CN104269451A - 一种硅基钙钛矿叠层太阳电池及其制造方法 - Google Patents
一种硅基钙钛矿叠层太阳电池及其制造方法 Download PDFInfo
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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
- H01L31/04—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
- H01L31/0745—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 comprising a AIVBIV heterojunction, e.g. Si/Ge, SiGe/Si or Si/SiC solar cells
- H01L31/0747—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 comprising a AIVBIV heterojunction, e.g. Si/Ge, SiGe/Si or Si/SiC solar cells comprising a heterojunction of crystalline and amorphous materials, e.g. heterojunction with intrinsic thin layer or HIT® solar cells; 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
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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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
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
本发明属新型叠层太阳电池领域，具体为一种硅基钙钛矿叠层太阳电池及其制造方法，将硅基HIT太阳电池与新型钙钛矿薄膜太阳电池相结合，具有金属背电极/N型硅片/i-a-Si:H/p-a-SiOx:H/n-a-SiOx:H/CH3NH3PdI3-xClx/p-a-SiOx:H/TCO（FTO，ITO，AZO)和金属背电极/P型硅片/i-a-Si:H/n-a-SiOx:H/p-a-SiOx:H/CH3NH3PdI3-xClx/n-a-SiOx:H/TCO（FTO，ITO，AZO)两种结构，具有带隙匹配良好、能更多吸收太阳能光谱，有效提高太阳电池光电转换效率。
Description
技术领域
本专利涉及一种硅基钙钛矿叠层太阳电池及其制造方法，属于新型叠层太阳电池领域。
背景技术
能源是人类赖以生存的战略性基础资源，也是经济、社会发展必不可少的动力源泉。地球上的石化能源正在不断减少，化石能源的利用给环境带来了严重的污染。因此，加强可再生能源的开发利用，大力发展“低碳经济”，是应对能源、环境问题，实现人类社会可持续发展的必由之路。太阳能是一种取之不尽、用之不竭的清洁能源。高效、低成本、方便地利用太阳能，已成为科研工作者的一项重大课题。光伏技术是太阳能研究领域中一个重要的发展方向，其通过太阳电池将太阳能转换为电能，因此，太阳电池是光伏技术的核心。以硅基材料为基础的硅太阳电池以成熟的制备工艺，在各种光伏器件中占据主导地位。此外，自2009年以来一类以金属卤化物与有机烷氨杂化的钙钛矿（perovskite）结构半导体为光吸收层的所谓钙钛矿太阳电池引起人们注意。文献“A. Kojima, K.Teshima, Y. Shirai, T. Miyasaka, J. Am.Chem.Soc.2009, 131, 6050.”首先报道了采用钙钛矿材料作为吸收层的太阳电池；文献“M.M.Lee, J. Teuscher, T. Miyasaa, T. N. Murami, H. J. Snaith, Science (2012)”、“Mingzhen Liu, Michael B. Johnston & Henry J. Snaith，Nature（2013）” 和 “Dianyi Liu and Timothy L. Kelly, Nature (2013)”跟进报道并在较短的时间内其光电转换效率从起初的4%迅速提高到15%以上并即将达到20%。美国加州斯坦福大学M. McGehee 小组报道，他们研制的钙钛矿/CIGS 叠层电池效率达到18.6%。另一方面，一种结合晶体硅和非晶硅优势为一体的异质结薄膜硅太阳电池（HIT）近年来发展迅速，其光电转换效率已突破25%。
发明内容
针对背景技术中各类太阳电池的优势与缺点，本专利提出硅基钙钛矿叠层太阳电池及其制造方法，将硅基HIT太阳电池与新型钙钛矿薄膜太阳电池相结合，提出带隙为1.12eV的硅基材料与带隙为1.5eV的钙钛矿结构烷氨金属卤化物（CH3NH3PdI3-xClx）叠层太阳电池及其制造方法。本发明包括两种结构，分别为：
金属背电极/N型硅片/i-a-Si:H/p-a-SiOx:H/n-a-SiOx:H/CH3NH3PdI3-xClx/p-a-SiOx:H
/TCO（FTO，ITO，AZO)和金属背电极/P型硅片/i-a-Si:H/n-a-SiOx:H/p-a-SiOx:H
/CH3NH3PdI3-xClx/n-a-SiOx:H/TCO（FTO，ITO，AZO)两种结构。
本发明提供一种硅基钙钛矿叠层太阳电池的制造方法，其技术方案包括：
1）采用单晶硅片为基底，对其进行腐蚀清洗处理，而后用N2吹干；
2）利用丝网印刷技术在单晶硅片上制备背电极并进行烧结；
3）清洗腐蚀晶体硅片的另一面；
4）利用PECVD等在单晶硅片的清洁面制备本征硅薄层（~5nm）和两层a-SiOx:H（~10-20nm）隧道结；
5）利用热蒸发技术在隧道结硅基薄膜上制备（CH3NH3PdI3-xClx）吸收层；
6）在（CH3NH3PdI3-xClx）吸收层上利用PECVD技术制备a-SiOx:H硅基窗口层薄膜；
7）利用溅射或蒸发技术制备TCO（FTO，ITO，AZO）薄膜。
本发明与公知技术相比具有的优点及积极效果：
本专利提供的硅基钙钛矿叠层太阳电池及其制造方法，利用单晶硅HIT薄膜太阳电池及钙钛矿型薄膜异质结形成叠层太阳电池，带隙匹配良好、更多吸收太阳能光谱，有效提高太阳电池光电转换效率。
附图说明：
图1为本发明提供的硅基钙钛矿叠层太阳电池及其制造方法的工艺流程图；
图2为本发明提供的硅基钙钛矿叠层太阳电池结构图1；
图3为本发明提供的硅基钙钛矿叠层太阳电池结构图2；
具体实施方式：
实施例1
本实施例按以下步骤：
1）采用N型单晶硅片为基底，利用混合酸腐蚀去除表面氧化层，单晶硅片厚度为200~250nm，再依次使用丙酮、无水乙醇和去离子水分别对N型硅基底进行超声清洗10~15min，N2吹干；
2）采用丝网印刷技术，在硅片背面刷上Ag/Al浆，退火处理制备背电极，再次利用混合酸腐蚀去除表面氧化层，并使用丙酮、无水乙醇和去离子水分别硅片正面进行超声清洗10~15min，N2吹干；；
3）利用三室等离子体增强汽相化学沉积（PECVD）镀膜系统，系统本底真空为6×10-5Pa；在本征室中以SiH4，H2等为放电气体，在合适的生长压力、氢稀释比、衬底温度和功率密度条件下，制备本征非晶硅层，厚度约~5nm；
4）P型掺杂室中，放电气体为氢气、硅烷（SiH4）、CO2和掺杂气体(5%的氢稀释)氟化硼(BF3)为放电气体，生长时的压力、温度和功率密度分别为100~120Pa、200℃、100～200mW/cm2，制备p-a-SiOx:H，厚度为10~20nm；
5）N型掺杂室中，以氢气、SiH4，CO2，和10%的稀释磷烷(PH3+H2)为放电气体，衬底温度150~200℃，放电功率密度100～200mW/cm2，制备n-a-SiOx:H，厚度为20~25nm；
6）80℃衬底温度、10Pa气压条件下真空沉积300nmABX3有机无机杂化钙钛矿吸收层；
7）P型掺杂室中，放电气体为氢气、硅烷（SiH4）、CO2和掺杂气体(5%的氢稀释)氟化硼(BF3)为放电气体，生长时的压力、温度和功率密度分别为100~120Pa、200℃、100～200mW/cm2，制备p-a-SiOx:H，厚度为10~20nm；
8）利用磁控溅射镀膜系统在P层硅薄膜表面溅射制备ITO透明导电氧化层，本底真空为6.0×10-4pa，工作压强为1.0~1.5pa，ITO陶瓷靶为靶材，溅射气体为纯度为99.999%的Ar，溅射功率为60~120W，厚度为60-70nm。
实施例2
本实施例按以下步骤：
1）采用P型单晶硅片为基底，利用混合酸腐蚀去除表面氧化层，单晶硅片厚度为200~250nm，再依次使用丙酮、无水乙醇和去离子水分别对P型硅基底进行超声清洗10~15min，N2吹干；
2）采用丝网印刷技术，在硅片背面刷上Ag/Al浆，退火处理制备背电极，再次利用混合酸腐蚀去除表面氧化层，并使用丙酮、无水乙醇和去离子水分别硅片正面进行超声清洗10~15min，N2吹干；；
3）利用三室等离子体增强汽相化学沉积（PECVD）镀膜系统，系统本底真空为6×10-5Pa；在本征室中以SiH4，H2等为放电气体，在合适的生长压力、氢稀释比、衬底温度和功率密度条件下，制备本征非晶硅层,，厚度约~5nm；
4）N型掺杂室中，以氢气、SiH4，CO2，和10%的稀释磷烷(PH3+H2)为放电气体，衬底温度150~200℃，放电功率密度100～200mW/cm2，制备n-a-SiOx:H，厚度为20~25nm；
5）P掺杂室中，放电气体为氢气、硅烷（SiH4）、CO2和掺杂气体(5%的氢稀释)氟化硼(BF3)为放电气体，生长时的压力、温度和功率密度分别为100~120Pa、200℃、100～200mW/cm2，制备p-a-SiOx:H，厚度为10~20nm；
6）80℃衬底温度、10Pa气压条件下真空沉积300nmABX3有机无机杂化钙钛矿吸收层；
7）N型掺杂室中，以氢气、SiH4，CO2，和10%的稀释磷烷(PH3+H2)为放电气体，衬底温度150~200℃，放电功率密度100～200mW/cm2，制备n-a-SiOx:H，厚度为20~25nm；
8）利用磁控溅射镀膜系统在P层硅薄膜表面溅射制备ITO透明导电氧化层，本底真空为6.0×10-4pa，工作压强为1.0~1.5pa，ITO陶瓷靶为靶材，溅射气体为纯度为99.999%的Ar，溅射功率为60~120W，厚度为60-70nm。
Claims (1)
1.一种硅基钙钛矿叠层太阳电池及其制造方法，其特征是：“将硅基HIT太阳电池与新型钙钛矿薄膜太阳电池相结合，提出带隙为1.12eV的硅基材料与带隙为1.5eV的钙钛矿结构烷氨金属卤化物（CH3NH3PdI3-xClx）叠层太阳电池及其制造方法，其结构为金属背电极/N型硅片/i-a-Si:H/p-a-SiOx:H/n-a-SiOx:H/CH3NH3PdI3-xClx/p-a-SiOx:H/TCO（FTO，ITO，AZO)和金属背电极/P型硅片/i-a-Si:H/n-a-SiOx:H/p-a-SiOx:H/CH3NH3PdI3-xClx/n-a-SiOx:H/TCO（FTO，ITO，AZO)两种结构”。
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| CN104979474A (zh) * | 2015-05-25 | 2015-10-14 | 中国科学院半导体研究所 | 基于钙钛矿电池和hit电池的叠层太阳能电池及制作方法 |
| CN105047823A (zh) * | 2015-06-24 | 2015-11-11 | 华南师范大学 | 一种半透明钙钛矿晶体硅串列叠层太阳能电池及其制备方法 |
| CN105428535A (zh) * | 2015-11-15 | 2016-03-23 | 河北工业大学 | 薄膜晶硅钙钛矿异质结太阳电池的制备方法 |
| CN105449103A (zh) * | 2015-11-15 | 2016-03-30 | 河北工业大学 | 一种薄膜晶硅钙钛矿异质结太阳电池及其制备方法 |
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| CN104979474A (zh) * | 2015-05-25 | 2015-10-14 | 中国科学院半导体研究所 | 基于钙钛矿电池和hit电池的叠层太阳能电池及制作方法 |
| CN105047823A (zh) * | 2015-06-24 | 2015-11-11 | 华南师范大学 | 一种半透明钙钛矿晶体硅串列叠层太阳能电池及其制备方法 |
| CN105449103B (zh) * | 2015-11-15 | 2018-06-22 | 河北工业大学 | 一种薄膜晶硅钙钛矿异质结太阳电池及其制备方法 |
| CN105449103A (zh) * | 2015-11-15 | 2016-03-30 | 河北工业大学 | 一种薄膜晶硅钙钛矿异质结太阳电池及其制备方法 |
| CN105428535A (zh) * | 2015-11-15 | 2016-03-23 | 河北工业大学 | 薄膜晶硅钙钛矿异质结太阳电池的制备方法 |
| KR101723797B1 (ko) * | 2016-01-11 | 2017-04-07 | 한밭대학교 산학협력단 | 페로브스카이트-비정질 실리콘 이종접합 태양전지 및 그의 제조 방법 |
| US10355149B2 (en) | 2016-06-17 | 2019-07-16 | Industrial Technology Research Institute | Tandem solar cell module |
| CN106410039A (zh) * | 2016-11-07 | 2017-02-15 | 大连理工大学 | 一种钙钛矿叠层太阳电池及其制备方法 |
| CN106449812A (zh) * | 2016-11-15 | 2017-02-22 | 云南师范大学 | 溅射锡靶和硫化铜靶制备铜锡硫薄膜及电池的方法 |
| CN106409961A (zh) * | 2016-11-23 | 2017-02-15 | 常熟理工学院 | 一种n‑Si/CdSSe叠层太阳电池及其制备方法 |
| CN106409961B (zh) * | 2016-11-23 | 2018-06-29 | 常熟理工学院 | 一种n-Si/CdSSe叠层太阳电池及其制备方法 |
| CN107369767A (zh) * | 2017-07-20 | 2017-11-21 | 南开大学 | 一种钙钛矿/硅异质结两端叠层太阳电池 |
| WO2022242797A1 (de) * | 2021-05-21 | 2022-11-24 | Meyer Burger (Germany) Gmbh | Mehrfachsolarzelle |
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