CN102625953B - 太阳能电池前接触件掺杂 - Google Patents
太阳能电池前接触件掺杂 Download PDFInfo
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- CN102625953B CN102625953B CN201080037509.3A CN201080037509A CN102625953B CN 102625953 B CN102625953 B CN 102625953B CN 201080037509 A CN201080037509 A CN 201080037509A CN 102625953 B CN102625953 B CN 102625953B
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- 238000000034 method Methods 0.000 claims abstract description 73
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- 239000000758 substrate Substances 0.000 claims description 63
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 42
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- 239000011701 zinc Substances 0.000 claims description 22
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims description 21
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims description 21
- 239000011787 zinc oxide Substances 0.000 claims description 21
- 229910052782 aluminium Inorganic materials 0.000 claims description 20
- 239000004411 aluminium Substances 0.000 claims description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 20
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 claims description 19
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 19
- 229910052725 zinc Inorganic materials 0.000 claims description 19
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 18
- 229910001887 tin oxide Inorganic materials 0.000 claims description 18
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 16
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 16
- 229910052796 boron Inorganic materials 0.000 claims description 16
- 229910052731 fluorine Inorganic materials 0.000 claims description 16
- 239000011737 fluorine Substances 0.000 claims description 16
- 229910052738 indium Inorganic materials 0.000 claims description 15
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 15
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 13
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 13
- 229910052801 chlorine Inorganic materials 0.000 claims description 13
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- 229910052802 copper Inorganic materials 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 13
- 229910052733 gallium Inorganic materials 0.000 claims description 13
- 238000000137 annealing Methods 0.000 claims description 10
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 9
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- 239000011777 magnesium Substances 0.000 claims description 9
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 claims description 8
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 claims description 8
- UQMZPFKLYHOJDL-UHFFFAOYSA-N zinc;cadmium(2+);disulfide Chemical compound [S-2].[S-2].[Zn+2].[Cd+2] UQMZPFKLYHOJDL-UHFFFAOYSA-N 0.000 claims description 8
- 238000005546 reactive sputtering Methods 0.000 claims description 7
- 239000005083 Zinc sulfide Substances 0.000 claims description 6
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
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- TZNSLBQRBDSHQV-UHFFFAOYSA-N cadmium(2+) manganese(2+) disulfide Chemical compound [S-2].[Mn+2].[Cd+2].[S-2] TZNSLBQRBDSHQV-UHFFFAOYSA-N 0.000 claims description 4
- QWUZMTJBRUASOW-UHFFFAOYSA-N cadmium tellanylidenezinc Chemical compound [Zn].[Cd].[Te] QWUZMTJBRUASOW-UHFFFAOYSA-N 0.000 claims description 2
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- 238000005477 sputtering target Methods 0.000 description 21
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- 229940071182 stannate Drugs 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- JYMITAMFTJDTAE-UHFFFAOYSA-N aluminum zinc oxygen(2-) Chemical compound [O-2].[Al+3].[Zn+2] JYMITAMFTJDTAE-UHFFFAOYSA-N 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000007596 consolidation process Methods 0.000 description 2
- 229910003437 indium oxide Inorganic materials 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 238000000462 isostatic pressing Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- HTJNDQNBKKHPAQ-UHFFFAOYSA-N oxotin zirconium Chemical compound [Sn]=O.[Zr] HTJNDQNBKKHPAQ-UHFFFAOYSA-N 0.000 description 2
- DOVLZBWRSUUIJA-UHFFFAOYSA-N oxotin;silicon Chemical compound [Si].[Sn]=O DOVLZBWRSUUIJA-UHFFFAOYSA-N 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- AKVPCIASSWRYTN-UHFFFAOYSA-N zinc oxygen(2-) silicon(4+) Chemical compound [Si+4].[O-2].[Zn+2].[O-2].[O-2] AKVPCIASSWRYTN-UHFFFAOYSA-N 0.000 description 2
- UPAJIVXVLIMMER-UHFFFAOYSA-N zinc oxygen(2-) zirconium(4+) Chemical compound [O-2].[O-2].[O-2].[Zn+2].[Zr+4] UPAJIVXVLIMMER-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 244000287680 Garcinia dulcis Species 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 201000009310 astigmatism Diseases 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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Classifications
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- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
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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
- H01L31/0248—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
- H01L31/02966—Inorganic materials including, apart from doping material or other impurities, only AIIBVI compounds, e.g. CdS, ZnS, HgCdTe including ternary compounds, e.g. HgCdTe
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- H01L31/02—Details
- H01L31/0224—Electrodes
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- H—ELECTRICITY
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- 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
- H01L31/0324—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIVBVI or AIIBIVCVI chalcogenide compounds, e.g. Pb Sn Te
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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
- H01L31/036—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
- H01L31/0392—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
- H01L31/03925—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 AIIBVI compound materials, e.g. CdTe, CdS
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- 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
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- 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 potential barriers the potential barriers being only of the PN heterojunction type
- H01L31/073—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 potential barriers the potential barriers being only of the PN heterojunction type comprising only AIIBVI compound semiconductors, e.g. CdS/CdTe solar cells
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- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/20—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials
- H01L31/208—Particular post-treatment of the devices, e.g. annealing, short-circuit elimination
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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
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- Manufacturing & Machinery (AREA)
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Abstract
一种对太阳能电池前接触件掺杂的方法可以提高基于CdTe的或其它类型的太阳能电池的效率。
Description
本申请要求于2009年7月13日提交的第61/224,941号美国临时专利申请的优先权,该临时专利申请通过引用全部包含于此。
技术领域
本发明涉及一种具有掺杂的前接触件的太阳能电池。
背景技术
光伏装置可以使用同样是电荷的导体的透明薄膜。导电薄膜可以包括透明导电层,透明导电层包含透明导电氧化物(TCO),例如,氧化锡或氧化锌。TCO可以允许光穿过半导体窗口层到达活性吸光材料,并且起到欧姆接触的作用以将光生电荷载流子传输离开吸光材料。
发明内容
根据本发明的一方面,提供了一种光伏装置,所述光伏装置包括:基底;前接触层,与基底相邻,其中,前接触层被掺杂剂掺杂;半导体吸收剂层,与掺杂的前接触层相邻,其中,半导体吸收剂层包括碲化镉。
根据本发明的另一方面,提供了一种制造光伏装置的方法,所述方法包括:与基底相邻地沉积透明导电氧化物层,其中,在沉积后,透明导电氧化物层具有表面;使透明导电氧化物层的所述表面暴露于掺杂剂,其中,在基底上能够留下掺杂剂层;与掺杂剂层相邻地沉积窗口层;使掺杂剂进入到窗口层中;与窗口层相邻地沉积吸收剂层,其中,吸收剂层包括碲化镉。
根据本发明的又一方面,提供了一种制造光伏装置的方法,所述方法包括:与基底相邻地沉积透明导电氧化物层;通过从掺杂的靶进行溅射与透明导电氧化物层相邻地沉积窗口层,其中,掺杂的靶是用掺杂剂掺杂的;与窗口层相邻地沉积吸收剂层,其中,吸收剂层包括碲化镉。
根据本发明的再一方面,提供了一种制造光伏装置的方法,所述方法包括:与基底相邻地沉积透明导电氧化物层;通过从掺杂的靶进行溅射与透明导电氧化物层相邻地沉积前驱体层,其中,掺杂的靶是用掺杂剂掺杂的;与前驱体层相邻地沉积缓冲层;对前驱体层和缓冲层进行退火以形成掺杂的缓冲层;与掺杂的缓冲层相邻地沉积吸收剂层,其中,吸收剂层包括碲化镉。
附图说明
图1是具有多个半导体层和金属背接触件的光伏装置的示意图。
图2是具有多个半导体层和金属背接触件的光伏装置的示意图。
图3是制造掺杂的溅射靶的工艺流程图。
图4是示出了前接触层的溅射沉积工艺的示意图。
图5是包括洗涤/清洗步骤的沉积和处理前接触层的工艺流程图。
图6是示出了基底的洗涤/清洗掺杂工艺的示意图。
图7是示出了基底的洗涤/清洗掺杂工艺的示意图。
图8是示出了基底的洗涤/清洗掺杂工艺的示意图。
图9是示出了基底的洗涤/清洗掺杂工艺的示意图。
图10是示出了退火工艺后的基底和透明导电氧化物层的示意图。
具体实施方式
在光伏装置的制造期间,可以将半导体材料的层沉积在包括前接触件和吸收剂层的基底上。前接触件可以包括允许太阳辐射穿透到吸收剂层的半导体窗口层,在吸收剂层将光学能转换为电能。一些光伏装置可以使用同样是电荷的导体的透明薄膜。前接触件也可以包括透明导电层,透明导电层包含透明导电氧化物(TCO),例如,锡酸镉。TCO可以允许光穿过半导体窗口层到达活性吸光材料,并且还起到欧姆接触的作用以将光生电荷载流子传输离开吸光材料。在特定实施例中,前接触件还可以包括位于TCO和吸收剂层之间的层。
对于薄膜太阳能电池,透明导电氧化物(TCO)材料能够影响装置性能。会期望的是具有高的导电率的TCO层。对于由氧化锌或氧化锡制成的TCO层,可以增大其厚度以降低片电阻。在实践中,厚的TCO层会导致成本增加、剥离和粘附问题以及制造困难。开发出制造掺杂的TCO层的方法以在不增加TCO层的厚度的情况下降低太阳能电池前接触件的片电阻。
在一个方面,光伏装置可以包括:基底;前接触层,与基底相邻,其中,用掺杂剂掺杂前接触层;半导体吸收剂层,与掺杂的前接触层相邻,其中,半导体吸收剂层可以包括碲化镉。前接触层可以包括与基底相邻的透明导电氧化物层和与透明导电氧化物层相邻的缓冲层。前接触层还可以包括与缓冲层相邻的半导体窗口层。透明导电氧化物层可以包括氧化锌。透明导电氧化物层可以包括氧化锡。掺杂剂可以包括N型掺杂剂。掺杂剂可以包括铝。掺杂剂可以包括铟。掺杂剂可以包括硼。掺杂剂可以包括铜。掺杂剂可以包括氯。掺杂剂可以包括镓。掺杂剂可以包括氟。掺杂剂可以包括镁。基底可以包括玻璃。缓冲层可以包括碲化锌。缓冲层可以包括碲化镉锌。缓冲层可以包括硫化镉。窗口层可以包括硫化镉。窗口层可以包括碲化锌。窗口层包括硫化镉锌。窗口层可以包括氧化锌。窗口层可以包括硫化锌。窗口层可以包括氧化锌锰。窗口层可以包括硫化镉锰。窗口层可以包括氧化镉。
在另一方面,制造光伏装置的方法可以包括与基底相邻地沉积透明导电氧化物层。在沉积后,透明导电氧化物层具有表面。该方法可以包括:使透明导电氧化物层的所述表面暴露于掺杂剂,其中,可以在基底上留下掺杂剂层;与掺杂剂层相邻地沉积窗口层;使掺杂剂进入到窗口层中;与窗口层相邻地沉积吸收剂层。吸收剂层可以包括碲化镉。沉积窗口层的步骤可以包括溅射工艺。使透明导电氧化物层的所述表面暴露的步骤可以包括用掺杂剂的盐洗涤所述表面。所述盐可以包括硼酸盐。掺杂剂可以包括N型掺杂剂。掺杂剂可以包括铝。掺杂剂可以包括铟。掺杂剂可以包括硼。掺杂剂可以包括铜。掺杂剂可以包括氯。掺杂剂可以包括镓。掺杂剂可以包括氟。掺杂剂可以包括镁。基底可以包括玻璃。透明导电氧化物层可以包括氧化锌。透明导电氧化物层可以包括氧化锡。窗口层可以包括硫化镉。窗口层可以包括碲化锌。窗口层可以包括硫化镉锌。窗口层可以包括氧化锌。窗口层可以包括硫化锌。窗口层可以包括氧化锌锰。窗口层可以包括硫化镉锰。窗口层可以包括氧化镉。窗口层可以包括M1-xGxOy半导体,M可以选自于由锌和锡组成的组,G可以选自于由铝、硅和锆组成的组。窗口层可以包括氧化锌铝。氧化锌铝的分子式可以为Zn1-xAlxOy,其中,x可以在0.05至0.30的范围内。窗口层可以包括氧化锌硅。氧化锌硅的分子式可以为Zn1-xSixOy,其中,x可以在0.10至0.25的范围内。窗口层可以包括氧化锌锆。氧化锌锆的分子式可以为Zn1-xZrxOy,其中,x可以在0.30至0.50的范围内。窗口层可以包括氧化锡铝。氧化锡铝的分子式可以为Sn1-xAlxOy,其中,x可以在0.10至0.30的范围内。窗口层可以包括氧化锡硅。氧化锡硅的分子式可以为Sn1-xSixOy,其中,x可以在0.05至0.25的范围内。窗口层可以包括氧化锡锆。氧化锡锆的分子式可以为Sn1-xZrxOy,其中,x可以在0.30至0.60的范围内。沉积窗口层的步骤可以包括气相传输沉积工艺。沉积窗口层的步骤可以包括与掺杂剂层相邻地沉积硫化镉窗口层以及在硫化镉窗口层上沉积含锌层。溅射工艺可以包括在不活泼气氛下从陶瓷靶进行溅射。溅射工艺可以包括从金属靶进行反应溅射。所述方法还可以包括退火步骤。
在另一方面,制造光伏装置的方法可以包括:与基底相邻地沉积透明导电氧化物层;通过从掺杂的靶进行溅射来与透明导电氧化物层相邻地沉积窗口层;与窗口层相邻地沉积吸收剂层。掺杂的靶可以掺杂有掺杂剂。吸收剂层可以包括碲化镉。掺杂剂可以包括N型掺杂剂。掺杂剂可以包括铝。掺杂剂可以包括铟。掺杂剂可以包括硼。掺杂剂可以包括铜。掺杂剂可以包括氯。掺杂剂可以包括镓。掺杂剂可以包括氟。掺杂剂可以包括镁。基底可以包括玻璃。透明导电氧化物层可以包括氧化锌。透明导电氧化物层可以包括氧化锡。窗口层可以包括硫化镉。窗口层可以包括碲化锌。窗口层可以包括硫化镉锌。窗口层可以包括氧化锌。窗口层包括可以硫化锌。窗口层可以包括氧化锌锰。窗口层可以包括硫化镉锰。窗口层可以包括氧化镉。溅射工艺可以包括在不活泼气氛下从陶瓷靶进行溅射。溅射工艺可以包括从金属靶进行反应溅射。所述方法还可以包括退火步骤。
在另一方面,制造光伏装置的方法可以包括:与基底相邻地沉积透明导电氧化物层;通过从掺杂的靶进行溅射来与透明导电氧化物层相邻地沉积前驱体层;与前驱体层相邻地沉积缓冲层;对前驱体层和缓冲层进行退火以形成掺杂的缓冲层;与掺杂的缓冲层相邻地沉积吸收剂层。掺杂的靶可以掺杂有掺杂剂。吸收剂层可以包括碲化镉。掺杂剂可以包括N型掺杂剂。掺杂剂可以包括铝。掺杂剂可以包括铟。掺杂剂可以包括硼。掺杂剂可以包括铜。掺杂剂可以包括氯。掺杂剂可以包括镓。掺杂剂可以包括氟。掺杂剂可以包括镁。基底可以包括玻璃。透明导电氧化物层可以包括氧化锌。透明导电氧化物层可以包括氧化锡。前驱体层可以包括硫化镉。前驱体层可以包括氧化镉。缓冲层可以包括碲化锌。缓冲层可以包括硫化镉锌。沉积前驱体层的步骤包括在不活泼气氛下从陶瓷靶进行溅射。沉积前驱体层的步骤包括从金属靶进行反应溅射。所述方法还可以包括退火步骤。
光伏装置可以包括与基底相邻的透明导电氧化物层和半导体材料的多个层。半导体材料的层可以包括双层,所述双层可以包括n型半导体窗口层和p型半导体吸收剂层。光子在与n型窗口层接触时释放电子-空穴对,从而将电子发送到n侧并将空穴发送到p侧。电子可以通过外部电流通路返回流到p侧。所得的电子流提供了电流,所述电流与从电场所得的电压一起产生电能。该结果是将光子能转换为电能。
参照图1,光伏装置100可以包括与基底110相邻地沉积的掺杂的透明导电氧化物层120。可以通过溅射、化学气相沉积或任何其它适合的沉积方法在基底110上沉积透明导电氧化物层120。基底110可以包括玻璃,例如,钠钙玻璃。透明导电氧化物层120可以包括任何适合的透明导电氧化物材料,所述任何适合的透明导电氧化物材料包括锡酸镉、铟掺杂的氧化镉或锡掺杂的氧化铟。半导体双层130可以与可以退火后的透明导电氧化物层120相邻地形成或沉积。半导体双层130可以包括半导体窗口层131和半导体吸收剂层132。半导体双层130的半导体窗口层131可以与透明导电氧化物层120相邻地沉积。半导体窗口层131可以包括诸如硫化镉的任何适合的窗口材料,并且可以通过诸如溅射或气相传输沉积的任何适合的沉积方法来沉积。半导体吸收剂层132可以与半导体窗口层131相邻地沉积。半导体吸收剂层132可以沉积在半导体窗口层131上。半导体吸收剂层132可以是诸如碲化镉的任何适合的吸收剂材料,并且可以通过诸如溅射或气相传输沉积的任何适合的方法来沉积。背接触件140可以与半导体吸收剂层132相邻地沉积。背接触件140可以与半导体双层130相邻地沉积。背支撑件150可以与背接触件140相邻地设置。光伏装置可以具有作为半导体窗口层的硫化镉(CdS)层和作为半导体吸收剂层的碲化镉(CdTe)层。
光伏装置的可替换构造主要由三种半导体材料构成,并且将被称作“p-i-n装置”。“i”代表“本征的”,是指处于平衡时具有数量相对少的任一电荷类型的电荷载流子或者其中的载流子的净数量可以少于大约5×1014cm-3,这里,“净”应当是p型电荷载流子的浓度减去n型载流子的浓度的绝对值,其中,2×1015cm-3是p-i-n装置的上限。典型地,i层的主要功能是吸收光学光子并将光学光子转换为电子-空穴对。光生电子和空穴在i层内随着在漂流和扩散作用下的驱动而移动,直到它们在i层内、在p-i界面处或在i-n界面处相互“复合”,或者直到它们分别被n型和p层收集。
参照图2,光伏装置200可以包括与基底210相邻地沉积的透明导电氧化物层220。可以通过溅射、化学气相沉积或者任何其它适合的沉积方法在基底210上沉积透明导电氧化物层220。
可以通过铸锭冶金来制造溅射靶。溅射靶可以包括将要被沉积或者形成在表面(例如,基底)上的层或膜的一种或多种组分。例如,溅射靶可以包括将要沉积在基底上的TCO层的一种或多种组分,例如,用于氧化锌TCO层的锌、用于氧化锡TCO层的锡或者诸如N型掺杂剂或P型掺杂剂的掺杂剂(例如,铝、铟、硼、氯、铜、镓或氟)。溅射靶可以包括将要被沉积的窗口层的一种或多种组分,例如,用于硫化镉窗口层的镉、用于氧化锌窗口层的锌或者诸如N型掺杂剂或P型掺杂剂的掺杂剂(例如,铝、铟、硼、氯、铜、镓、氟或镁)。所述组分可以以化学计量的合适量存在于靶中。溅射靶可以制造为任何适合形状的单个块。溅射靶可以是管。可以通过将金属材料浇铸成任何适合的形状(例如,管)来制造溅射靶。
可以由一个以上的块来制造溅射靶。可以由一块以上的金属来制造溅射靶,例如,由一块用于氧化锌TCO的锌和一块掺杂剂材料(例如,铝)来制造溅射靶。所述组分可以以任何适合的形状(例如,套筒)形成,并且可以以任何适合的方式或构造接合或连接。例如,可以将一块锌和一块铝焊接在一起以形成溅射靶。一个套筒可以位于另一套筒内。
可以通过粉末冶金来制造溅射靶。可以使金属粉末固结而形成靶来形成溅射靶。可以通过任何适合的工艺(例如,压制,如等静压制)以任何适合的形状来固结金属粉末。可以在任何适合的温度下进行固结。可以由包括一种以上的金属粉末的金属粉末来形成溅射靶。一种以上的金属粉末可以以化学计量的合适量存在。
可以通过将包括靶材的线与基体相邻地设置来制造溅射靶。例如,可以将包括靶材的线缠绕在基体管的周围。所述线可以包括以化学计量的合适量存在的多种金属。基体管可以由将不被溅射的材料形成。可以(例如,通过等静压制)对所述线进行压制。
可以通过将靶材溅射到基体上来制造溅射靶。可以通过包括热喷涂和等离子体喷涂在内的任何适合的喷涂工艺来喷涂金属靶材。金属靶材可以包括以化学计量的合适量存在的多种金属。其上将要喷涂金属靶材的基体可以是管。
基底210可以包括玻璃,例如,钠钙玻璃。透明导电氧化物层220可以包括任何适合的透明导电氧化物材料,所述任何适合的透明导电氧化物材料包括锡酸镉、铟掺杂的氧化镉或锡掺杂的氧化铟。可以与退火后的透明导电氧化物层220相邻地形成或沉积半导体三层结构230。半导体三层结构230可以包括第一半导体层231、半导体界面层232和第二半导体层233。半导体三层结构230的第一半导体窗口层231可以与退火后的透明导电氧化物层220相邻地沉积。第一半导体窗口层231可以包括诸如硫化镉的任何适合的窗口材料,并且可以通过诸如溅射或气相传输沉积的任何适合的沉积方法来形成。半导体界面层232可以与第一半导体层231相邻地沉积。半导体界面层232可以是诸如碲化锌的任何适合的半导体材料,并且可以通过诸如溅射或气相传输沉积的任何适合的沉积方法来沉积。第二半导体层233可以沉积在半导体界面层232上。第二半导体层233可以是诸如碲化镉的任何适合的半导体材料,并且可以通过诸如溅射或气相传输沉积的任何适合的方法来沉积。背接触件240可以与第二半导体层233相邻地沉积。背接触件240可以与半导体三层结构230相邻地沉积。背支撑件250可以与背接触件240相邻地设置。
总是期望的是具有高的光学透射率、高的导电率和良好的散光性能的TCO层。TCO层可以具有每平方大约5欧姆甚至更低的片电阻。对于由纯的氧化锌或氧化锡制成的TCO层,可以通过增加层厚度来降低TCO层的片电阻(例如,降至每平方大约5欧姆)。在实践中,厚的TCO层会导致成本增加。在厚的TCO膜中还可以出现裂纹,造成剥离和粘附问题。此外,在用于批量生产的连续连接的生产步骤期间在图案化TCO的同时,非常厚的TCO膜可以产生辅助困难。
可以对TCO层进行掺杂以降低太阳能电池前接触件的片电阻,而无需增大TCO层的厚度。制造掺杂的TCO层的方法可以包括从掺杂的靶的溅射工艺。
可以利用相似的工艺沉积掺杂的窗口层。在特定实施例中,用掺杂的窗口层制造光伏装置的方法可以包括以下步骤:沉积与基底相邻的透明导电氧化物层;通过从掺杂的靶溅射来沉积与透明导电氧化物层相邻的窗口层;沉积与窗口层相邻的吸收剂层,其中,吸收剂层可以包括碲化镉。
窗口层的沉积还可以包括沉积与掺杂剂层相邻的硫化镉窗口层的步骤和在硫化镉窗口层上沉积含锌层的步骤。
在特定实施例中,掺杂的TCO或掺杂的窗口层的溅射工艺可以包括在非活泼气氛下从陶瓷靶溅射或者从金属靶的反应溅射。
参照图3,制造掺杂的溅射靶的方法可以包括以下步骤:准备具有至少一种掺杂剂的原料氧化物粉末;装入粉末;对具有至少一种掺杂剂的粉末进行热等静压制;机械加工成最终形式;最终清洁;检验。制造掺杂的溅射靶的方法还可以包括退火或任何其它适合的冶金技术或其它处理。掺杂的溅射靶可以包括氧化物,例如,氧化锡或者具有至少一种诸如硼、钠、氟或铝的掺杂剂的氧化锡。
参照图4,前接触层溅射系统300可以包括室310和射频源匹配电路360。基底370可以安装在板380上或者以任何其它适合的方式设置。接地固定件330可以以面向下的方式夹持住掺杂的溅射靶340。室310内的气体来自于具有不同的气体源的入口320。室310内的气体可以包括氩。在溅射工艺期间,颗粒350可以从靶340沉积到基底370。溅射工艺可以是反应溅射工艺。室310内的气体还可以包括含有硼、钠、氟或铝的掺杂剂气体。系统300可以包括排出气体的出口390。在其它实施例中,溅射工艺可以是DC溅射、磁控溅射沉积或离子辅助沉积。
参照图5,对前接触层的沉积和处理可以包括基底洗涤/清洗的步骤、溅射沉积的步骤或任何其它适合的后处理步骤。在基底洗涤/清洗的步骤期间,可以加入盐以处理基底。盐可以包括硼砂。沉积和处理还可以包括任何其它适合的化学浴步骤。沉积和处理还可以包括在基底的表面上形成透明导电氧化物前驱体层以用于进一步的处理。
制造掺杂的TCO层的方法也可以包括基底洗涤工艺。其可以包括用掺杂剂洗涤基底的步骤和沉积与基底相邻的掺杂的透明导电氧化物层的步骤,其中,透明导电氧化物层因掺杂剂而变得被掺杂。对基底的洗涤可以包括将流体喷涂、浸渍、辊涂、喷雾或旋涂到表面上。掺杂剂可以是洗涤流体的组分,洗涤流体可以可选地包括另外的组分。可以用掺杂剂的盐(例如,硼砂)来洗涤基底。
参照图6至图9,示出了基底的洗涤/清洗掺杂工艺。如图6所示,可以用掺杂剂源430洗涤基底410。掩模420可以可选地用来覆盖不需要被洗涤的区域。掩模420可以是光致抗蚀剂或任何适合的掩模材料。可以将盐(例如,硼砂)加入到掺杂剂源430中。如图7所示,洗涤/清洗工艺可以留下与基底相邻的包括掺杂剂的层440。如图8所示,可以与包括掺杂剂的层440相邻地沉积透明导电氧化物前驱体层450。透明导电氧化物前驱体层450可以包括锌或锡。另外的退火工艺将前驱体层450转换为可以包括氧化锌或氧化锡的透明导电氧化物层。掺杂剂原子可以扩散到晶格中的取代位置,带来半导体材料的电学特性的期望的变化。如图9所示,透明导电氧化物前驱体层450可以因来自层440的掺杂剂而变得被掺杂。透明导电氧化物前驱体层450也可以因掺杂剂源430留在基底410上的掺杂剂而变得被掺杂。参照图10,在退火后,基底410与具有包括N型掺杂剂钠、硼、氟的掺杂区451的透明导电氧化物层460接触。
所述工艺可以在洗涤后包括热处理或任何适合的驱入处理。所述工艺还可以包括利用气化形式的杂质离子的另外扩散掺杂工艺。制造掺杂的TCO层的方法还可以包括在沉积掺杂的透明导电氧化物层之后对基底进行退火的附加步骤。
可以利用相似的工艺沉积掺杂的窗口层。在特定实施例中,制造具有掺杂的前接触件的光伏装置的方法可以包括以下步骤:与基底相邻地沉积透明导电氧化物层;使透明导电氧化物层的表面暴露于掺杂剂,其中,掺杂剂层可以留在所述表面上;与掺杂剂层相邻地沉积窗口层;使掺杂剂进入到窗口层中;与窗口层相邻地沉积吸收剂层,其中,吸收剂层包括碲化镉。
在特定实施例中,制造具有掺杂的前接触件的光伏装置的方法可以包括以下步骤:与基底相邻地沉积透明导电氧化物层;通过从掺杂的靶进行溅射来与透明导电氧化物层相邻地沉积前驱体层;与前驱体层相邻地沉积缓冲层;对前驱体层和缓冲层进行退火以形成掺杂缓冲层;与掺杂的缓冲层相邻地沉积吸收剂层,其中,吸收剂层包括碲化镉。
在特定实施例中,前接触层可以包括位于TCO层和半导体吸收剂层之间的层。前接触层可以包括硫化镉。前接触层还可以具有氧化锡/硫化镉堆叠结构或基于此的任何适合的修改结构。前接触层可以通过反应溅射、气相传输沉积或任何其它适合的沉积方法来沉积。前接触层还可以被适合的掺杂剂掺杂。掺杂剂可以包括N型掺杂剂或P型掺杂剂,例如,铝、铟、硼、氯、铜、镓或氟。
在特定实施例中,制造光伏装置的方法可以包括:用掺杂剂洗涤基底的表面;在基底的洗涤表面上沉积半导体窗口层并使掺杂剂进入到半导体窗口层中;以及与半导体窗口层相邻地沉积半导体吸收剂层。基底可以包括玻璃板和透明导电氧化物堆叠件。半导体窗口层可以包括硫化镉、碲化锌、硫化镉锌、氧化锌、硫化锌或氧化锌锰。半导体窗口层的沉积可以包括溅射、气相传输沉积或任何其它适合的沉积方法。基底的洗涤还可以包括使基底的表面暴露于掺杂剂的盐的步骤。掺杂剂可以包括N型掺杂剂或P型掺杂剂,例如,铝、铟、硼、氯、铜、镓或氟。半导体吸收剂层可以包括碲化镉。透明导电氧化物堆叠件可以包括氧化锡或氧化锌。得到的半导体窗口层的掺杂剂浓度可以在大约1013cm-3至大约1020cm-3或大约1014cm-3至大约1019cm-3的范围内。
在特定实施例中,制造光伏装置的方法可以包括:与基底相邻地沉积半导体窗口层,其中,用掺杂剂掺杂半导体窗口层;与掺杂的半导体窗口层相邻地沉积半导体吸收剂层。基底可以包括玻璃板和透明导电氧化物堆叠件。半导体窗口层可以包括硫化镉、碲化锌、硫化镉锌、氧化锌、硫化锌或氧化锌锰。沉积半导体窗口层可以包括从掺杂的靶进行溅射、气相传输沉积或任何其它适合的沉积方法。掺杂剂可以包括N型掺杂剂或P型掺杂剂,例如,铝、铟、硼、氯、铜、镓或氟。半导体吸收剂层可以包括碲化镉。透明导电氧化物堆叠件可以包括氧化锡。透明导电氧化物堆叠件可以包括氧化锌。得到的半导体窗口层的掺杂剂浓度可以在大约1013cm-3至大约1020cm-3或大约1014cm-3至大约1019cm-3的范围内。
已经描述了本发明的多个实施例。然而,应该理解的是,在不脱离本发明的精神和范围的情况下可以做出各种修改。还应当理解的是,附图不一定是按比例的,呈现的是示出本发明的基本原理的各种优选特征的一定程度的简化表现形式。
Claims (44)
1.一种光伏装置,包括:
基底;
透明导电氧化物层,其中,透明导电氧化物层被第一掺杂剂掺杂;
缓冲层,被第二掺杂剂掺杂,其中,透明导电氧化物层位于基底与缓冲层之间;
半导体窗口层,被第三掺杂剂掺杂;
半导体吸收剂层,其中,半导体吸收剂层包括碲化镉,其中,半导体窗口层位于缓冲层和半导体吸收剂层之间,
其中,第一掺杂剂、第二掺杂剂和第三掺杂剂包括从由铝、钠、铟、硼、铜、氯、镓、氟和镁组成的组中选择的至少一种元素。
2.如权利要求1所述的光伏装置,其中,透明导电氧化物层包括氧化锌。
3.如权利要求1所述的光伏装置,其中,透明导电氧化物层包括氧化锡。
4.如权利要求1所述的光伏装置,其中,第一掺杂剂、第二掺杂剂和第三掺杂剂包括N型掺杂剂。
5.如权利要求1所述的光伏装置,其中,第一掺杂剂、第二掺杂剂和第三掺杂剂包括铝。
6.如权利要求1所述的光伏装置,其中,第一掺杂剂、第二掺杂剂和第三掺杂剂包括铟。
7.如权利要求1所述的光伏装置,其中,第一掺杂剂、第二掺杂剂和第三掺杂剂包括硼。
8.如权利要求1所述的光伏装置,其中,第一掺杂剂、第二掺杂剂和第三掺杂剂包括铜。
9.如权利要求1所述的光伏装置,其中,第一掺杂剂、第二掺杂剂和第三掺杂剂包括氯。
10.如权利要求1所述的光伏装置,其中,第一掺杂剂、第二掺杂剂和第三掺杂剂包括镓。
11.如权利要求1所述的光伏装置,其中,第一掺杂剂、第二掺杂剂和第三掺杂剂包括氟。
12.如权利要求1所述的光伏装置,其中,第一掺杂剂、第二掺杂剂和第三掺杂剂包括镁。
13.如权利要求1所述的光伏装置,其中,基底包括玻璃。
14.如权利要求1所述的光伏装置,其中,缓冲层包括碲化锌。
15.如权利要求1所述的光伏装置,其中,缓冲层包括碲化镉锌。
16.如权利要求1所述的光伏装置,其中,缓冲层包括硫化镉。
17.如权利要求1所述的光伏装置,其中,窗口层包括硫化镉。
18.如权利要求1所述的光伏装置,其中,窗口层包括碲化锌。
19.如权利要求1所述的光伏装置,其中,窗口层包括硫化镉锌。
20.如权利要求1所述的光伏装置,其中,窗口层包括氧化锌。
21.如权利要求1所述的光伏装置,其中,窗口层包括硫化锌。
22.如权利要求1所述的光伏装置,其中,窗口层包括氧化锌锰。
23.如权利要求1所述的光伏装置,其中,窗口层包括硫化镉锰。
24.如权利要求1所述的光伏装置,其中,窗口层包括氧化镉。
25.一种制造光伏装置的方法,所述方法包括:
与基底相邻地沉积透明导电氧化物层,其中,透明导电氧化物层被第一掺杂剂掺杂;
通过从掺杂的靶进行溅射与透明导电氧化物层相邻地沉积前驱体层,其中,掺杂的靶是用掺杂剂掺杂的;
与前驱体层相邻地沉积缓冲层;
对前驱体层和缓冲层进行退火以形成掺杂的缓冲层,其中,缓冲层被第二掺杂剂掺杂;
与掺杂的缓冲层相邻地沉积半导体窗口层,其中,半导体窗口层被第三掺杂剂掺杂;
与半导体窗口层相邻地沉积半导体吸收剂层,其中,半导体吸收剂层包括碲化镉,
其中,第一掺杂剂、第二掺杂剂和第三掺杂剂包括从由铝、钠、铟、硼、铜、氯、镓、氟和镁组成的组中选择的至少一种元素。
26.如权利要求25所述的方法,其中,第一掺杂剂、第二掺杂剂和第三掺杂剂包括N型掺杂剂。
27.如权利要求25所述的方法,其中,第一掺杂剂、第二掺杂剂和第三掺杂剂包括铝。
28.如权利要求25所述的方法,其中,第一掺杂剂、第二掺杂剂和第三掺杂剂包括铟。
29.如权利要求25所述的方法,其中,第一掺杂剂、第二掺杂剂和第三掺杂剂包括硼。
30.如权利要求25所述的方法,其中,第一掺杂剂、第二掺杂剂和第三掺杂剂包括铜。
31.如权利要求25所述的方法,其中,第一掺杂剂、第二掺杂剂和第三掺杂剂包括氯。
32.如权利要求25所述的方法,其中,第一掺杂剂、第二掺杂剂和第三掺杂剂包括镓。
33.如权利要求25所述的方法,其中,第一掺杂剂、第二掺杂剂和第三掺杂剂包括氟。
34.如权利要求25所述的方法,其中,第一掺杂剂、第二掺杂剂和第三掺杂剂包括镁。
35.如权利要求25所述的方法,其中,基底包括玻璃。
36.如权利要求25所述的方法,其中,透明导电氧化物层包括氧化锌。
37.如权利要求25所述的方法,其中,透明导电氧化物层包括氧化锡。
38.如权利要求25所述的方法,其中,前驱体层包括硫化镉。
39.如权利要求25所述的方法,其中,前驱体层包括氧化镉。
40.如权利要求25所述的方法,其中,缓冲层包括碲化锌。
41.如权利要求25所述的方法,其中,缓冲层包括硫化镉锌。
42.如权利要求25所述的方法,其中,沉积前驱体层的步骤包括在不活泼气氛下从陶瓷靶进行溅射。
43.如权利要求25所述的方法,其中,沉积前驱体层的步骤包括从金属靶进行反应溅射。
44.如权利要求25所述的方法,所述方法还包括退火步骤。
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CN (1) | CN102625953B (zh) |
IN (1) | IN2012DN00356A (zh) |
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US20150270423A1 (en) | 2012-11-19 | 2015-09-24 | Alliance For Sustainable Energy, Llc | Devices and methods featuring the addition of refractory metals to contact interface layers |
TWI584162B (zh) * | 2012-11-26 | 2017-05-21 | 揚昇照明股份有限公司 | 觸控裝置的製造方法 |
US9520530B2 (en) * | 2014-10-03 | 2016-12-13 | Taiwan Semiconductor Manufacturing Co., Ltd. | Solar cell having doped buffer layer and method of fabricating the solar cell |
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CN107123693B (zh) * | 2017-04-14 | 2020-05-22 | 华南理工大学 | 一种基于溶液法加工的具有高透明窗口层材料的高效CdTe纳米晶太阳电池及其制备方法 |
EP3820252A4 (en) * | 2018-07-02 | 2022-03-30 | Tokyo Institute of Technology | OPTOELECTRONIC ELEMENT, FLAT SCREEN IN WHICH IT IS USED AND METHOD FOR MANUFACTURING OPTOELECTRONIC ELEMENT |
EP3857611B1 (en) | 2018-10-24 | 2023-07-05 | First Solar, Inc. | Buffer layers for photovoltaic devices with group v doping |
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- 2010-07-09 JP JP2012520589A patent/JP5878465B2/ja not_active Expired - Fee Related
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IN2012DN00356A (zh) | 2015-08-21 |
WO2011008254A1 (en) | 2011-01-20 |
EP2454755A1 (en) | 2012-05-23 |
JP2012533187A (ja) | 2012-12-20 |
US9153730B2 (en) | 2015-10-06 |
TW201115753A (en) | 2011-05-01 |
US20110005591A1 (en) | 2011-01-13 |
JP5878465B2 (ja) | 2016-03-08 |
EP2454755A4 (en) | 2016-03-30 |
US20150380600A1 (en) | 2015-12-31 |
KR20120052310A (ko) | 2012-05-23 |
CN102625953A (zh) | 2012-08-01 |
TWI545785B (zh) | 2016-08-11 |
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