CN104981890A - Cigs膜以及使用其的cigs太阳能电池 - Google Patents

Cigs膜以及使用其的cigs太阳能电池 Download PDF

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CN104981890A
CN104981890A CN201480008053.6A CN201480008053A CN104981890A CN 104981890 A CN104981890 A CN 104981890A CN 201480008053 A CN201480008053 A CN 201480008053A CN 104981890 A CN104981890 A CN 104981890A
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寺地诚喜
西井洸人
渡边太一
山本祐辅
河村和典
峯元高志
贾卡潘·柴塔那
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Nitto Denko Corp
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Abstract

本发明提供能够抑制表面的氧化的CIGS膜以及使用该CIGS膜来抑制转换效率的降低和偏差的CIGS太阳能电池。用作该CIGS太阳能电池的光吸收层的CIGS膜具有：第1区域，随着从其背面至规定的第1厚度位置为止变厚Ga/(In+Ga)比逐渐减少；第2区域，随着从该第1区域上至规定的第1厚度位置为止变厚上述Ga/(In+Ga)比逐渐增加；进而，在上述第2区域上具有向着表面上述Ga/(In+Ga)比逐渐减少的第3区域。

Description

CIGS膜以及使用其的CIGS太阳能电池
技术领域
本发明涉及膜内的Ga/(In+Ga)比沿着厚度方向变化的CIGS膜以及将其用作光吸收层的CIGS太阳能电池。
背景技术
以非晶硅太阳能电池、化合物薄膜太阳能电池为代表的薄膜型太阳能电池与以往的晶体硅太阳能电池相比，可以大幅削减材料成本、制造成本。因此，近年来正迅速推进对它们的研究开发。其中，为以I族、III族、VI族的元素作为构成物质的化合物薄膜太阳能电池且使用由铜(Cu)、铟(In)、镓(Ga)、硒(Se)合金形成的CIGS膜作为光吸收层的CIGS太阳能电池由于完全不使用硅而且具有优异的太阳光转换效率(以下称为“转换效率”)，因此在薄膜太阳能电池中尤其受到瞩目。
上述CIGS太阳能电池通常如图8所示，是将基板81、背面电极层82、上述CIGS膜83、缓冲层84、以及透明导电层85依次层叠而成的。
作为这样的CIGS太阳能电池中的上述CIGS膜(光吸收层)83的制造方法，有能够得到高转换效率的、被称为3阶段法的方法。该方法在上述基板81的表面形成上述背面电极层82之后，工序分为3个阶段。即，在第1阶段中，在上述背面电极层82的表面蒸镀In、Ga、Se，形成(In,Ga)2Se3膜。接着，在第2阶段中，使上述基板81的温度上升至550℃，进一步蒸镀Cu、Se，形成Cu过量组成的CIGS膜中间体。对于该阶段的CIGS膜中间体而言，液相Cu(2-x)Se和固相CIGS这2相共存，由于Cu(2-x)Se而引起晶体的急剧的大粒化。已知由于该Cu(2-x)Se为低电阻，因此对太阳能电池特性带来不良影响。于是，在第3阶段中，为了减少上述Cu(2-x)Se，进一步蒸镀In、Ga、Se，作为CIGS膜83整体，使III族变为稍微过量的组成。对于由这样的3阶段法得到的CIGS膜83，晶体变为大粒径，而且可以成为在晶体学上高品质的薄膜晶体组织(例如，参照专利文献1。)。
对于如上述那样制造的CIGS膜83，如图9所示，从背面(与上述背面电极层82的界面)至规定的厚度位置83a(参照图8)为止，膜内的下述(A)的Ga/(In+Ga)比随着变厚而逐渐减少且从其上向着表面逐渐增加的呈V字状(双梯度结构)。将这样结构的CIGS膜83用于光吸收层的CIGS用作光吸收层的CIGS太阳能电池(参照图8)能够提高转换效率。(A)Ga/(In+Ga)比为镓(Ga)的原子数浓度相对于铟(In)的原子数浓度和该镓(Ga)的原子数浓度之和的比。
现有技术文献
专利文献
专利文献1：日本特表平10-513606号公报
发明内容
发明要解决的问题
然而，即使是上述CIGS太阳能电池，也存在转换效率非常低、转换效率的偏差大的情况。
于是，本发明人等为了查明其原因反复进行了研究。其结果，得知其原因在于上述CIGS膜83的表面(与缓冲层84的接触面)的氧化。即，对于上述双梯度结构的CIGS膜83，如上所述，表面侧的Ga/(In+Ga)比从规定的厚度位置83a向着表面逐渐增加，因此表面的Ga的比例变高。该Ga比In容易氧化，因此上述CIGS膜83的表面暴露于空气(氧气)的时间越长，Ga的氧化越加剧。而且，得知若在该Ga氧化了的状态下，在上述CIGS膜83的表面形成缓冲层84、透明导电膜85而制造CIGS太阳能电池时，该CIGS太阳能电池的转换效率大大降低，转换效率的偏差也变大。
本发明鉴于这样的情况而完成的，其目的在于，提供能够抑制表面的氧化的CIGS膜、以及使用该CIGS膜来抑制转换效率的降低和偏差的CIGS太阳能电池。
用于解决问题的方案
为了达到上述目的，本发明的第1要点在于，一种CIGS膜，其用作CIGS太阳能电池的光吸收层，且具有：第1区域，随着从其背面至规定的厚度为止变厚下述(A)Ga/(In+Ga)比逐渐减少；以及第2区域，位于该第1区域上，上述Ga/(In+Ga)比向着表面侧逐渐增加；其中，在上述第2区域上形成有向着表面上述Ga/(In+Ga)比逐渐减少的第3区域。
(A)Ga/(In+Ga)比为镓(Ga)的原子数浓度相对于铟(In)的原子数浓度和该镓(Ga)的原子数浓度之和的比。
另外，本发明的第2要点在于，一种CIGS太阳能电池，其为依次层叠有基板、背面电极、光吸收层、缓冲层、以及透明导电膜的CIGS太阳能电池，其中，上述光吸收层为上述CIGS膜，该CIGS膜的背面为位于上述背面电极层侧的面。
需要说明的是，本发明中，原子数浓度例如可以使用能量色散荧光X射线分析装置(堀场制作所制造，EX-250)或者D-SIMS(dynamic SIMS)评价装置(available from Ulvac-Phi,Inc.公司制造)等来测定。
发明的效果
对于本发明的CIGS膜，形成于表面侧的第3区域的Ga/(In+Ga)比，随着从其下的第2区域上向着表面而逐渐减少，因此易氧化的Ga的比例在表面侧减少。因此，即使该表面侧暴露于空气(氧气)的时间变长，也能够抑制氧化。而且，若将该CIGS膜作为光吸收层用于CIGS太阳能电池时，能够抑制该CIGS太阳能电池中的转换效率的降低和偏差。
尤其，在上述第2区域的Ga/(In+Ga)比的峰值在0.3～0.6的范围内、上述第3区域的Ga/(In+Ga)比的减少值在0.02～0.3的范围内的情况下，在能够较高地维持该CIGS膜作为光吸收层用于CIGS太阳能电池时的转换效率、并且能够使该转换效率的偏差变小的状态下，抑制CIGS膜的表面侧的氧化。
另外，在上述第3区域的厚度在30～200nm的范围内的情况下，在取得上述转换效率的降低和偏差的抑制和平衡的状态下，使表面侧的氧化的抑制更优化。
而且，本发明的CIGS太阳能电池将如上所述的本发明的CIGS膜用作光吸收层，该CIGS膜的背面为位于背面电极层侧的面。因此，本发明的CIGS太阳能电池在抑制上述CIGS膜的表面侧的氧化的状态下，在该表面上层叠有缓冲层，由此能够有效地抑制转换效率的降低和偏差。
附图说明
图1是示意性地示出本发明的CIGS太阳能电池的一个实施方式的截面图。
图2是示意性地示出本发明的CIGS膜的一个实施方式的厚度方向的Ga/(In+Ga)比的变化的图表。
图3的(a)～(d)是示意性地示出上述太阳能电池的制法的说明图。
图4的(a)～(b)是示意性地示出继图3之后的上述太阳能电池制法的的说明图。
图5的(a)～(b)是示意性地示出继图4之后的上述太阳能电池的制法的说明图。
图6的(a)～(b)是示意性地示出继图5之后的上述太阳能电池的制法的说明图。
图7的(a)～(b)是示意性地示出继图6之后的上述太阳能电池的制法的说明图。
图8是示意性地示出以往的CIGS太阳能电池的截面图。
图9是示意性地示出以往的CIGS膜的厚度方向的Ga/(In+Ga)比的变化的图表。
具体实施方式
接下来，根据附图对本发明的实施方式详细说明。
图1是示意性地示出将本发明的CIGS膜的一个实施方式用作光吸收层的、本发明的CIGS太阳能电池的一个实施方式的截面图。该实施方式的CIGS太阳能电池是将基板1、背面电极层2、CIGS膜3、缓冲层4、以及透明导电膜5依次层叠而构成的。而且，如图2所示，在从位于上述背面电极层2侧的上述CIGS膜3的背面至规定的第1厚度位置3a(参照图1)为止的第1区域31中，上述CIGS膜3中的Ga/(In+Ga)比随着变厚而逐渐减少，在从该第1区域31上至规定的第2厚度位置3b(参照图1)为止的第2区域32中，该比随着变厚(向着表面侧)而逐渐增加，在从该第2区域32上至表面为止的第3区域33中，该比随着变厚(向着表面)而逐渐减少。像这样，本发明的一大特征在于，在CIGS膜3的表面侧形成将易氧化的Ga的比例减少的第3区域33，由此能够抑制CIGS膜3的表面侧的氧化。
上述CIGS太阳能电池可以用如下所述的制法来制造。
首先，准备上述基板1[参照图3的(a)]。该基板1是作为支承基板而使用的，为了耐受之后的加热工序中的加热，可以使用对520℃以上的温度具有耐性的材料。作为这样的材料，例如可以举出钠钙玻璃(SLG)、SUS、钛等，其中，从操作性的观点出发，优选铁氧体系SUS430。
接着，如图3的(a)所示，在上述基板1的表面，利用溅射法形成上述背面电极层2。作为该背面电极层2的形成材料，例如可以举出钼、钨、铬、钛等。上述背面电极层2可以为单层，也可以为多层。而且，其厚度优选在100nm～1000nm的范围内。
接着，为了在上述背面电极层2的表面形成上述CIGS膜3的第1区域31(参照图1)，首先，如图3的(b)所示，在上述背面电极层2的表面利用蒸镀法形成硒化镓膜31A，然后利用蒸镀法在该硒化镓膜31A的表面形成硒化铟膜31B。接着，如图3的(c)所示，在该硒化铟膜31B的表面，与上述同样地操作，蒸镀形成硒化镓膜31A，然后在该硒化镓膜31A的表面蒸镀形成硒化铟膜31B。反复进行该操作，如图3的(d)所示，将包括下层的硒化镓膜31A以及其上层的硒化铟膜31B的层叠组310层叠一组至多组(图中为3组)。
此时，如先前所述，为了实现所形成的第1区域31的Ga/(In+Ga)比随着第1区域31变厚而逐渐减少，设定上述层叠组310中的硒化镓膜31A的厚度(Y)与硒化铟膜31B的厚度(X)的膜厚比(Y/X)。对于其设定，在本实施方式中，通过使硒化铟膜31B的厚度(X)恒定并在每次重复层叠时使硒化镓膜31A的厚度(Y)变薄，由此将上述膜厚比(Y/X)设定成每次重复层叠时变小。上述厚度的设定，例如可以通过Ga等的蒸镀源的温度控制(升高温度时变厚，降低时变薄)、蒸镀源的开口直径的尺寸控制(增大开口直径时变厚，减小时变薄)等来进行。需要说明的是，从使所形成的第1区域31的Ga/(In+Ga)比更优化的观点出发，对于上述膜厚比(Y/X)，优选将最初的层叠组310设定为0.5～1.3的范围内的值、将最后的层叠组310设定为小于其的0.2～0.5的范围内的值。
然后，如图4的(a)所示，在将最后的层叠组310层叠之后，为了晶体生长，在该层叠组310的上层的硒化铟膜31B的表面蒸镀Cu和Se，形成蒸镀层(硒化铜)31C。如此操作，制造包含多个上述层叠组310和1层上述蒸镀层31C的层叠体α。在该层叠体α的形成工序中，上述基板1的保持温度优选设定为251～400℃的范围内，更优选设定为290～360℃的范围内。这是因为，若基板1的保持温度超过400℃，则在形成上述蒸镀层31C时，变得容易产生向该蒸镀层31C内的扩散，在接下来的工序中不引起均匀的晶体生长，而且从上述多组层叠组310发生Se的再蒸发，存在使晶体品质降低的倾向。
其后，如图4的(b)所示，将上述层叠体α在520℃以上进行加热，使晶体生长，形成上述CIGS膜3的第1区域31。即，通过上述加热，使上述蒸镀层(硒化铜)31C液相化，该Cu均匀地扩散到上述层叠体α的整体，引起晶体生长。因此，所形成的第1区域31变得比上述层叠体α厚。如此操作，形成的上述第1区域31中，Ga/(In+Ga)比从背面起随着变厚而逐渐减少(参照图2)。
接着，如图5的(a)所示，为了在上述第1区域31的表面形成上述CIGS膜3的第2区域32(参照图1)，在维持上述520℃以上的温度的状态下，在上述第1区域31上，将包含下层的硒化镓膜32A以及其上层的硒化铟膜32B的层叠组320与上述同样地操作[参照图3的(b)～(d)]层叠一组至多组(图中为2组)。
此时，如先前所述，为了实现所形成的第2区域32的Ga/(In+Ga)比从上述第1区域31上向着表面侧逐渐增加，设定上述层叠组320中的硒化镓膜32A的厚度(Y)与硒化铟膜32B的厚度(X)的膜厚比(Y/X)。对于其设定，在本实施方式中，通过使硒化铟膜32B的厚度(X)恒定并在每次重复层叠时使硒化镓膜32A的厚度(Y)变厚，由此将上述膜厚比(Y/X)设定成每次重复层叠时变大。需要说明的是，从使所形成的第2区域32的Ga/(In+Ga)比更优化的观点出发，对于上述膜厚比(Y/X)，优选将最初的层叠组320设定为0.2～0.5的范围内的值、将最后的层叠组320设定为大于其的0.5～1.3的范围内的值。
该工序中，如上所述，在维持520℃以上的温度的状态下蒸镀形成上述硒化镓膜32A和硒化铟膜32B，因此在蒸镀形成这些各膜32A、32B时，在该膜中引起晶体生长。因此，所形成的上述第2区域32变得比上述各个膜32A、32B的总厚度厚。如此操作，如图5的(b)所示，形成上述第2区域32。而且，在该第2区域32中，Ga/(In+Ga)比从上述第1区域31上向着表面侧逐渐增加(参照图2)。该Ga/(In+Ga)比的峰值，从能够较高地维持所制造的CIGS太阳能电池的转换效率、并且减小其转换效率的偏差的观点出发，优选设定在0.3～0.6的范围内。
接着，如图6的(a)所示，为了在上述第2区域32的表面形成上述CIGS膜3的第3区域33(参照图1)，在维持上述520℃以上的温度的状态下，在上述第2区域32上，与上述同样地操作，蒸镀形成硒化铟膜33B。该工序中，如上所述，在维持520℃以上的温度的状态下蒸镀形成上述硒化铟膜33B，因此在蒸镀形成该硒化铟膜33B时，在该膜33B中引起晶体生长。因此，所形成的上述第3区域33变得比上述硒化铟膜33B厚。如此操作，如图6的(b)所示，形成上述第3区域33，形成包含上述第1～第3区域31、32、33的CIGS膜3。
在上述第3区域33的形成中，由于没有形成包含镓的膜，因此Ga/(In+Ga)比从上述第2区域32上向着CIGS膜3的表面逐渐减少(参照图2)。从在能够较高地维持所制造的CIGS太阳能电池的转换效率、并且使其转换效率的偏差变小的状态下，能够抑制CIGS膜3的表面侧的氧化的观点出发，该Ga/(In+Ga)比的减少值优选设定在0.02～0.3的范围内。
另外，从在取得上述转换效率的降低和偏差的抑制和平衡的状态下，使表面侧的氧化的抑制能够更优化的观点出发，上述第3区域33的厚度优选在30～200nm的范围内。
而且，若使上述CIGS膜3的Cu、In、Ga的组成比满足式0.70＜Cu/(In+Ga)＜0.95的(摩尔比)，则在能够进一步阻止Cu(2-x)Se被过量地吸收到上述CIGS膜3内，而且在能够作为膜整体使Cu稍微不足的方面，是优选的。另外，使同族元素的Ga与In之比优选在0.10＜Ga/(In+Ga)＜0.40的范围。
进而，上述CIGS膜3的厚度优选在1.0～3.0μm的范围，更优选在1.5～2.5μm的范围。若厚度过薄，则用作光吸收层时的光吸收量变少，出现元件的性能降低的倾向，相反若过厚，则膜的形成所消耗的时间增加，出现生产率变差的倾向。
接着，如图7的(a)所示，在上述CIGS膜3的表面形成前述缓冲层4。作为该缓冲层4，例如可以举出包含ZnMgO、Zn(O,S)等的单层的缓冲层、包含CdS和ZnO的多层的缓冲层。上述各层可由适当的方法形成，例如，上述CdS可利用化学浴沉积法形成，上述ZnO可利用溅射法形成。另外，上述缓冲层4为了能够与上述CIGS膜3进行pn接合，优选高电阻的n型半导体。而且，缓冲层4的厚度不论单层还是多层优选设定在30～200nm的范围内。需要说明的是，作为缓冲层4，若重叠使用多种的层则能够使与上述CIGS膜3的pn接合更加良好，但在pn接合足够良好的情况下，不必一定设置多层。
然后，如图7的(b)所示，在上述缓冲层4的表面，利用溅射法等形成前述透明导电膜5。作为该透明导电膜5，可以举出氧化铟锡(ITO)、氧化铟锌(IZO)、氧化锌铝(Al:ZnO)等。另外，上述透明导电膜5的厚度优选设定在100～300nm的范围内。
如此操作，能够得到依次层叠有基板1、背面电极层2、CIGS膜3、缓冲层4、以及透明导电膜5的CIGS太阳能电池。
在上述CIGS太阳能电池的制法中，在CIGS膜3的表面侧形成有易氧化的Ga的比例减少的第3区域33。因此，该CIGS膜3抑制了表面侧的氧化。而且，使用了这样的CIGS膜3的上述CIGS太阳能电池能够有效地抑制转换效率的降低和偏差。
另外，如上所述，在CIGS膜3的表面侧形成有易氧化的Ga的比例减少的第3区域33，因此即使在形成该第3区域33之后(形成CIGS膜3之后)至在该表面形成缓冲层4为止，因耗费时间等而使上述第3区域33的表面(CIGS膜3的表面)暴露于空气(氧气)中的时间变长，也能够抑制其表面的氧化。即，即使从形成上述第3区域33(形成CIGS膜3)后至形成缓冲层4的时间变长，也不会对所制造的CIGS太阳能电池的转换效率的降低和偏差产生大的影响。因此，上述CIGS太阳能电池的生产方法的自由度增加，能够更优化生产管理。
需要说明的是，上述各实施方式中，使CIGS太阳能电池以基板1、背面电极层2、CIGS膜3、缓冲层4、以及透明导电膜5依次在接触的状态下层叠而成，但也可以根据需要在相互接触的构成层之间、基板1的背面、透明导电膜5的表面形成其它层。
另外，上述实施方式中，在形成CIGS膜3的第1区域31时层叠的层叠组310以及形成第2区域32时层叠的层叠组320中，分别在下层配置了硒化镓膜31A、32A，在上层配置了硒化铟膜31B、32B，但该配置也可以相反(下层为硒化铟膜31B、32B，上层为硒化镓膜31A、32A)。
接下来，结合现有例对实施例进行说明。但本发明并不限于实施例。
实施例
[实施例1]
<基板的准备、背面电极层的形成>
与上述实施方式同样地操作制造CIGS太阳能电池。即，首先，准备包含钠钙玻璃的基板[30mm×30mm×0.55mm(厚度)]，在其表面利用溅射法形成钼制的背面电极层(厚度500nm)。
<第1区域的形成>
接着，使用蒸镀装置，在使上述基板保持为330℃状态下，在上述背面电极层的表面形成硒化镓膜(厚度130nm)。其后，在该硒化镓膜的表面形成硒化铟膜(厚度330nm)。然后，在该硒化铟膜的表面蒸镀Cu、Se，形成包含硒化铜的蒸镀层(厚度1400nm)。如此操作，制造包含硒化镓膜和硒化铟膜以及硒化铜(蒸镀层)的层叠体。其后，一边供给微量的Se蒸汽一边加热该层叠体，将基板保持温度为550℃的状态保持5分钟，使晶体生长，形成第1区域。
<第2区域的形成>
接着，在一边供给微量的Se气体一边使基板保持为550℃的状态下，与上述同样地操作，在上述第1区域的表面形成硒化铟膜，然后在该表面形成硒化镓膜。此时，各个膜的厚度，在使基板为330℃时，以使硒化镓膜的厚度成为30nm、硒化铟膜的厚度成为80nm的方式形成。
<第3区域的形成>
接着，在一边供给微量的Se气体一边使基板保持为550℃的状态下，与上述同样地操作，在上述第2区域的表面蒸镀形成1层硒化铟膜(厚度10nm)，形成第3区域。在该第3区域的形成中没有形成包含镓的膜，因此Ga/(In+Ga)比从上述第2区域上向着表面逐渐减少。如此操作，形成包括上述第1～第3区域的CIGS膜(厚度2.0μm)。
[实施例2]
在上述实施例1的第3区域的形成中，将蒸镀形成的硒化铟膜的厚度设定为20nm。除此以外，与上述实施例1同样地操作。
[实施例3]
在上述实施例1的第3区域的形成中，将蒸镀形成的硒化铟膜的厚度设定为25nm。除此以外，与上述实施例1同样地操作。
[实施例4]
在上述实施例1的第2区域的形成中，使硒化镓膜的厚度和硒化铟膜的厚度在基板为330℃时，为硒化镓膜的厚度成为25nm、硒化铟膜的厚度成为85nm的方式形成。除此以外，与上述实施例3同样地操作。
[现有例]
在上述实施例1中，利用现有的3阶段法形成CIGS膜，除此以外，与上述实施例1同样地操作。即，首先，与上述实施例1同样地操作，在基板的表面形成背面电极层。接着，在使基板的保持温度为350℃的状态下，将In、Ga、Se一次性蒸镀，形成包含In、Ga、Se的层。接着，在加热使基板的保持温度成为550℃的状态下，在该层上蒸镀Cu、Se，使晶体生长而得到CIGS膜中间体。进而，在一边供给微量的Se蒸汽一边将基板保持温度保持为550℃的状态下，将In、Ga、Se一次性蒸镀至该CIGS膜中间体，从而得到CIGS膜(厚度2.0μm)。
<缓冲层、透明电极层的形成>
将上述实施例1～4和现有例的CIGS膜分别制造2个，对于其中的1个，在形成上述CIGS膜之后，在2小时以内(使CIGS膜暴露于空气的时间在2小时以内)，利用化学浴沉积法在该CIGS膜的表面形成CdS层(厚度50nm)，然后利用溅射法在该表面形成ZnO层(厚度70nm)，形成包含上述CdS层和ZnO层的缓冲层。然后，在该缓冲层的表面，利用溅射法形成包含ITO的透明电极层(厚度200nm)，得到CIGS太阳能电池。对于其余的1个，在形成上述CIGS膜之后，将该CIGS膜暴露于空气中24小时，然后与上述同样地操作，在该CIGS膜的表面形成缓冲层和透明电极层，得到CIGS太阳能电池。
[转换效率的测定]
对于上述实施例1～4以及现有例的、CIGS膜形成后在2小时以内形成缓冲层的CIGS太阳能电池以及在24小时后形成缓冲层的CIGS太阳能电池而言，将模拟太阳光(AM1.5)照射到表面面积以上的区域，利用太阳模拟器(CELL TESTER YSS150，山下电装株式会社制造)测定转换效率。其结果示于表1。
[Ga/(In+Ga)比的测定]
对上述实施例1～4以及现有例的各个CIGS膜，使用动态二次离子质谱仪(Ulvac-Phi,Inc.制造)来测定厚度方向的Ga/(In+Ga)比。然后，将第2区域的Ga/(In+Ga)比的峰值、显示该峰值的部分距CIGS膜的表面的深度(第3区域的厚度)、第3区域的Ga/(In+Ga)比的减少值示于下述表1。
表1
由上述表1的结果可知，实施例1～4的CIGS太阳能电池与现有例的CIGS太阳能电池相比显示出高转换效率。另外可知，在实施例1～4中，与现有例相比，即使CIGS膜暴露于空气中的时间变长，转换效率也没有明显降低。得知其原因在于，与现有例的CIGS膜的表面相比，实施例1～4的CIGS膜的表面即使暴露于空气中也变得不易氧化。得知这是因为，实施例1～4的CIGS膜在表面侧形成有易氧化的Ga的比例减少的第3区域，与此相对，现有例的CIGS膜没有形成这样的层，表面的Ga的比例变高。
上述实施例中示出了本发明的具体的方式，然而上述实施例只不过是例示，并不能限定性地解释。本领域技术人员清楚各种变形例包括在本发明的范围内。
产业上的可利用性
本发明的CIGS膜可利用于抑制表面的氧化的情况，本发明的CIGS太阳能电池可利用于抑制转换效率的降低和偏差的情况。

Claims (4)

1.一种CIGS膜，其特征在于，其用作CIGS太阳能电池的光吸收层，且具有：第1区域，随着从其背面至规定的厚度为止变厚下述(A)Ga/(In+Ga)比逐渐减少；以及第2区域，位于该第1区域上，所述Ga/(In+Ga)比向着表面侧逐渐增加；其中，在所述第2区域上形成有向着表面所述Ga/(In+Ga)比逐渐减少的第3区域，
(A)Ga/(In+Ga)比为镓(Ga)的原子数浓度相对于铟(In)的原子数浓度与该镓(Ga)的原子数浓度之和的比。
2.根据权利要求1所述的CIGS膜，其中，所述第2区域的Ga/(In+Ga)比的峰值在0.3～0.6的范围内，所述第3区域的Ga/(In+Ga)比的减少值在0.02～0.3的范围内。
3.根据权利要求1或2所述的CIGS膜，其中，所述第3区域的厚度在30～200nm的范围内。
4.一种CIGS太阳能电池，其特征在于，其为依次层叠有基板、背面电极、光吸收层、缓冲层、以及透明导电膜的CIGS太阳能电池，其中，所述光吸收层为所述权利要求1～3中任一项所述的CIGS膜，该CIGS膜的背面为位于所述背面电极侧的面。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107305914A (zh) * 2016-04-22 2017-10-31 赖志煌 大面积薄膜太阳能电池的制法

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI677105B (zh) 2014-05-23 2019-11-11 瑞士商弗里松股份有限公司 製造薄膜光電子裝置之方法及可藉由該方法獲得的薄膜光電子裝置
TWI661991B (zh) 2014-09-18 2019-06-11 瑞士商弗里松股份有限公司 用於製造薄膜裝置之自組裝圖案化
US10651324B2 (en) 2016-02-11 2020-05-12 Flisom Ag Self-assembly patterning for fabricating thin-film devices
US10658532B2 (en) 2016-02-11 2020-05-19 Flisom Ag Fabricating thin-film optoelectronic devices with added rubidium and/or cesium

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5981868A (en) * 1996-10-25 1999-11-09 Showa Shell Sekiyu K.K. Thin-film solar cell comprising thin-film light absorbing layer of chalcopyrite multi-element compound semiconductor
CN101506990A (zh) * 2005-03-16 2009-08-12 纳米太阳能公司 金属分散体和用于光伏器件活性层的化合物膜的形成
US20110174363A1 (en) * 2010-01-21 2011-07-21 Aqt Solar, Inc. Control of Composition Profiles in Annealed CIGS Absorbers
US20110232762A1 (en) * 2010-03-26 2011-09-29 Fujifilm Corporation Method for manufacturing photoelectric conversion element, and photoelectric conversion element and thin-film solar cell

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5441897A (en) 1993-04-12 1995-08-15 Midwest Research Institute Method of fabricating high-efficiency Cu(In,Ga)(SeS)2 thin films for solar cells
US5356839A (en) 1993-04-12 1994-10-18 Midwest Research Institute Enhanced quality thin film Cu(In,Ga)Se2 for semiconductor device applications by vapor-phase recrystallization
US5436204A (en) 1993-04-12 1995-07-25 Midwest Research Institute Recrystallization method to selenization of thin-film Cu(In,Ga)Se2 for semiconductor device applications
JP4919710B2 (ja) * 2006-06-19 2012-04-18 パナソニック株式会社 薄膜太陽電池
JP2011100976A (ja) 2009-10-09 2011-05-19 Fujifilm Corp 光電変換素子とその製造方法、及び太陽電池
US20130316490A1 (en) * 2010-12-28 2013-11-28 Universite Du Luxembourg Solar cell and solar cell production method
JP5812487B2 (ja) * 2011-10-06 2015-11-11 国立研究開発法人産業技術総合研究所 太陽電池の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5981868A (en) * 1996-10-25 1999-11-09 Showa Shell Sekiyu K.K. Thin-film solar cell comprising thin-film light absorbing layer of chalcopyrite multi-element compound semiconductor
CN101506990A (zh) * 2005-03-16 2009-08-12 纳米太阳能公司 金属分散体和用于光伏器件活性层的化合物膜的形成
US20110174363A1 (en) * 2010-01-21 2011-07-21 Aqt Solar, Inc. Control of Composition Profiles in Annealed CIGS Absorbers
US20110232762A1 (en) * 2010-03-26 2011-09-29 Fujifilm Corporation Method for manufacturing photoelectric conversion element, and photoelectric conversion element and thin-film solar cell

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107305914A (zh) * 2016-04-22 2017-10-31 赖志煌 大面积薄膜太阳能电池的制法

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