CN104157738A - 全溶液法制备cigs太阳能光电池 - Google Patents
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- H01L31/00—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
- H01L31/04—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 adapted as photovoltaic [PV] conversion devices
- H01L31/06—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 adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier
- H01L31/072—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 adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type
- H01L31/0749—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 adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type including a AIBIIICVI compound, e.g. CdS/CulnSe2 [CIS] heterojunction solar cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
本发明公开了一种CIGS太阳能光电池,其包括:导电衬底;CIGS活性层,n型半导体层,该n半导体层制作在所述CIGS活性层上,并与之形成pn结;窗口层,该窗口层制作在所述n型半导体层用来保护所述N型半导体层;透明电极层,该透明电极层制作在所述窗口层上;采集电极,该采集电极制作在所述透明电极层上。该CIGS太阳能光电池的制备采用全溶液法,整个器件活性层的制备都可用非真空卷对卷的方式来进行,比如喷涂、打印、印刷等。这一发明将极大的降低CIGS太阳能电池的生产成本,对其产业化的发展提供了强有力的手段。
Description
技术领域
本发明属于光电子器件领域,涉及到一种新的铜(Cu)铟(In)镓(Ga)硒(Se)(简称:CIGS)薄膜太阳能电池以及这种薄膜电池的制备方法。
背景技术
随着能源危机的日趋严重,可再生能源越来越受到人们的重视。而其中,太阳光能以其取之不尽,清洁无污染成为最具潜力的技术。硅基太阳能技术是目前最为成熟的,也是市场占有率最高的,但是受制于高耗能、高污染的制备过程,使其并不能成为最理想的太阳能技术。近年来,薄膜太阳能技术开始兴起,具有重量轻、成本低、易安装等优点。CIGS则是薄膜太阳能技术中效率最高的(20.1%),其制备过程主要是真空沉积方法。不过由于CIGS是多元化合物,如利用真空沉积技术,不管是溅射/硒化,还是共蒸发,都有过程复杂,难规模化的问题。最近NANOSOLAR和IBM的研究组分别开发了利用溶液法来制备CIGS活性膜的技术。这类技术不需要真空蒸镀设备,大大减低制作成本,而且容易规模化。但是在这类技术里,窗口层的制备仍是需要依靠真空沉积的方法。这里,我们报告了一种利用溶液法来制备氧化锌窗口层的新方法,并结合CIGS和n型半导体层的溶液制备法,从而实现了全溶液法来制备CIGS太阳能光电池,为大规模的制备高转换效率,低成本的CIGS太阳能光电池提供了可能。
发明内容
针对上述现有技术的不足,本发明要解决的技术问题是CIGS薄膜太阳能电池全溶液的制备方法。
为解决上述技术问题,本发明采用如下技术方案:
一种CIGS太阳能光电池,其包括:导电衬底;CIGS活性层,该CIGS活性层制备在所述导电衬底上,主要作为吸光层,n型半导体层,该n半导体层制作在所述CIGS活性层上,并与之形成pn结,可有效增大光生激子的解离和输出;窗口层,该窗口层制作在所述n型半导体层用来保护所述N型半导体层;透明电极层,该透明电极层制作在所述窗口层上;采集电极,该采集电极制作在所述透明电极层上,具有采集光生光流的作用。
优选的,所述导电衬底为金属导电薄膜,其选用钼、铝、钛、铜或不锈钢,厚度为200-2000纳米。
优选的,所述CIGS活性层的厚度在0.5-10微米之间。
优选的,所述n型半导体层厚度在20-200nm之间,为硫化镉、硫化锌、硒化镉、硒化锌、碲化镉、碲化锌、或其他II-VI组三元化合物。
优选的,所述窗口层材料选用氧化锌或掺杂氧化锌薄膜,掺杂元素为铝、镓或镉,厚度为20-200纳米。
优选的,所述透明电极层为氧化铟锡薄膜或掺铝、镓、镉的氧化锌薄膜。
优选的,所述采集电极选用镍、铝、金、银、铜、钛、铬中的一种或多种。
本发明还公开了一种上述CIGS太阳能光电池的制备方法,其中CIGS活性层通过溶液法制作在导电衬底上,厚度为0.1-10微米。最后在200-1000度的环境下高温退火形成CIGS的连续膜。
优选的,所述溶液法包括旋涂法、喷涂法、糟模法。
优选的,n型半导体层采用CBD的方法制作在CIGS活性层(2)上,形成pn结,使光生激子解离和输出。
优选的,窗口层采用纳米颗粒或者溶胶-凝胶的方法制作在n型半导体层(3)上,形成pn结,使光生激子解离和输出。
上述技术方案具有如下有益效果:该CIGS太阳能光电池的CIGS活性层,n型半导体层和窗口层的制备均采用溶液法,具有便宜快捷的优点,极大的降低了太阳能电池的生产成本。
上述说明仅是本发明技术方案的概述,为了能够更清楚了解本发明的技术手段,并可依照说明书的内容予以实施,以下以本发明的较佳实施例并配合附图详细说明如后。本发明的具体实施方式由以下实施例及其附图详细给出。
附图说明
图1为本发明实施例的结构示意图。
具体实施方式
下面结合附图对本发明的优选实施例进行详细介绍。
如图1所示,为CIGS太阳能光电池的结构示意图。该器件包括:导电衬底1;CIGS活性层2,该CIGS活性层2是用三溶液法制作在导电衬底1上的;n型半导体层3,该n型半导体层3是利用CBD沉积法制作在CIGS活性层2上的;窗口层4,该半导体层是利用溶液法将纳米颗粒或者溶胶-凝胶制作在n型半导体层3上的;透明电极层5;和金属采集电极6。
所述的导电衬底1为金属导电薄膜,通常为钼电极厚度200-2000纳米但不局限于钼,也包括其他适用金属材料,如铝、钛、铜和不锈钢等。导电衬底1上面是采用溶液法(泛指一切涂料法,如旋涂法,喷涂法,糟模法等)制备的CIGS活性层2。如用旋涂法,通过控制旋涂速度、溶液浓度和不同的旋涂次数便可以改变该CIGS活性层2的厚度,通常情况下该缓冲层的厚度在0.1-10微米之间。CIGS活性层2上面的n型半导体层3是采用CBD或者纳米颗粒/溶胶-凝胶溶液法制备的,该功能层是为了与CIGS层形成有效的pn结,从而提高光生激子的分离和输出,该n型半导体层3的厚度通常情况下在20-200纳米之间,该n型半导体层3一般为硫化镉(CdS)材料,但不局限于此,也包括其他n型半导体,例如硫化锌、硒化镉、硒化锌、碲化镉、碲化锌,以及其他II-VI组三元化合物。n型半导体层3上面是窗口层4和透明电极层5。窗口层4的材料选用氧化锌或掺杂氧化锌薄膜,掺杂元素为铝、镓或镉,厚度为20-200纳米,是采用纳米颗粒/溶胶-凝胶溶液法制备的。透明电极层为氧化铟锡薄膜或掺铝、镓、镉的氧化锌薄膜。最后是金属采集电极6,一般是镍/铝,但不局限于此,还包括其他金属,包括金、银、铜、钛、铬等。
下面以旋涂法为例对上述CIGS太阳能光电池的制备方法进行详细介绍。
1.制备CIGS先驱体的工艺如下:
(1)纳米先驱体:将12毫升的OLEYLAMIN,1.5毫摩的氯化铜和1.0毫摩的氯化铟,0.5毫摩的氯化镓放入100毫升容积的三颈反应瓶。在氩气保护下升温到130度,保持30分钟。然后将反应温度升高到225度,并迅速注入含有1摩尔硫的3毫升OLEYLAMINE。反应30分钟后,冷却到60度并加入10毫升的甲苯。最后加入毫升乙醇,离心分离出来,按所需浓度分散到甲苯中作为CIGS的先驱体。
(2)溶液先驱体:先制备四种不同的先驱体,然后按照所需要不同的元素组成比混合成最终的溶液先驱体。先驱体A:0.955克硫化铜,0.3848克硫和12毫升无水联氨;先驱体B:1.8661克硒化铟,0.3158克硒和12毫升无水联氨;先驱体C:0.4183克镓,0.9475克硒和12毫升无水联氨;先驱体D:0.9475克硒和6毫升无水联氨。
2.将钠钙玻璃在清洗剂中反复清洗,然后再经过去离子水,丙酮和异丙醇溶液浸泡并超声各15分钟,最后用氮气吹干并经过紫外臭氧处理15分钟。
3.用真空沉积得方法制备钼电极800纳米左右。
4.将过滤后的具有一定化学组分比的溶液以800转/分钟的转速旋涂在金属衬底上,低温退火后(150-350度),再重复同样的旋涂过程,达到所需的厚度,其化学组分比分别为:Cu0.92In1-xGaxS1-ySey。完成全部旋涂后,最后再高温(250-550度)退火30分钟,使前驱体反应结晶,形成连续CIGS膜。
5.采用CBD或者纳米颗粒/溶胶-凝胶方法制作n型硫化镉层
6.采用纳米颗粒/溶胶-凝胶方法制作窗口层
制备氧化锌溶液的工艺如下:
(1)纳米颗粒溶液:缓慢的将化学计量比相同的羟化四甲胺的乙醇溶液(0.55M)滴加到二水醋酸锌的二甲基亚砜溶液中,连续搅拌反应一个小时,然后离心分离出来。
(2)溶胶-凝胶溶液:配制0.02M的二水醋酸锌的甲醇溶液,充分溶解后即成氧化锌的溶胶-凝胶溶液。
7.然后再用溅射真空沉积法制备氧化铟锡透明电极。
8.最后用热蒸发制备镍/铝采集电极。
该CIGS太阳能光电池采用全溶液的制备方法具有便宜快捷的优点,对其产业化的发展提供了强有力的手段。
以上对本发明实施例所提供的一种全溶液法制备铜铟镓硒薄膜太阳能光电池进行了详细介绍,对于本领域的一般技术人员,依据本发明实施例的思想,在具体实施方式及应用范围上均会有改变之处。综上所述,本说明书内容不应理解为对本发明的限制,凡依本发明设计思想所做的任何改变都在本发明的保护范围之内。
Claims (11)
1.一种CIGS太阳能光电池,其特征在于,其包括:
导电衬底;
CIGS活性层,该CIGS活性层制备在所述导电衬底上,主要作为吸光层,n型半导体层,该n半导体层制作在所述CIGS活性层上,并与之形成pn结,可有效增大光生激子的解离和输出;
窗口层,该窗口层制作在所述n型半导体层用来保护所述N型半导体层;透明电极层,该透明电极层制作在所述窗口层上;
采集电极,该采集电极制作在所述透明电极层上,具有采集光生光流的作用。
2.根据权利要求1所述的CIGS太阳能光电池,其特征在于:所述导电衬底为金属导电薄膜,其选用钼、铝、钛、铜或不锈钢,厚度为200-2000纳米。
3.根据权利要求1所述的CIGS太阳能光电池,其特征在于:所述CIGS活性层的厚度在0.5-10微米之间。
4.根据权利要求1所述的CIGS太阳能光电池,其特征在于:所述n型半导体层厚度在20-200nm之间,为硫化镉、硫化锌、硒化镉、硒化锌、碲化镉、碲化锌、或其他II-VI组三元化合物。
5.根据权利要求1所述的CIGS太阳能光电池,其特征在于:所述窗口层材料选用氧化锌或掺杂氧化锌薄膜,掺杂元素为铝、镓或镉,厚度为20-200纳米。
6.根据权利要求1所述的CIGS太阳能光电池,其特征在于:所述透明电极层为氧化铟锡薄膜或掺铝、镓、镉的氧化锌薄膜。
7.根据权利要求1所述的CIGS太阳能光电池,其特征在于:所述采集电极选用镍、铝、金、银、铜、钛、铬中的一种或多种。
8.一种CIGS太阳能光电池的制备方法,其特征在于,CIGS活性层通过溶液法制作在导电衬底上,厚度为0.1-10微米。最后在200-1000度的环境下高温退火形成CIGS的连续膜。
9.根据权利要求8所述的CIGS太阳能光电池的制备方法,其特征在于:所述溶液法包括旋涂法,喷涂法,糟模法。
10.根据权利要求8所述的CIGS太阳能光电池的制备方法,其特征在于:n型半导体层采用CBD或者真空沉积的方法制作在CIGS活性层(2)上,形成pn结,使光生激子解离和输出。
11.根据权利要求8所述的CIGS太阳能光电池的制备方法,其特征在于:窗口材料采用喷涂/旋涂/打印法将氧化锌纳米颗粒或者溶胶-凝胶溶液制作在n型半导体衬底上,厚度为10-1000纳米。最后在20-1000度的环境下高温退火,形成致密的ZnO薄膜。
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