CN102569442B - 薄膜太阳能电池及其制作方法 - Google Patents

薄膜太阳能电池及其制作方法 Download PDF

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CN102569442B
CN102569442B CN201110441126.9A CN201110441126A CN102569442B CN 102569442 B CN102569442 B CN 102569442B CN 201110441126 A CN201110441126 A CN 201110441126A CN 102569442 B CN102569442 B CN 102569442B
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彭洞清
方嘉锋
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Abstract

本发明是有关于薄膜太阳能电池及其制作方法，其中，薄膜太阳能电池是包括：一基板；一第一电极，是设置于基板上；一阻挡层，是设置于第一电极上，其中阻挡层的材料是为一导电材料；一欧姆接触层，是设置于阻挡层上；一吸收层，是设置于欧姆接触层上；一缓冲层，是设置于吸收层上；一透明导电层，是设置于缓冲层上；以及一第二电极，是设置于透明导电层上。

Description

薄膜太阳能电池及其制作方法
技术领域
本发明是关于一种薄膜太阳能电池及其制作方法，尤指一种铜铟硒系薄膜太阳能电池及其制造方法。
背景技术
随着人类文明发展，全球面临严重的能源危机及环境污染等问题。其中，以能将太阳能直接转变成电能的太阳能电池，由于发电过程中不会产生二氧化碳等温室气体，且不会对环境造成污染，故为一种可再生的环保发电方式。目前已发展出多种不同材料所制作的太阳能电池，如硅基太阳能电池、染料敏化太阳能电池及有机材料电池等。
其中，以铜铟镓硒(CIGS)、或铜铟铝硒(CIAS)为吸收层的铜铟硒(CuInSe)系太阳能电池，因具有很高的吸收系数及高转换效率，且在户外环境下稳定性相当好，故视为一种次世代的太阳能电池。
一般的铜铟硒系太阳能电池的结构是如图1所示，其包括：一基板11，以及由下往上依序叠层在基板11上的背电极12、p型吸收层13、n型缓冲层14、透明导电层15、以及一上电极16。
于制作铜铟硒系太阳能电池的工艺中，一般是以钼做为背电极12材料；而p型吸收层13可以共蒸镀、涂布或以先驱物沉积后硒化方式制作。于硒化的过程中，背电极12与p型吸收层13接面会产生钼的硒化物，如MoSe2。虽然，MoSe2可使接面呈欧姆接触，但是高温高压的硒化工艺环境下，常常导致太厚的钼层被转换成MoSe2，而太厚的MoSe2会导致串联电阻的升高，甚至于影响吸收层附着，导致吸收层脱离或脱落。此外，如使用低压的硒化工艺虽可避免太厚的钼层被转换成MoSe2，但形成的吸收层容易呈现颗粒状结构堆栈，而导致平坦度不足及形成粗糙的吸收层表面，造成缓冲层薄膜覆盖率不足，而导致漏电流太大，造成转换效率降低。另外，吸收层呈现颗粒状结构叠层亦使载子复合机率增加，亦会降低转换效率。
因此，目前亟需发展出一种薄膜太阳能电池及其制作方法，其可控制硒化钼(MoSe2)的生成及生成厚度，进而防止串联电阻的升高及吸收层脱离或脱落，且提升吸收层表面平坦度以提升转换效率。
发明内容
本发明的主要目的是在提供一种薄膜太阳能电池，以便能具有适当的薄膜太阳能电池欧姆接触层(硒化钼)厚度。
本发明的另一目的是在提供一种薄膜太阳能电池的制作方法，通过于背电极(第一电极)上依序形成一阻挡层及一含钼金属层，而可控制欧姆接触层厚度。
为达成上述目的，本发明的薄膜太阳能电池，包括：一基板；一第一电极，是设置于基板上；一阻挡层，是设置于第一电极上，其中阻挡层的材料是为一导电材料；一欧姆接触层，是设置于阻挡层上；一吸收层，是设置于欧姆接触层上；一缓冲层，是设置于吸收层上；一透明导电层，是设置于缓冲层上；以及一第二电极，是设置于透明导电层上。
此外，本发明所提供的薄膜太阳能电池的制作方法，包括下列步骤：(A)提供一基板；(B)形成一第一电极于基板上；(C)形成一阻挡层于第一电极上，其中阻挡层的材料是为一导电材料；(D)形成一含钼金属层于阻挡层上；(E)形成一吸收层前趋物于含钼金属层上，并进行一硒化工艺或一硫化工艺，以反应该吸收层前趋物形成一吸收层，且反应含钼金属层形成一欧姆接触层；(F)形成一缓冲层于吸收层上；(G)形成一透明导电层于缓冲层上；以及(H)形成一第二电极于透明导电层上。此外，于步骤(F)后，还可包括一步骤(F1)：形成一i-ZnO薄膜于该缓冲层上，由此可降低漏电流。
于本发明的薄膜太阳能电池的制作方法中，于第一电极(钼背电极)及吸收层间插入一不与硒或硫反应的阻挡层及一含钼金属层。由于阻挡层具有导电性，故可同时做为一电极材料。同时，阻挡层更可防止硒穿透至第一电极，防止第一电极因硒化工艺而过度硒化。此外，更通过形成一含钼金属层，以达到控制欧姆接触层(硒化钼)厚度的目的，使所形成的薄膜太阳能电池的欧姆接触层不致于太厚而增加串联电阻。
因此，于本发明的薄膜太阳能电池及其制作方法中，经高温高压的硒化工艺，可形成具有适当厚度的欧姆接触层，进而提高电池制作时的一致性，且可避免吸收层脱离或脱落以提升吸收层工艺良率。同时，可使吸收层有较好的结晶及平坦的CIGS表面，并使缓冲层、i-ZnO薄膜及透明导电层容易完全覆盖于吸收层，且可降低漏电流及降低载子复合机率，而达到较多的载子收集及增加转换效率。
于本发明的薄膜太阳能电池及其制作方法中，阻挡层的材料可为Al、La、Ta、Ir、Os、或其合金。较佳为，阻挡层的材料是为Al、La、或其合金。更佳为，阻挡层的材料是掺杂有B、Al、或Ga。通过硒化的高温做适当的扩散至吸收层，达到有梯度的掺杂，而可形成有梯度的吸收层能隙，由此梯度的能隙产生背电场，以减少载子复合机率或增加载子收集能力。在此，阻挡层除了可防止硒穿透至第一电极，且因阻挡层是为一导电材料，故亦可做为电极。
此外，于本发明的薄膜太阳能电池的制作方法中，含钼金属层是为一钼层。因此，所制得的薄膜太阳能电池，其欧姆接触层是为一硒化钼层。其中，欧姆接触层的厚度可为1-150nm。较佳为，欧姆接触层的厚度为1-100nm。更佳为，欧姆接触层的厚度为20-70nm。
再者，于本发明的薄膜太阳能电池中，基板与第一电极间可还包括一掺铝的钼层。当基板为一玻璃基板时，后续高温高压的硒化工艺可使铝往玻璃基板扩散，可于基板与掺铝的钼层的接口形成Al2O3，此Al2O3可提升第一电极与基板间的附着性。
于本发明的薄膜太阳能电池的制作方法中，第一电极的材料可为本技术领域常用的电极材料。较佳为，第一电极是为一钼电极。
此外，于本发明的薄膜太阳能电池的制作方法中，基板可为硬式基板或可挠式基板，如：玻璃基板、金属基板、或塑料基板。其中，金属基板可为一不锈钢基板、一钛基板、一铜基板、或一钼基板；塑料基板可为一橡胶基板、PEN基板、或PET基板。
再者，于本发明的薄膜太阳能电池的制作方法中，吸收层是为CIS吸收层、CIGS吸收层、CZTS吸收层、或CIAS吸收层。此外，透明导电层的材料是为ITO、经Al掺杂的ZnO、或经In掺杂的ZnO。
附图说明
为使审查员对本发明的目的、特征及功效能够有更进一步的了解与认识，以下请配合附图详述如后，其中：
图1是已知的铜铟硒系太阳能电池的剖面示意图。
图2A至2E是本发明实施例1的薄膜太阳能电池的制作流程剖面示意图。
具体实施方式
以下是通过特定的具体实施例说明本发明的实施方式，熟习此技术的人士可由本说明书所揭示的内容轻易地了解本发明的其它优点与功效。本发明亦可通过其它不同的具体实施例加以施行或应用，本说明书中的各项细节亦可针对不同观点与应用，在不悖离本发明创作的精神下进行各种修饰与变更。
实施例1
如图2A所示，提供一基板21，且并于基板21上以溅镀法沉积一钼层，此钼层是做为一第一电极22。于本实施例中，基板21是为一玻璃基板。
而后，如图2B所示，以溅镀或蒸镀法，于第一电极22上沉积一可导电且不易与硒或硫反应的阻挡层23。于本实施例中，阻挡层23的材料是为Al。在此，阻挡层23除了可避免第一电极22在后续的硒化或硫化工艺中形成硒或硫的化合物外，因阻挡层23具有导电性，故亦可做为一电极材料。
如图2C所示，以溅镀法沉积一含钼金属层24于阻挡层23上。于本实施例中，此含钼金属层24是为一钼层，且含钼金属层24的厚度是为100nm。
接着，如图2D所示，沉积一吸收层前趋物25于含钼金属层24上。于本实施例中，吸收层前趋物25是为一铜铟镓(CuInGa)混合材料，其可通过铜铟镓各别溅镀、共溅镀、各别电镀、或共电镀，而沉积于含钼金属层24上。
而后，请同时参阅图2D及图2E，于形成吸收层前趋物25后，是进行一硒化工艺或一硫化工艺，以反应吸收层前趋物25形成一吸收层25a，且反应含钼金属层24形成一欧姆接触层24a。于本实施例中，是进行一硒化工艺，而硒化工艺可为本技术领域常用的工艺，其工艺步骤大致如下：将有吸收层前趋物25的基板21放入硒化炉内将硒化炉抽真空使腔体压力约为102torr；将硒化炉加热到约400℃-700℃，并进行退火处理20分钟到3小时，由于硒化炉内布设有硒(Se)粉或通入H2Se气体，高压的硒蒸气，可扩散进入吸收层前趋物25中，而反应形成吸收层25a，而硒蒸气亦可扩散进入含钼金属层24中，而形成欧姆接触层24a，如图2E所示。经由上述工艺后，所形成的欧姆接触层24a是为一硒化钼层，而吸收层25a是为一CIGS吸收层。
而后，如图2E所示，以本技术领域常用的工艺，沉积CdS于吸收层25a上而形成缓冲层26。并依序沉积ZnO薄膜(i-layer)及铝掺杂的ZnO透明导电膜于缓冲层26上，以形成透明导电层27。最后，再于透明导电层27上沉积Ni/Al金属以形成第二电极28。
经由上述工艺，则制得本实施例的薄膜太阳能电池，包括：一基板21；一第一电极22，是设置于基板21上；一阻挡层23，是设置于第一电极22上，其中阻挡层23的材料是为一导电材料；一欧姆接触层24a，是设置于阻挡层23上；一吸收层25a，是设置于欧姆接触层24a上；一缓冲层26，是设置于吸收层25a上；一透明导电层27，是设置于缓冲层26上；以及一第二电极28，是设置于透明导电层27上。
实施例2
本实施例的薄膜太阳能电池及其制作方法是与实施例1相同，除了本实施例的阻挡层23材料是为掺杂有Al的La金属。由于本实施例的阻挡层23材料为掺杂有Al的La金属，故于后续硒化工艺中，阻挡层23的铝元素会扩散至吸收层25a，进而使吸收层25a有梯度的掺杂Al，而达到有梯度的吸收层能隙。
实施例3
本实施例的薄膜太阳能电池及其制作方法是与实施例1相同，除了本实施例的含钼金属层24材料是为掺杂有Al的钼金属。由于本实施例的含钼金属层24材料为掺杂有Al的钼金属，故于后续硒化工艺中，含钼金属层24的铝元素会扩散至吸收层25a，进而使吸收层25a有梯度的掺杂Al，而达到有梯度的吸收层能隙。
上述实施例仅是为了方便说明而举例而已，本发明所主张的权利范围自应以权利要求范围所述为准，而非仅限于上述实施例。

Claims (13)

1.一种薄膜太阳能电池，包括：
一基板；
一第一电极，设置于该基板上，该第一电极为一钼电极；
一阻挡层，设置于该第一电极上，其中该阻挡层的材料为一导电材料，其中该阻挡层的材料为Al、La、Ta、Ir、Os、或其合金，且该阻挡层的材料掺杂有B、Al、或Ga；
一欧姆接触层，设置于该阻挡层上，该欧姆接触层为一硒化钼层；
一吸收层，设置于该欧姆接触层上；
一缓冲层，设置于该吸收层上；
一透明导电层，设置于该缓冲层上；以及
一第二电极，设置于该透明导电层上。
2.如权利要求1所述的薄膜太阳能电池，其中该阻挡层的材料为Al、La、或其合金。
3.如权利要求1所述的薄膜太阳能电池，其中该欧姆接触层的厚度为1-150nm。
4.如权利要求1所述的薄膜太阳能电池，其中该基板为一玻璃基板、一金属基板、或一塑料基板。
5.如权利要求4所述的薄膜太阳能电池，其中该金属基板为一不锈钢基板、一钛基板、一铜基板、或一钼基板。
6.如权利要求1所述的薄膜太阳能电池，其中该吸收层为CIS吸收层、CIGS吸收层、CZTS吸收层、或CIAS吸收层。
7.如权利要求1所述的薄膜太阳能电池，其中该透明导电层的材料为ITO、经Al掺杂的ZnO、或经In掺杂的ZnO。
8.一种薄膜太阳能电池的制作方法，包括下列步骤：
(A)提供一基板；
(B)形成一第一电极于该基板上，该第一电极为一钼电极；
(C)形成一阻挡层于该第一电极上，其中该阻挡层的材料为一导电材料，其中该阻挡层的材料为Al、La、Ta、Ir、Os、或其合金，且该阻挡层的材料掺杂有B、Al、或Ga；
(D)形成一含钼金属层于该阻挡层上；
(E)形成一吸收层前趋物于该含钼金属层上，并进行一硒化工艺，以反应该吸收层前趋物形成一吸收层，且反应该含钼金属层形成一欧姆接触层，该含钼金属层为一钼层，且该欧姆接触层为一硒化钼层；
(F)形成一缓冲层于该吸收层上；
(G)形成一透明导电层于该缓冲层上；以及
(H)形成一第二电极于该透明导电层上。
9.如权利要求8所述的薄膜太阳能电池的制作方法，其中该欧姆接触层的厚度为1-150nm。
10.如权利要求8所述的薄膜太阳能电池的制作方法，其中该基板为一玻璃基板、一金属基板、或一塑料基板。
11.如权利要求10所述的薄膜太阳能电池的制作方法，其中该金属基板为一不锈钢基板、一钛基板、一铜基板、或一钼基板。
12.如权利要求8所述的薄膜太阳能电池的制作方法，其中该吸收层为CIS吸收层、CIGS吸收层、CZTS吸收层、或CIAS吸收层。
13.如权利要求8所述的薄膜太阳能电池的制作方法，其中该透明导电层的材料为ITO、经Al掺杂的ZnO、或经In掺杂的ZnO。
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