CN101764169B - 太阳能电池元件及其制作方法 - Google Patents
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- 238000000224 chemical solution deposition Methods 0.000 description 2
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- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 description 2
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Abstract
一种太阳能电池元件及其制作方法，该元件包含一基板、一金属层、一p型半导体层、一n型半导体层及一透明导电层。该基板具有一粗糙面；金属层可包含钼金属，且形成于基板的该粗糙面上。p型半导体层形成于该金属层上，可包含铜铟镓硒硫、铜铟镓硒、铜铟硫、铜铟硒或包含铜、硒或硫二者或二者以上的化合物材料。n型半导体层形成于该p型半导体层上，且与该p型半导体层形成粗糙的p-n结。n型半导体层可为硫化镉。透明导电层形成于该n型半导体层上。一实施例中，该粗糙面的粗糙度介于0.01μm至100μm之间。本发明可有效增加太阳能电池元件中p型半导体及n型半导体的p-n结的表面积，以增加光电流密度，提升发电效率。
Description
技术领域
本发明涉及一种太阳能电池元件及其制作方法，尤涉及一种含铜铟镓硒(简称CIGS)或含铜铟硒(简称CIS)的薄膜太阳能电池元件及其制作方法。
背景技术
薄膜太阳能电池中，铜铟镓硒太阳能电池(Copper Indium Gallium Diselenide Solar Cells)类型的光电电池计有两种：一种含铜铟硒三元素(简称CIS)以及一种含铜铟镓硒四元素(简称CIGS)。由于其高光电效率及低材料成本，被许多人看好。在实验室完成的CIGS光电池，光电效率最高可达约19％，就模块而言，最高也可达约13％。
图1公开一传统的CIGS太阳能电池结构10，其为层叠结构且包含一基板11、一金属层12、一CIGS层13、一缓冲层14以及一透明电极层(TCO)15。基板11一般为玻璃基板，金属层12可以钼(Mo)金属层组成，以配合CIGS的化学性质及可承受沉积CIGS层13时的相对高温。CIGS层13属p型半导体层。缓冲层14可为硫化镉(CdS)，其为n型半导体层，且与CIGS层13形成p-n结。透明导电层15可为掺铝氧化锌(AZO)或其他透明导电材料。导电层15也有称为窗层(window layer)，其可让上方的光线通过而至其下的CIGS层13。
美国专利US 6,258,620公开一CIGS太阳能电池结构，其类似图1所示的太阳能电池结构。其中透明电极层15采用AZO，且于透明电极15与缓冲层14间设有一本征(intrinsic)ZnO层。因CIGS在长晶的过程中，经常会有空隙产生，电池较容易发生作为阴极(负极)的透明导电层15和作为阳极(正极)的金属层12间产生短路的情形。本征ZnO层具有高阻值特性，从而可改善短路的情况。如此一来可能降低太阳能电池元件的发电效率，因此有待技术上的进一步突破。
发明内容
本发明提供一种太阳能电池元件及其制作方法，其使用粗糙基板，以有效增加太阳能电池元件中p型半导体及n型半导体的p-n结的面积，以增加光电流密度。
根据本发明一实施例的太阳能电池元件，其包含一基板、一金属层、一p型半导体层、一n型半导体层及一透明导电层。该基板具有一粗糙面；金属层可包含钼金属，且形成于基板的该粗糙面上。p型半导体层形成于该金属层上，可包含铜、硒和硫中二者或二者以上的化合物材料。n型半导体层形成于该p型半导体层上，且与该p型半导体层形成粗糙的p-n结，该p-n结的粗糙度介于0.01μm至100μm间。一实施例中，n型半导体层可为硫化镉(CdS)。透明导电层形成于该n型半导体层上。一实施例中，该粗糙面的粗糙度介于0.01μm至100μm之间。
制作上述的太阳能电池元件包含以下步骤：提供一基板；粗糙化该基板，于该基板形成一粗糙面；形成一金属层于该粗糙面上；形成一p型半导体层于该金属层上，该p型半导体层包含铜铟镓硒或铜铟镓硒的合金材料；形成一n型半导体层于该p型半导体层上，其中该n型半导体层与该p型半导体层形成粗糙的p-n结，该p-n结的粗糙度介于0.01μm至100μm间；以及形成一透明导电层于该n型半导体层上。
一实施例中，基板为玻璃基板，其可利用喷砂、蚀刻进行粗糙化。其由尤以先行喷砂后蚀刻为优选。另一实施例中，可搭配镀金属膜及蚀刻进行粗糙化。若基板为金属材质，可利用机械压花进行粗糙化。
本发明使用粗糙基板，可有效增加太阳能电池元件中p型半导体及n型半导体的p-n结的表面积，以增加光电流密度，进而提升发电效率。
附图说明
图1为一公知的太阳能电池元件示意图；
图2为本发明一实施例的太阳能电池元件示意图；
图3为本发明一实施例的太阳能电池元件的制作方法示意图；以及
图4和图5为本发明的太阳能电池元件的基板粗糙化的制作实施例。
上述附图中的附图标记说明如下：
10 太阳能电池元件 11 基板
12 金属层 13 CIGS层
14 缓冲层 15 透明导电层
20 太阳能电池元件 21 基板
22 金属层 23 p型半导体层
24 n型半导体层 25 载子阻挡层
26 透明导电层 27 粗糙面
28 p-n结 S31～S36 步骤
具体实施方式
以下详细讨论该目前优选实施例的制作和使用。不过，应当理解，本发明提供许多可应用的发明概念，其可在各种各样的具体情况下实施。该讨论的具体实施例仅说明了制作和使用该发明的具体方式，并没有限制本发明的范围。
图2为本发明一实施例的太阳能电池元件。太阳能元件20为层叠结构，其包含一基板21、一金属层22、一p型半导体层23、一n型半导体层24、一载子阻挡层25及一透明导电层26。基板21可为玻璃基板、塑胶软板、不锈钢、钼、铜、钛、铝等金属板或金属箔片，其具有一粗糙面27。上述基板21并非限定为板状，而仅当作成膜基材之用，其他例如球状或其他各种特定或不规则形状，也可为本发明所使用。一实施例中，基板21的表面粗糙度Ra范围介于0.01μm至100μm之间。金属层22可包含例如厚度约0.5μm至1μm的钼金属层，且形成于该基板21的粗糙面27，作为电池的背接触金属层(Back contact metal layer)。p型半导体层23形成于该金属层22的表面，例如包含铜铟镓硒硫(CIGSS)、铜铟镓硒(CIGS)、铜铟硫(CIS)、铜铟硒(CIS)或包含铜、硒或硫二者或二者以上的化合物材料，其厚度约2μm至3μm。n型半导体层24形成于该p型半导体层23的表面，且与p型半导体层23形成粗糙的p-n结28。一实施例中，n型半导体层24可为硫化镉(CdS)、硫化锌(ZnS)、硫化铟(InS)，其必须远薄于p型半导体层23(例如厚度约50nm)，且必须足够透明以利太阳光线通过。载子阻挡层25形成于该n型半导体层 24的表面，其可为本征ZnO层，以防止金属层22及透明导电层26间短路。透明导电层26形成于载子阻挡层25的表面，其可选自铟锡氧化物(ITO)、铟锌氧化物(IZO)、铝锌氧化物(AZO)、镓锌氧化物(GZO)、铝镓锌氧化物(GAZO)、镉锡氧化物、氧化锌及二氧化锆。
参照图3，其显示本发明的太阳能元件的制造方法流程示意图。于步骤S31中，将基板21进行粗糙化处理。一实施例中，基板21的表面粗糙度Ra范围系介于0.01μm至100μm之间。若粗糙度不够，p-n结28增加的面积及增加的光线吸收量有限；若过于粗糙，会造成后续金属膜22不易成膜其上。
于步骤S32中，溅镀形成金属层22。一实施例中，选择钼(Mo)金属层组成，以配合CIS或CIGS的化学性质及其可承受沉积p型半导体层23(例如CIGS层)时的相对高温。
于步骤S33中，形成p型半导体层23，本实施例进行CIGS镀膜工艺于金属层22上。CIGS镀膜可利用元素源共同蒸镀(Co-evaporation from elemental sources)、金属前驱物硒化(Selenization of metallic precursor layer)、化合物源蒸镀(Evaporation from compound source)、化学气相沉积(chemical vapor deposition)、封闭空间气相传输(close-spaced vapor transport)、喷雾热解(spray pyrolysis)、电镀(electrodeposition)、前驱物低温液相沉积(low temperature liquid phase method for precursor deposition)、粒状前驱物黄铜晶化(chalcogenization of particulate precursor layer)等方法制作。
于步骤S34中，形成n型半导体层24，即缓冲层。一实施例中，使用化学浴沉积法(chemical bath deposition)，形成一厚度约50nm的硫化镉(CdS)层。硫化镉层可提供对CIGS层的保护，以避免后续溅镀(ZnO层)工艺时造成结构的损坏。
因基板21经粗糙化后，后续披覆其上的p型半导体层23及n型半导体层24间将依粗糙面形状成膜，而形成粗糙结，也即，可增加p型半导体层23及n型半导体层24间p-n结28的表面积。
于步骤S35中，形成载子阻挡层25，一实施例中，载子阻挡层25可为本征ZnO层(I-ZnO)，其可利用RF溅镀方法形成。
于步骤S36中，形成透明导电层36于该载子阻挡层35上。一实施例中， 同样利用RF溅镀法，形成一厚度约0.35μm至0.5μm的掺杂氧化锌作为透明导电层，其中使用铝做施主。此层可记载为ZnO:Al。
由于本发明的太阳能电池元件采上面照光，因此基板21本身可为透光或不透光。若基板21采用透光的玻璃基板，其可利用蚀刻、喷砂或喷砂后蚀刻等方式进行粗糙化。使用蚀刻粗糙化的一实施例中使用BaSO4+(NH4)HF2+H2O进行蚀刻。喷砂后蚀刻方式的蚀刻液可包含氢氟酸(HF)，以去除喷砂完成后的玻璃碎片残留，其流程如图4所示。若因喷砂导致粗糙面27过于粗糙，可先对基板21作初步研磨后再进行蚀刻。一般而言蚀刻后的粗糙面较平坦，而喷砂后的粗糙面较粗糙，喷砂后加蚀刻可获得两者的优点。
另外，也可于基板21上先行形成第一金属膜，之后以干蚀刻或湿蚀刻方式蚀刻第一金属膜而形成粗糙面，并接着形成第二金属膜而形成粗糙化基板21，其流程如图5所示。其中蚀刻粗糙化该第一金属膜的程序次数可为一次以上，也就是可重复多次以增加基板的粗糙度。
此外，若基板21本身即为金属基板，则可利用机械压花方式粗糙化基板21。
下表显示太阳能电池结构中包含经粗糙化的基板及未经粗糙化的基板的电性实验结果。其中Jsc是短路电流密度；Voc是开路电压；Jmax是最大功率时的电流密度；Vmax是最大功率时的电压；Fill factor是填充因子；Efficiency代表发电效率。
由表中可知，具有粗糙化基板的太阳能光电元件具有较高的发电效率。换言之，本发明使用粗糙基板，可有效增加太阳能电池元件中p型半导体及n型半导体的p-n结的表面积，以增加光电流密度，进而提升发电效率。
本发明的技术内容及技术特点已揭示如上，然而熟悉本领域普通技术人员仍可能基于本发明的教示及揭示而作种种不背离本发明精神的替换及修 饰。因此，本发明的保护范围应不限于实施例所揭示的范围，而应包括各种不背离本发明的替换及修饰，并为所附的权利要求所涵盖。
Claims (24)
1.一种太阳能电池元件，包含：
一基板，具有一粗糙面；
一金属层，形成于该基板的该粗糙面上；
一p型半导体层，形成于金属层的表面，包含铜、硒和硫中二者或二者以上的化合物材料；
一n型半导体层，形成于该p型半导体层上，且与该p型半导体层形成粗糙的p-n结，该p-n结的粗糙度介于0.01μm至100μm间；以及
一透明导电层，形成于该n型半导体层上。
2.根据权利要求1的太阳能电池元件，其中该化合物材料为铜铟镓硒硫、铜铟镓硒、铜铟硫或铜铟硒。
3.根据权利要求1的太阳能电池元件，其中该粗糙面的粗糙度介于0.01μm至100μm间。
4.根据权利要求1的太阳能电池元件，其中该基板为玻璃基板、塑胶软板、金属板或金属箔片。
5.根据权利要求4的太阳能电池元件，其中该粗糙面是由喷砂或蚀刻形成。
6.根据权利要求4的太阳能电池元件，其中该粗糙面是由喷砂后进行蚀刻形成。
7.根据权利要求4的太阳能电池元件，其中该金属板或金属箔片的材质为不锈钢、钼、铜、钛或铝。
8.根据权利要求7的太阳能电池元件，其中该粗糙面是由蚀刻或机械压花形成。
9.根据权利要求1的太阳能电池元件，其中该金属层包含钼。
10.根据权利要求1的太阳能电池元件，其中该n型半导体层包含硫化镉、硫化锌或硫化铟。
11.根据权利要求1的太阳能电池元件，其中该n型半导体层与透明导电层间另包含一载子阻挡层。
12.根据权利要求1的太阳能电池元件，其中该透明导电层选自铟锡氧化物、铟锌氧化物、铝锌氧化物、镓锌氧化物、铝镓锌氧化物、镉锡氧化物、氧化锌及二氧化锆。
13.一种太阳能电池元件的制造方法，包含：
提供一基板；
粗糙化该基板，于该基板形成一粗糙面；
形成一金属层于该粗糙面上；
形成一p型半导体层于该金属层上，该p型半导体层包含铜、硒和硫中二者或二者以上的化合物材料；
形成一n型半导体层于该p型半导体层上，其中该n型半导体层与该p型半导体层形成粗糙的p-n结，该p-n结的粗糙度介于0.01μm至100μm间；以及
形成一透明导电层于该n型半导体层上。
14.根据权利要求1的太阳能电池元件，其中该化合物材料为铜铟镓硒硫、铜铟镓硒、铜铟硫或铜铟硒。
15.根据权利要求13的太阳能电池元件的制造方法，其中该粗糙面的粗糙度介于0.01μm至100μm间。
16.根据权利要求13的太阳能电池元件的制造方法，其中该基板是玻璃基板，粗糙化该基板的步骤包含蚀刻或喷砂。
17.根据权利要求16的太阳能电池元件的制造方法，其中粗糙化该基板的步骤包含喷砂后蚀刻。
18.根据权利要求16的太阳能电池元件的制造方法，其中蚀刻是利用氢氟酸。
19.根据权利要求13的太阳能电池元件的制造方法，其中该基板是金属基板，粗糙化该基板的步骤包含蚀刻或机械压花。
20.根据权利要求13的太阳能电池元件的制造方法，其中粗糙化该基板包含：
形成一第一金属膜于该基板；
蚀刻粗糙化该第一金属膜；以及
形成一第二金属膜于该第一金属膜上。
21.根据权利要求20的太阳能电池元件的制造方法，其中蚀刻粗糙化该第一金属膜的程序次数为一次以上。
22.根据权利要求13的太阳能电池元件的制造方法，其中形成该金属层是利用溅镀。
23.根据权利要求13的太阳能电池元件的制造方法，其中形成该p型半导体层是利用元素源共同蒸镀、金属前驱物硒化、化合物源蒸镀、化学气相沉积、封闭空间气相传输、喷雾热解、电镀、前驱物低温液相沉积或粒状前驱物黄铜晶化。
24.根据权利要求13的太阳能电池元件的制造方法，其中形成透明导电层于该n型半导体层上之前另包含形成一载子阻挡层的步骤，使得该载子阻挡层形成于该n型半导体层及透明导电层之间。
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