CN102712999B - 涂覆基材的方法 - Google Patents

涂覆基材的方法 Download PDF

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CN102712999B
CN102712999B CN201080045703.6A CN201080045703A CN102712999B CN 102712999 B CN102712999 B CN 102712999B CN 201080045703 A CN201080045703 A CN 201080045703A CN 102712999 B CN102712999 B CN 102712999B
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zinc oxide
base material
layer
etching
present
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CN102712999A (zh
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D·伯雷罗
E·瓦拉特-萨维恩
J·斯德恩豪瑟
U·克罗尔
J·迈耶
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TEL Solar AG
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Abstract

本发明提供一种在基材上涂覆氧化锌膜的方法，该方法包含以下步骤：-提供一具有至少一实质上平坦表面的基材；-将至少部分的该表面进行一等离子刻蚀工艺；-在该经刻蚀的表面上沉积一层，该层包含氧化锌；本发明方法特别适用于制造具有提升效能的太阳能电池。

Description

涂覆基材的方法
技术领域
本发明关于薄膜涂层领域。特定言之，本发明关于在基材上涂覆氧化锌膜，其特别用于制造太阳能电池及/或太阳能面板的目的。
背景技术
光伏打装置(photovoltaic devices)或太阳能电池为能将光(特别是日光)转换成直流(DC)电能的装置。针对低成本、大规模的生产而言，薄膜太阳能电池的益处在于其可使用玻璃、玻璃陶瓷、或其它刚性或可挠性基材来取代硅晶或多晶硅，以作为基础材料或基材。至今，已有多种可自市面上购得的太阳能电池技术。在低温下且大规模地处理此种电池的可行性乃为此种技术的主要优点。
太阳能电池的结构(即，层序列(layer sequence))为掌控或促成光伏打效应的要素。这些层可各别借由已知的真空沉积技术(例如物理气相沉积(PVD)、化学气相沉积(CVD)、等离子辅助化学气相沉积(PECVD)、常压化学气相沉积(APCVD)，上述技术皆可用于半导体技术中)来涂覆或沉积成薄层。
传统的薄膜太阳能电池通常包含一沉积在基材上的透明电极层(亦称为前电极(front electrode))。在此第一电极层的顶端上通常沉积有一由薄的非晶质硅膜及/或薄的微晶硅膜所形成的光电转换半导体层(photoelectric conversionsemiconductor layer)，以及一背电极层(back electrode layer)。该背电极可再包含一透明导电层、一反射体层、及一导电并反射的金属层或与其技术相当者。
详言之，图1(已知技术)所示为一基本、简单的光伏打电池10，包含一透明基材12，其上沉积有一透明导电氧化物(transparent conductive oxide，TCO)14。此层也称为前触点(front contact)且作为该光伏打组件的第一电极。基材12与前触点14的结合也称为覆层(superstrate)。其下的层16作为活性光伏打层(active photovoltaic layer)并呈现出三层形成p-i-n结(junction)的“次层”。该层16包含氢化的微晶硅、纳米晶硅、非晶质硅或前述的组合。次层18(邻接TCO前触点14)为正电性掺杂(positively doped)，邻接的次层20为本征的(intrinsic)，而最后的次层22为负电性掺杂(negatively doped)。在另一实施方式中，如上所述的层序列p-i-n可反转成n-i-p。此时，次层18即为负电性掺杂层(n层)，次层20一样为本征的，而次层22则为正电性掺杂层(p层)。
最后，该电池含有一后触点(rear contact)层24(也称为背触点)。此外，再提供一反射层26。或者，可具有一金属背触点(metallic back contact)，其可结合背反射体26与背触点24的物理特性。为达例示的目的，箭头代表照射光。
一般所知，当光(例如太阳辐射)照射在光电装置(如太阳能电池)上时，会在i层中生成电子空穴对(electron-hole pairs)。所生成对中的空穴会朝p区域移动，而电子会朝n区域移动。触点通常直接或间接地接触p区域及n区域。只要光持续产生电子空穴对，电流就会流过与这些触点所连接的外部电路。
透明导电(transparent conducting，TC)层(如前述用作层14及/或层24者)为结合可见光范围的光学穿透性及导电性的薄膜材料，其适合用在光电应用。
已有多种应用使用到透明导电层，例如平面显示器的除霜窗或透明电极及太阳能电池。在这些应用中，通常会要求将其透明导电层的电导度(conductance)及穿透率(transmittance)最大化。
有多种工艺可制造透明导电层。其中最常用的技术有：溅镀(PVD)、化学气相沉积(CVD)、脉冲激光沉积、喷雾热解及蘸湿(wet dip)沉积。这些工艺采用不同材料来作为基材，例如玻璃、塑料薄片等。这些材料可为可挠性或刚性。
为提升光伏打装置的电转换效能，应尽量使活性硅层中吸收尽可能多的照射光。
透明导电材料的特性或与高穿透率结合的高导电率通常难以同时实现，原因在于在可见光范围内的光学透明度通常需要能带间隙(band gap)大于3.3电子伏特的材料，然而，此种大能带间隙的材料使载体掺杂难以实现，因此难以达到高导电率。
除此基本限制外，通常，制作过程会在层中诱发缺陷，这也限制透明度及导电率。此缺陷为例如孔隙、晶界(grain boundary)及杂质污染。
美国专利第6,420,644B1号揭露一种具有一板的太阳能电池，该板具有一表面且具有多个自板表面外突而出的球截形(spherical segments)。为界定出该多个球截形，可在板表面上进行压印。其中，可在板的顶端提供一由铬所制成的第一电极。
美国专利第US2005/0022860A1号揭露一种薄膜光伏打模块。其中，为提升此模块的利用性，在基材上提供多个实质上呈半球状的突起物。在基材为金属基材的情况下，该突起物借由压印金属基材形成。而在提供塑料基材的情况下，该突起物可借由射出成型形成。
发明内容
本发明的一目的在于提供一种涂覆基材的方法，其克服上述缺陷中的至少一者。
本发明的另一目的在于提供一种涂覆基材的方法，其可用来形成太阳能电池，使该太阳能电池效能提升。
此目的可藉由如权利要求1的方法实现。此目的更可借由如权利要求9的太阳能电池实现。附属项列出多种有利的实施方式。
本发明关于一种在基材上涂覆氧化锌膜的方法，该方法包含以下步骤：
-提供一具有至少一实质上平坦表面的基材；
-将至少部分的该表面进行一等离子刻蚀工艺；
-在该经刻蚀的表面上沉积一层，该层包含氧化锌。
由于等离子刻蚀工艺，故可在基材上具有一经结构化的表面。其可为形成太阳能电池或太阳能模块的基础。详言之，该经结构化的基材可用来形成一薄膜太阳能电池。
相较于在平坦基材上沉积透明导电层，本发明将基材刻蚀以获得一清楚的形貌，此同时会提升透明导电层的电导度而改变这些透明导电层的成长。
因此，一平坦(或实质上平坦)的表面应是指未进行导入清楚结构的处理的表面。详言之，是未借由如压印或铸模的方式导入凹槽(deepenings)或突起物。
借由使用等离子刻蚀工艺，可在表面上获得十分清楚的结构。此可提供具有十分明确特性的经结构化的表面。详言之，由于该基材的结构化表面的作用，自基材传送至活性层的光(特别是日光)会被散射。此会提升活性相中光的吸收度，并借此提升包含此经结构化的基材的太阳能电池的效能。
令人惊讶地，经本案发明人发现，将基材的表面以等离子刻蚀工艺结构化，并随后涂覆一氧化锌层，以此与基材结合可提升该氧化锌层的导电率。不受特定理论限制下，假设此结果是借由上述特征的有利协同效应所实现的。特定言之，根据本发明可实现绝佳透明度及提升导电率的组合。
因此，由于采用等离子刻蚀工艺及同时使用氧化锌涂层的特殊组合与其协同效应，透明度以及特别是在导电率上有所提升，故根据本发明涂覆的基材非常适合作为制造太阳能电池的基础。
在本发明一较佳实施方式中使用玻璃基材。玻璃基材具有较佳的特性，其可达到一有效的、十分明确的刻蚀工艺(特别在使用等离子刻蚀工艺时)。特定言之，借由使用玻璃基材，基材的表面可借由利用平滑刻蚀条件，以所欲且十分明确的方式进行结构化。
玻璃基材可为技艺人士所已知的任何适合用来制造薄膜装置的玻璃基材。本发明的薄膜层可借由技艺人士所知的各种沉积技术来进行沉积。
在本发明的另一较佳实施方式中使用一六氟化硫(sulphur hexafluoride，SF6)与氧(O2)比例为5/1的混合物的等离子。此混合物可提供一可在基材表面上产生十分清楚的结构或形貌的等离子。详言之，尤其在结合玻璃基材的情况下，此气体混合物因采用六氟化硫作为刻蚀气体而具有优势。
在本发明的另一较佳实施方式中，在等离子刻蚀工艺中所使用的功率为1瓦/平方厘米。此功率是相当低的，得以实现节能反应条件。然而，使用如上述定义的刻蚀功率仍可产生反应性刻蚀气体或刻蚀等离子以实现有效刻蚀工艺，使在更理想的条件下进行该工艺。
在本发明的另一较佳实施方式中，在刻蚀工艺期间所使用的压力为30毫托。此压力可在等离子刻蚀基材时实现特别顺利且有效的反应条件。特定言之，此压力对刻蚀玻璃基材是较佳的。
在本发明的另一较佳实施方式中，刻蚀时间持续30分钟。对于结构化基材表面，即使对工业制程而言，特别是对制造太阳能电池或太阳能模块而言，此段时间是合理的。然而，此时间仍可适合用来实现基材表面所要求的刻蚀程度或形貌。
在本发明的另一较佳实施方式中，氧化锌借由低压气相沉积(low pressurevapour deposition，LPCVD)沉积。此工艺对在基材上涂覆尤其是氧化锌而言是较佳的。此涂覆工艺可提供高纯度且同时呈薄膜形式(即具有非常薄的厚度)的氧化锌膜。此外，由于氧化锌用作为透明导电氧化层，因此除上述导电性之外，使透明度达到所要求的值亦为相当重要的。此可借由使用氧化锌的低压气相沉积来实现。
然而，根据本发明，其它涂覆技术亦为可行的，特别是化学气相沉积(CVD)或如真空溅镀工艺的物理气相沉积(PVD)。更佳地，该气相沉积工艺为等离子辅助化学气相沉积(plasma enhanced CVD，PECVD)及/或常压化学气相沉积(atmospheric pressure CVD，APCVD)。
在本发明的另一较佳实施方式中，氧化锌掺杂有硼。以经掺杂的氧化锌涂覆基材可进一步提升导电性。此外，借由该掺杂工艺，可尤其将氧化锌层的电子特性调整至所要求的应用，特别是针对太阳能电池或太阳能模块的应用。
本发明更关于一太阳能电池，其包含一根据本发明方法涂覆有氧化锌的基材。特定言之，借由在太阳能电池中提供经本发明涂覆的基材，可实现的协同效应是有利的。详言之，该氧化锌层可用作为透明导电氧化层。关于此，导电率及透明度已经提升的氧化锌层是特别佳的。特定言之，本发明提升太阳能电池中的氧化锌层的导电率。此可使本发明的光伏打电池、或太阳能电池及太阳能模块的效能提升。
因此，本发明的方法可有利地实现一容易但极为有效的方法，以增加制造薄膜装置时(较佳是在制造太阳能电池时)的效能、产率及产量。
在本发明的一较佳实施方式中，氧化锌涂层的导电度为14.5欧姆-平方(Ohm-square)或更低。根据本发明，这些数值可容易地实现。此特征可提供包含一导电率经特别提升，且因而特别有效率的透明导电氧化层的太阳能电池。
如技艺人士所明了，本发明方法的较佳实施方式可自前述本发明的创新方法的详细说明中推导而得。然而，下文将明确揭露本发明方法的更佳的实施方式。
附图说明
参照于下文中所述的实施方式以说明并阐述本发明这些及其它的方面。
图1所示为根据已知技术的薄膜太阳能电池的示意图；
图2a所示为一根据已知技术的经涂覆的基材的横截面扫描式电子显微影像；
图2b所示为根据本发明的经涂覆的基材的横截面扫描式电子显微影像；
图3所示为根据已知技术与本发明的氧化锌涂层的薄膜电阻的比较结果；以及
图4所示为根据已知技术与本发明的氧化锌涂层的薄膜电阻的另一比较结果。
具体实施方式
图2a所示为一已知技术的涂覆有氧化锌的玻璃基材的横截面扫描式电子显微影像。可发现该基材的表面为平坦，此表示其不具任何突起物或凹槽。详言之，该表面未借由如压印或铸造的方式进行过表面修饰。在该平坦表面上沉积有一氧化锌(ZnO)层。
与上述相反，图2b所示为本发明的涂覆有氧化锌的玻璃基材的横截面扫描式电子显微影像。沉积在该玻璃基材上的氧化锌层的上部分较沉积在平坦玻璃上的层(图2a)呈现较大的晶粒。这些较大晶粒可说明此基材上的氧化锌层的增加的电导度。事实上，大晶粒的材料较小晶粒的材料展现较高的导电率。再者，大晶粒减少光学穿透性的损失。
在基材与透明材料间存在一粗糙界面时将使光漫射(diffusion)，该界面借由本发明的等离子刻蚀工艺所获得。在太阳能电池应用中，此光漫射为所欲的，以捕捉光进入电池的活化层中。再者，此粗糙界面亦减少照入光在玻璃表面与氧化锌层间的界面上的反射，使透明度增加。
这些结果显示本发明的基材表面形貌的修饰影响了氧化锌层的成长且明显增加其电导度、均质性及透明性。
实施本发明的方法所实现的效果、以及玻璃基材表面的形貌对二种类型的氧化锌层(沉积在基材表面上)的导电率的影响详示于图3及图4中。
详言之，实施以下本发明的实施例。
在所有实验中，在一反应离子刻蚀机(RIE)中，以氧(O2)与六氟化硫(SF6)混合的等离子对Schott Borofloat33玻璃的表面进行刻蚀。在RIE工艺中所采用的参数如下：
具有经30分钟刻蚀冲击的表面形貌的玻璃称为“玻璃A”，而具有经120分钟刻蚀冲击者称为“玻璃B”。
待在基材表面上导入结构或形貌后，借由低压化学气相沉积(LPCVD)沉积二种类型的氧化锌。类型1为沉积在平坦基材上、厚度约500纳米、未掺杂的氧化锌(ZnO)的薄层，以及另外沉积在“玻璃A”基材上者。类型2为沉积在“玻璃A”基材上、厚度约1000纳米、掺杂硼的氧化锌(ZnO:B)的薄层，以及另外沉积在“玻璃B”基材上者。各类型是在相同的沉积操作下同时沉积在平坦玻璃基材及经刻蚀的玻璃基材上。
以四点探针(four probe)法对所有层测量薄膜电阻(sheet resistances，Rsq)。该薄膜电阻与导电度的关系如下方程序所示：
G＝1/R＝W/(Rsq.L)
其中，G为导电度，R为电阻，且W及L各别为层宽度及层长度。
图3所示为同时沉积在平坦玻璃及“玻璃A”上的类型1氧化锌的薄膜电阻值。在使用“玻璃A”取代平坦玻璃时，该层的薄膜电阻从11.5×10-6欧姆/平方下降至4.5×10-6欧姆/平方。
图4所示为同时沉积在平坦玻璃、“玻璃A”及“玻璃B”上的类型2氧化锌的薄膜电阻值。相较于沉积在平坦玻璃上的氧化锌，沉积在“玻璃A”上的层的薄膜电阻从20.3欧姆/平方下降至14.5欧姆/平方，而沉积在“玻璃B”上的层的薄膜电阻从20.3欧姆/平方下降至10.2欧姆/平方。
此显示借由实施本发明的方法，氧化锌层的导电度可显著地提升。本发明的方法因而可特别适用于制造效能提升的光伏打组件或太阳能电池。
当以附图及上述说明详细描述及说明本发明时，该描述及说明应当视为示范及例示所用，而非用以限制本发明。本发明并不限于所揭露的实施方式。本领域的一般技艺人士在实际应用本发明时，可经由图示、揭露内容及随附权利要求范围的教示而了解并实现所揭露实施方式的其它变化。在权利要求范围中，“包含”一词不排除其它组件或步骤，而不定冠词“一”不排除复数形式。单独记载于相互不同的附属项中的特定方法并不代表不可有利地使用这些方法的组合。权利要求范围中的任何参考符号不应视为限定本发明的范围。

Claims (8)

1.一种在基材上涂覆氧化锌膜的方法，该方法包含以下步骤：
提供一具有至少一实质上平坦表面的基材；
将至少部分的该表面进行一等离子刻蚀工艺；
以化学气相沉积(CVD)或物理气相沉积(PVD)在该经刻蚀的表面上沉积一层，该层包含氧化锌；
其中使用一玻璃基材，并使用一六氟化硫与O2比例为5/1的混合物的等离子。
2.如权利要求1的方法，其中在该等离子刻蚀工艺中所使用的功率为1000瓦。
3.如权利要求1或2的方法，其中在该刻蚀工艺期间所使用的压力为30毫托。
4.如权利要求1或2的方法，其中该刻蚀的时间持续30分钟。
5.如权利要求1或2的方法，其中氧化锌以低压气相沉积法沉积。
6.如权利要求1或2的方法，其中氧化锌掺杂有硼。
7.一种太阳能电池，其包含一根据权利要求1至6中任一项的方法涂覆有氧化锌的基材。
8.如权利要求7的太阳能电池，其中该氧化锌涂层的薄膜电阻为14.5欧姆/平方(Ohm/square)或更低。
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