CN101807612B - 薄膜太阳能电池及其制造方法 - Google Patents

薄膜太阳能电池及其制造方法 Download PDF

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CN101807612B
CN101807612B CN2009102539538A CN200910253953A CN101807612B CN 101807612 B CN101807612 B CN 101807612B CN 2009102539538 A CN2009102539538 A CN 2009102539538A CN 200910253953 A CN200910253953 A CN 200910253953A CN 101807612 B CN101807612 B CN 101807612B
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conductive particles
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oxide
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金泰润
朴元绪
李正禹
朴成基
沈敬珍
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LG Display Co Ltd
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Abstract

本发明公开了薄膜太阳能电池及其制造方法。根据本发明一个实施例的薄膜太阳能电池包括：衬底；位于衬底上的第一电极，该第一电极包括多个导电颗粒，并具有在其表面上的凸起；位于第一电极上的吸收层；以及位于吸收层上的第二电极，其中所述多个导电颗粒的颗粒尺寸在0.01到0.7μm的范围内。

Description

薄膜太阳能电池及其制造方法
本申请要求于2009年2月16日在韩国提交的专利申请10-2009-0012342的优先权，这里将其引入作为参考。
技术领域
本发明涉及一种薄膜太阳能电池及其制造方法。
背景技术
正进行各种研究来寻找化石燃料的替代物，以解决迫在眉睫的能源危机。特别是，为了替代在今后几十年内将枯竭的石油资源，研究者正致力于如何利用诸如风能、原子能和太阳能的天然资源。
不同于其它潜在的替代物，太阳能电池对环境无污染，并利用无限量的太阳能。因此，自从硒太阳能电池在1983年被开发出以来，太阳能电池在过去的几十年内已经被大量研究。由于较高的制造和安装成本，现今利用单晶体硅(single crystal bulk silicon)的商业太阳能电池并未得到广泛使用。
为了解决成本问题，薄膜太阳能电池得到了积极的研究。特别是，利用非晶硅(a-Si:H)的薄膜太阳能电池作为能低成本制造大面积太阳能电池的技术得到了格外的关注。
一般来说，薄膜太阳能电池可以由第一电极、吸收层和第二电极堆叠在第一衬底上的多层结构制成。为了提高薄膜太阳能电池的效率，执行变形工艺(texturing process)以在第一电极的表面上形成大的凸起(unevenness)。传统的变形工艺采用使用酸/碱溶液的化学蚀刻方法。
当太阳能电池的制造工艺主要在真空状态下进行时，由于采用上述化学蚀刻方法的变形工艺使用了酸/碱溶液，因此会破坏真空工艺，并且为了返回真空状态，延长了工艺的生产节拍时间(tact time)。
此外，蚀刻溶液必须根据第一电极的材料而改变，并且很难任意地控制凸起的形状。还有，第一电极的表面可能会被破坏，这导致了电阻值的增加。再一个问题是酸/碱蚀刻溶液废弃物的处理。
发明内容
本发明致力于提供薄膜太阳能电池及其制造方法，凭借该方法可用缩短的生产时间容易地形成太阳能电池的第一电极的凸起，并能防止太阳能电池的电学性能的恶化。
根据本发明一个实施例的薄膜太阳能电池包括：衬底；位于衬底上的第一电极，该第一电极包括多个导电颗粒，并具有形成在第一电极表面上的凸起；位于第一电极上的吸收层；以及位于吸收层上的第二电极，其中所述多个导电颗粒的颗粒尺寸在0.01到0.7μm的范围内。
附图说明
所包含的用于提供对本发明的进一步解释并组成本说明书的一部分的附图图解了本发明的实施例，并与说明书一起用于解释本发明的原理。
图1图解了根据本发明一个实施例的薄膜太阳能电池；
图2A到2G图解了根据本发明一个实施例制造薄膜太阳能电池的各个工艺；
图3A到3B图解了根据本发明实施例检测薄膜太阳能电池的第一电极表面的SEM图像。
具体实施方式
现在将对其实例已在附图中图解的本发明的实施例进行详细描述。
根据本发明一个实施例的薄膜太阳能电池包括：衬底；位于衬底上的第一电极，该第一电极包括多个导电颗粒，并具有形成在第一电极表面上的凸起；位于第一电极上的吸收层；以及位于吸收层上的第二电极。
多个导电颗粒可以包括从由氧化锌(ZnO)、氧化锡(SnO)、氧化镉(Cd2O3)和氧化铟锡(ITO)组成的群组中选择的不止一种。
多个导电颗粒可以掺杂从由镓(Ga)、铝(Al)、硼(B)、氟(F)和锡(Sn)组成的群组中选择的一种。
多个导电颗粒的颗粒尺寸可以基本上在0.01到0.7μm的范围内。
根据本发明一个实施例制造薄膜太阳能电池的方法包括：在衬底上形成表面具有凸起的第一电极，该第一电极包括多个导电颗粒；在第一电极上形成吸收层；以及在吸收层上形成第二电极。
多个导电颗粒可以被涂覆有溶液。
多个导电颗粒可以通过旋涂、浸涂或者印刷法中的任意一种形成。
第一电极的形成包括：在衬底上涂覆包含多个导电颗粒的溶液；通过加热衬底去除该溶液；以及在形成有多个导电颗粒的衬底上沉积透明导电材料。
多个导电颗粒的颗粒尺寸可以基本上在0.01到0.7μm的范围内。
多个导电颗粒可以掺杂从由镓(Ga)、铝(Al)、硼(B)、氟(F)和锡(Sn)组成的群组中选择的任意一种。
下面将参考必要的附图来描述本发明的实施例。
图1图解了根据本发明一个实施例的薄膜太阳能电池。
参考图1，根据本发明一个实施例的薄膜太阳能电池100包括：衬底110；位于衬底110上的第一电极120，该第一电极120包括多个导电颗粒125并具有形成在其表面上的凸起128；位于第一电极120上的吸收层130；和位于吸收层130上的第二电极140。
衬底110可以使用玻璃或透明树脂膜。玻璃可以是玻璃面板，其成分为具有良好的透明度和非导电性的二氧化硅(SiO2)、氧化钠(Na2O)和氧化钙(CaO)。
第一电极120可以由透明导电氧化物或金属组成。透明导电氧化物可以由从由氧化锌(ZnO)、氧化锡(SnO)、氧化镉(Cd2O3)和氧化铟锡(ITO)组成的群组中选择的任意一种制成，优选地由氧化钢锡(ITO)制成。至于金属，可以使用银(Ag)或铝(Al)。
第一电极120可以是由透明导电氧化物或金属形成的单层，但不限于此，也可以是由透明导电氧化物/金属形成的两层或多于两层的多层。
同时，第一电极120可以包括多个导电颗粒125。多个颗粒125便于凸起128在第一电极120的表面上形成，以扩大第一电极120的表面积。
多个导电颗粒125可以由从由氧化锌(ZnO)、氧化锡(SnO)、氧化镉(Cd2O3)和氧化铟锡(ITO)组成的群组中选择的任意一种形成。
同样地，多个导电颗粒125可以掺杂从由镓(Ga)、铝(Al)、硼(B)、氟(F)和锡(Sn)组成的群组中选择的任意一种。
多个导电颗粒125的颗粒尺寸可以基本上在0.01到0.7μm的范围内。如果导电颗粒125的尺寸大于0.01μm，那么可以在第一电极120上形成凸起，从而扩大了第一电极120的表面积。另一方面，如果导电颗粒125的尺寸小于0.7μm，那么也可以具有防止第一电极120的厚度变厚的有益效果。
因多个导电颗粒125的缘故，多个凸起128可在第一电极120的表面上形成。凸起128扩大了第一电极120的表面积，因此引起了入射到第一电极120上的光的色散，从而具有延长光路的有益效果。
同时，吸收层130可以由非晶硅、CdTe或CIGS(CuInGaSe2)形成，并且可以具有销型(pin)结构。为了举例说明，假设吸收层130为非晶硅，则销型结构可以由p+型非晶硅层/i(本征)-型非晶硅层/n+型非晶硅层形成。
在上述的假设中，销型结构的硅薄膜层吸收入射的太阳光，并产生电子-空穴对。在销型结构中，由通过p-n结所建立的内建电势先前产生的电子和空穴分别向n型半导体和p型半导体移动，用于后续使用。
尽管在本实施例中吸收层130为单层，但吸收层130可以为由p+型非晶硅层/i(本征)-型非晶硅层/n+型非晶硅层组成的结构。
与第一电极120相同，第二电极140也可以由透明导电氧化物或金属组成。透明导电氧化物可以由氧化铟锡(ITO)、氧化锡(SnO)或氧化锌(ZnO)制成，优选由氧化铟锡(ITO)制成。至于金属，可以使用银(Ag)或铝(Al)。
第二电极140可以是由透明导电氧化物或金属形成的单层，但不限于此，也可以是由透明导电氧化物/金属形成的两层或多于两层的多层。
下面将描述根据本发明一个实施例的薄膜太阳能电池的制造方法。
图2A到2G图解了根据本发明一个实施例制造薄膜太阳能电池的各个工艺。
根据本发明一个实施例制造薄膜太阳能电池的方法包括：在衬底上形成表面具有凸起的第一电极，该第一电极包括多个导电颗粒；在第一电极上形成吸收层；以及在吸收层上形成第二电极。
首先，在下文中将参考图2A描述在衬底210上形成包含多个导电颗粒225的第一电极230。
(A)用包含多个导电颗粒225的溶液220涂覆衬底210。
此时，衬底210可以使用玻璃或透明树脂膜。玻璃可以是平整的玻璃面板，其成分为具有良好的透明度和非导电性的二氧化硅(SiO2)、氧化钠(Na2O)和氧化钙(CaO)。
溶液220可以是诸如甲醇、乙醇或酒精的任何物质，只要其能够使多个导电颗粒225散开。
使用溶液220的涂覆方法可以是旋涂、浸涂或者印刷法中的任意一种。
同时，多个导电颗粒225可以由从由氧化锌(ZnO)、氧化锡(SnO)、氧化镉(Cd2O3)和氧化铟锡(ITO)组成的群组中选择的任意一种形成。
同样地，多个导电颗粒225可以掺杂从由镓(Ga)、铝(Al)、硼(B)、氟(F)和锡(Sn)组成的群组中选择的任意一种。在这种情况下，掺杂密度可在3％到7％的范围内。
多个导电颗粒225的颗粒尺寸可以基本上在0.01到0.7μm的范围内。如果导电颗粒225的尺寸大于0.01μm，那么随后可以在第一电极230上形成凸起，从而扩大第一电极230的表面积。另一方面，如果导电颗粒225的尺寸小于0.7μm，那么也可以具有防止第一电极230的厚度变厚的有益效果。
然后，(B)通过加热涂覆有包含多个导电颗粒225的溶液220的衬底210来去除溶液220。
可通过在150℃下在干燥箱中加热1到10分钟来去除溶液220。
随后，(C)通过在已经将溶液去除的衬底210上沉积透明导电材料来形成包含多个导电颗粒225的第一电极230。
在通过先前的加热工艺已经将溶液去除的衬底210上，仅留有多个导电颗粒225。因此，如果在形成有多个导电颗粒225的衬底210上沉积透明导电材料，那么因多个导电颗粒225的缘故，能形成表面具有凸起228的第一电极230。
第一电极230可以由透明导电氧化物或金属组成。透明导电氧化物可以由从由氧化锌(ZnO)、氧化锡(SnO)、氧化镉(Cd2O3)和氧化铟锡(ITO)组成的群组中选择的任意一种制成，优选由氧化铟锡(ITO)制成。至于金属，可以使用银(Ag)或铝(Al)。
第一电极230可以是由透明导电氧化物或金属形成的单层，但不限于此，也可以是由透明导电氧化物/金属形成的两层或多于两层的多层。
同样地，第一电极230可以通过化学气相沉积(CVD)、物理气相沉积(PVD)或电子束(E-beam)法来形成。
因此，如图2B所示，可以形成第一电极230，第一电极230具有形成在其表面上的凸起228和形成在衬底210上的多个导电颗粒225。
如上所述，通过利用多个导电颗粒225在第一电极的表面上形成凸起，可以取代利用酸/碱蚀刻溶液在第一电极上形成凸起的传统工艺。
因此，通过调整导电颗粒的尺寸，可以很容易地调整第一电极的凸起的尺寸，并能防止由于对第一电极的损坏而引起的电学性能的恶化。同样地，由于保持了真空工艺，因此能缩短工艺的生产节拍时间。
然后，参考图2C，对第一电极230进行构图。
此时，可以使用光刻胶法、喷砂法或激光划片(laser scribing)法对第一电极230构图。在这种情况下，可利用第一构图线235分隔第一电极230。
随后，参照图2D，在已经完成构图工艺的第一电极230上形成吸收层240。
吸收层240可以由非晶硅、CdTe或CIGS(CuInGaSe2)形成，并且可以具有销型(pin)结构。为了举例说明，假设吸收层240为非晶硅，则销型结构可以由p+型非晶硅层/i(本征)-型非晶硅层/n+型非晶硅层形成。
在上述的假设中，销型结构的硅薄膜层吸收入射的太阳光，并产生电子-空穴对。在销型结构中，由通过p-n结所建立的内建电势先前产生的电子和空穴分别向n型和p型半导体移动，用于后续使用。
尽管在本实施例中吸收层240为单层，但吸收层240还可以为由p+型非晶硅层/i(本征)-型非晶硅层/n+型非晶硅层组成的结构。
此时，可以通过等离子体增强化学气相沉积(PECVD)法沉积吸收层240。
然后，参考图2E，对吸收层240进行构图。
此时，对吸收层240进行构图。在这种情况下，吸收层240的构图方法可以使用光刻胶法、喷砂法或激光划片法。
因此，吸收层240可由第二构图线245进行分隔。
然后，参照图2F，在已经完成吸收层240的构图工艺的衬底210上形成第二电极250。
与第一电极230相同，第二电极250可以由透明导电氧化物或金属组成。透明导电氧化物可以由氧化铟锡(ITO)、氧化锡(SnO)或氧化锌(ZnO)制成，优选由氧化铟锡(ITO)制成。至于金属，可以使用银(Ag)或铝(Al)。
第二电极250可以是由透明导电氧化物或金属形成的单层，但不限于此，也可以是由透明导电氧化物/金属形成的两层或多于两层的多层。
此时，与第一电极230相同，第二电极250可以通过化学气相沉积(CVD)、物理气相沉积(PVD)或电子束(E-beam)法形成。
最后，参考图2G，为了电绝缘，对形成在衬底210上的吸收层240和第二电极250进行构图。
此时，通过对吸收层240和第二电极250进行构图，可以由第三构图线255实现电绝缘。
于是，如上所述，可制造出根据本发明一个实施例的薄膜太阳能电池。
如上所述，通过利用多个导电颗粒在第一电极的表面上形成凸起，可以取代利用酸/碱蚀刻溶液在第一电极上形成凸起的传统工艺。
因此，通过调整导电颗粒的尺寸，可以很容易地调整第一电极的凸起的尺寸，并能防止由于对第一电极的损坏而引起的电学性能的恶化。同样地，由于保持了真空工艺，因此能缩短工艺的生产节拍时间。
在下文中，将描述本发明的优选实施例。下面的实施例仅用于说明目的，因此，本发明并不限于下面的实施例。
<实施例1>
用溶解有尺寸为0.7μm的镓掺杂的氧化锌(ZnO)颗粒的溶液涂覆玻璃衬底。在干燥箱中以150℃对该玻璃衬底进行五分钟加热处理，利用该加热处理来去除该溶液。随后，利用溅射法在厚度为0.4μm的玻璃衬底上沉积氧化锌(ZnO)来形成第一电极。
<实施例2>
溶解有尺寸为0.4μm的镓掺杂的氧化锌(ZnO)颗粒的溶液涂覆玻璃衬底。在干燥箱中以150℃对该玻璃衬底进行五分钟加热处理，利用该加热处理来去除该溶液。随后，利用溅射法在厚度为0.4μm的玻璃衬底上沉积氧化锌(ZnO)来形成第一电极。
表1示出了根据本发明第一实施例和第二实施例制造的第一电极的被测方块电阻和透射率。利用SEM测量第一电极的表面。图3A和3B表示测量结果。
【表1】
  方块电阻(Ω/sq)   透射率(％)
  实施例1   35   93
  实施例2   30   91
根据表1以及图3A和3B，可以得出根据第一实施例和第二实施例制造的第一电极的方块电阻和透射率都满足大规模生产的标准。
如上所述，通过利用多个导电颗粒在第一电极的表面上形成凸起，可以取代利用酸/碱蚀刻溶液在第一电极上形成凸起的传统工艺。
因此，通过调整导电颗粒的尺寸，可以很容易地调整第一电极的凸起的尺寸，并能防止由于对第一电极的损坏而引起的电学性能的恶化。同样地，由于保持了真空工艺，因此能缩短工艺的生产节拍时间。
前述实施例和优点仅为示范性的，不应理解为对本发明的限制。本教导可以很容易地应用到其它类型的装置。前述实施方式的描述意在起到说明作用，并不能限制权利要求的保护范围。对本领域技术人员来说，多种改变、修改和变型是显而易见的。

Claims (6)

1.一种薄膜太阳能电池，包括：
衬底；
位于所述衬底上的第一电极，所述第一电极包括多个导电颗粒，并具有在第一电极表面上的凸起；
位于所述第一电极上的吸收层；以及
位于所述吸收层上的第二电极，
其中所述多个导电颗粒的颗粒尺寸在0.01到0.7μm的范围内。
2.根据权利要求1所述的薄膜太阳能电池，其中所述多个导电颗粒包括从由氧化锌(ZnO)、氧化锡(SnO)、氧化镉(Cd2O3)和氧化铟锡(ITO)组成的群组中选择的不止一种。
3.根据权利要求2所述的薄膜太阳能电池，其中所述多个导电颗粒掺杂有从由镓(Ga)、铝(Al)、硼(B)、氟(F)和锡(Sn)组成的群组中选择的一种。
4.一种制造薄膜太阳能电池的方法，包括：
在衬底上涂覆包含多个导电颗粒的溶液；
通过加热所述衬底去除所述溶液；
在形成有所述多个导电颗粒的衬底上沉积透明导电材料，以形成第一电极；
在所述第一电极上形成吸收层；以及
在所述吸收层上形成第二电极，
其中所述多个导电颗粒的颗粒尺寸在0.01到0.7μm的范围内。
5.根据权利要求4所述的方法，其中所述涂覆包括旋涂、浸涂或者印刷法中的任意一种。
6.根据权利要求4所述的方法，其中所述多个导电颗粒掺杂有从由镓(Ga)、铝(Al)、硼(B)、氟(F)和锡(Sn)组成的群组中选择的任意一种。
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