CN101061588B - 在箔衬底上太阳能电池的形成 - Google Patents

在箔衬底上太阳能电池的形成 Download PDF

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CN101061588B
CN101061588B CN2005800369091A CN200580036909A CN101061588B CN 101061588 B CN101061588 B CN 101061588B CN 2005800369091 A CN2005800369091 A CN 2005800369091A CN 200580036909 A CN200580036909 A CN 200580036909A CN 101061588 B CN101061588 B CN 101061588B
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克雷格·莱德霍尔姆
布兰特·博尔曼
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Abstract

本发明涉及光生伏打装置的制作，更具体地说，是涉及光生伏打装置吸收体层的处理和退火。本发明的实施例，能实现铝箔衬底上CIGS吸收层的制作。例如，一种光生伏打装置，包括；铝箔衬底(102)、可供选择的基本电极(104)、和包括包含IB族、IIIA族、和VIA(可供选择的)族元素材料的初生吸收体(106)。

Description

在箔衬底上太阳能电池的形成
技术领域
本发明涉及光生伏打装置的制作，更具体地说，是涉及光生伏打装置吸收体层的处理和退火。
背景技术
已经用吸收体层制成高效的光生伏打装置，诸如太阳能电池，该吸收体层由包含IB族、IIIA族、和VIA族元素的合金，例如铜与铟和/或镓的合金，或铝与硒和/或硫的合金制成。该种吸收体层常常称作CIGS层，而得到的装置常常称作CIGS太阳能电池。CIGS吸收体层可以淀积在衬底上。在铝箔衬底上制作这种吸收体层是理想的，因为铝箔相对便宜、轻、和可弯曲。遗憾的是，目前用于淀积CIGS吸收体层的技术，与把铝箔作衬底使用不相容。
典型的淀积技术，包括蒸发、溅射、化学汽相淀积、等等。这些淀积过程通常在高温下进行并持续长的时间。该两个因素都能导致正在其上进行淀积的衬底的损坏。这种损坏直接因衬底材料暴露在热中，和/或因淀积过程的热激发不希望有的化学反应引起。因此，CIGS太阳能电池的制作，通常要求非常牢固的衬底材料。这些限制已经把铝和铝箔基的箔的使用排除在外。
一种替代的淀积办法，是在衬底上进行CIGS前体(precursor)材料的溶液基印刷。溶液基印刷技术的例子，例如在公开的PCT申请WO 2002/084708和共同转让的U.S.Patent Application 10/782,017中说明，本文引用该两申请，供参考。该淀积办法的优点，包括相对较低的淀积温度和淀积过程的迅速性两者。两个优点的作用，是使正在其上进行淀积的衬底的热致损坏最小。
虽然在CIGS太阳能电池制作中，溶液淀积是相对低温度的步骤，但它不是仅有的步骤。除淀积外，CIGS太阳能电池制作中的关键步骤，是CIGS吸收体层的硒化和退火。硒化是把硒引进大块的CIG或CI吸收体层，把硒掺进膜中，而退火是提供有适当结晶结构的吸收体层。在现有技术中，硒化和退火，是通过在H2Se或Se蒸汽中加热衬底，并把该初生吸收体层长时间保持在高温中进行的。
虽然用铝作太阳能电池装置的衬底，由于这种衬底的低成本和轻的性质两者，应是理想的，但有效地使CIGS吸收体层退火的常规技术，同样把衬底加热到高温，导致Al衬底的损坏。在Al衬底长时间暴露在热和/或含硒化合物的时候，有若干因素导致Al衬底降质。首先，在长时间加热的时候，在镀钼的Al衬底内个别的层能够熔融，并形成该装置的金属间的后接点，该金属间的后接点降低钼层计划要达到的电子功能。其次，钼层界面的形态在加热期间被改变，对随后CIGS粒子通过钼层表面引起的成核模式的变化而生长，有负面影响。第三，在长时间加热的时候，Al能够迁移进CIGS吸收体层，瓦解半导体的功能。第四，在Al箔中通常存在的杂质(如Si、Fe、Mn、Ti、Zn、和V)，在长时间加热的时候，能够随同移动的Al传播，扩散进太阳能电池中，瓦解电池的电子和光电子两种功能。第五，当Se暴露在Al中相对长的时间和相对高的温度时，能够形成不稳定的硒化铝。在潮湿的空气中，硒化铝能够与水蒸气反应，形成氧化铝和硒化氢。硒化氢是巨毒气体，它的自由形成能够造成对安全的危害。因为所有这些理由，从而高温淀积、退火、和硒化，对铝或铝合金制成的衬底是不能实现的。
因为高温、长时间淀积、和退火步骤，CIGS太阳能电池不能在铝衬底(如由Al和/或Al基合金构成的可弯曲箔)上有效地制作，相反，必须在更牢固(也更昂贵)的材料，例如不锈钢、钛、或钼箔、玻璃衬底、或金属或金属氧化物涂敷的玻璃制成的更重衬底上制作。因此，即使基于铝箔的CIGS太阳能电池比不锈钢、钛、或钼箔、玻璃衬底、或金属或金属氧化物涂敷的玻璃衬底更轻、可弯曲、和不昂贵，但目前的实践不允许把铝箔用于衬底。
因此，本领域需要一种在铝箔衬底上制作CIGS太阳能电池的方 法。
附图说明
借助阅读下面结合附图的详细说明，能够容易了解本发明的教导，附图中：
图1是剖面示意图，表明按照本发明一个实施例的吸收体层的制作。
具体实施方式
虽然为演示的目的，下面的详细说明包含许多具体的细节，本领域任一个一般人员将明白，下面的详细描述的许多变化和更改，都包含在本发明的范围内。因此，下面说明的本发明示例性的实施例，在阐述中对要求的发明不失任何普遍性和不加限制。
本发明的实施例能在铝箔衬底上制作CIGS吸收体层。按照本发明的实施例，借助溶液淀积，在铝衬底上形成包含IB族和IIIA族元素的初生吸收体层，可以借助快速加热进行退火，该快速加热是从环境温度到约200℃和约600℃之间的平稳温度范围。使该温度维持在平稳范围中约2分钟和约30分钟之间，然后降温。另外，可以调制该退火温度，使它在温度范围内振荡而不是维持在特定的平稳温度上。
图1画出局部已制作的光生伏打装置100和快速加热单元110。该装置一般包括铝箔衬底102、可供选择的基本电极104、和初生吸收体层106。铝箔衬底102厚约5微米到一百或更多微米，并有任何合适的宽度与长度。铝箔衬底102可以由铝或铝基合金制成。另外，铝箔衬底102可以由金属化的聚合物箔衬底制成，其中的金属化聚合物箔衬底，是选自如下一组的聚合物：聚酯(polyester)、聚萘二甲酸乙二醇酯(polyethylene naphtalate)、聚醚亚胺(polyetherimide)、聚醚砜(polyethersulfone)、聚醚醚酮(polyetheretherketone)、聚酰亚胺(polyimide)、和/或以上的组合。举例说，衬底102的形式可以是适合供卷筒到卷筒(roll-to-roll)处理的长片铝箔。基本电极104由与初生吸收体层106的处理兼容的导电材料制成。举例说，基本电极104可以是钼层，例如厚约0.1到25微米，更可取的是从约0.1到5微米厚。基本电极层的淀积，可以用溅射或蒸发淀积，或者用化学汽相淀积(CVD)、原子层淀积(ALD)、溶胶凝胶涂敷、电镀、等等。
铝和钼能够，且常常确实彼此相互扩散，对装置100产生有害的电子和/或光电子作用。为了防止这种相互扩散，可以在铝箔衬底102和钼基本电极104之间夹入中间的界面层103。界面层可以由如下各种材料的任一种构成，这些材料包括，但不限于：铬、钒、钨、和玻璃，或诸如氮化物(包括氮化钽、氮化钨、和氮化硅)、氧化物、和/或碳化物的复合物。该层的厚度可以在从10nm到50nm范围，更可取的是从10nm到30nm的范围。
初生吸收体层106可以包括含有IB族、IIIA族、和(可供选择)VIA族元素的材料。最好是，吸收体层的IB族元素是铜(Cu)，IIIA族元素是镓(Ga)和/或铟(In)和/或铝，而硒(Se)和/或硫(S)可以作为VIA族元素。当初生吸收体层106开始进行溶液淀积时，或在随后的处理期间，把VIA族元素掺进初生吸收体层106中，从初生吸收体层106形成最后的吸收体层。当淀积时，初生吸收体层106可以约1000nm厚。随后的快速热处理和掺入VIA族元素，可以改变得到的吸收体层的形态，使它厚度增加(如在某些情况下，增加至初生层厚度的约两倍)。
在铝箔衬底102上制作吸收体层，是较为直接的。首先，或者直接在铝上，或者直接在诸如电极104的最顶层上，把初生吸收体层淀积在衬底102上。举例说，但不失一般性，可以按包含纳米粒子的溶液基前体材料膜的形式，淀积初生吸收体层，这种纳米粒子包括一种或多种IB族、IIIA族、和(可供选择地)VIA族元素。这类溶液基印刷技术的这类膜的例子，例如在共同转让的U.S.Patent Application10/782,017中说明，标题是“SOLUTION-BASED FABRICATION OFPHOTOVOLTAIC CELL”，在PCT公布WO 02/084708中也有说明，标题为“METHOD OF FORMING SEMICONDUCTOR COMPOUND FILM FOR FABRICATION OF ELECTRONICDEVICE AND FILM PRODUCED BY SAME”，在此引用两者公开的内容，供参考。
另外，初生吸收体层106可以通过一系列原子层淀积反应形成，或通过其他一般用于形成这类层的常规过程形成。IB-IIIA-VIA吸收体层的原子层淀积，例如在共同转让、共同待决的申请序号10/934,658中说明，标题是“FORMATION OF CIGS ABSORBER LAYERMATERIALS USING ATOMIC LAYER DEPOSITION AND HIGHTHROUGHPUT SURFACE TREATMENT ON COILED FLEXIBLESUBSTRATES”，本文上面已经引用该文，供参考。
然后，用加热单元110，通过迅速从环境温度到约200℃和约600℃之间的平均平稳温度范围，加热初生吸收体层106和/或衬底101，使初生吸收体层106退火。加热单元110最好能提供足够的热，使初生吸收体层106和/或衬底101(或其有意义部分)快速升温，例如在约5℃/s和约150℃/s之间。举例说，加热单元110可以包括一个或多个能提供足够辐射热的红外灯。举例说，8个定额为500瓦的IR灯，各置于离衬底102表面约1/8″到约1″(4个在衬底上和4个在衬底下，全部朝向衬底)，能够在4″管炉中，提供足够的辐射供约每小时25cm2衬底面积的热处理。灯可以按可控方式逐渐升温，例如以平均约10℃/秒的升温速率。本领域那些熟练人员应能设计其他类型和配置的热源，供加热单元110使用。例如，在滚筒到滚筒的生产线中，加热和其他处理，能够用间隔1″的IR灯沿处理区的长度，等距排列在衬底之上和之下，这里，衬底上和衬底下的IR灯，都朝向衬底。另外，IR灯也可以仅放置在衬底102之上或之下，和/或按增大的侧向加热配置，从加热室一侧到衬底102的一侧。
使吸收体层106和/或衬底102维持在平均平稳温度范围约2分钟和约30分钟之间。例如，通过把加热单元110的加热量降低到适当的水平，可以使温度保持在需要的范围。在IR灯的例子中，通过简单地断开加热灯，可以降低加热。或者，可以主动地使灯冷却。例 如，通过进一步降低或关断来自加热单元110的热，可以基本上降低吸收体层106和/或衬底102的温度。
在本发明的一些实施例中，可以在退火阶段之前或之中，把VIA族元素，如硒或硫掺进吸收体层中。另外，两个或多个分离的或连续的退火阶段，能够相继地进行，其中在第二阶段或更后的阶段中，把VIA族元素，如硒或硫掺入。例如，可以在迅速加热或快速热处理(RTP)之前或期间，使初生吸收体层106暴露于H2Se气体、H2S气体、或Se蒸汽中。在该实施例中，暴露的相对简易性，能使铝衬底更好地耐受这些气体或蒸汽的存在，特别是在高加热水平上。
一旦初生吸收体层106已经退火，可以形成另外的层，完成装置100。例如，通常用作吸收体层的汇接配对的窗口层。举例说，汇接配对层可以包括硫化钙(CdS)、硫化锌(ZnS)、或硒化锌(ZnSe)，或它们两种或更多种的组合。这些材料的层，可以通过例如化学浴淀积、化学表面淀积、或喷涂热分解，到达约50nm至约100nm的厚度。此外，透明的电极，如导电氧化层，可以用溅射、汽相淀积、CVD、ALD、电化学原子层外延等等，在窗口层上形成。
本发明的实施例，通过对淀积或其他方法形成在铝衬底上的初生CIGS吸收体层的快速热处理，克服与现有技术有关的缺点。铝衬底比常规的衬底便宜且轻得多。因此，基于铝衬底的太阳能电池，当与常规的硅基太阳能电池相比时，能够使电力生产有每瓦更低的成本和短得多的能量偿还周期。此外，铝衬底能实现可弯曲的形状因子，该可弯曲的形状因子在太阳能电池制作过程中，允许高生产率的卷筒到卷筒印刷，并在太阳能模块及系统的安装中，允许更快更容易的安装过程。
本发明的实施例，能实现在铝衬底上制作轻而便宜的光生伏打装置。初生吸收体层106的迅速加热/快速热处理，能实现适当的退火和VIA族元素的掺入，不损害或破坏铝箔衬底102。平稳的温度范围远在铝熔点(约600℃)以下，避免损害或破坏铝箔衬底。铝箔衬底的使用，能够极大地降低在这种衬底上制成的光生伏打装置的材料费 用，如太阳能电池的材料费用，从而降低每瓦的成本。借助以卷筒到卷筒方式处理铝箔衬底，当衬底通过一系列淀积、退火、和其他处理阶段时，在该衬底上构建光生伏打装置各层，获得成规模的经济效果。
虽然上面完整地说明本发明的优选实施例，但能够使用各种各样的替代、修改、和等价物。因此。本发明的范围不应当参照以上说明确定，而应参照附上的权利要求书连同它们完整的等价范围确定。在权利要求书中，不定冠词“某一”或“某个”是指其后条目的一种或多种量值，除非另有明确记载。附上的权利要求书不应解释为包含意义加功能的限制，除非这种限制在给定的权利要求中用“意为”明显记载。

Claims (16)

1.一种形成光生伏打装置吸收体层的方法，包括如下步骤：
提供衬底、至少一个界面层和至少一个导电基本电极层，所述衬底包括至少一个导电铝箔衬底，所述至少一个导电基本电极层包括钼层，其中，所述界面层位于铝箔衬底和基本电极层之间，并且其中，所述界面层禁止在加热期间所述电极中的钼和所述衬底中的铝的相互扩散；
淀积包含纳米粒子的溶液基前体材料，以便在所述衬底上形成初生薄膜吸收体层，所述纳米粒子包括一种或多种IB族、IIIA族和可供选择的VIA族元素；
通过在离衬底表面1/8″到1″处使用辐射热来迅速加热涂覆有纳米粒子的衬底，以便以5℃/s和150℃/s之间的速率，从环境温度快速增加纳米粒子和衬底的温度，从而实现适当的退火和来自VIA族蒸汽环境的VIA族元素的掺入，而铝箔衬底不被衬底在滚筒到滚筒的处理中通过炉的连续处理所损害或破坏，并且不从铝箔衬底产生硒化氢。
2.按照权利要求1的方法，还包括：
从环境温度快速加热初生吸收体层和/或衬底到200℃和600℃之间的平稳温度范围；
在该平稳温度范围中，维持吸收体层和/或衬底2分钟和30分钟之间；和
降低吸收体层和/或衬底的温度。
3.按照权利要求2的方法，还包括在快速加热初生吸收体层和/或衬底之前或期间，把一种或多种VIA族元素掺进初生吸收体层中。
4.按照权利要求2的方法，其中的一种或多种VIA族元素包括硒。
5.按照权利要求2的方法，其中的一种或多种VIA族元素包括硫。
6.按照权利要求2的方法，其中使用一个或多个红外灯进行辐射加热。
7.按照权利要求2的方法，其中形成并快速加热初生吸收体层的步骤是当衬底通过滚筒到滚筒的处理时发生的。
8.按照权利要求2的方法，还包括在快速加热初生吸收体层和/或衬底之后，把一种或多种VIA族元素掺进初生吸收体层中。
9.按照权利要求1的方法，其中，该界面层还包括：铬、钒、钨、玻璃、和/或氧化物。
10.按照权利要求1的方法，其中的形成初生吸收体层包括在衬底上淀积包含IB族和IIIA族元素的油墨膜。
11.一种光生伏打装置，包括：
铝箔衬底；
至少一个界面层；
包括钼层的至少一个导电基本电极层；和
薄膜吸收体层，
其中，所述界面层位于铝箔衬底和基本电极层之间，并且其中，所述界面层禁止在加热期间所述电极中的钼和所述衬底中的铝的相互扩散，
其中，所述薄膜吸收体层是通过淀积包含纳米粒子的溶液基前体材料而在所述铝箔衬底上形成的，所述纳米粒子包括一种或多种IB族、IIIA族和可供选择的VIA族元素，
其中，通过在离衬底表面1/8″到1″处使用辐射热来迅速加热涂覆有纳米粒子的衬底，以便以5℃/s和150℃/s之间的速率，从环境温度快速增加纳米粒子和衬底的温度，从而实现适当的退火和来自VIA蒸汽环境的VIA族元素的掺入，而铝箔衬底不被衬底在滚筒到滚筒的处理中通过炉的连续处理所损害或破坏，并且不从铝箔衬底产生硒化氢。
12.一种形成光生伏打装置吸收体层的方法，包括如下步骤：
提供衬底、至少一个界面层和至少一个导电基本电极层，所述衬底包括至少一个金属化聚合物箔衬底，所述至少一个导电基本电极层包括钼层，其中，所述界面层位于金属化聚合物箔衬底和基本电极层之间，并且其中，所述界面层禁止在加热期间所述电极中的钼和所述衬底中的金属的相互扩散；
淀积包含纳米粒子的溶液基前体材料，以便在所述衬底上形成初生薄膜吸收体层，所述纳米粒子包括一种或多种IB族、IIIA族和可供选择的VIA族元素；
通过在离衬底表面1/8″到1″处使用辐射热来迅速加热涂覆有纳米粒子的衬底，以便以5℃/s和150℃/s之间的速率，从环境温度快速增加纳米粒子和衬底的温度，从而实现适当的退火和来自VIA蒸汽环境的VIA族元素的掺入，而金属化聚合物箔衬底不被衬底在滚筒到滚筒的处理中通过炉的连续处理所损害或破坏，并且不从金属化聚合物箔衬底产生硒化氢。
13.按照权利要求12的方法，其中的箔衬底，是选自如下一组的聚合物：聚酯、聚醚亚胺、聚醚砜、聚醚醚酮、聚酰亚胺和/或以上的组合。
14.按照权利要求13的方法，其中聚酯包括聚萘二甲酸乙二醇酯。
15.按照权利要求12的方法，其中用作聚合物箔衬底金属化的金属，是铝，或铝与一种或多种金属的合金。
16.一种光生伏打装置，包括：
金属化的聚合物箔衬底；
至少一个界面层；
包括钼层的至少一个导电基本电极层；和
薄膜吸收体层，
其中，所述界面层位于金属化聚合物箔衬底和基本电极层之间，并且其中，所述界面层禁止在加热期间所述电极中的钼和所述衬底中的金属的相互扩散，
其中，所述薄膜吸收体层是通过淀积包含纳米粒子的溶液基前体材料而在所述金属化的聚合物箔衬底上形成的，所述纳米粒子包括一种或多种IB族、IIIA族和可供选择的VIA族元素，
其中，通过在离衬底表面1/8″到1″处使用辐射热来迅速加热涂覆有纳米粒子的金属化的聚合物箔衬底，以便以5℃/s和150℃/s之间的速率，从环境温度快速增加纳米粒子和金属化的聚合物箔衬底的温度，从而实现适当的退火和来自VIA蒸汽环境的VIA族元素的掺入，而金属化的聚合物箔衬底不被衬底在滚筒到滚筒的处理中通过炉的连续处理所损害或破坏，并且不从金属化的聚合物箔衬底产生硒化氢。
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CN102136522A (zh) 2011-07-27
US20120329195A1 (en) 2012-12-27
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US20090305455A1 (en) 2009-12-10
ATE462200T1 (de) 2010-04-15
EP2348540B1 (en) 2013-02-13
CN101061588A (zh) 2007-10-24
ES2342091T3 (es) 2010-07-01
EP2348540A2 (en) 2011-07-27
ATE540428T1 (de) 2012-01-15
US20060060237A1 (en) 2006-03-23
EP2348540A3 (en) 2011-11-09
EP2230693B1 (en) 2012-01-04
DE602005020174D1 (de) 2010-05-06

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