CN100517766C - 黄铜矿型太阳能电池 - Google Patents

黄铜矿型太阳能电池 Download PDF

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CN100517766C
CN100517766C CNB2006800324644A CN200680032464A CN100517766C CN 100517766 C CN100517766 C CN 100517766C CN B2006800324644 A CNB2006800324644 A CN B2006800324644A CN 200680032464 A CN200680032464 A CN 200680032464A CN 100517766 C CN100517766 C CN 100517766C
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米泽谕
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Abstract

本发明提供一种具有较高的转换效率的同时具有优良的挠性的太阳能电池。作为基板(1)采用云母基板或集成云母基板。云母和集成云母具有较高的绝缘性和耐热温度，因此可在气相硒化处理中以最佳的处理温度进行硒化，并能得到较高的转换效率。而且，由于具有优良的可挠性能，因此也可以适应于大批量生产。另一方面，由于云母和集成云母的表面具有较大的表面粗糙度，如果直接形成黄铜矿系光吸收层(6)，则易于诱发漏泄因而无法得到较高的转换效率。因此，在本发明中，使厚度为2μm以上、20μm以下的含有陶瓷系材料的中间层和厚度为3000以上、8000以下的粘合剂层(4)介于云母基板(1)与钼电极(5)之间。设置该中间层(2)和粘合剂层(4)。

Description

黄铜矿型太阳能电池
技术领域
本发明涉及具有黄铜矿(chalcopyrite)化合物的光吸收层的太阳能电池(solar cell)，尤其涉及在基板原材料中使用了具有挠性的云母或含有云母的材料的太阳能电池。
背景技术
接受光并转换为电能的太阳能电池根据半导体层的厚度分为块状型和薄膜型。其中，薄膜型太阳能电池是半导体层具有数十微米～数微米以下的厚度的太阳能电池，分为Si薄膜系和化合物薄膜系。而且，在化合物薄膜系中有II-V族化合物、黄铜矿型等的类型，迄今为止已有几种被产品化。其中，黄铜矿型太阳能电池根据所使用的物质，又被称为CIGS(Cu(InGa)Se)系薄膜太阳能电池、CIGS太阳能电池或I-III-VI族系。
黄铜矿型太阳能电池是将黄铜矿化合物形成为光吸收层的太阳能电池，具有效率高、不会光恶化(老化)、耐放射线特性优良、光吸收波长区域宽、光吸收系数高等特征，目前正进行着面向大批量生产的研究。
在图1中示出一般的黄铜矿型太阳能电池的剖视结构。如图1所示，黄铜矿型太阳能电池由在玻璃基板上形成的下部电极薄膜、含有铜、铟、镓、硒的光吸收层薄膜、在光吸收层薄膜的上侧形成的缓冲层薄膜和上部电极薄膜构成。当太阳光等的光照射该黄铜矿型太阳能电池时，产生电子(-)和空穴(+)对，在p型半导体和n型半导体的结面上，电子(-)向n型半导体汇集、空穴(+)聚集到p型半导体，其结果是，在n型半导体和p型半导体之间产生电动势。通过在该状态下将导线连接于电极，可以将电流输出到外部。
在图2和图3中示出制造黄铜矿型太阳能电池的工序。首先，通过溅射在钠钙玻璃等的玻璃基板上形成用作下部电极的Mo(钼)电极薄膜。然后，如图3的(a)所示，通过激光照射等分割Mo电极(第1次划线)。在第1次划线后，用水等清洗削下的碎屑，并通过溅射等附着铜(Cu)、铟(In)和镓(Ga)，形成前体。通过将该前体投入炉中并在H2Se气体的气氛中进行退火，形成黄铜矿型光吸收层薄膜。该退火工序通常被称为气相硒化或简称为硒化。
接着，在光吸收层上层叠CdS、ZnO或InS等n型缓冲层。作为一般的工艺，缓冲层用溅射或CBD(Chemical Bath Deposition：化学浴沉积)等方法形成。然后，如图3的(b)所示，利用激光照射或金属针等分割缓冲层和前体(第2次划线)。
之后，如图3的(c)所示，通过溅射等形成用作上部电极的ZnOAl等透明电极(TCO)。最后，如图3的(d)所示，通过利用激光照射或金属针等分割TCO、缓冲层和前体(第3次划线)，从而完成CIGS系薄膜太阳能电池。
此处得到的太阳能电池被称为电池单元，在实际使用时，封装多个电池单元，加工为模块(面板)。电池单元通过各划线工序被分割为形成多个串联级的太阳能电池，通过变更该串联级数，可以任意设计变更电池单元的电压。
这种现有的黄铜矿型太阳能电池作为其基板材料使用了玻璃基板。其原因是基于玻璃基板具有绝缘性、容易得到、价格比较低廉、与Mo电极层(下部电极薄膜)的粘着性高以及表面平滑。进一步，还可以举出通过使玻璃中所含有的钠成分扩散到光吸收层(p层)中可以提高能量转换效率。其负面是存在着以下缺点：玻璃熔点低、因在硒化工序中不能将退火温度设定得较高而会将能量转换效率抑制得较低、因基板厚且质量大而使制造设备规模较大、制造后的处理也不方便、因几乎不能变形而无法应用连续卷带(roll to roll)工艺等的大批量生产工序。
为解决这些课题，提出了使用高分子薄膜基板的黄铜矿型太阳能电池(例如，参照专利文献1)。另外，还提出了一种使用在不锈钢基板的上侧和下侧表面上形成了氧化硅或氟化铁层的基体并在其上形成黄铜矿型太阳能电池结构体的技术(例如，参照专利文献2)。进一步，还公开了作为黄铜矿系基板材料列举了玻璃、氧化铝、云母、聚酰亚胺、钼、钨、镍、石墨、不锈钢的技术(例如，参照专利文献3)。
专利文献1：日本特开平5-259494号公报
专利文献2：日本特开2001-339081号公报
专利文献3：日本特开2000-58893号公报
发明内容
在作为黄铜矿型太阳能电池的基板材料采用玻璃以外的原材料的现有技术中，对于专利文献1所述的采用高分子薄膜的技术，在特性上，例如在聚酰亚胺的情况下，不能在260℃以上的高温进行处理，因此，不能采用像气相硒化那样的超过500℃的高温工艺，结果无法制造转换效率高的电池。
另外，在专利文献2所述的在不锈钢基板的上下形成氧化硅或氟化铁层(保护层)的技术中，在气相硒化工序中因H2Se气的浸蚀性而无法充分地保护不锈钢基板，存在着使Mo电极层(内表面电极薄膜)从已腐蚀的不锈钢基板剥离等问题。而且，保护层被剥离后，将使导电性的不锈钢基板露出，因此不能引入使用金属针的划线工序。
进一步，在专利文献3所述的技术中，虽然提出了各种各样的基板材料，但在其实施方式中作为完成的实施例所述的技术全部采用了玻璃基板，因此对所提出的各种基板材料没有详细地公开到使从业者能够实施的程度。例如，在各实施例中，使基板在385℃到495℃之间退火，这对钠钙玻璃是适合的，但是否可以用所列举的其他基板材料以同样的工序制作就不清楚了。
这样，在现有的技术中，实际情况是没有采用满足绝缘性高、容易得到、价格比较低廉、与Mo电极层(下部电极薄膜)的粘着性良好、表面平滑、熔点为600℃以上、薄且重量轻、富有挠性的必要条件的基板材料。
因此，本发明人在先提出过如下方案：作为具有优良的挠性、适合于连续卷带工艺的大批量生产工序、并且具有较高的转换效率的太阳能电池，对基板选定云母或含有云母的材料以确保挠性，进一步，为解决将云母或含有云母的材料作为基板时的问题、即为实现表面平滑性而在基板的表面设置由陶瓷材料构成的中间层，并在该中间层上隔着粘合剂形成黄铜矿型的光吸收层。
另外，作为将含有云母的材料用作基板时的问题，本发明人研究得知从基板向光吸收层扩散钾(K)会使转换效率降低。
为解决上述课题，本发明的黄铜矿型太阳能电池包括：由云母或含有云母的材料构成的基板；在上述基板上形成的厚度为2μm以上、20μm以下的含有陶瓷系(ceramic-type)材料的中间层；在上述中间层上层叠的厚度为
Figure C20068003246400061
以上、
Figure C20068003246400062
以下的氮化钛(TiN)或氮化钽(TaN)等氮化物系(nitride-type)的粘合剂层；在上述粘合剂层上形成的下部电极层；在上述下部层上形成的由黄铜矿化合物构成的p型的光吸收层；在上述光吸收层上形成的n型的缓冲层；在上述缓冲层上形成的透明电极层。
在本发明中，作为基板使用云母或将云母作为主要成分的材料的基板。云母具有1012～1616Ω的高绝缘性，同时耐热温度高达800～1000℃，而且，具有对酸、碱和H2Se气的耐受性也较高的特性。因此，可以在最佳的温度下进行气相硒化处理，所以可以得到较高的转换效率。即，在CIGS太阳能电池的制造工序中，如果在钠钙玻璃基板所使用的500℃左右的较低处理温度下进行硒化处理，则因Ga在未结晶的状态下偏析到光吸收层的下部电极薄膜一侧，因而带隙较小、电流密度降低。与此不同，当在600℃以上、700℃以下的温度进行气相硒化的热处理时，Ga均匀地扩散到光吸收层中，而且未结晶状态被消除，因此带隙扩大，结果使开路电压(Voc)提高。因此，通过将云母或以云母为主体的材料用作基板材料，可以实现转换效率高的太阳能电池。进一步，由于云母或集成云母具有较高的挠性，可以用连续卷带制造工序进行生产，因此，也可以适合大批量生产的要求。
但是，研究表明云母或作为以云母为主体的材料的集成云母基板的表面不平滑，在几十微米的范围内存在着5～6μm的最大表面粗糙度。如果使用具有这样大的表面粗糙度的基板，表面覆盖性就不充分，存在着诱发漏泄并使太阳能电池的开路电压(Voc)降低的倾向，将产生得不到足够的转换效率的问题。为解决这一课题，在本发明中，在云母或集成云母基板与金属电极之间，形成用于使基板表面平坦化或平滑化的厚膜的中间层。通过形成该中间层，可以确保在基板上形成的构成太阳能电池的各种层间的相容性，并可以解决转换效率降低的问题。
上述中间层的厚度，从使云母或集成云母的表面平坦化的观点考虑优选为2μm以上，从确保基板的挠性的观点考虑设定为20μm以下。另一方面，当形成厚膜的中间层时，如果通过溅射等真空处理形成氧化膜、氮化膜，则不仅膜的形成需花费很长时间、使太阳能电池折曲或弯曲时在氧化膜、氮化膜上会产生裂纹，而且将产生挠性也减低的问题。因此，在本发明中，厚膜的中间层例如通过用毛刷的涂敷、喷涂、丝网印刷、旋转涂敷等的非真空处理形成。通过利用基于这些非真空处理的膜形成技术，可以很容易地形成所需厚度的中间层。
进一步，在本发明中，在云母或集成云母的基板上形成的中间层与在其上侧形成的钼电极之间，设置TiN或TaN等氮化物系化合物的粘合剂层。该粘合剂层具有抑制杂质扩散的阻挡效果，同时在与钼等之间具有较高的粘着性。使该粘合剂层的厚度为
Figure C20068003246400071
以上、
Figure C20068003246400072
以下，是因为如小于
Figure C20068003246400073
则从云母基板向光吸收层的钾的扩散不在现有的玻璃基板以下，而如超过则使挠性恶化并容易剥离。
本发明的太阳能电池的最佳实施例是由将云母粉状体与树脂混合后通过压延工序和烧结工序而制造的集成云母构成基板。集成云母虽然因混合了树脂而使其耐热性低于纯粹的云母基板，但仍具有600℃～800℃的耐热温度，可以在气相硒化处理的最佳温度即600℃～700℃下进行处理。而且，由于具有较高的挠性，适合于连续卷带工艺。并且，成本比玻璃基板大幅度降低。因此，通过将集成云母用作基板，可以用更低的制造成本制造适合于大批量生产并具有较高的转换效率的太阳能电池。
此外，也可以在中间层的表面上设置SiN或SiO2的硅系的平滑层。由此，可以使由陶瓷系材料构成的中间层的表面平滑，并能提高与粘合剂层的粘着性。
按照本发明，由于用预定厚度的陶瓷系材料(中间层)涂敷云母基板或集成云母基板并在该中间层上隔着预定厚度的氮化物系粘合剂层设置了黄铜矿光吸收层，因此可以得到不会使来自基板的杂质(特别是钾)扩散到光吸收层、重量轻而富有挠性、且转换效率高的黄铜矿型太阳能电池。
另外，氮化物系粘合剂层虽然价格较高，但通过将低价的陶瓷系材料用作中间层可以使粘合剂层的厚度减薄，与现有的使用了玻璃基板的黄铜矿型太阳能电池相比能以较低的成本进行制造。
附图说明
图1是表示现有的黄铜矿型太阳能电池的结构的剖视图。
图2是表示现有的黄铜矿型太阳能电池的一系列的制造工序的图。
图3是用于说明制造工序中的主要部分的图。
图4是表示集成云母基板的表面形状的曲线图。
图5的(A)和(B)是表示在集成云母基板表面上形成厚膜的中间层后的表面形状的曲线图。
图6是表示本发明的太阳能电池的一个结构例的剖视图。
图7是表示基于粘合剂层的膜厚变化的转换效率的曲线图。
图8的(a)是按粘合剂层的有无和粘合剂层的厚度示出扩散到光吸收层中的元素种类和检测计数值的柱形图，(b)是将(a)的检测计数值进行对数表示的柱形图。
具体实施方式
在说明实施例之前，先说明集成云母基板的表面形状。图4的(A)和(B)示出集成云母基板的任意2处的表面形状的测定结果。在图4中，横轴表示集成云母基板的横向的位置，纵轴表示高度方向的位置。作为集成云母基板的特征是最大高低差非常急剧地变化(纵横比大)。从图4可知，沿着横向在数十微米的范围内存在着5～6μm的最大高低差。其原因可以解释为起因于集成云母的制法，由于粉碎后的云母混合在树脂中，因此在表面上存在着粉碎云母片，纵横比极大。此外，集成云母基板的表面粗糙度，在所测定的2处分别为Ra＝1.6μm和Ra＝0.8μm。在这种表面状态的情况下，即使在基板上直接形成Mo等的电极薄膜并在其上形成光吸收层，表面的覆盖也是不完全的状态，会诱发漏泄并使作为太阳能电池的功能显著降低。具体而言，会使太阳能电池的开路电压(Voc)降低，并使转换效率降低。
接着，在图5的(A)和(B)中示出在集成云母基板表面上涂敷了8μm厚的作为中间层材料的陶瓷系涂料后的表面形状的测定结果。图5示出任意2处的测定结果。从图5可知，虽然测定出了基板原来具有的较大的起伏，但消除了在集成云母基板的表面形状测定中所观察到的数微米的范围内产生的5～6μm的最大高低差。因此，根据图4和图5中示出的测定结果，中间层的厚度在2μm以上即可，优选为5μm。
图6是表示本发明的太阳能电池的一个结构例的剖视图。在本例中，作为基板使用集成云母基板1。集成云母是将粉状的云母与树脂混合在一起并经压延和烧结而制造的高绝缘性材料。集成云母的耐热温度为600～800℃左右，与现有的太阳能电池中使用的钠钙玻璃的耐热温度(500～550℃)相比可以耐受高温。另外，由于气相硒化处理中的最佳处理温度为600℃～700℃，所以在形成黄铜矿型光吸收层时也可以在最佳温度下形成。而且，集成云母具有较高的挠性，因此也适于以连续卷带进行生产的情况。
在集成云母基板1上形成厚膜的中间层2。该中间层2用于使集成云母基板表面平坦化或平滑化，形成为2～20μm的厚度。该中间层2由陶瓷系材料构成。作为一个例子，使用钛为39重量％、氧为28.8重量％、硅为25.7重量％、碳为2.7重量％、铝为1.6重量％的涂料。另外，作为厚膜的中间层2的形成方法，例如通过用毛刷涂敷、喷涂、丝网印刷、旋转涂敷等形成涂膜并经干燥和烧结工序而形成。为了使集成云母的表面平坦化，该中间层需要2μm以上的厚度，为确保形成太阳能电池时的挠性而设定为20μm以下。在中间层的形成中使用的陶瓷材料系涂料将以溶胶-凝胶工艺制成的无机树脂作为基体，并由离子键使硅和氧强力结合，具有1200℃左右的耐热温度。因此，即使在后述的用于形成黄铜矿型光吸收层的气相硒化处理的理想处理温度下也具有足够的耐热性。
通过在基板表面涂敷陶瓷系材料，可以提高开路电压(Voc)，改善填充因数(FF)值，结果转换效率变高。其原因是以往表面平滑层和粘合剂层无法跟随集成云母基板表面的急剧的高低差变化，即氧化膜、氮化膜没有进入深陷的部分，因而不能改善表面的平滑性。
此外，也考虑到通过进行多次溅射形成较厚的氧化膜(氮化膜)而使表面平滑，但在这种情况下，当使太阳能电池折曲时有可能会使氧化膜(氮化膜)破裂，损伤下部电极层、光吸收层，因此，将使作为集成云母基板的优点的挠性变差。进一步，由于溅射本身的成本高，因此不适于大批量生产。
接着，在中间层2上形成表面平滑层3。作为该表面平滑层3，可以用SiN或SiO2，通过溅射等干法工艺形成。作为使用Si系材料的理由，可以举出可使中间层2的表面成为更平滑的面，可以提高基底的陶瓷系材料的中间层与后述的粘合剂层的粘着性。该表面平滑层3可以根据需要形成，也可以省略。
在表面平滑层3上，形成粘合剂层4。该粘合剂层4的形成是为了防止来自基底的云母基板和中间层的杂质或组成物的扩散并改善在其上形成的钼、钨等金属电极5与云母基板结构体(包括云母基板1和中间层2)之间的粘着性。作为该粘合剂层4的材料优选是TiN、TaN等的氮化物系化合物。该粘合剂层4的厚度，根据实验结果，为确保其阻挡性而需要在
Figure C20068003246400111
以上，虽然为了兼顾阻挡性和粘着性越厚越好，但如超过
Figure C20068003246400112
则容易发生剥离，因而应在
Figure C20068003246400113
以下。
在粘合剂层4上，与现有的黄铜矿型太阳能电池同样地形成各层。即，首先通过溅射形成用作下部电极的钼(Mo)电极5，利用激光照射分割Mo电极5(第1次划线)。
接着，通过溅射等附着铜(Cu)、铟(In)和镓(Ga)以形成前体后，将该前体配置在炉中，通过在H2Se气的气氛中进行退火的气相硒化处理而形成黄铜矿系光吸收层6。此外，在必要的情况下，也可以在气相硒化处理之前进行添加作为碱金属的钠(Na)的工序。这是由于通过将Na扩散到光吸收层中，光吸收层的微粒(晶粒)生长，由此能量转换效率变高。
光吸收层6是p型半导体层，在该光吸收层上，用溅射或CBD(化学浴沉积)等方法形成CdS、ZnO、InS等起着n型半导体层的作用的n型缓冲层7为例如数百埃米
Figure C20068003246400114
的厚度。此外，可以在该n型缓冲层7上，根据需要形成高电阻层8为数百埃米的厚度。然后，利用激光照射或金属针分割光吸收层和缓冲层(第2次划线)。
之后，通过溅射或CBD等形成用作上部电极的ZnOAl等透明电极(TCO)9，在其上形成防止反射膜10。进一步，利用激光照射或金属针等分割防止反射膜、透明电极、粘合剂层和光吸收层(第3次划线)。最后，在下部电极层5和上部电极层9上形成引出电极11和12，从而完成黄铜矿系薄膜太阳能电池。
此外，对于钼电极5的形成工序以后的工序，通过将CBD等湿法工艺置换为干法工艺，可以引入从卷带供给集成云母基板并形成太阳能电池的“连续卷带工艺”。此外，当引入连续卷带工艺时，也可以预先在集成云母基板上进行形成陶瓷系材料的中间层的工序，或者，也可以将其组合在连续卷带工艺中。
图7是表示基于粘合剂层的膜厚变化的转换效率曲线图，从该曲线图可知，在没有粘合剂层的状态下，具有中间层的太阳能电池与不具备中间层时相比，转换效率高出4％左右，在粘合剂层为
Figure C20068003246400121
的状态下，具有中间层的太阳能电池与不具备中间层时相比，转换效率高出近7％。
因此，可以说由于中间层的存在而提高了粘合剂层的效果。而且在有中间层的情况下，在膜厚小的阶段中表现出粘合剂层的效果。因此，当有中间层时可以减薄粘合剂层。
在图8中示出对粘合剂层的膜厚依赖性的进一步的验证结果。图8是在集成云母基板上形成作为中间层的陶瓷材料系涂膜并在其与Mo电极之间形成了粘合剂层的情况下，在气相硒化处理后用SIMS(Time of Flight Secondary Ion Mass Spectrometry：飞行时间二次离子质谱)法测定了扩散后的杂质数的图，(a)是用线性刻度示出检测计数值的柱形图，(b)是将(a)的检测计数值进行对数表示的柱形图。
从图8的(a)的柱形图可知，对太阳能电池的转换效率产生影响的杂质元素为钾(K)，以及钾(K)的扩散依赖于粘合剂层的厚度。另外，从(b)的曲线图可知，为使钾(K)的浓度比使用玻璃基板时低，需要使粘合剂层的厚度在300nm
Figure C20068003246400122
以上。

Claims (2)

1.一种黄铜矿型太阳能电池，其特征在于：
包括
由云母或含有云母的材料构成的基板；
形成在上述基板上的厚度为2μm以上20μm以下的含有陶瓷系材料的中间层；
层叠在上述中间层上的厚度为
Figure C2006800324640002C1
以上
Figure C2006800324640002C2
以下的氮化物系的粘合剂层；
形成在上述粘合剂层上的下部电极层；
形成在上述下部层上的由黄铜矿化合物构成的p型的光吸收层；
形成在上述光吸收层上的n型的缓冲层；以及
形成在上述缓冲层上的透明电极层。
2.根据权利要求1所述的黄铜矿型太阳能电池，其特征在于：
上述粘合剂层由含有氮化钛或氮化钽的膜形成。
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