CN107112377A - 用于薄膜太阳能电池的层结构和制造方法 - Google Patents

用于薄膜太阳能电池的层结构和制造方法 Download PDF

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CN107112377A
CN107112377A CN201580062144.2A CN201580062144A CN107112377A CN 107112377 A CN107112377 A CN 107112377A CN 201580062144 A CN201580062144 A CN 201580062144A CN 107112377 A CN107112377 A CN 107112377A
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罗兰·伍尔兹
迈克尔·颇瓦拉
菲利普·杰克逊
迪米特里奥斯·哈里斯科斯
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Baden Wurttemberg Solar Energy And Hydrogen Research Center
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Abstract

用于薄膜太阳能电池的层结构和制造方法。本发明涉及一种用于薄膜太阳能电池(1)的层结构，包括光伏吸收剂层(5)，所述光伏吸收剂层(5)至少在与光伏吸收剂层的表面(6)邻近的区域中掺杂有至少一种碱金属。本发明还涉及一种用于制造这种层结构的方法。根据本发明，所述层结构在光伏吸收剂层(5)的表面(6)上具有，设计成保护光伏吸收剂层免受腐蚀的氧化钝化层(8)。

Description

用于薄膜太阳能电池的层结构和制造方法
本发明涉及用于薄膜太阳能电池的层结构，所述层结构包括光伏吸收剂层，光伏吸收剂层至少在与光伏吸收剂层的表面邻近的区域中掺杂有至少一种碱金属。本发明还涉及用于制造这种层结构的方法。
通用的层结构和相关的制造方法从WO 2014/097112 A1而被公众所知。通常，将具有光伏吸收剂层的层结构整合到薄膜太阳能电池中。研究表明，碱金属掺杂可以有利地影响与光电活性相关的吸收剂层(其通常包含化合物半导体材料)的性质，并且可以使得薄膜太阳能电池的效率显著提高。然而，碱金属掺杂并不是没有一定的困难。具体来说，与相同构造的其他薄膜太阳能电池相比，一些这种类型的薄膜太阳能电池的填充因子可能显著降低并且因此效率也可能显著降低。
本发明解决的技术问题是提供一种具有改善的化学性能和物理性能的层结构以提高具有这种层结构的薄膜太阳能电池的效率，并且还提供一种制造这种层结构的方法。
本发明通过提供一种具有权利要求1所述的特征的层结构和一种具有权利要求9所述的特征的用于制造层结构的方法来解决这个问题。
本发明的层结构在光伏吸收剂层的表面上具有氧化钝化层，氧化钝化层设计成保护光伏吸收剂层免受腐蚀。
氧化钝化层包含具有氧化合物的材料或由具有氧化合物的材料组成。氧化钝化层可设置在表面上和/或可内置在到光伏吸收剂层中的表面上。内置可意味着可以在表面上使光伏吸收剂层转化。氧化钝化层无间隙地覆盖光伏吸收剂层；氧化钝化层不中断。除了与掺杂区域邻近的表面之外，光伏吸收剂层可具有例如与导电的背接触件层相对的界面。
通常，通过掺杂引入的碱金属使得吸收剂层材料在环境条件下、至少在表面处的区域中更易受化学腐蚀，特别是在吸收剂层包含化合物半导体材料的情况下。这种腐蚀对薄膜太阳能电池的光电性能造成不利影响。因为作为由于与大气氧交换电子的氧化还原事件的结果或作为由于与环境空气中的水分相互作用的水解过程的结果的腐蚀可能在光伏吸收剂层的表面处出现材料缺陷，伴随着三维分布的单独氧化物的形成。这些材料缺陷导致光诱导载流子的复合增加。三维分布的氧化物不具有钝化作用。它们也不会保护光伏吸收剂层免受进一步的腐蚀，特别是在表面下方的光伏吸收剂层的体积中，例如沿着多晶吸收剂层结构的晶界。
通常，作为常规CdS缓冲层(硫化镉CdS)的可选方案，在薄膜太阳能电池的进一步处理期间，将至少一个含氧缓冲层施加到光伏吸收剂层。通常，缓冲层包含氧化材料(例如，氧化锌ZnO、氧化锌镁ZnMgO)和/或氧代硫化材料(例如，氧代硫化锌Zn(O、S))或者由这些材料中的至少一种组成。这些纯的或部分氧化的材料或施加的含氧缓冲层不能提供具有充分防腐蚀保护的光伏吸收剂层。
本发明的氧化钝化层允许有效保护包含碱金属掺杂的光伏吸收剂层免受腐蚀，并且与所述光伏吸收剂层联合以免形成电活性杂质，特别是在封装薄膜太阳能电池之前的进一步的层结构和/或薄膜太阳能电池处理期间和/或在较长时间内未完全密封封装的情况下。防腐蚀保护至少包括腐蚀过程在时间上的延迟。此外，氧化钝化层允许减少或防止光诱导的载流子在光伏吸收剂层的表面上的复合。更具体地，氧化钝化层可以设计成防止在光伏吸收剂层的表面或界面处的光电流损失。换句话说，氧化钝化层可设计成使不饱和键(被称为“悬空键”)饱和，具体地通过形成氧化合物，以防止在表面或界面处形成正电荷和/或避免表面处的电活动。通过这种方式，可以利用碱金属掺杂的优点，并且避免了其缺点，使得由此生成的薄膜太阳能电池的效率特别高并且理论上在薄膜太阳能电池的整个寿命期间都保持为高的。
此外，可以通过氧化钝化层来促进例如由CdS、Zn(O、S)或In2S3构成的缓冲层的应用，从而使得可以提高缓冲层的质量，并且从而降低缓冲层厚度。此外，对于光伏吸收剂层与缓冲层之间的界面区域中的原子/离子扩散，氧化钝化层可以充当弱扩散屏障。
在本发明的开发中，光伏吸收剂层包括黄铜矿材料(并且具体地Cu(In1-xGax)Se1- ySy)2(铜Cu、铟In、镓Ga、硒Se、硫S)(其中0≤x、y≤1))和/或包括硫铜锡锌矿材料(例如Cu2ZnSn(Se1-xSx)4(锡Sn)(其中0≤x≤1))或者由这些材料中的至少一种组成。这些化合物半导体材料具有几个eV(电子伏特)的直接电带隙。此外，它们可以有效地掺杂有碱金属。因此，它们理想地应用到薄膜太阳能电池中。
由于固有缺陷，化合物半导体层通常为轻度p-掺杂的。通常，薄膜太阳能电池中的p-n反转部通过将重度n-掺杂Al(铝)的ZnO层施加到至少一个上述缓冲层来获得。通过p-n反转部，在薄膜太阳能电池的各层上生成电场，并且由此，由光子吸收生成的电子-空穴对可在空间上分离。在本发明的开发中，与光伏吸收剂层的表面邻近的区域以为了呈现p-n反转部的方式进行掺杂。这可以通过在整个掺杂区域中、具有较高掺杂的适当掺杂分布来实现。因此，在光伏吸收剂层中生成的电子-空穴对可以更有效地分离。更具体地，可以减少电子-空穴对的复合。因此，可以实现对薄膜太阳能电池的效率的提高。有利地，光伏吸收剂层可在表面上为n-掺杂的。
迄今用于掺杂光伏吸收剂层的碱金属是钠(Na)和钾(K)。Na通常不会在表面处的区域中实现p-n反转部。用K来提高薄膜太阳能电池的效率是不稳定的；换句话说，这种高效率的薄膜太阳能电池的重现性较低。在本发明的一种开发中，所述至少一种碱金属是铷Rb和/或铯Cs。这些碱金属可以被固定在光伏吸收剂层的表面上，从而使得可以在光伏吸收剂层的表面上的区域中实现p-n反转部。出人意料地，结果显示，具有这些特定碱金属的薄膜太阳能电池的效率可以显著提高，并且提高的效率的重现性得以改善。
在本发明的开发中，氧化钝化层包含(In、Ga)2O3、Mx(In、Ga)yOz(氧O)(其中M＝K、Rb、Cs并且其中0<x、y、z)和/或氧化铝Al2O3，或者由这些材料中的至少一种组成。可选地或另外，氧化钝化层可以包含ZnO和/或SnOx(其中x＝1至2)和/或这两种材料的混合物，或者可以由这些材料中的至少一种组成，并且碱金属部分也可能由于从表面或界面的扩散而存在。换句话说，所述材料在每种情况下都不能以掺杂量浓度存在，而是以化学计量的量存在。对于由黄铜矿材料构成或包含黄铜矿材料的光伏吸收剂层，可以由光伏吸收剂层和氧生成或生长具有例如(In、Ga)2O3、Mx(In、Ga)yOz的氧化钝化层；在这种情况下，可以使光伏吸收剂层的表面转化。对于由硫铜锡锌矿材料组成或包含硫铜锡锌矿材料的光伏吸收剂层，可以由光伏吸收剂层和氧生长或生成具有例如ZnO、SnOx的氧化钝化层；在这种情况下，可以使光伏吸收剂层的表面转化。另外或可选地，可以通过将Al2O3施加到光伏吸收剂层来生成具有Al2O3的氧化钝化层。具体地，Al2O3不仅可以保护Al层而且可以保护其他材料层免受腐蚀。
在本发明的开发中，氧化钝化层的厚度在1nm至50nm(纳米)的范围内，优选在3nm至5nm的范围内。通过这种方式，一方面可以实现有效地保护光伏吸收剂层免受腐蚀。另一方面，仍然可以确保从光伏吸收剂层通过氧化钝化层并且到任选的缓冲层和/或前接触件层的有效电输送。在氧化钝化层由光伏吸收剂层和氧生成或生长的情况下，这种生成或生长通过存在至少一种碱金属来促进，优选地通过存在Rb和/或Cs来促进，并且因此可以在不破坏光伏吸收剂层的其余部分的情况下实现所述范围内的厚度。相反，在不具有碱金属掺杂的光伏吸收剂层的情况下，由这个层和氧生长具有高于亚单层范围的厚度的氧化物层甚至是根本不可能的，或者如果通过高温和长的生长周期强制进行，将对光伏吸收剂层造成损害，在这种情况下氧化物层不一致并且也没有钝化作用。损害光伏吸收剂层意味着光伏吸收剂层失去其半导体性能，并且因此不能再用于薄膜太阳能电池。
在本发明的用于制造本发明的层结构的方法中，在步骤a中，在基底上生成光伏吸收剂层，所述光伏吸收剂层至少在与光伏吸收剂层的表面邻近的区域中掺杂有至少一种碱金属。此外，同时或此后，在步骤b中，在光伏吸收剂层的表面上形成氧化钝化层，具体地使得其保护光伏吸收剂层免受腐蚀，并且与所述光伏吸收剂层联合以免形成电活性杂质。优选地，步骤b可以包括将表面上的氧化钝化层内置于光伏吸收剂层中，为此可以使光伏吸收剂层在表面上转化。步骤b也可以紧跟步骤a之后，即它们之间不存在步骤。
步骤a可以包括：在已经添加有至少一种碱金属的基底上生长光伏吸收剂层；以及在较高的温度下将至少一种碱金属从基底扩散到光伏吸收剂层中。可选地或另外，步骤a以包括：将碱金属氟化物前体施加到基底；在基底上生长光伏吸收剂层；以及在较高的温度下将至少一种碱金属从碱金属氟化物前体扩散到光伏吸收剂层中。
在本发明的开发中，步骤a包括：作为子步骤ax，生成光伏吸收剂层；以及作为子步骤az，至少在与光伏吸收剂层的表面邻近的区域中，使光伏吸收剂层掺杂有至少一种碱金属。子步骤az可以与子步骤ax同时开始，或者可以在其之后或之前或者在子步骤ax已经完全结束时开始。此外，子步骤az可以与子步骤ax同时完成或在其之后完成。所述至少一种碱金属可以通过碱金属氟化物(例如RbF和/或CsF)和/或其他碱金属化合物来提供，其他碱金属化合物例如为碱金属氧化物、碱金属碳酸盐、碱金属硒化物和/或其他碱金属卤化物(例如RbCl、CsCl、RbBr、CsBr、RbI和/或CsI)。通过这种方法，能够具体地利用Rb和/或Cs在与光伏吸收剂层的表面邻近的区域中生成p-n反转部。
在本发明的实施方式中，所述方法可以包括将至少一种碱金属施加到光伏吸收剂层的表面的步骤。步骤ax可以在该步骤之前完全结束，之后该步骤可称为后沉积处理(PDT)。可以在Se气氛和/或S气氛下将碱金属以例如碱金属氟化物和/或另一种碱金属化合物的形式通过气相沉积施加到光伏吸收剂的表面。与此同时或此后，步骤az可以通过使至少一种碱金属至少扩散到与光伏吸收剂层的表面邻近的区域中的形式来执行，更具体地并且在一些情况下强制地在Se气氛和/或S气氛下执行。在这种情况下，光伏吸收剂层可以被加热到至少350℃。在碱金属氟化物的情况下，在Se气氛和/或S气氛下的气相沉积和扩散期间，氟可在光伏吸收剂层外部进入与Se和/或S的化学键中，使得只有碱金属而不是F能够扩散到光伏吸收剂层中。对于其他碱金属化合物，可能采取类似的机理。
在本发明的开发中，步骤b包括在相对于室温升高的温度下、在含氧的气氛中掺杂碱金属的吸收剂层退火。在由黄铜矿组成或包含黄铜矿的光伏吸收剂层的情况中，具体地以这种方式可以生成或生长具有(In、Ga)2O3、Mx(In、Ga)yOz的氧化钝化层；在这种情况中，可以使光伏吸收剂层的表面转化。更具体地，在由硫铜锡锌矿材料组成或包含硫铜锡锌矿材料的光伏吸收剂层的情况中，通过这种方式可以生成或生长具有ZnO、SnO2的氧化钝化层；在这种情况下，可以使光伏吸收剂层的表面转化。由于在表面或界面处的扩散过程，ZnO/SnOx混合氧化物层也可包含碱金属。退火过程的温度相对于室温增加至少80开尔文。优选地可以在不低于约120℃下执行退火，更具体地在从120℃至250℃的范围内执行退火。退火可持续至少1分钟，最长可达30分钟。可以在至少为10-1毫巴的氧分压下执行退火，优选在从1毫巴至环境空气中氧分压的范围内的氧分压下执行退火。
在本发明的开发中，步骤b包括将氧化物施加到具有碱金属掺杂的光伏吸收剂层的表面。更具体地，氧化物可以包含Al2O3。
在本发明的开发中，所述方法包括将具有例如CdS、Zn(O、S)或In2S3的缓冲层施加到氧化钝化层的步骤。
本发明的有利实施方式在附图中示出并且在下文进行描述。在这些附图中：
图1示出穿过薄膜太阳能电池的示意性剖视图，以及
图2示出用于制造图1的薄膜太阳能电池的方法的流程图。
图1示出根据有利实施方式的穿过薄膜太阳能电池1的示意性剖视图。图2在流程图中示出了薄膜太阳能电池1的示例性制造方法中的本文关注的必要步骤。在第一步骤I中，提供例如由玻璃制成的基底2。在第二步骤II中，例如，旨在用作薄膜太阳能电池1的背接触件的Mo层3(钼)在减压下通过阴极溅射施加到玻璃基底2上，厚度为约500nm。
此后，在共蒸发过程(步骤III，ax)中，例如，在玻璃基底2的温度为约600℃下通过气相沉积施加元素Cu、In、Ga和Se。通过这种方式，例如，由化合物半导体材料Cu(In、Ga)Se2(CIGS)组成的光伏吸收剂层5在Mo层3上生长，厚度为2μm至3μm(微米)。在这个时间点上，由于CIGS材料中的固有缺陷，并且由于可能外在地掺杂有来自玻璃基底的钠和钾(如果玻璃基底存在钠和钾)，光伏吸收剂层5各处均为轻度p-掺杂的。
在已经生成光伏吸收剂层5之后，RbF和/或CsF在减压下通过气相沉积从在至少约400℃的坩埚温度下的气化坩埚施加到光伏吸收剂层5的表面6上(步骤IV)。在玻璃基底2的约为至少350℃的轻度升高的温度下，至少一种碱金属扩散到光伏吸收剂层5中(步骤V，az)。在这种方法中，Rb和/或Cs原子/离子由于其较大的离子半径而将来自表面6的Cu原子在钼层3的方向上不可逆地移动到光伏吸收剂层5的体积中。由于这种交换，在光伏吸收剂层5中，在表面附近出现最大的碱金属浓度。这在表面6附近的光伏吸收剂层5中导致p-n反转部9。Rb或Cs渗透到光伏吸收剂层5的体积中，优选地沿着CIGS材料中的晶界直到钼层3，如果钼层3中存在钠和钾，则其在所述钼层3中可以部分地置换钠和钾。在这种情况下，步骤IV和V是PDT过程。在可选的实施方式中，可以在Se气氛和/或S气氛下通过气相沉积来施加RbF和/或CsF。可选地或另外，至少一种碱金属可以在Se气氛和/或S气氛下扩散到光伏吸收剂层中。
此后，例如，通过使目前生成的层结构在约200℃的环境空气中退火，在光伏吸收剂层5的表面6上生成氧化钝化层8(步骤VI，b)。在这种方法中，表面6上的氧内置到掺杂碱金属的CIGS材料中；光伏吸收剂层5在表面6上被转化。在这种情况下，氧化钝化层8例如包括材料(In、Ga)2O3和Mx(In、Ga)yOz，其中，M＝Rb和/或Cs，并且其中0<x、y、z。氧化钝化层8以例如约3nm至5nm的厚度D向下延伸到图1中的光伏吸收剂层5中。氧化钝化层8保护光伏吸收剂层5的主要剩余部分免受腐蚀，特别是在薄膜太阳能电池1的进一步生产期间。
随后，在化学浴沉积中，在光伏吸收剂层5和/或氧化钝化层8的表面6上沉积或生长约30nm至50nm厚的CdS缓冲层10(步骤VII)。由于吸收剂层5的表面极性发生变化，所以氧化钝化层8促进了CdS缓冲层10的生长，并且提高了其质量。
接下来，通过在真空下溅射形成约50nm至100nm厚的未掺杂的i-ZnO层11(步骤VIII)以及约150nm至250nm厚的重度n掺杂铝的ZnO:Al层12(步骤IX)。CdS缓冲层10和i-ZnO层11确保光伏吸收剂层5的CIGS材料与ZnO:Al层12之间的带匹配。ZnO:Al层12是透明且导电的，并且旨在用作薄膜太阳能电池1的前接触件。
大约几μm厚的Ni-Al-Ni栅格结构13(镍Ni)(步骤X)和MgF的抗反射层14(步骤XI)施加至ZnO:Al层12。
在如上所述制造的薄膜太阳能电池1上可测量到高达21.7％的效率。
在所示的实施方式中，光伏吸收剂层包括CIGS材料。另外或可选地，光伏吸收剂层可以包含其他化合物半导体材料或者可以由它们组成，更具体地Cu(In1-xGax)(Se1-ySy)2和/或Cu2ZnSn(Se1-xSx)4，这些材料可以通过所述元素的共蒸发或通过将前驱层硒化/硫化到涂覆有Mo的基底(例如玻璃、金属、陶瓷、塑料)上来制造。
此外，光伏吸收剂层不需要完全掺杂或具有p-n反转部；与光伏吸收剂层的表面邻近的至少一个区域掺杂有至少一种碱金属。此外，可以通过其他常规方法而不是上述PDT过程在与光伏吸收剂层的表面邻近的至少一个区域中生成光伏吸收剂层与至少一种碱金属的掺杂。
此外，作为RbF和/或CsF的可替代方案或除它们之外，可以通过不同的碱金属氟化物和/或不同的碱金属化合物来提供至少一种碱金属，例如碱金属氧化物、碱金属碳酸盐、碱金属硒化物和/或其他碱金属卤化物(例如RbCl、CsCl、RbBr、CsBr、RbI和/或CsI)。
作为材料(In、Ga)2O3和Mx(In、Ga)yOz(其中M＝Rb和/或Cs)的可替代方案或除它们之外，氧化钝化层可以包含材料Al2O3或可由材料Al2O3组成，并且Al2O3可以施加到光伏吸收剂层的表面。此外，可选地或另外，特别是对于由硫铜锡锌矿材料组成或包含硫铜锡锌矿材料的光伏吸收剂层，氧化钝化层可以包含ZnO和/或SnOx(其中x＝1至2)和/或两种材料的混合物，或者可以由这些材料中的至少一种组成，在这种情况下，由于从表面或界面的扩散也可能存在碱金属部分。
作为CdS的可选方案或除其之外，施加到氧化钝化层的缓冲层可以包含不同材料或由不同材料组成，更具体地Zn(O、S)和/或In2S3，这些材料可以通过化学浴沉积或通过气相过程沉积。
作为i-ZnO材料的替代方案或除其之外，施加到CdS缓冲层的层可以包含i-Zn1- xMgxO(其中0≤x≤0.4)，或者可以由这种材料组成，所述材料可以与i-ZnO类似地通过阴极溅射来施加。
例如，通过优化钝化氧化物层的厚度和光电性能(材料的组合、掺杂、带隙等)，它不仅可以满足化学需求(例如，保护光伏吸收剂层免受腐蚀)，而且还可以进一步满足物理要求，诸如光伏吸收剂层的材料与前接触件的层之间的带匹配。因此，可以省略随后的缓冲层和/或i-ZnO和/或ZnMgO层。已经对常规的CIGS太阳能电池进行了多次说明，其中，基于优化CdS和/或Zn(O、S)缓冲层的厚度和沉积过程，可以省略随后的i-ZnO和/或i-ZnMgO层。
根据所示出的实施方式和以上说明的那些可以清楚地看出，本发明提供了用于薄膜太阳能电池的有利层结构，其包括位于光伏吸收剂层的表面上的氧化钝化层，所述氧化钝化层设计成保护光伏吸收剂层免受腐蚀，从而允许提高薄膜太阳能电池的效率。

Claims (15)

1.一种用于薄膜太阳能电池的层结构，包括
光伏吸收剂层(5)，所述光伏吸收剂层(5)至少在与所述光伏吸收剂层的表面(6)邻近的区域中掺杂有至少一种碱金属，
其特征在于
位于所述光伏吸收剂层(5)的所述表面(6)上的氧化钝化层(8)，所述氧化钝化层设计成保护所述光伏吸收剂层免受腐蚀。
2.如权利要求1所述的层结构，其特征在于，所述表面(6)上的所述氧化钝化层(8)内置于所述光伏吸收剂层(5)中，所述光伏吸收剂层在所述表面上被转化。
3.如权利要求1或2所述的层结构，其特征在于，所述光伏吸收剂层(5)包含：Cu(In1- xGax)(Se1-ySy)2，其中0≤x，y≤1；和/或Cu2ZnSn(Se1-xSx)4，其中0≤x≤1。
4.如权利要求1至3中任一项所述的层结构，其特征在于，与所述光伏吸收剂层(5)的所述表面(6)邻近的所述区域被掺杂以使得其呈现p-n反转部(9)。
5.如权利要求1至4中任一项所述的层结构，其特征在于，所述至少一种碱金属是铷和/或铯。
6.如权利要求1至5中任一项所述的层结构，其特征在于，所述氧化钝化层(8)包含：(In,Ga)2O3、Mx(In,Ga)yOz，其中M＝K、Rb、Cs并且其中0<x、y、z；和/或Al2O3；和/或ZnO、SnOx，其中x＝1至2。
7.如权利要求1至6中任一项所述的层结构，其特征在于，所述氧化钝化层(8)的厚度(D)在从1nm至50nm的范围内。
8.如权利要求1至7中任一项所述的层结构，其特征在于，所述氧化钝化层(8)承载施加的缓冲层(10)。
9.一种用于制造如权利要求1至8中任一项所述的用于薄膜太阳能电池的层结构的方法，包括以下步骤：
a.在基底上生成光伏吸收剂层(5)，所述光伏吸收剂层(5)至少在与所述光伏吸收剂层的表面(6)邻近的区域中掺杂有至少一种碱金属，以及
b.在所述光伏吸收剂层的所述表面上生成氧化钝化层(8)，所述氧化钝化层设计成保护所述光伏吸收剂层免受腐蚀。
10.如权利要求9所述的方法，其特征在于，步骤b包括将所述表面(6)上的所述氧化钝化层(8)内置于所述光伏吸收剂层(5)中，为此在所述表面上转化所述光伏吸收剂层(5)。
11.如权利要求9或10所述的方法，其特征在于，步骤a包括以下子步骤：
ax.生成所述光伏吸收剂层(5)，以及
az.至少在与所述光伏吸收剂层的所述表面(6)邻近的所述区域中使所述光伏吸收剂层掺杂有所述至少一种碱金属。
12.如权利要求11所述的方法，其特征在于将所述至少一种碱金属施加到所述光伏吸收剂层(5)的所述表面(6)的步骤，所述步骤az包括优选地在Se气氛和/或S气氛下使所述至少一种碱金属向内扩散到与所述光伏吸收剂层的所述表面邻近的所述区域中。
13.如权利要求9至12中任一项所述的方法，其特征在于，步骤b包括在相对于室温升高的温度下、在含氧的气氛中使具有碱金属掺杂的所述光伏吸收剂层(5)退火，优选地所述氧化钝化层(8)由所述光伏吸收剂层和氧生成。
14.如权利要求9至13中任一项所述的方法，其特征在于，步骤b包括将氧化物施加到具有碱金属掺杂的所述光伏吸收剂层(5)的所述表面(6)。
15.如权利要求9至14中任一项所述的方法，其特征在于将缓冲层(10)施加到所述氧化钝化层(8)的步骤。
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