CN1214469C - 制造光伏箔的方法 - Google Patents

制造光伏箔的方法 Download PDF

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CN1214469C
CN1214469C CNB018077951A CN01807795A CN1214469C CN 1214469 C CN1214469 C CN 1214469C CN B018077951 A CNB018077951 A CN B018077951A CN 01807795 A CN01807795 A CN 01807795A CN 1214469 C CN1214469 C CN 1214469C
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E·米德尔曼
G·J·约恩格登
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Akzo Nobel NV
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Abstract

本发明涉及一种制造光伏箔的方法，该光伏箔包括一个TCO层、一个光伏层，和一个背电极，制造光伏箔的方法包括以下步骤：提供一个导电的临时衬底；在临时衬底上施加一TCO层；用电沉积法在TCO上施加一光伏层，同时在电沉积期间至少穿过临时衬底输送电流；施加一背电极；如果希望这样，施加一永久衬底；除去临时衬底。本发明的关键是，导电的临时衬底和TCO的组件在光伏层电沉积期间起电极作用。由于这点，与现有技术的沉积速率相比，光伏层的沉积速率可以增加。此外，得到一种具有更均匀层厚的光伏层。

Description

制造光伏箔的方法
本发明涉及一种光伏箔的制造方法，更具体地说，涉及这样一种光伏箔的方法，其中已通过电沉积施加了光伏层。
薄膜太阳能电池箔，也通称为光伏箔，一般包括一个载体和一个光伏(PV)层，该光伏层包括一种半导体材料，该半导体材料设置在一个前电极(在箔材的正面处)和一个背电极(在箔材的背面处)之间，前电极包括一种透明的导电氧化物(TCO)。前电极是透明的，能使入射光到达半导体材料，在此处入射辐射转变成电能。利用这种方法，可以产生电流，这种用光产生的电流提供一种有趣的，比如说，矿物燃料和核能的替代物。
在制造光伏箔时，通常是利用真空沉积法。这些方法通常比在常压条件下进行的类似方法更昂费。因此，人们希望在大气压力下，于适度的过程条件下制造活性层。这可以用，比如半导体层的电化学沉积来实现。这些方法是已知，尤其是从US 4,816,120及G.C.Morris和R.Vanderveen，S01.Energy Mater.S01.Cells 27(1992)305中。伽伐尼(电化学)沉积，此后也叫做电沉积，要求在其上进行沉积的这层是导电的。
一种用于达到这一目的方法是在制备太阳能电池薄板时用一种金属衬底。这些方法在US 4,341,610和DE 196 34 580中已有介绍。金属衬底同时起衬底和背电极作用。用这种方法制备的光伏箔包括一个金属衬底、一个通过电沉积镀覆的光伏层，和一个作为正面电极的透明导电氧化物(TCO)。然而，首先施加PV层和然后加透明导体层的顺序对所用的透明导体材料产生了严重的限制。比如，一种很合适的透明电极层是掺F氧化锡。然而，为了使其具有所希望的性质和构造，优选的是它应该在至少400℃温度下施加。这种高温可以毁坏PV层，尤其是由于结晶、掺杂剂的扩散(如果存在的话)、杂质的扩散、裂纹的形成、和/或氢的损失等造成的。
另一种利用电沉积来沉积光伏层的方法，是在具有一层透明导电氧化物(TCO)的玻璃上沉积。Raffaelle等(R.P.Raffaelle等，ElectrodepositedCdS on CIS pn junctions，Solar Energy Material & Solar Cells 57(1999)167-178)介绍了在涂覆氧化铟锡的玻璃上连续电沉积CIS和CdS。
Das等(S.K.Das和G.C.Morris，Preparation and characterizationof electrodeposited n-CdS/p-CdTe thin film solar cells，Solar EnergyMaterial & Solar Cells 28(1993)305-316)介绍了在涂覆氧化铟锡的玻璃上连续电沉积CdS和CdTe。在电沉积碲化镉时，利用其上设置有CdS缓冲层的TCO作为电极。
然而，这些方法的主要缺点是光伏层的低生长率。生长速率受TCO的低导电性限制，因为所需电子必须穿过这层传送。由于这层的厚度，通常＜1微米，所以电阻高。这本身意味着生长率与所设置的两个电接触点的距离有关。生长速率的不同导致光伏层最终一层厚度上的变化，这是不希望有的。
人们曾试图通过在TCO上或下面，提供具有低电阻的条形导电体，如金属来解决低沉积速率的问题。这使它有可能应用较大的平面，而同时保持多少可接受的生长速率。然而，这种方法的缺点是，导体在活性层上产生阴影，同时使模块的电流-单位面积比降低。此外，在这种情况下，沉积速率与电导体之间的距离有关，同时形成一个厚度不均匀的光伏层。
按照另一种方法，首先将导电金属的薄层施加到TCO上。这将在某种程度上改善导电性，但是，由于导电金属层阻挡入射光，所以它也导致电池中的光量减少，并因此导致发出的电流量减少。
因此，需要有一种制造光伏箔的方法，其中可以在高沉积速率下利用电沉积均匀施加光伏层，并且其中TCO的性质可以独立地从光伏层的性质中选定。
人们现已发现，通过将TCO施加在一个导电的临时衬底上，并至少穿过该临时衬底输送用于电沉积的电流，可以解决这个问题。结果，临时衬底和TCO构成的组件在电沉积PV层期间将起电极的作用。显然，TCO和临时衬底应处于良好的电阻性接触。由于衬底比TCO厚得多，并且一般具有极优越的导电性，所以与现有技术相比，输送到衬底和TCO系统的电流量可以增加。这使最大沉积速率增加，可用来得到均匀的光伏层。由于衬底的高导电性，TCO的电位在整个表面上基本上相同。由于这种结果，沉积了一层均匀厚度的PV层。由于TCO沉积在临时衬底上，而不是沉积在光伏层上，所以TCO可以单独地从光伏层的性质中选出。
因此，本发明涉及一种包括下列步骤的方法：
·提供一个导电的临时衬底；
·在TCO和临时衬底处于良好的电阻性接触的条件下将TCO层施加到临时衬底上；
·利用电沉积将光伏层施加在TCO层上，至少穿过临时衬底供给用于电沉积的电流；
·施加一背电极；
·如果希望的话，加一永久衬底；
·除去临时衬底。
导电性的临时衬底最好是挠性的，使方法能以卷到卷(roll to roll)的形式进行。永久衬底可以是刚性的或挠性的，视应用而定。对大多数应用，永久衬底优选的是也是挠性的。按照本发明所述的方法优选的是用连续法进行。更优选的是，连续法是卷到卷的方法。
按照本发明所述方法的另一优点如下：为了减少光伏箔中的电阻损失，及为了减少经常需要的转换器中的损失，常常把光伏箔划分成若干单个单元(cell)，然后将这些单个的单元串联连接。这种方法，尤其是，要求在TCO层中设置沟槽。在一种TCO加在不导电的载体，比如说，玻璃载体上的系统中，光伏层的电沉积只在TCO上发生，并且在TCO中可以设置的任何沟槽中，都没有或几乎没有任何沉积。这使得不可能很容易地提供串联连接。
在按照本发明的方法中，其中使用导电衬底，光伏层也沉积在TCO中的沟槽内，其结果是可以进行简单的串联连接。因而可以如下进行本发明所述的方法：设置一个临时衬底，该临时衬底涂覆有一个带沟槽的TCO。利用电沉积，将一光伏层施加在TCO上和设置在TCO上的若干沟槽中。在TCO内沟槽附近的光伏层中，设置若干沟槽或若干(排)孔。如果希望这样的话，设置一个永久衬底，在此之后除去临时衬底。
在根据本发明方法一种可供选择的设置串联连接的方法中，首先在光伏层中设置若干沟槽或若干(排)孔。接着设置一个背电极，利用比如，一网罩在沉积期间或者在此之后，在背电极中形成若干沟槽。然后将PV箔与背电极一起叠层在永久衬底上，并除去临时衬底。然后，在已除去临时衬底情况下，在已变成可以接近的TCO中，或在PV层中，设置若干沟槽。沟槽可以通过这种已知的方法设置。这些方法包括电腐蚀金属去除法、湿法侵蚀、干法侵蚀、激光烧蚀、用腐蚀性粉末或冻结的液体颗粒喷射、及用一硬质划线尖头进行机械划线。
如上所述，本发明的关键是，由导电性临时衬底和TCO组成的组件在电沉积期间起电极作用。由于临时衬底的导电率高于TCO的导电率，所以在TCO中电流的方向基本上垂直于衬底层方向。结果，TCO的电位基本上是均匀的，这使沉积的光伏层的层厚基本上均匀，与平均厚度的偏差通常小于10％，优选的是小于5％，更优选的是小于2％。
按照本发明方法的一个好的实施例是，把临时衬底与设置于其上的TCO一起引导到一个辊上，同时通过上述辊输送用于电沉积的电流。该辊在用于沉积PV层所要求的电解质中旋转。这导致电流非常均匀的输送到TCO上。此外，该系统具有工艺上的意义，因为它适合于在卷到卷方式中整体化。
在按照本发明所述方法的一个不同实施例中，通过一个或一个以上的导向辊，把其上设置有TCO的临时衬底导入电解槽，同时该一个或多个导辊还用作与箔的电接触。这种配置使沉积能在高电流密度下，并因此在高速下进行。当在沉积期间有高电流和在接触辊之间有大的间隙时，在箔的机器方向上将有一个电位(电压降或电压升)，该电位可以降低生长速在那种情况下连续地实施该方法将会具有另外的优点。因为电位只在过程方向上存在，并且箔也朝这个方向上运动，所以尽管电位不同，仍会形成均匀厚度的光伏层。图1中示出一种实施这个方法的装置。在图1中，具有TCO(1)的临时衬底通过一组接地的导向辊(2)引导穿过电解槽(3)，该电解槽(3)装有必需的电解质(4)。电极(5)提供需要的电流。
在按照本发明的方法中，通过用电流电沉积施加PV层，该电流经由导电的临时衬底输送。如果希望这样，也可以通过用电流电沉积施加一层或多层其它层，如TCO、背电极、和任何可选的现有的缓冲层，上述电流经由导电的临时衬底输送。在按照本发明所述方法特别有利的实施例中，TCO、任何可选的现有的缓冲层、光伏层、和背电极，每个都在连续过程中通过用电流接连电沉积施加，该电流经由导电的临时衬底输送。
在第一步的另外改变中，通过电沉积在比如，一个鼓形件或连续皮带上制备临时衬底，此后用一种连续法接连地通过电沉积把TCO、任何可选的现有的缓冲层、光伏层、和背电极施加到临时衬底上。然后，从载体中去掉包括临时衬底、TCO、任何可选的缓冲层、PV层和背电极组成的复合物并进一步处理。图2中显示了用于实施该实施例的装置。该图示出一个电沉积槽(1)，该电沉积槽(1)通过隔板(2)分成各种不同的段。每个段都装有一个电极(3)和特定沉积所需的电解质(4)。一个比如用氧化铬制造的接地的鼓形件(5)在电解槽中旋转。在电解槽的每一部分中，从临时衬底开始，沉积一层光伏箔，接着沉积TCO、任何缓冲层、PV层和背电极。然后从电解槽中取出包括临时衬底、TCO、任选的缓冲层、和背电极的系统(6)，以便经受另一些加工步骤。
正如前面所表明的，卷到卷法构成按照本发明所述方法的优选实施例。用临时基板制造薄膜太阳能电池薄板的各种方法在该技术中是已知的。特别合适的卷到卷法在WO 98/13882中已有介绍。
临时衬底
临时衬底必须满足许多条件。它必须是充分导电的，以便在电沉积光伏层期间能传导足够的电流。它必须是十分耐热，以便能忍受在制造薄膜太阳能电池薄板期间、更具体地说在沉积TCO和PV层期间一些主要的条件。它必须足够强固，以便能在它制造期间承载薄膜太阳能电池箔。它必须是很容易从TCO层中除去而不损坏TCO层。该技术的技术人员将能在这些准则内选择合适的临时衬底。
在按照本发明方法中应用的临时衬底优选的是一种金属或金属合金箔。这样做的主要原因是这些箔显示良好的导电性、一般能承受高加工温度、蒸发慢，及用已知的侵蚀技术比较容易除去。选择金属箔，更具体地说是铝或铜箔的另一原因是，最终，薄膜太阳电池薄板必须设置边缘电极，该边缘电极必须把薄膜太阳电池薄板连接到装置或电网上。未除去的临时衬底部分可以用于这个目的，其结果是不必单独准备边缘电极。
合适的金属包括钢、铝、铜、铁、镍、银、锌、钼、铬、及其合金或多层结构。由于经济上原因，其中优选的是应用Fe、Al、Cu，或它们的合金。若规定它们的性能(并考虑成本问题)，则最优选比如通过图2的整体法电沉积制造的铝、铁，和比如通过图2的整体法电沉积制造的铜。
用于除去金属的合适侵蚀剂及技术是已知的，并且尽管每种金属的侵蚀剂及技术都不同，但本领域的技术人员将能选择合适的那些。优选的侵蚀剂包括酸(Lewis酸和Brфnstedt酸二者)。因此在铜的情况下，优选的是用FeCl3、硝酸、硫酸。铝的合适的侵蚀剂包括NaOH、KOH、及磷酸与硝酸的混合物。
如果用通过电沉积任意制备的铜作为临时衬底，则优选的是提供任意通过电沉积的铜，该铜具有一个非还原性的扩散性阻挡层，比如，一种防腐层，更具体地说，氧化锌。这是由于铜可以具有穿过PV层在TCO层中扩散的趋向。也可以选择能防止这种扩散的TCO，比如，SnO2或ZnO。防扩散层可以通过例如电沉积、或通过物理汽相沉积(PVD)或通过化学汽相沉积(CVD)施加。防扩散层一般与临时基板一起从TCO中除去。
为了便于除去，临时基质最好是尽可能薄。当然，它的厚度必须是这样，以便其它层可以设置于其上，并且它必须能使这些层保持在一起，但这一般要求它的厚度不大于500微米(0.5mm)。厚度优选的是在1-200μm(0.2mm)范围内。视弹性模量而定，大量材料的最小厚度将是5μm。因此，优选5-150μm的厚度，更具体地说10-100μm的厚度。
TCO层
合适的透明导电氧化物(TCOs)的一些例子是氧化铟锡、氧化锌、搀杂铝的氧化锌、氟、镓或硼、硫化镉、氧化镉、氧化锡，和，最优选的是搀杂F的SnO2。上述最后说到的透明电极材料是优选的，因为当它在超过400℃，优选的是在500-600℃范围内施加时，或者在上述温度下处理之后，它可以形成一种理想的具有柱状光散射构造(columnar light scatteringtexture)的结晶表面。正是在这种TCO情况下，用能够承受这种高温的临时衬底是极具吸引力的。此外，材料抗大多数侵蚀剂，并且具有比更多使用的氧化铟锡更好的耐化学制品性。另外，它是费用少得多。
TCO可以用该领域已知的方法施加，比如，用金属有机物化学气相沉积(MOCVD)、溅射、大气压化学气相沉积(APCVD)、等离子体增强化学汽相沉积(PECVD)、喷雾热解、蒸发(物理汽相沉积)、电沉积(在结合到PV层电沉积中的一个方法中任选的)，无电极电镀、丝网印刷、溶胶-凝胶法，等等。优选的是在超过250℃，优选的是超过400℃，更优选的是在500和600℃之间的温度下施加并后处理TCO层，以便可以得到具有所希望组成、性质和/或构造的TCO层。
缓冲层
如果希望这样，则缓冲层可以存在于TCO层和光伏层之间。缓冲层用来保护TCO层免受沉积PV层期间主要条件的影响。缓冲层的性质取决于PV层的性质。用于各种PV层的合适缓冲层在该技术领域中是已知的。可以提到的有碲化镉、CdS、In(OH、S)和Zn(OH、S)。
如果在本说明书中提到在TCO层上沉积PV层，则在TCO层上总可以有一缓冲层
光伏层
在应用TCO层之后，通过电沉积施加光伏(PV)层。这里应该注意，在本说明书中，术语“PV层”或“光伏层”包括吸收光并将光转变成电所必需的各层整个系统。要通过电沉积施加的合适层构造是已知的，正如施加它们的方法一样。作为该领域中的普通的一般知识，可以参见YukinoroKuwano，的“光伏电池”，Ullmann’s Encyclopedia，V01.A20(1992)，161和“太阳能技术”，Ullmann’s Encyclopedia，V01.A24(1993)，369。用于电沉积光伏层的方法，在，比如，US 4,816,120，US 5,472,910，US4,456,630和US 4,388,483中，以及在比如说，G.C.Morris和R.J.Vanderveen，Applied Surface Seience 92(1996)，630-634中已有介绍。
为了工作状况良好起见，应该注意，不必都用电沉积法施加光伏层的所有分层。例如，硫化镉可以用，比如，CVD、浸没、无电极电镀、溅射或真空蒸发法施加，接着用电沉积法施加碲化镉。
在用电沉积法制造PV层时，可以使用各种薄膜半导体。一些例子是CIS(二硒化铜铟，CuInSe2)，CuInS2、碲化镉(CdTe)、CIGSS(Cu(In，Ga)(Se，S))、Cu(In，Ga)Se2、ZnSe/CIS、ZnO/CIS，和/或Mo/CIS/CdS/ZnO，及染料增感式太阳能电池。
PV层的总厚度一般将在100-10000nm范围内，更具体地说是在约200和6000nm之间，优选的是在约250和5000nm之间，更优选的是在约300和1000nm之间。
背电极
在按照本发明的薄膜太阳能电池薄板中的背电极，优选的用作反射器和电极。一般，背电极将具有约50-500nm的厚度，并且它可以包括任何合适的具有反射光性质的材料，优选的是铝、银、或二者层的组合，并与相邻的半导体层形成良好的电阻接触。优选的是，能在比较低的温度下，比如说低于250℃，通过比如，电沉积，(在真空中)物理汽相沉积或溅射，施加金属层。在银情况下，优选的是首先施加一层粘附促进剂层。TiO2、TiN、ZnO、和氧化铬是用于粘附促进剂层合适材料的例子，并且当以合适的厚度，比如50-100nm施加时，还具有反射性质的优点。所要求的背电极可以是透明的或者是不透明的。背电极优选的是通过电沉积施加，可以在集成在PV层电沉积中的过程中进行。
永久衬底
尽管对按照本发明所述的方法来说不是必需的，但通常，优选的是提供一种具有永久衬底的薄膜太阳能电池板。因为，否则的话，薄膜将如此之薄，以致它的脆性造成难以处置。当应用时，永久衬底施加在背电极上。合适的衬底层材料包括市售聚合物薄膜，如聚对苯二甲酸乙二酯、聚2，6-萘二甲酸乙二酯，聚碳酸酯、聚氯乙烯、聚偏氟乙烯(PVDF)、聚偏氯乙烯(PVDC)、或具有良好性质的聚合物薄膜如芳族聚酰胺或聚酰胺薄膜，而且还有，例如，金属箔，其上可以加一个绝缘(介电)表面层，或者塑料和增强纤维及填充料的组成。优选的是设置有热塑性粘合层的“共挤塑”聚合薄膜，该热塑性粘合层具有一个软化点，该软化点比衬底本身的软化点低。如果希望这样，则共挤塑薄膜可以设置一个比如，用聚酯(PET)，共聚多酯或铝制的防扩散层。衬底的厚度优选的是50μm-10mm。优选的范围是75μm-3mm和100μm-300μm。衬底的弯曲刚度在本说明书的情况下定义为弹性模量E(单位为N/mm2)与厚度t的三次方(单位mm)的乘积(E×t3)，优选的是高于16×10-2Nmm，和一般将低于15×106Nmm。
衬底可以包括一种如供最终使用所要求的结构。因此衬底可以包括瓦类、屋面板和元件、正面元件、汽车和大蓬车的车顶面等。然而，一般，偏爱的衬底是挠性的。在那种情况下得到一卷薄膜太阳能电池板，该卷薄膜太阳能电池板随时可以使用，并在那里将具有所希望电力和电压的板切离该卷。然后可以将这些合并到(杂配)屋面元件中，或者如所希望的，施加到瓦、屋面板、小汽车和大蓬车车顶上，等等。
如果希望这样，顶面涂层或表面层可以设置在太阳能电池的TCO一侧上，以便保护TCO免受外部影响。一般，表面层将是一种聚合物薄板(如果希望这样，具有空腔)或者聚合物膜。要求表面层具有高传输作用，并且例如包括下列材料：无定形(全)氟化高聚物、聚碳酸酯、聚甲基丙烯酸甲酯、PET、等离子体增强化学汽相沉积氮化硅(PEN)或任何可用的透明涂层，如汽车工业所用的一种。如果希望这样，则可以设置一另外的防反射或防中毒层。如果希望，整个太阳能电池可以包括在这一密封剂中。

Claims (15)

1.一种制造光伏箔的方法，该光伏箔包括一个TCO层、一个光伏层、和一个背电极，上述方法包括下列步骤：
·提供一种导电的临时衬底；
·在临时衬底上施加一TCO层；
·通过电沉积把光伏层施加在TCO上，至少穿过临时衬底输送用于电沉积的电流；
·施加一个背电极；
·除去临时衬底。
2.按照权利要求1所述的方法，其中在施加一个背电极之后并且在除去临时衬底之前，施加一永久衬底。
3.按照权利要求1的方法，其中将其上设置TCO的临时衬底引导到一个辊上，将用于电沉积的电流通过该辊输送。
4.按照权利要求1的方法，其中设置有TCO的临时衬底通过至少一个导向辊导向到装有电极的电解槽中，该一个或多个导向辊还用作光伏箔的电接触。
5.按照权利要求1-4中任意一个的方法，其中，在施加TCO层之后并且在施加光伏层之前，一电导缓冲层被施加。
6.按照权利要求5的方法，其中从TCO层、任何导电的缓冲层和背电极中选出的一层或多层也通过电沉积施加，电流输送穿过临时衬底。
7.按照权利要求6的方法，其中TCO层、任何导电的缓冲层、光伏层和背电极，是在连续过程中接连通过电沉积施加的。
8.按照权利要求7的方法，其中在第一步中，临时衬底是在一载体上通过电沉积制备的，以此之后在一连续过程中接连沉积施加TCO层、任何导电的缓冲层，光伏层和背电极。
9.按照权利要求1-4中任意一个的方法，其特征在于：临时衬底是金属箔。
10.按照权利要求7的方法，其特征在于：临时衬底是金属箔。
11.一种制造光伏箔的方法，该光伏箔包括一个TCO层、一个光伏层、和一个背电极，上述方法包括下列步骤：
·提供一个临时衬底；
·施加一TCO，在该TCO中设置有若干沟槽；
·通过电沉积在TCO及设置于其中的沟槽上施加一光伏层；
·在靠近TCO中沟槽的光伏层中设置若干沟槽、若干孔或若干排孔；
·施加一个背电极，该背电极在靠近光伏层中若干沟槽、若干孔或若干排孔附近设置有若干沟槽；
·除去临时衬底。
12.按照权利要求11所述的方法，其中在施加一个背电极之后并且在除去临时衬底之前，施加一永久衬底。
13.一种制造光伏箔的方法，该光伏箔包括一个TCO层、一个光伏层、和一个背电极，上述方法包括下列步骤：
·提供一个临时衬底；
·施加一TCO；
·通过电沉积施加一个光伏层；
·在光伏层中设置若干沟槽、若干孔或若干排孔；
·施加一个设置若干沟槽的背电极；
·除去临时衬底；
·在TCO中设置若干沟槽。
14.按照权利要求13所述的方法，其中在施加一个背电极之后并且在除去临时衬底之前，施加一永久衬底。
15.按照权利要求1或2的方法，以一种连续的卷到卷法进行。
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EP1273048A1 (en) 2003-01-08
WO2001078156A1 (en) 2001-10-18
KR20020086703A (ko) 2002-11-18
US20030160243A1 (en) 2003-08-28
ES2435479T3 (es) 2013-12-19
CA2405177A1 (en) 2001-10-18
AU2001254762A1 (en) 2001-10-23
KR100798234B1 (ko) 2008-01-24
EP1273048B8 (en) 2013-10-02
CN1440572A (zh) 2003-09-03
JP2003530702A (ja) 2003-10-14
US6951770B2 (en) 2005-10-04

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