CN105244394B - 一种cigs基薄膜太阳能电池及其制备方法 - Google Patents
一种cigs基薄膜太阳能电池及其制备方法 Download PDFInfo
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- 210000001142 back Anatomy 0.000 claims abstract description 22
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- AKUCEXGLFUSJCD-UHFFFAOYSA-N indium(3+);selenium(2-) Chemical compound [Se-2].[Se-2].[Se-2].[In+3].[In+3] AKUCEXGLFUSJCD-UHFFFAOYSA-N 0.000 description 1
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- H01L31/03923—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 characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate including AIBIIICVI compound materials, e.g. CIS, CIGS
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Abstract
本发明提供了一种CIGS基薄膜太阳能电池及其制备方法,包括:衬底,在衬底上形成背电极层,在背电极层上形成一层合金膜层,在合金膜层上形成p型光吸收层,在p型光吸收层上形成缓冲层,在缓冲层上形成透明导电层。所述合金膜层由银、铂、铬和镓中的至少一种元素与锑元素组成。在背电极层上形成一层上述合金膜层可以提高p型光吸收层的结晶颗粒的尺寸,提高短路电流,同时减少背电极层受硫族元素的腐蚀,从而提高薄膜太阳能电池的性能,降低制造成本。
Description
技术领域
本发明涉及薄膜太阳能电池技术领域,更具体的,本发明提供一种CIGS基薄膜太阳能电池及其制备方法。
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,已超过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。
传统的CIGS基薄膜太阳能电池的结构如图1所示。为了提高CIGS基薄膜太阳能电池的开路电压和短路电流,通常需要光吸收层的结晶颗粒要足够大。光吸收层为了获得较为理想的结晶颗粒,其热处理温度通常要达到550℃,有时甚至达到600℃,较高的热处理温度会使衬底容易翘起变形,且会使膜层之间的界面遭受破坏,较高的热处理温度也会造成制造成本的增加;若形成光吸收层的热处理温度较低,则光吸收层获得的结晶颗粒就较小,从而影响了薄膜电池的性能。
当进行热处理形成CIGS基薄膜太阳能电池的光吸收层时,钼背电极层会受到硫族元素的腐蚀而形成一层硒化钼层或硫化钼层。在高温热处理后会形成较厚的硒化钼层或硫化钼层,这会影响其膜层间的欧姆接触,将会导致电池的串联电阻升高,使电池的性能下降。
发明内容
本发明的目的在于克服现有技术之不足,本发明通过在背电极层上沉积一层合金膜层,接着再在合金膜层上形成p型光吸收层,使其能够在较低的热处理温度下就可获得较大的结晶颗粒,同时能够有效抑制硒化过程中硒化钼厚度的增长,可减少载流子在该界面处的复合,提高薄膜电池的开路电压和短路电流,从而提高薄膜太阳能电池的性能。
本发明解决其技术问题所采用的技术方案是:一种CIGS基薄膜太阳能电池,其特征在于:包括衬底,覆盖衬底的背电极层,覆盖背电极层的合金膜层,覆盖合金膜层的p型光吸收层,覆盖p型光吸收层的缓冲层,形成覆盖缓冲层的透明导电层;所述合金膜层由银、铂、铬和镓中的至少一种元素与锑元素组成,所述合金膜层的厚度不大于200nm。
所述合金膜层中没有含镓的情况下,所述合金膜层中锑的含量至多为50at%(at%为原子比百分比)。
所述合金膜层为锑镓合金膜层时,所述合金膜层中锑的含量至少为50at%;所述锑镓合金膜层可形成于p型光吸收层的预制层中,所述预制层为铜铟镓膜层、铜铟膜层、铜铟镓硒膜层、铜铟镓硫膜层或铜铟镓硒硫膜层。
所述合金膜层的厚度优选不大于100nm。
所述p型光吸收层为p型铜铟镓硒、p型铜铟镓硫、p型铜铟镓硒硫、p型铜铟镓铝硒、p型铜铟镓铝硫、p型铜铟镓铝硒硫、p型铜铟铝硒硫、p型铜铟铝硒、p型铜铟铝硫、p型铜铟硒硫、p型铜铟硫或p型铜铟硒中的一种,所述p型光吸收层中含有碱元素,所述p型光吸收层中优选含有钠。
进一步的,在缓冲层与透明导电层之间插入一层具有高电阻率的氧化锌膜层,所述具有高电阻率的氧化锌膜层选自本征氧化锌膜层、具有电阻率为0.08Ωcm至95Ωcm的掺杂氧化锌膜层或它们的组合。所述具有高电阻率的氧化锌膜层可采用磁控溅射法沉积、真空蒸发法沉积或化学气相沉积法沉积
进一步的,在衬底与背电极层之间插入一层电介质材料层;所述电介质材料层选自氧化硅、氮化硅、氮氧化硅、氮化钛、氧化钛、氮氧化钛、氮氧化锆、氧化锆、氮化锆、氮化铝、氧化铝、氧化硅铝、氮化硅铝、氮氧化硅铝、锌锡氧化物或它们的混合物组成;所述电介质材料层或由硅、锆和钛中的至少一种元素与钼组成的至少两种元素的氧化物、氮化物或氮氧化物组成;当衬底为玻璃基板时,所述电介质材料层可由一含有Li、K中至少一种元素的碱过滤层替代,该碱过滤层包含Li、K中的至少一种元素和Si、Al、O三种元素。所述电介质材料层采用磁控溅射沉积或真空蒸发法沉积。
所述衬底为玻璃基板、聚酰亚胺板、铝薄板、钛薄板或不锈钢板中的一种;所述背电极层为Mo层、Ti层、Cr层、Cu层或AZO层中的至少一种,所述背电极层优选为Mo层,所述背电极层中含有氧,所述背电极层中也可含有碱元素;所述缓冲层为硫化镉、氧化锌、硫化锌、硒化锌、硫硒化锌、硫硒化铟、硒化铟、硫化铟或锌镁氧化物中的至少一种;所述透明导电层选用银基透明导电膜、氧化铟掺杂锡(ITO)、氧化锌掺杂铝(AZO)、氧化锌掺杂镓(GZO)、氧化锌掺杂铟(IZO)、氧化锡掺杂氟(FTO)、氧化锡掺杂碘、氧化锡掺杂锑(ATO)或石墨烯中的至少一种。
本发明提供一种CIGS基薄膜太阳能电池的制备方法,其特征在于:在一衬底上沉积背电极层,在背电极层上真空沉积合金膜层,在合金膜层上形成p型光吸收层,在p型光吸收层上沉积缓冲层,在缓冲层上沉积透明导电层;所述合金膜层由银、铂、铬和镓中的至少一种元素与锑元素组成,所述合金膜层的厚度不大于200nm。
使用磁控溅射法沉积背电极层;使用磁控溅射法或真空蒸镀法沉积合金膜层;使用磁控溅射后硒化工艺、共蒸发工艺、反应溅射沉积工艺或直接溅射沉积工艺制备p型光吸收层;使用化学水浴法、溅射法或者MOCVD法沉积缓冲层;使用磁控溅射法或者真空蒸镀法沉积透明导电窗口层。
与现有技术相比本发明具有以下优点:
1、本发明通过在合金膜层上形成p型光吸收层,能够使在相对较低的热处理温度下就能获得结晶颗粒较大的光吸收层,可提高薄膜电池的短路电流;使用相对较低的热处理温度来形成光吸收层,使薄膜太阳能电池的各膜层的界面相对良好,从而减少了载流子在界面的复合,提高了薄膜太阳能电池的性能。
2、本发明通过在合金膜层上形成p型光吸收层,使光吸收层的热处理温度相对较低,可使用应变点较低的玻璃基板作为衬底,因而可降低制造成本。
3、本发明通过在合金膜层上形成p型光吸收层,能够有效抑制形成p型光吸收层的热处理过程中硒化钼层或硫化钼层厚度的过度增长,因而可降低薄膜太阳能电池的串联电阻,提高薄膜太阳能电池的性能。
4、本发明的合金膜层的沉积采用磁控溅射沉积,能够实现大面积均匀成膜,与CIGS基薄膜电池的生产工艺相匹配,可实现大规模连续生产。
附图说明
图1为传统的CIGS基薄膜太阳能电池的结构示意图;
图2为本发明的CIGS基薄膜太阳能电池的一种结构示意图;
图3为本发明的CIGS基薄膜太阳能电池的另一种结构示意图。
图中数字说明:1-衬底,21-电介质材料层,2-背电极层,31-合金膜层,3-p型光吸收层,4-缓冲层,5-本征氧化锌膜层,6-透明导电层,7-减反射膜层。
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。
本发明的一种CIGS基薄膜太阳能电池,其结构示意图如图2所示,通过在衬底上采用溅射法沉积背电极层钼层,接着在钼层上采用溅射法沉积一层合金膜层,接着在合金膜层上采用溅射法沉积铜铟镓预制层,接着将预制层进行硒化和/或硫化热处理形成p型光吸收层,接着在p型光吸收层上采用水浴法沉积硫化镉膜层作为缓冲层,接着在缓冲层上采用溅射法沉积本征氧化锌膜层,接着在本征氧化锌膜层上采用溅射法沉积AZO膜层作为透明导电层。
以下涉及的实施例,均是在干净的衬底表面上依次形成各膜层。衬底所使用的钠钙玻璃不是高应变点玻璃。
实施例1
在衬底为钠钙玻璃上采用磁控溅射沉积500nm的金属钼电极层;接着在钼背电极层上采用磁控溅射沉积30nm的锑镓合金膜层,锑镓合金膜层中含50at%的锑;接着在锑镓合金膜层上形成2.0um厚的具有黄铜矿结构的p型铜铟镓硒膜层,形成所述p型铜铟镓硒膜层的热处理温度为520℃;接着在p型铜铟镓硒膜层上采用化学浴(CBD)方法沉积45nm的CdS膜层作为缓冲层;在缓冲层上采用磁控溅射沉积40nm的本征ZnO膜层;接着在本征ZnO膜层上采用磁控溅射沉积600nm的AZO膜层。
p型铜铟镓硒膜层形成后,钠钙玻璃衬底没有出现翘起变形;通过测试,p型铜铟镓硒膜层的晶粒颗粒尺寸至少为1um以上;观察薄膜太阳能电池的截面,在钼电极层与p型铜铟镓硒膜层之间的硒化钼层很薄,只有几十个纳米厚;通过测试,薄膜太阳能电池的短路电流为32.5mA/cm2;薄膜太阳能电池的开路电压为0.656V。
实施例2
在衬底为钠钙玻璃上采用磁控溅射沉积500nm的金属钼电极层;接着在钼背电极层上采用磁控溅射沉积100nm的锑镓合金膜层,锑镓合金膜层中含65at%的锑;接着在锑镓合金膜层上形成2.0um厚的具有黄铜矿结构的p型铜铟镓硒膜层,形成所述p型铜铟镓硒膜层的热处理温度为520℃;接着在p型铜铟镓硒膜层上采用化学浴(CBD)方法沉积45nm的CdS膜层作为缓冲层;在缓冲层上采用磁控溅射沉积40nm的本征ZnO膜层;接着在本征ZnO膜层上采用磁控溅射沉积600nm的AZO膜层。
p型铜铟镓硒膜层形成后,钠钙玻璃衬底没有出现翘起变形;通过测试,p型铜铟镓硒膜层的晶粒颗粒尺寸至少为1um以上;观察薄膜太阳能电池的截面,在钼电极层与p型铜铟镓硒膜层之间的硒化钼层很薄,只有几十个纳米厚;通过测试,薄膜太阳能电池的短路电流为33.1mA/cm2;薄膜太阳能电池的开路电压为0.651V。
实施例3
在衬底为钠钙玻璃上采用磁控溅射沉积500nm的金属钼电极层;接着在钼背电极层上采用磁控溅射沉积40nm的银锑合金膜层,银锑合金膜层中含60at%的银;接着在银锑合金膜层上形成2.1um厚的具有黄铜矿结构的p型铜铟镓硒膜层,形成所述p型铜铟镓硒膜层的热处理温度为520℃;接着在p型铜铟镓硒膜层上采用化学浴(CBD)方法沉积40nm的CdS膜层作为缓冲层;在缓冲层上采用磁控溅射沉积50nm的本征ZnO膜层;接着在本征ZnO膜层上采用磁控溅射沉积800nm的AZO膜层。
p型铜铟镓硒膜层形成后,钠钙玻璃衬底没有出现翘起变形;通过测试,p型铜铟镓硒膜层的晶粒颗粒尺寸至少为1um以上;观察薄膜太阳能电池的截面,在钼电极层与p型铜铟镓硒膜层之间的硒化钼层很薄,只有几十个纳米厚;通过测试,薄膜太阳能电池的短路电流为32.1mA/cm2;薄膜太阳能电池的开路电压为0.66V。
实施例4
在衬底为钠钙玻璃上采用磁控溅射沉积500nm的金属钼电极层;接着在钼背电极层上采用磁控溅射沉积20nm的铂锑合金膜层,铂锑合金膜层中含50at%的铂;接着在铂锑合金膜层上形成1.8um厚的具有黄铜矿结构的p型铜铟镓硫膜层,形成所述p型铜铟镓硫膜层的热处理温度为520℃;接着在p型铜铟镓硫膜层上采用化学浴(CBD)方法沉积45nm的CdS膜层作为缓冲层;在缓冲层上采用磁控溅射沉积40nm的本征ZnO膜层;接着在本征ZnO膜层上采用磁控溅射沉积900nm的AZO膜层。
p型铜铟镓硫膜层形成后,钠钙玻璃衬底没有出现翘起变形;通过测试,p型铜铟镓硫膜层的晶粒颗粒尺寸至少为1um以上;观察薄膜太阳能电池的截面,在钼电极层与p型铜铟镓硫膜层之间的硫化钼层很薄,只有几十个纳米厚;通过测试,薄膜太阳能电池的短路电流为31.9mA/cm2;薄膜太阳能电池的开路电压为0.648V。
实施例5
在衬底为钠钙玻璃上采用磁控溅射沉积500nm的金属钼电极层;接着在钼背电极层上采用磁控溅射沉积70nm的铬锑合金膜层,铬锑合金膜层中含75at%的铬;接着在铬锑合金膜层上形成1.9um厚的具有黄铜矿结构的p型铜铟镓硒硫膜层,形成所述p型铜铟镓硒硫膜层的热处理温度为520℃;接着在p型铜铟镓硒硫膜层上采用化学浴(CBD)方法沉积40nm的CdS膜层作为缓冲层;在缓冲层上采用磁控溅射沉积55nm的本征ZnO膜层;接着在本征ZnO膜层上采用磁控溅射沉积600nm的AZO膜层。
p型铜铟镓硒硫膜层形成后,钠钙玻璃衬底没有出现翘起变形;通过测试,p型铜铟镓硒硫膜层的晶粒颗粒尺寸至少为1um以上;观察薄膜太阳能电池的截面,在钼电极层与p型铜铟镓硒硫膜层之间的硒化钼层很薄,只有几十个纳米厚;通过测试,薄膜太阳能电池的短路电流为32.4mA/cm2;薄膜太阳能电池的开路电压为0.659V。
实施例6
在衬底为钠钙玻璃上采用磁控溅射沉积60nm的氮化硅膜层作为电介质材料层;接着在氮化硅膜层上采用磁控溅射沉积500nm的金属钼电极层;接着在钼背电极层上采用磁控溅射沉积30nm的锑镓合金膜层,锑镓合金膜层中含50at%的锑;接着在锑镓合金膜层上形成2.0um厚的具有黄铜矿结构的p型铜铟镓硒膜层,形成所述p型铜铟镓硒膜层的热处理温度为520℃;接着在p型铜铟镓硒膜层上采用化学浴(CBD)方法沉积45nm的CdS膜层作为缓冲层;在缓冲层上采用磁控溅射沉积40nm的本征ZnO膜层;接着在本征ZnO膜层上采用磁控溅射沉积600nm的AZO膜层;接着在AZO膜层上采用磁控溅射沉积100nm的MgF2膜层作为减反射膜层。本实施例的薄膜电池的结构如图3所示。
p型铜铟镓硒膜层形成后,钠钙玻璃衬底没有出现翘起变形;通过测试,p型铜铟镓硒膜层的晶粒颗粒尺寸至少为1um以上;观察薄膜太阳能电池的截面,在钼电极层与p型铜铟镓硒膜层之间的硒化钼层很薄,只有几十个纳米厚;通过测试,薄膜太阳能电池的短路电流为32.7mA/cm2;薄膜太阳能电池的开路电压为0.657V。
对比例1
在衬底为钠钙玻璃上采用磁控溅射沉积500nm的金属钼电极层;接着在钼背电极层上形成1.9um厚的具有黄铜矿结构的p型铜铟镓硒膜层,形成所述p型铜铟镓硒膜层的热处理温度为520℃;接着在p型铜铟镓硒膜层上采用化学浴(CBD)方法沉积40nm的CdS膜层作为缓冲层;在缓冲层上采用磁控溅射沉积55nm的本征ZnO膜层;接着在本征ZnO膜层上采用磁控溅射沉积600nm的AZO膜层。
p型铜铟镓硒膜层形成后,钠钙玻璃衬底没有出现翘起变形;通过测试,p型铜铟镓硒膜层的晶粒颗粒尺寸小于800nm;观察薄膜太阳能电池的截面,在钼电极层与p型铜铟镓硒膜层之间的硒化钼层有几百纳米厚;通过测试,薄膜太阳能电池的短路电流为26.9mA/cm2;薄膜太阳能电池的开路电压为0.52V。
对比例2
在衬底为钠钙玻璃上采用磁控溅射沉积500nm的金属钼电极层;接着在钼背电极层上形成1.9um厚的具有黄铜矿结构的p型铜铟镓硒膜层,形成所述p型铜铟镓硒膜层的热处理温度为560℃;接着在p型铜铟镓硒膜层上采用化学浴(CBD)方法沉积40nm的CdS膜层作为缓冲层;在缓冲层上采用磁控溅射沉积55nm的本征ZnO膜层;接着在本征ZnO膜层上采用磁控溅射沉积600nm的AZO膜层。
p型铜铟镓硒膜层形成后,钠钙玻璃衬底有出现翘起变形;通过测试,p型铜铟镓硒膜层的晶粒颗粒尺寸可达1um;观察薄膜太阳能电池的截面,在钼电极层与p型铜铟镓硒膜层之间的硒化钼层有几百纳米厚;通过测试,薄膜太阳能电池的短路电流为27.3mA/cm2;薄膜太阳能电池的开路电压为0.617V。
从实施例与对比例中可以看出,本发明的薄膜太阳能电池的光吸收层的结晶颗粒较大,形成的硒化钼层厚度较薄,短路电流和开路电压都较高,且钠钙玻璃衬底不会出现变形。由于不是使用高应变点玻璃作为衬底,且光吸收层的形成温度相对较低,因而可降低制造成本。
Claims (9)
1.一种CIGS基薄膜太阳能电池,其特征在于:包括衬底,覆盖衬底的背电极层,覆盖背电极层的合金膜层,覆盖合金膜层的p型光吸收层,覆盖p型光吸收层的缓冲层,覆盖缓冲层的透明导电层;其中,所述合金膜层由银、铂、铬中的至少一种元素与镓和锑元素组成;所述合金膜层的厚度不大于200nm。
2.根据权利要求1所述的一种CIGS基薄膜太阳能电池,其特征在于:所述合金膜层中锑的含量至少为50at%。
3.根据权利要求1所述的一种CIGS基薄膜太阳能电池,其特征在于:所述合金膜层的厚度不大于100nm。
4.根据权利要求1所述的一种CIGS基薄膜太阳能电池,其特征在于:所述p型光吸收层为p型铜铟镓硒、p型铜铟镓硫、p型铜铟镓硒硫、p型铜铟镓铝硒、p型铜铟镓铝硫、p型铜铟镓铝硒硫、p型铜铟铝硒硫、p型铜铟铝硒、p型铜铟铝硫、p型铜铟硒硫、p型铜铟硫或p型铜铟硒中的一种,所述p型光吸收层中含有碱元素。
5.根据权利要求1所述的一种CIGS基薄膜太阳能电池,其特征在于:在缓冲层与透明导电层之间插入一层具有高电阻率的氧化锌膜层,所述具有高电阻率的氧化锌膜层选自本征氧化锌膜层、具有电阻率为0.08Ωcm至95Ωcm的掺杂氧化锌膜层或它们的组合。
6.根据权利要求1所述的一种CIGS基薄膜太阳能电池,其特征在于:在基板与背电极层之间插入一层电介质材料层;所述电介质材料层选自氧化硅、氮化硅、氮氧化硅、氮化钛、氧化钛、氮氧化钛、氮氧化锆、氧化锆、氮化锆、氮化铝、氧化铝、氧化硅铝、氮化硅铝、氮氧化硅铝、锌锡氧化物或它们的混合物;所述电介质材料层或由硅、锆和钛中的至少一种元素与钼组成的至少两种元素的氧化物、氮化物或氮氧化物组成;当基板为玻璃基板时,所述电介质材料层由一含有Li、K中至少一种元素的碱过滤层替代,该碱过滤层包含Li、K中的至少一种元素和Si、Al、O三种元素。
7.一种CIGS基薄膜太阳能电池的制备方法,其特征在于:在一衬底上沉积背电极层,在背电极层上真空沉积合金膜层,在合金膜层上形成p型光吸收层,在p型光吸收层上沉积缓冲层,在缓冲层上沉积透明导电层;所述合金膜层由银、铂、铬中的至少一种元素与镓和锑元素组成,所述合金膜层的厚度不大于200nm。
8.根据权利要求7所述的一种CIGS基薄膜太阳能电池的制备方法,其特征在于:使用磁控溅射法沉积背电极层;使用磁控溅射法或真空蒸镀法沉积合金膜层;使用磁控溅射后硒化工艺、共蒸发工艺、反应溅射沉积工艺或直接溅射沉积工艺制备p型光吸收层;使用化学水浴法、溅射法或者MOCVD法沉积缓冲层;使用磁控溅射法或者真空蒸镀法沉积透明导电窗口层。
9.根据权利要求7所述的一种CIGS基薄膜太阳能电池的制备方法,其特征在于:所述p型光吸收层为p型铜铟镓硒、p型铜铟镓硫、p型铜铟镓硒硫、p型铜铟镓铝硒、p型铜铟镓铝硫、p型铜铟镓铝硒硫、p型铜铟铝硒硫、p型铜铟铝硒、p型铜铟铝硫、p型铜铟硒硫、p型铜铟硫或p型铜铟硒中的一种,所述p型光吸收层中含有碱元素。
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