent Conductive Oxide)等的透光性导电物质构成。
第二电极120位于第一电极110的对面，从中光被入射。如前面所述，n-i-p型光电装置的情况下，由于光是通过第二单元电池140入射，因此相比于第一电极110，光先入射至第二电极120。因此，第二电极120可以由透光性导电物质构成。
第一单元电池130位于第一电极110和第二电极120之间，并包括纯半导体层133，该半导体层包括在第二电极120表面形成凹凸的晶硅晶粒。第一单元电池130包括依次层压的n型半导体层131、纯半导体层133和p型半导体层135。因此，在n型半导体层131、纯半导体层133和p型半导体层135中，n型半导体层131离第一电极110最近。
在本发明的实施例中，第一单元电池130相比于第二单元电池140光后入射，因此比起短波长区域的光更多吸收长波长区域的光。为了更加充分地吸收长波长区域的光，第一单元电池130的纯半导体层133可以包括氢化微晶硅物质层。氢化微晶硅物质层可以由氢化微晶硅(i-μc-Si:H)或氢化微晶硅锗(i-μc-SiGe:H)构成。
氢化微晶硅物质层包括，氢化非晶硅物质133a和被氢化非晶硅物质133a围住的晶硅晶粒133b。由于晶硅晶粒133b向第二电极120突出，因此在纯半导体层133的表面中第二电极120的表面上形成凹凸。关于如上所述的使晶硅晶粒133b向第二电极120突出的方法，下面进行详细的说明。
通过如上所述的通过晶硅晶粒133b形成的表面凹凸，在第二单元电池140的n型半导体层141、纯半导体层143和p型半导体层145的表面上也形成凹凸。因此，入射到第二单元电池140的光可以散射。
n-i-p型光电装置的情况下，即使在基板100表面或第一电极110表面上形成凹凸，但由于第一单元电池130和第二单元电池140的厚度大，因此在光入射的第二单元电池140的表面上可能形成不了充分的凹凸。即，由于第一单元电池130和第二单元电池140的厚度大，因此通过沉积形成第一单元电池130和第二单元电池140时，其表面可能变得平坦。
与此相反，根据本发明实施例的光电装置的情况下，第一单元电池130的晶硅晶粒向第二单元电池140突出，因此在第一单元电池130上形成第二单元电池140时，第二单元电池140上形成凹凸。
如上所述，包括氢化微晶硅物质层的纯半导体层133的平均结晶体体积分率可以为25％～75％。
纯半导体层133的结晶体体积分率为25％以上时，可以防止纯半导体层133和p型半导体层135之间的界面或纯半导体层133和n型半导体层131之间的界面上生成氢化非晶硅孵化层(incubation layer)。因此，可以圆满形成空穴跃迁(hole transition)或电子跃迁(electron transition)，由此减少再结合，并提高光电转换效率。
纯半导体层133的结晶体体积分率为75％以下时，可以防止晶硅晶粒的大小过分变大，因此可以防止晶粒间(grain boundary)体积变大。
第二单元电池140位于第一单元电池130和第二电极120之间。第二单元电池140包括，依次层压的n型半导体层141、纯半导体层143和p型半导体层145。因此，在n型半导体层141、纯半导体层143和p型半导体层145中p型半导体层145离第二电极120最近。
此时，第一单元电池130和第二单元电池140的p型半导体层135、145掺杂三族杂质，第一单元电池130和第二单元电池140的n型半导体层131、141掺杂五族杂质。
另一方面，如图1b所示，根据本发明实施例的光电装置还可以包括位于第一单元电池130和第二单元电池140之间的中间反射膜150。波长为600nm时，中间反射膜150的平均折射率为1.7～2.5。中间反射膜150的平均折射率为1.7～2.5时，形成折射率匹配(refractive index matching)。因此，短波长区域的光反射至第二单元电池140，并提高光电转换效率。
下面参照附图，对本发明实施例的光电装置的制造方法进行详细的说明。
如图2a所示，准备通过溅射法形成有第一电极110的基板100。在形成第一电极110之前可以进行洗净工序。第一电极110由金属构成的情况下，为了提高第一电极110和基板1oo之间的粘着力，在第一电极110和基板100之间可以形成ZnO层。对于基板在前面已经做了详细的说明，因此省略。
如图2b所示，在第一电极110上形成第一单元电池130的n型半导体层131。
如图2c所示，第一单元电池130的纯半导体层133形成在n型半导体层131上。此时，第一单元电池130的纯半导体层133包括围住晶硅晶粒133b的非晶硅物质133a。即，第一单元电池130的纯半导体层133可以包括具有混合相(mixed phase)的氢化微晶硅物质层。如前面所述，纯半导体层133的平均结晶体体积分率可以为25％～75％。
如图2d所示，对纯半导体层133表面进行蚀刻。此时，通过氢等离子体蚀刻或氩等离子体蚀刻等干蚀刻工序，对纯半导体层133表面进行蚀刻。根据本发明实施例的光电装置包括柔性基板的情况下，如果进行化学蚀刻，则可能改变或损伤由金属或聚合物构成的柔性基板的外形，但是干蚀刻工序相比于化学蚀刻(chemical etching)，对柔性基板的影响小。
因此，对纯半导体层133进行适合的蚀刻。即，纯半导体层133如前面所述包括蚀刻率相互不同的晶硅晶粒和非晶硅物质。非晶硅物质相比于晶硅晶粒，在相同条件下蚀刻得更快。由此，如果进行干蚀刻，被非晶硅物质围住的晶硅晶粒突出。通过如此突出的晶硅晶粒，在纯半导体层133的表面上形成凹凸。
同时，由于非晶硅物质被去除，因此在纯半导体层133内提高空穴传输(holetransport)，进而提高光电装置的开路电压和光电转换效率。
如图2e所示，已进行蚀刻的纯半导体层133上可以形成厚度为5nm左右的钝化膜PL。如果纯半导体层133的表面被蚀刻，则在纯半导体层133的表面上可以增加再结合。由此，已进行蚀刻的纯半导体层133的表面上可以形成钝化膜PL。此时，钝化膜PL可以由氢化微晶硅物质构成。纯半导体层133也包括氢化微晶硅物质层，因此可以简化制造工序。
如图2f所示，在纯半导体层133上形成第一单元电池130的p型半导体层135。此时，p型半导体层135可以由氢化微晶硅((p-μc-Si:H)构成。
如图2g所示，n型半导体层141、纯半导体层143和p型半导体层145依次层压在第一单元电池130上。在形成有表面凹凸的第一单元电池130上形成第二单元电池140，因此在第二单元电池140表面上也形成凹凸。第二单元电池140的纯半导体层143可以由氢化非晶硅(i-a-Si:H)、氢化非晶碳化硅(i-a-SiC:H)、氢化非晶氧化硅(i-a-SiO:H)、氢化原晶硅(i-pc-Si:H)或具有多层结构的氢化原晶硅等构成。
如图2h所示，通过溅射法或低压化学气相沉积(LPCVD)法在第二单元电池140上形成第二电极120。此时，第二电极120可以由铟锡氧化物(ITO，Indium Tin Oxide)或掺氟氧化锡(SnO2:F)或氧化锌(ZnO)构成。
如上所述，通过晶硅晶粒133b在第二电极120的表面上形成凹凸。为了散射入射的光，第二电极120表面的凹凸可具有50nm～500nm的平均间距。如图2h所示，平均间距可以是相互邻接的凹凸的凸起部之间距离(P)的平均值。如此的，光入射的第二电极120的平均间距为50nm～500nm的情况下，第二电极120的表面凹凸可以充分散射可视光区域的光。
另一方面，由于通过晶硅晶粒133b在第二电极120的表面上形成凹凸，因此中间反射膜150的厚度不必超过必要的厚度。例如，为了通过由氧化锌(ZnO)构成的中间反射膜150的沉积在第二电极120的表面上形成凹凸，要充分形成中间反射膜150的表面凹凸。如此地，为了形成中间反射膜150的表面凹凸，中间反射膜150的厚度应为1.6μm以上，这将导致工序时间增加。
特别是，在卷对卷式制造系统中形成中间反射膜150的情况下，由于基板100被连续移送，因此在工序腔室内停留一定的时间。由此，如果要增加中间反射膜150的厚度和工序时间，可以增加用于形成中间反射膜150的工序腔室数量。
与此相反，根据本发明实施例的光电装置，通过晶硅晶粒133b在第二电极120的表面上充分形成凹凸，因此可以防止中间反射膜150的厚度增加。根据本发明实施例的中间反射膜150的厚度可以为20nm～200nm。如果中间反射膜150的厚度小于20nm，则可能难以形成折射率匹配。另外，中间反射膜150的厚度大于200nm时，随着中间反射膜150的厚度增加，在中间反射膜150上吸收的光的量可能增加。因此，根据本发明实施例的光电装置即使包括柔性基板100，但也可以防止工序时间的增加。
在本发明的实施例中，对双重接合串联光电装置进行了说明，但是也可能适用于三重接合光电装置的中层电池或下层电池。
上面，结合附图对本发明的实施例进行了说明。本发明所属的技术领域的技术人员，可以理解在不变更本发明的技术思想或必要特征的情况下，可以由另外具体方式实施。因此，上述的实施例只是举例而已，本发明并不只局限于上述实施例。

Claims (19)

1.一种光电装置，包括：
基板；
第一电极，位于上述基板上；
第二电极，位于上述第一电极的对面，从中光被入射；
第一单元电池，位于上述第一电极和上述第二电极之间，并包括纯半导体层，该纯半导体层包括在上述第二电极一侧的表面上形成凹凸的晶硅晶粒；
第二单元电池，位于上述第一单元电池和上述第二电极之间。
2.根据权利要求1所述的光电装置，其特征在于：上述基板为柔性基板。
3.根据权利要求1所述的光电装置，其特征在于：上述第一单元电池和上述第二单元电池分别包括依次层压的n型半导体层、纯半导体层和p型半导体层。
4.根据权利要求1所述的光电装置，其特征在于：上述第一单元电池的纯半导体层包括氢化微晶硅物质层。
5.根据权利要求1所述的光电装置，其特征在于：上述晶硅晶粒被氢化非晶硅物质围住。
6.根据权利要求1所述的光电装置，其特征在于：在上述第二单元电池的p型半导体层的表面上形成有凹凸。
7.根据权利要求1所述的光电装置，其特征在于：上述第一单元电池的纯半导体层的平均结晶体体积分率为25％～75％。
8.根据权利要求1所述的光电装置，其特征在于：上述第二电极的表面凹凸的平均间距为50nm～500nm。
9.根据权利要求1所述的光电装置，其特征在于：上述第一单元电池和上述第二单元电池之间还包括中间反射膜，上述中间反射膜的厚度为20nm～200nm。
10.一种n-i-p型光电装置的制造方法，所述n-i-p型光电装置包括第一单元电池和第二单元电池，且光从所述二单元电池侧入射，该方法包括：
形成上述第一单元电池的n型半导体层的步骤；
在上述n型半导体层上形成包括围住晶硅晶粒的非晶硅物质的上述第一单元电池的纯半导体层的步骤；
对上述纯半导体层的表面进行蚀刻的步骤；
上述纯半导体层上形成上述第一单元电池的p型半导体层的步骤。
11.根据权利要求10所述的光电装置的制造方法，其特征在于：上述光电装置形成在柔性基板上。
12.根据权利要求10所述的光电装置的制造方法，其特征在于：上述第一单元电池的纯半导体层包括氢化微晶硅物质层。
13.根据权利要求10所述的光电装置的制造方法，其特征在于：上述第一单元电池的纯半导体层的平均结晶体体积分率为25％～75％。
14.根据权利要求10所述的光电装置的制造方法，其特征在于：对上述纯半导体层表面进行干蚀刻。
15.根据权利要求14所述的光电装置的制造方法，其特征在于：上述干蚀刻为氢等离子体蚀刻或氩等离子体蚀刻。
16.根据权利要求10所述的光电装置的制造方法，其特征在于：上述非晶硅物质相比于上述晶硅晶粒蚀刻得更快。
17.根据权利要求10所述的光电装置的制造方法，其特征在于：已进行蚀刻的上述纯半导体层上形成钝化膜。
18.根据权利要求17所述的光电装置的制造方法，其特征在于：上述钝化膜由氢化微晶硅物质构成。
19.根据权利要求10所述的光电装置的制造方法，其特征在于：上述第二电极的表面凹凸平均间距为50nm～500nm。
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