CN103515464B - 太空高效超导太阳能电池 - Google Patents

太空高效超导太阳能电池 Download PDF

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CN103515464B
CN103515464B CN201310393988.8A CN201310393988A CN103515464B CN 103515464 B CN103515464 B CN 103515464B CN 201310393988 A CN201310393988 A CN 201310393988A CN 103515464 B CN103515464 B CN 103515464B
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姜廷旭
李兆廷
王恩忠
高立伟
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NINGXIA DONGXU SOLAR ENERGY SCIENCE & TECHNOLOGY Co Ltd
Tunghsu Group Co Ltd
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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
    • H01L31/0248—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
    • H01L31/0352—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 shape or by the shapes, relative sizes or disposition of the semiconductor regions
    • 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
    • H01L31/0248—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
    • H01L31/0256—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 the material
    • H01L31/0264—Inorganic materials
    • H01L31/0296—Inorganic materials including, apart from doping material or other impurities, only AIIBVI compounds, e.g. CdS, ZnS, HgCdTe
    • H01L31/02963—Inorganic materials including, apart from doping material or other impurities, only AIIBVI compounds, e.g. CdS, ZnS, HgCdTe characterised by the doping material
    • 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
    • H01L31/0248—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
    • H01L31/0256—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 the material
    • H01L31/0264—Inorganic materials
    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
    • 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
    • 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
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/541—CuInSe2 material PV cells

Abstract

本发明涉及一种太空高效超导太阳能电池，其膜层结构从基板到受光面依次包括背电极MO层、CIGS吸收层、改良过渡层、i-ZnO窗口层和沉积有ZnO:AL的透明电极层，所述透明电极层上设有引线，其特征是：所述改良过渡层为掺杂有Nb-Ti合金的ZnSe层。本发明的太空高效超导太阳能电池与原有CIGS电池相比，突破了原有近地表面使用范围，使CIGS应用于太空低温环境，并利用太空低温环境，通过改良过渡层以达到超导效应用以提高电池发电性能及过渡层与吸收层晶格匹配，提高了提高电子传输及光电转换效率。

Description

太空高效超导太阳能电池
技术领域
本发明涉及太阳能电池应用领域，特别是涉及一种可利用光能转换成电能，并且可自行发电的太空高效超导太阳能电池。
背景技术
铜铟镓硒（CIGS）薄膜太阳能电池由于效率高、无衰退、抗辐射、寿命长、成本低廉等特点，成为备受人们关注的一种新型光伏电池产品，经过近30年的研究和发展，其光电转化效率为所有已知薄膜太阳能电池中最高的，而且其光谱响应范围宽。铜铟镓硒CuInSe2（简称CIS）薄膜材料是属于Ⅰ-Ⅲ-Ⅵ2族化合物直接带隙半导体，薄膜厚度约为1-2μm就能吸收太阳光，其禁带宽度为1.02eV。通过掺入适量的Ga元素以代替部分的In，成为CuInSe2与CuGaSe2的固溶半导体CuIn1-xGaxSe2。
在电池的带隙优化或电池转换效率方面，国际上普遍采用CIGS电池在制作过程中，通过控制不同的Ga掺入量用以代替In，改变晶体的晶格常数，其禁带宽度可在1.02-1.67eV范围内调整，这就为太阳能电池的带隙优化提供了很好的途径。此外缓冲层如CdS或ZnSe也改进了电池结构，使电池效率大幅提升。
但应用于外太空，铜铟镓硒发电效率及使用寿命受环境温度影响甚大，外太空温度接近绝对零度（3-10K），对于铜铟镓硒来说，如何改善过渡层结构，更好的适应太空生活及提高发电效率尤其重要。
发明内容
本发明的目的在于克服上述现有技术中的缺陷，提供一种掺杂微量杂质元素改善过渡层内部结构，形成超导效应提高电子传输及高效转化效率的太空高效超导太阳能电池。
为实现上述发明目的所采取的技术方案为：
一种太空高效超导太阳能电池，其膜层结构从基板到受光面依次包括背电极MO层、CIGS吸收层、改良过渡层、i-ZnO窗口层和沉积有ZnO:AL的透明电极层，所述透明电极层上设有引线，其特征是：所述改良过渡层为掺杂有Nb-Ti合金的ZnSe层。
所述改良过渡层按照ZnSe：Nb：Ti=9:0.5:0.5的质量配比制备。
所述改良过渡层是指采用真空蒸发法将ZnSe、Nb和Ti靶材原子在真空环境、1150-1300℃条件下在吸收层成膜而形成。
所述引线为掺杂了Nb-Ti合金的AL导线。
本发明的太空高效超导太阳能电池与原有CIGS电池相比，突破了原有近地表面使用范围，使CIGS应用于太空低温环境，并利用太空低温环境，通过改良过渡层以达到超导效应用以提高电池发电性能及过渡层与吸收层晶格匹配，从而提高了电子传输及光电转换效率。
如图1所示，本发明的太空高效超导太阳能电池的吸收系数高于图中其他电池吸收系数。在获得相同电子伏特或称发电效率时采用铜铟镓硒或碲化镉材料电池的面积将更小，换句话说，相同面积上的超导电池发电效率将是普通非晶硅或单晶硅的1.2倍左右。
附图说明
图1为本发明的太空高效超导太阳能电池与其他电池吸收系数比较图；
图2为本发明的太空高效超导太阳能电池膜层结构示意图；
图3为本发明的太空高效超导太阳能电池激光划线及内部电子流向图；
图4为本发明的太空高效超导太阳能电池模拟替代晶格结构——类闪锌矿晶格机构；
图5为本发明的太空高效超导太阳能电池模拟替代晶格结构——类黄铜矿晶格结构；
附图中：○代表Se、Ti；●代表Cu、In、Nb。
具体实施方式
下面结合附图对本发明进一步说明。
如图2所示，本发明的太空高效超导太阳能电池，其膜层结构从基板6到受光面依次包括背电极5、CIGS吸收层4、改良过渡层3、窗口层2和沉积有ZnO:AL的透明电极层1，所述透明电极层1上设有引线7。
基板6采用钠钙玻璃或柔性衬底或其他良好新型材料衬底。在基板6上使用直流脉冲磁控溅射背电极MO层5。将Cu、In和Se按一定的原子配比制备成Cu/In/Se/Cu/In/Se/Cu/In/Se多层膜系统，在一定的升温速率下加热而形成CIS；通过掺入适量的Ga元素以代替部分的In，成为CuInSe2与CuGaSe2的固溶半导体CuIn1-xGaxSe2，形成CIGS吸收层4。利用真空蒸发法在真空环境、高温1150-1300℃下使靶材原子ZnSe:Nb：Ti=9:0.5:0.5在吸收层成膜，形成改良过渡层3。利用磁控溅射方法沉积i-ZnO形成窗口层2。利用磁控溅射方法沉积ZNO:AL到透明电极上形成透明电极1。最后打孔引出电流引线7，引线7是掺杂了Nb-Ti合金的AL导线。电池内部电子流向如图3所示。
本发明运用模型模拟计算法进行效能估算，计算所用的太空太阳能光谱，模拟计算中的光透过率主要通过琼斯矩阵非线性方程获得，光子利用率主要由泊松方程获得，这主要研究电池内部器件电子的输运特性，由泊松方程来计算自由载流子布局数、被俘获电子的布局数，在运用求解耦合非线性方程来估算出光子的利用率及电池效率。
考虑到掺杂了Nb-Ti合金元素在改善ZnSe层结构及形成超导现象条件因素关系方面具有直接关系，又因太空特定环境下，地面难以模拟，为更好的研究其关系及可行性，特提供具体实施例。
假设波尔兹曼近似成立，假设注入的少数载流子密度小于多数载流子的密度成立，根据肖克莱方程：（qVkT-1）DJJe（3-7）DJ，当处于太空环境，且光辐射进入时，由于光生载流子的作用，在CIGS吸收层4产生光生电流LJ，则有LqVkTDJ=J(e-1)-J（3-8），光生载流子复合由DJ决定，在改良过渡层3处，运用上式可得对于ZnSe：Nb：Ti=9:0.5:0.5近于类黄铜矿晶格结构（图5），异质结的晶格常数近于0.517nm时，有利的消除了界面复合，运用泊松方程与琼斯矩阵非线性方程计算光辐射利用率，得出电子复合中心处态密度表达式。由于太空特定温度，需要研究其温度与CIGS及ZnSe：Nb-Ti中的复合中心态密度及近似超导现象引发的Tc值，已知Nb-33Ti，Tc=9.3K，Hc=11.0T，对于实际比例Nb：Ti=1：1类合金态原子匹配Tc值需实验论证。理论上证明通过改良吸收层3结构可以达到电子利用效率及发电效率。

Claims (2)

1.一种太空高效超导太阳能电池，其膜层结构从基板（6）到受光面依次包括背电极MO层（5）、CIGS吸收层（4）、改良过渡层（3）、i-ZnO窗口层（2）和沉积有ZnO:AL的透明电极层（1），所述透明电极层（1）上设有引线（7），其特征是：所述改良过渡层（3）为掺杂有Nb-Ti合金的ZnSe层，其是采用真空蒸发法将ZnSe、Nb和Ti靶材原子在真空环境、1150-1300℃条件下在吸收层成膜而形成，其中ZnSe、Nb和Ti按照9:0.5:0.5的质量配比。
2.按照权利要求1所述的太空高效超导太阳能电池，其特征是：所述引线（7）为掺杂了Nb-Ti合金的AL导线。
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