CN104617183A - 一种cigs基薄膜太阳电池及其制备方法 - Google Patents
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- FBQNUPMLPWPLKH-UHFFFAOYSA-N [SeH-]=[Se].[SeH-]=[Se].[SeH-]=[Se].[SeH-]=[Se].[SeH-]=[Se].[Se]=[SeH2].[Se]=[SeH2].S.[Cu+2].[In+3] Chemical compound [SeH-]=[Se].[SeH-]=[Se].[SeH-]=[Se].[SeH-]=[Se].[SeH-]=[Se].[Se]=[SeH2].[Se]=[SeH2].S.[Cu+2].[In+3] FBQNUPMLPWPLKH-UHFFFAOYSA-N 0.000 description 1
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- PNHVEGMHOXTHMW-UHFFFAOYSA-N magnesium;zinc;oxygen(2-) Chemical compound [O-2].[O-2].[Mg+2].[Zn+2] PNHVEGMHOXTHMW-UHFFFAOYSA-N 0.000 description 1
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- 238000005221 zone crystallization Methods 0.000 description 1
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- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
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Abstract
一种CIGS基薄膜太阳电池及其制备方法,该制备方法如下:在玻璃基板上形成一含有Li、K中至少一种元素的碱过滤层、在碱过滤层上形成一背电极层、在背电极上形成一光吸收层、在光吸收层上形成一缓冲层、在缓冲层上形成一n型透明导电层,其特征在于具有一定厚度的碱过滤层允许一部分碱金属离子从玻璃基板扩散进入CIGS基光吸收层中,更进一步在CIGS基光吸收层的外侧添加一定量的碱金属。
Description
技术领域
本发明涉及薄膜太阳能电池技术领域,特别是一种具有黄铜矿结构的铜铟镓硒(硫)薄膜电池的碱过滤层及其制备方法。
背景技术
随着全球气候变暖、生态环境恶化和常规能源的短缺,越来越多的国家开始大力发展太阳能利用技术。太阳能光伏发电是零排放的清洁能源,具有安全可靠、无噪音、无污染、资源取之不尽、建设周期短、使用寿命长等优势,因而备受关注。铜铟镓硒(CIGS)是一种直接带隙的P型半导体材料,其吸收系数高达105/cm,2um厚的铜铟镓硒薄膜就可吸收90%以上的太阳光。CIGS薄膜的带隙从1.04eV到1.67eV范围内连续可调,可实现与太阳光谱的最佳匹配。铜铟镓硒薄膜太阳电池作为新一代的薄膜电池具有成本低、性能稳定、抗辐射能力强、弱光也能发电等优点,其转换效率在薄膜太阳能电池中是最高的,可接近20%的转化率,因此日本、德国、美国等国家都投入巨资进行研究和产业化。
太阳能在环境上是清洁的并且从某种角度上已经成功,但是,在使其进入普通百姓的家庭之前,仍有许多问题有待解决。例如,单晶硅太阳能电池能够将光能转化为电能,然而,单晶硅材料是比较昂贵的。传统在使用薄膜技术制造太阳能电池时,也存在一些问题:如传统的非晶硅薄膜太阳电池效率低,其在使用过程容易造成衰减;而高性能CIGS薄膜组件的产品良率偏低,并且从高效率薄膜电池到获得同样效率的大尺寸组件的过程受复杂生产设备的限制而难以短时间实现等。
在CIGS薄膜电池中,钠钙玻璃基板中的钠金属离子通过热扩散进入p型光吸收层,这可以促进晶粒生长和影响载流子浓度。换句话说,如果进入p型光吸收层的钠离子太多或分布不均匀,将容易发生p型光吸收层从背电极层剥落和光吸收层结晶不理想等问题。因此制造一CIGS基薄膜太阳能电池的过程中,对于均匀控制最佳的钠离子量进入p型光吸收层是相当重要的,它可以改善电池的光电转换效率。
铜铟镓硒薄膜太阳能电池基本采用如下结构,先在一基板上沉积钼电极层,接着在其上沉积铜铟镓硒光吸收层,接着沉积硫化镉缓冲层,接着沉积透明导电氧化物窗口层,接着是沉积金属栅状电极和减反射层。传统的结构会存在如下问题:若基板为钠钙玻璃时,在硒化热处理过程,基板中的钠离子会不受控的扩散通过钼电极层进入光吸收层中,这会影响光吸收层的结晶状态,从而影响电池的转化效率。
发明内容
本发明的主要目的在于解决现有技术中存在的问题:在硒化和/或硫化过程中,玻璃基板中的钠离子会不受控的热扩散进入光吸收层,造成光吸收层的结晶不理想,从而导致电池的转化效率较低。
本发明为解决现有技术中存在的问题采用如下技术方案:一种CIGS基薄膜太阳电池的制备方法,该制备方法包括如下步骤:在玻璃基板上形成一含有Li、K中至少一种元素的碱过滤层、在碱过滤层上形成一金属背电极层、在金属背电极层上形成CIGS基光吸收层、在光吸收层上形成一缓冲层、在缓冲层上形成一n型透明导电膜层,其特征在于:所述的碱过滤层厚度为1–15nm,且允许玻璃基板中的一部分碱金属离子通过热扩散进入到CIGS光吸收层中,此外,所述的光吸收层中的碱金属离子可以是从玻璃基板中的碱金属离子扩散进入光吸收层,也可以是从玻璃基板中的碱金属离子和含有碱金属离子的铜铟镓金属预制层中的碱金属离子一同扩散进入光吸收层;所述CIGS基光吸收层可由铜铟镓金属预制层或含有碱金属离子的铜铟镓金属预制层进行硒化和/或硫化热处理后获得;所述碱金属离子是Na、K、Li中的至少一种,优选是Na。
所述碱过滤层的厚度为1–15nm,优选厚度为2-13nm,更优选厚度为3-10nm,最优选厚度为4-8nm。
所述碱过滤层优选包括由Li、K中的至少一种元素和Si、Al、O三种元素组成;在Si和Al两种元素中,Si所占的质量百分比为X,其中1.59wt%≤X<100wt%。所述碱过滤层可由溅射镀膜获得。
所述碱过滤层含有0.005-5wt%的Li、K中的至少一种元素,优选含有0.01-4wt%的Li、K中的至少一种元素,更优选含有0.05-3wt%的Li、K中的至少一种元素,最优选含有0.08-2wt%的Li、K中的至少一种元素。
在优选实施例中,碱过滤层为LiOa-AlOb-SiOc碱过滤层(a≤0.5,b≤1.5,c≤2),或是KOa-AlOb-SiOc碱过滤层(a≤0.5,b≤1.5,c≤2),或是LiOa-KOb-AlOc-SiOd碱过滤层(a≤0.5,b≤0.5,c≤1.5,d≤2)。
所述含有碱金属离子的铜铟镓金属预制层含有0.01at%-0.15at%的碱金属离子,优选含有0.02at%-0.13at%的碱金属离子,更优选含有0.03at%-0.12at%的碱金属离子,最优选含有0.05at%-0.1at%的碱金属离子。
所述玻璃基板为普通超白钠钙玻璃或高应变点钠钙玻璃。
所述含有碱金属离子的铜铟镓金属预制层是通过含有碱金属离子的溅射靶材溅射沉积或在铜铟镓金属预制层上沉积一层含有碱金属离子的薄膜层。
一种CIGS基薄膜太阳电池,其光吸收层选用具有黄铜矿结构的铜铟镓硒(硫)膜层或铜铟硒(硫)膜层,缓冲层选用硫化镉、氧化锌、硫化锌、硒化锌、硫化铟或锌镁氧化物中的一种,窗口层选用ITO(Sn掺杂In2O3)、AZO(Al掺杂ZnO)、GZO(Ga掺杂ZnO)、IZO(In掺杂ZnO)、FTO(F掺杂SnO2)、ATO(Sb掺杂SnO2)透明导电膜中的至少一种。
本发明提供了一种用于CIGS基薄膜太阳电池的制备方法,即在钠钙玻璃基板表面沉积一层较薄的含有Li、K中至少一种元素的碱过滤层,就能够有效控制钠钙玻璃基板中的钠离子热扩散进入光吸收层。
本发明具有以下优点:
在钠钙玻璃基板表面沉积一层含有Li、K中至少一种元素的碱过滤层,当进行硒化和/或硫化热处理时,钠钙玻璃基板中的钠离子就会扩散首先进入碱过滤层中,其中有一部分的钠离子会与碱过滤层中的Li、K产生“混合碱效应”,从而抑制了该部分的钠离子进一步扩散进入到光吸收层中;与此同时,碱过滤层具有一定的厚度,其也可以过滤掉钠钙玻璃基板中的一部分钠离子通过热扩散进入到光吸收层中;以上两者共同作用的结果:允许钠钙玻璃基板中的一部分钠离子能够较均匀的通过热扩散进入到光吸收层中,同时可在铜铟镓金属预制层的形成过程中或形成后添加一定量的钠离子,通过热处理使光吸收层获得理想的结晶状态,从而获得具有较高光电转换效率的薄膜太阳能电池。
附图说明
图1为本发明CIGS基薄膜太阳电池的多层膜结构示意图;
图2为一常见的CIGS基薄膜太阳电池的多层膜结构示意图;
具体实施方式
下面结合具体实施例对本发明进行详细说明。
正如众所周知的,在钠钙玻璃基板上沉积光伏材料,光伏材料的晶粒生长受益于基板中钠物质的存在。然而,已经知道,由钠钙玻璃基板的钠离子直接通过热扩散供给钠离子给光吸收层的,以这种方式提供的钠离子在光吸收层中的分布是不均匀的,将会引起光吸收层的结晶状态不理想,使薄膜太阳电池的光电转换效率较低且不稳定。本发明提供了一种用于CIGS基薄膜太阳电池的制备方法,即在钠钙玻璃基板表面沉积一层较薄的含有Li、K中至少一种元素的碱过滤层,就能够有效控制钠钙玻璃基板中的钠离子热扩散进入光吸收层,使钠离子在光吸收层中的分布比较均匀,同时可在铜铟镓金属预制层的形成过程中或形成后添加一定量的钠离子,通过热处理使光吸收层获得较为理想的结晶状态,从而获得具有较高光电转换效率的CIGS薄膜太阳电池。
碱过滤层的厚度不能太薄也不能太厚,若该膜层太薄起不到有效的过滤钠离子的效果,若该膜层太厚则阻挡了绝大部分的钠离子扩散进入光吸收层,这对光吸收层的结晶都会产生不利的影响,因此,碱过滤层的厚度为1–15nm,优选厚度为2-13nm,更优选厚度为3-10nm,最优选厚度为4-8nm。
以下涉及实施例及对比例,均是在干净的钠钙玻璃原片的空气面上依次沉积上各膜层。本发明实施例的膜层结构如图1所示,对比实施例的膜层结构如图2所示。
实施例1
在钠钙玻璃基板表面溅射沉积一层含有0.005wt%Li的LiOa-AlOb-SiOc碱过滤层(a=0.5,b=1.5,c=2),在碱过滤层中Si:Al=9:1(质量比),接着在碱过滤层上溅射沉积500nm钼背电极层,接着在钼背电极层上沉积含有Na的铜铟镓金属预制层,接着将样片送入加热炉内进行硒化热处理,形成光吸收层,接着在光吸收层上水浴沉积40nm硫化镉膜层,接着在硫化镉层上沉积50nmZnO膜层,接着在ZnO膜层上沉积600nmAZO透明导电膜层。本发明的实施例1结果如下表1。
表1
实施例2
在钠钙玻璃基板表面溅射沉积一层含有5wt%Li的LiOa-AlOb-SiOc碱过滤层(a=0.45,b=1.4,c=1.9),在碱过滤层中Si:Al=9:1(质量比),接着在碱过滤层上溅射沉积500nm钼背电极层,接着在钼背电极层上沉积含有Na的铜铟镓金属预制层,接着将样片送入加热炉内进行硒化热处理,形成光吸收层,接着在光吸收层上水浴沉积40nm硫化镉膜层,接着在硫化镉层上沉积50nmZnO膜层,接着在ZnO膜层上沉积600nmAZO透明导电膜层。本发明的实施例2结果如下表2。
表2
实施例3
在钠钙玻璃基板表面溅射沉积一层含有1wt%Li的LiOa-AlOb-SiOc碱过滤层(a=0.5,b=1.5,c=2),在碱过滤层中Si:Al=9:1(质量比),接着在碱过滤层上溅射沉积500nm钼背电极层,接着在钼背电极层上沉积含有Na的铜铟镓金属预制层,接着将样片送入加热炉内进行硒化热处理,形成光吸收层,接着在光吸收层上水浴沉积40nm硫化镉膜层,接着在硫化镉层上沉积50nmZnO膜层,接着在ZnO膜层上沉积600nmAZO透明导电膜层。本发明的实施例3结果如下表3。
表3
实施例4
在钠钙玻璃基板表面溅射沉积一层含有0.005wt%K的KOa-AlOb-SiOc碱过滤层(a=0.4,b=1.4,c=1.8),在碱过滤层中Si:Al=9:1(质量比),接着在碱过滤层上溅射沉积500nm钼背电极层,接着在钼背电极层上沉积含有Na的铜铟镓金属预制层,接着将样片送入加热炉内进行硒化热处理,形成光吸收层,接着在光吸收层上水浴沉积40nm硫化镉膜层,接着在硫化镉层上沉积50nmZnO膜层,接着在ZnO膜层上沉积600nmAZO透明导电膜层。本发明的实施例4结果如下表4。
表4
实施例5
在钠钙玻璃基板表面溅射沉积一层含有5wt%K的KOa-AlOb-SiOc碱过滤层(a=0.5,b=1.5,c=2),在碱过滤层中Si:Al=9:1(质量比),接着在碱过滤层上溅射沉积500nm钼背电极层,接着在钼背电极层上沉积含有Na的铜铟镓金属预制层,接着将样片送入加热炉内进行硒化热处理,形成光吸收层,接着在光吸收层上水浴沉积40nm硫化镉膜层,接着在硫化镉层上沉积50nmZnO膜层,接着在ZnO膜层上沉积600nmAZO透明导电膜层。本发明的实施例5结果如下表5。
表5
实施例6
在钠钙玻璃基板表面溅射沉积一层含有1wt%K的KOa-AlOb-SiOc碱过滤层(a=0.5,b=1.5,c=2),在碱过滤层中Si:Al=9:1(质量比),接着在碱过滤层上溅射沉积500nm钼背电极层,接着在钼背电极层上沉积含有Na的铜铟镓金属预制层,接着将样片送入加热炉内进行硒化热处理,形成光吸收层,接着在光吸收层上水浴沉积40nm硫化镉膜层,接着在硫化镉层上沉积50nmZnO膜层,接着在ZnO膜层上沉积600nmAZO透明导电膜层。本发明的实施例6结果如下表6。
表6
实施例7
在钠钙玻璃基板表面溅射沉积一层含有0.6wt%Li和0.4wt%K的LiOa-KOb-AlOc-SiOd碱过滤层(a=0.5,b=0.5,c=1.5,d=2),在碱过滤层中Si:Al=9:1(质量比),接着在碱过滤层上溅射沉积500nm钼背电极层,接着在钼背电极层上沉积含有Na的铜铟镓金属预制层,接着将样片送入加热炉内进行硒化热处理,形成光吸收层,接着在光吸收层上水浴沉积40nm硫化镉膜层,接着在硫化镉层上沉积50nmZnO膜层,接着在ZnO膜层上沉积600nmAZO透明导电膜层。本发明的实施例7结果如下表7。
表7
实施例8
在钠钙玻璃基板表面溅射沉积一层含有0.6wt%Li和0.4wt%K的LiOa-KOb-AlOc-SiOd碱过滤层(a=0.5,b=0.5,c=1.5,d=2),在碱过滤层中Si:Al=9:1(质量比),接着在碱过滤层上溅射沉积500nm钼背电极层,接着在钼背电极层上沉积铜铟镓金属预制层,接着将样片送入加热炉内进行硒化热处理,形成光吸收层,接着在光吸收层上水浴沉积40nm硫化镉膜层,接着在硫化镉层上沉积50nmZnO膜层,接着在ZnO膜层上沉积600nmAZO透明导电膜层。本发明的实施例8结果如下表8。
表8
对比实施例1
在钠钙玻璃基板表面直接溅射沉积500nm钼背电极层,接着在钼背电极层上沉积铜铟镓金属预制层,接着将样片送入加热炉内进行硒化热处理,形成光吸收层,接着在光吸收层上水浴沉积40nm硫化镉膜层,接着在硫化镉层上沉积50nmZnO膜层,接着在ZnO膜层上沉积600nmAZO透明导电膜层。对比实施例1结果如下表9。
表9
Claims (10)
1.一种CIGS基薄膜太阳电池的制备方法,该制备方法包括如下步骤:在玻璃基板上形成一含有Li、K中至少一种元素的碱过滤层、在碱过滤层上形成一金属背电极层、在金属背电极层上形成CIGS基光吸收层、在光吸收层上形成一缓冲层、在缓冲层上形成一n型透明导电膜层,其中,所述的碱过滤层厚度为1–15nm,且允许玻璃基板中的一部分碱金属离子通过热扩散进入到CIGS光吸收层中,此外,所述的光吸收层中的碱金属离子单从玻璃基板中的碱金属离子扩散进入光吸收层,或从玻璃基板中的碱金属离子和含有碱金属离子的铜铟镓金属预制层中的碱金属离子一同扩散进入光吸收层;所述CIGS基光吸收层由铜铟镓金属预制层或含有碱金属离子的铜铟镓金属预制层进行硒化和/或硫化热处理后获得。
2.根据权利要求1所述的一种CIGS基薄膜太阳电池的制备方法,其特征在于:所述碱过滤层的厚度为2–13nm。
3.根据权利要求1所述的一种CIGS基薄膜太阳电池的制备方法,其特征在于:所述碱过滤层包括Li、K中的至少一种元素和Si、Al、O三种元素。
4.根据权利要求3所述的一种CIGS基薄膜太阳电池的制备方法,其特征在于:所述碱过滤层含有0.005-5wt%的Li、K中的至少一种元素。
5.根据权利要求3所述的一种CIGS基薄膜太阳电池的制备方法,其特征在于:所述碱过滤层由溅射镀膜获得。
6.根据权利要求1所述的一种CIGS基薄膜太阳电池的制备方法,其特征在于:所述含有碱金属离子的铜铟镓金属预制层含有0.01at%-0.15at%的碱金属离子。
7.根据权利要求1所述的一种CIGS基薄膜太阳电池的制备方法,其特征在于:所述碱金属离子是Na、K、Li中的至少一种。
8.根据权利要求1所述的一种CIGS基薄膜太阳电池的制备方法,其特征在于:所述玻璃基板为普通超白钠钙玻璃或高应变点钠钙玻璃。
9.根据权利要求1所述的一种CIGS基薄膜太阳电池的制备方法,其特征在于:所述含有碱金属离子的铜铟镓金属预制层是通过含有碱金属离子的溅射靶材溅射沉积或在铜铟镓金属预制层上沉积一层含有碱金属离子的薄膜层。
10.一种CIGS基薄膜太阳电池,其特征在于:根据权利要求1至9任一项的方法制备而成。
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