TWI497727B - 控制光伏打薄膜組成物之方法 - Google Patents
控制光伏打薄膜組成物之方法 Download PDFInfo
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- TWI497727B TWI497727B TW099130357A TW99130357A TWI497727B TW I497727 B TWI497727 B TW I497727B TW 099130357 A TW099130357 A TW 099130357A TW 99130357 A TW99130357 A TW 99130357A TW I497727 B TWI497727 B TW I497727B
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- 238000000034 method Methods 0.000 title claims description 34
- 239000010409 thin film Substances 0.000 title claims description 19
- 239000000203 mixture Substances 0.000 title description 3
- 239000010408 film Substances 0.000 claims description 84
- 239000011241 protective layer Substances 0.000 claims description 49
- 238000000137 annealing Methods 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 13
- 229910052717 sulfur Inorganic materials 0.000 claims description 13
- 239000011593 sulfur Substances 0.000 claims description 13
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 12
- 239000006117 anti-reflective coating Substances 0.000 claims description 12
- 229910052711 selenium Inorganic materials 0.000 claims description 12
- 239000011669 selenium Substances 0.000 claims description 12
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 12
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims description 10
- 239000005083 Zinc sulfide Substances 0.000 claims description 10
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims description 10
- 229910052984 zinc sulfide Inorganic materials 0.000 claims description 10
- 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
- 229910052729 chemical element Inorganic materials 0.000 claims description 8
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 5
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 5
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 5
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims description 5
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 4
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 4
- 239000006059 cover glass Substances 0.000 claims description 4
- 229910003437 indium oxide Inorganic materials 0.000 claims description 4
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 4
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910001887 tin oxide Inorganic materials 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 238000004528 spin coating Methods 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 238000007743 anodising Methods 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 238000009713 electroplating Methods 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 238000007740 vapor deposition Methods 0.000 claims description 2
- BCZWPKDRLPGFFZ-UHFFFAOYSA-N azanylidynecerium Chemical compound [Ce]#N BCZWPKDRLPGFFZ-UHFFFAOYSA-N 0.000 claims 1
- 239000010410 layer Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 5
- 239000010949 copper Substances 0.000 description 4
- 229910052732 germanium Inorganic materials 0.000 description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 238000000231 atomic layer deposition Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910021423 nanocrystalline silicon Inorganic materials 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- PHPKKGYKGPCPMV-UHFFFAOYSA-N [SeH-]=[Se].[In+3].[SeH-]=[Se].[SeH-]=[Se] Chemical compound [SeH-]=[Se].[In+3].[SeH-]=[Se].[SeH-]=[Se] PHPKKGYKGPCPMV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- AQCDIIAORKRFCD-UHFFFAOYSA-N cadmium selenide Chemical compound [Cd]=[Se] AQCDIIAORKRFCD-UHFFFAOYSA-N 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052951 chalcopyrite Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- -1 copper sulfide zinc tetrasulfide Chemical compound 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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 potential barriers
- 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
- H01L31/0749—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 potential barriers the potential barriers being only of the PN heterojunction type including a AIBIIICVI compound, e.g. CdS/CulnSe2 [CIS] heterojunction solar cells
-
- 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
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
-
- 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
-
- 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
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- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Sustainable Energy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Photovoltaic Devices (AREA)
Description
本發明係關於控制光伏打薄膜組成物之方法。
製造光伏打薄膜電池之現有方法利用在空氣或含硒、碲或硫之氛圍中進行退火。
圖1說明用於製造含碲、硒或硫之化合物半導體薄膜之部分現有方法，諸如碲化鎘(CdTe)、硒化鎘(CdSe)、硫化鎘(CdS)、硫化鋅(ZnS)、四硫化錫(SnS4)、二硒化銅銦(CuInSe2)、二硫化銅銦(CuInS2)、二硒化銅鎵(CuGaSe2)、二硫化銅鎵(CuGaS2)、硫化銅鉍(Cu3BiS3)、銅鋅錫硫化物(copper sulfide zinc tin tetrasulfide，Cu2ZnSnS4)、二硒化銅銦鎵(CuInGaSe2)或二硫化銅銦鎵(CuInGaS2)光伏打薄膜電池。如圖1所示，該方法包括在硫或硒氛圍中之退火步驟。二硒化銅銦(CuInSe2)或二硒化銅銦鎵(CuInGaSe2)光伏打薄膜在退火期間可能損失諸如硒或硫之輕元素。儘管損失之硒可藉由在退火後進行額外加工步驟歸還，但此使形成光伏打薄膜電池之時間、成本及複雜性增加。
在圖1中，沈積後之薄膜結構104形成於基板108上。在硒氛圍中在450℃與500℃之間退火112後，所產生之退火後之薄膜結構116形成於基板108上。
根據本發明之例示性實施例，提供在退火製程期間降低光伏打薄膜之元素損失的方法。藉由以保護層塗佈薄膜實
現元素損失之降低，該保護層能夠在製造光伏打薄膜之退火製程期間防止薄膜之元素逸出。此方法可用於製造光伏打薄膜電池。因此，此方法可使製造光伏打薄膜電池之時間、成本及複雜性降低。
根據本發明之例示性實施例，在退火製程期間降低光伏打薄膜結構之元素損失的方法包含：在基板上沈積薄膜，其中薄膜包括單一化學元素或化合物；以保護層塗佈薄膜以形成經塗佈薄膜結構，其中保護層防止單一化學元素之部分或化合物之部分在退火製程期間逸出；及將經塗佈薄膜結構退火以形成經塗佈光伏打薄膜結構，其中經塗佈光伏打薄膜保留有在退火期間由保護層防止逸出之單一化學元素之部分或化合物之部分。
根據本發明之例示性實施例，光伏打薄膜電池包含：基板；安置於基板上之光伏打薄膜；塗佈光伏打薄膜之保護層，其中保護層包含選自由以下組成之群的化合物：氮化矽(SiN)、二氧化矽(SiO2)、二氧化鈦(TiO2)、五氧化二鉭(Ta2O5)、氧化鋁(Al2O3)、氧化鋅(ZnO)、二氧化錫(SnO2)、氧化銦錫(ITO)、氮化鈦(TiN)、矽化物(Si)、氧化錫(SnO)、氧化銦(In2O3)、氧化鎘(CdO)、氮化鉭(TaN)、硫化鋅(ZnS)及硫化鎘(CdS)；安置於保護層上之接觸柵格；安置於接觸柵格上之防反射塗層；及安置於防反射塗層上之防護玻璃罩(cover glass)。
根據本發明之例示性實施例，光伏打薄膜電池包含：基板；安置於基板上之光伏打薄膜；塗佈光伏打薄膜之保護
層，其中保護層係選自由金屬及非金屬組成之群；安置於保護層上之接觸柵格；安置於接觸柵格上之防反射塗層；及安置於防反射塗層上之防護玻璃罩。
根據本發明之例示性實施例，形成光伏打薄膜電池之方法包含：在基板上安置薄膜，其中薄膜包括單一化學元素或化合物；以保護層塗佈薄膜以形成第一經塗佈薄膜結構，其中保護層防止單一化學元素之部分或化合物之部分在退火製程期間逸出；將經塗佈薄膜結構退火以形成經塗佈光伏打薄膜結構，其中經塗佈光伏打薄膜保留有在退火期間由保護層防止逸出之單一化學元素之部分或化合物之部分；自經塗佈光伏打薄膜結構移除保護層以形成未經塗佈之光伏打薄膜結構；在未經塗佈之光伏打薄膜結構上安置接觸柵格；在接觸柵格上安置防反射塗層；及在防反射塗層上安置防護玻璃罩以形成光伏打薄膜電池。
上述特徵為代表性實施例且提供此等特徵以幫助理解本發明。應理解，此等特徵不欲視作對申請專利範圍所界定之本發明的限制，或對申請專利範圍之均等物的限制。因此，特徵之此概要不應視作判定均等物之決定性因素。本發明之其他特徵將自以下描述、圖式及申請專利範圍顯而易知。
根據本發明之例示性實施例，本文揭示製造光伏打薄膜電池之新穎方法。此方法併有在退火製程期間降低光伏打薄膜之元素損失的另一新穎方法。該兩種方法將在下文中
參看圖2進行詳細描述。
圖2說明用於根據本發明之例示性實施例製造光伏打薄膜電池之方法。
在圖2之(a)中，提供上面沈積有薄膜204之基板208。在此階段，薄膜204可為光伏打薄膜或不為光伏打薄膜。應理解，基板208可由非晶矽(a-Si或a-Si：H)、原生晶矽、奈米晶矽(nc-Si或nc-Si：H)或黑矽製成。薄膜204可例如由二硒化銅銦鎵(CuInGaSe2)、二硫化銅銦鎵(CuInGaS2)、二硒化銅鎵(CuGaSe2)、二硫化銅鎵(CuGaS2)、二硒化銅銦(CuInSe2)、二硫化銅銦(CuInS2)或任何含有銅、銦、硒、硫、鎵、碲、鎘、鋅、錫或鉍之材料製成。
在圖2之(b)中，以保護層212塗佈薄膜204以形成經塗佈薄膜結構。保護層212可由在退火製程(諸如熱退火)期間防止薄膜204之元素逸出的任何材料製成。構成保護層212之材料可例如包括氮化矽(SiN)、二氧化矽(SiO2)、二氧化鈦(TiO2)、五氧化二鉭(Ta2O5)、氧化鋁(Al2O3)、氧化鋅(ZnO)、二氧化錫(SnO2)、氧化銦錫(ITO)、聚合物溶液、碳奈米管、金屬或非金屬(諸如硫或硒)。保護層212可例如藉由旋塗、噴塗、陽極化、電鍍或氣相沈積技術塗佈。
應理解，可使用包括將擴散至薄膜中之雜質的其他保護層212。以此方式，保護層212可充當將允許以特定元素摻雜光伏打薄膜或形成特定界面之蓄意摻雜劑載體。本文給出之實例為摻雜有過量鈉、硫、磷或硼之保護層212或具有n+-p+-i界面之保護層212。舉例而言，包括硫之保護層
212可在退火期間使部分硫擴散至薄膜204中，而另一部分硫仍保留於保護層212中。
可使用藉由旋塗、電漿增強化學氧相沈積(PECVD)、化學氣相沈積(CVD)、原子層沈積(ALD)或陽極化進行沈積或形成之其他介電質作為保護層212。一些實例為二氧化鈦(TiO2)、氮化鈦(TiN)、矽化物(Si)、氧化銦錫(ITO)、氧化錫(SnO)、氧化銦(In2O3)、氧化鎘(CdO)、氮化鉭(TaN)、五氧化二鉭(Ta2O5)、氧化鋁(Al2O3)、氧化鋅(ZnO)、硫化鋅(ZnS)及硫化鎘(CdS)。
在圖2之(c)中，將經塗佈薄膜結構退火216以形成經塗佈光伏打薄膜結構。換言之，薄膜之退火216將其轉化成光伏打薄膜。舉例而言，若薄膜包含諸如Cu/In/Ga之金屬及硫，則在退火216後，所得光伏打薄膜為黃銅礦材料，諸如CuInGaS2。此外，若薄膜包含二元合金(諸如CuIn2及CuGa2)且經硒塗佈，則在退火216後，所得光伏打薄膜可為CuInGaSe2。退火216之溫度範圍可為約100℃至約900℃。一般而言，取決於薄膜及塗層，將經塗佈薄膜結構退火216至約300℃至約600℃之溫度。
因為圖2之(b)中之薄膜204塗有保護層212，所以在退火216期間僅存在最少量之光伏打薄膜元素(例如硒)損失。此係由於保護層212在退火216期間充當輕元素向外擴散的障壁。因此，圖2之(d)中之光伏打薄膜與圖2之(b)中之薄膜具有類似構造。換言之，圖2之(d)中之光伏打薄膜保留在退火216期間由保護層212防止逸出的圖2之(b)中之薄膜的
單一化學元素之部分或化合物之部分。因此，無需向圖2之(d)中之光伏打薄膜歸還損失之元素的後續加工步驟。
因為如上文所述使用保護層212，所以在圖2之(d)中在經塗佈光伏打薄膜與保護層212之間可能積聚一些雜質。該等雜質可能包括鈉、鉀、氯、過量硒、及硫。如圖2之(e)中所示，可藉由移除保護層212以清潔光伏打薄膜之頂面來移除此等雜質。此舉如何進行取決於用作保護層212之材料。舉例而言，若使用氮化矽(SiN)作為保護層212，則其可藉由蝕刻技術(諸如反應性離子蝕刻或乾式蝕刻)來移除。若使用旋塗氧化物或二氧化矽(SiO2)作為保護層，則其可藉由酸(諸如稀氫氟酸(HF))移除。此時，膜可在如圖2之(e)中所示之光伏打薄膜的經清潔表面上圖案化，形成結構與光伏打薄膜的中間接觸224。舉例而言，可在光伏打薄膜上沈積諸如接觸柵格之後續層，可在接觸柵格上沈積防反射塗層，且可在防反射塗層上沈積防護玻璃罩，藉此製造光伏打薄膜電池。
另一方面，如圖2之(f)所示，若使用由二氧化矽(SiO2)或氮化矽(SiN)製成之透光層作為保護層212，則保護層212可保留於光伏打薄膜上，且後續層220可在其上直接圖案化。在此情形中，保護層212用作遮罩。舉例而言，如圖2之(f)所示，可在保護層212上沈積諸如接觸柵格之後續層220，可在接觸柵格上沈積防反射塗層，且可在防反射塗層上沈積防護玻璃罩，藉此製造光伏打薄膜電池。
如自本發明之上文描述可見，光伏打薄膜可藉由納入保
護層而在無元素損失及無額外加工的情形下退火。此外，藉由使用可容易地清潔或作為摻雜缺乏層保留的保護層，可以節省成本之方式製造包含維持組成之光伏打薄膜之薄膜電池。此外，保護層允許以單一步驟形成大晶粒。
應理解，隨附圖式所示及本文所述之加工步驟之間的順序可取決於本發明用於形成諸如光伏打薄膜結構之最終產品的方式而不同。鑒於本發明之教示，一般技術者將能夠預期本發明之此等及類似實施或組態。
亦應理解，上述說明僅代表說明性實施例。為方便讀者起見，上述說明著重於可能實施例之一代表性樣品，該樣品說明本發明之原理。該說明並不試圖詳盡列舉所有可能的變化形式。可能未提供本發明之特定部分的替代實施例，或有其他未描述之替代物可用於一部分，此並不應視作否認彼等替代實施例。在不脫離本發明之精神及範疇的情形下可實施其他應用及實施例。
因此，希望本發明不限於該等明確描述之實施例，因為可創建上述內容之眾多排列及組合及涉及上述內容之非創造性替代之實施例，而且將根據隨附申請專利範圍界定本發明。應瞭解，許多彼等未描述之實施例在隨附申請專利範圍之字面範疇內，且其他實施例為均等物。
104‧‧‧沈積後之薄膜結構
108‧‧‧基板
116‧‧‧退火後之薄膜結構
204‧‧‧薄膜
208‧‧‧基板
212‧‧‧保護層
220‧‧‧後續層
224‧‧‧接觸
圖1說明用於製造光伏打薄膜電池之部分現有方法；及圖2說明用於根據本發明之例示性實施例製造光伏打薄膜電池之方法。
204‧‧‧薄膜
208‧‧‧基板
212‧‧‧保護層
220‧‧‧後續層
224‧‧‧接觸
Claims (7)
- 一種形成光伏打薄膜電池之方法，其包含：在一基板上安置一薄膜，其中該薄膜包括一化合物；以一保護層塗佈該薄膜以形成一第一經塗佈薄膜結構，其中該保護層防止該化合物之部分在退火製程期間逸出；將該經塗佈薄膜結構退火以形成一經塗佈光伏打薄膜結構，其中該經塗佈光伏打薄膜保留有在該退火期間由該保護層防止逸出之該化合物之該部分；自該經塗佈光伏打薄膜結構移除該保護層以形成一未經塗佈之光伏打薄膜結構；在該未經塗佈之光伏打薄膜結構上安置一接觸柵格；在該接觸柵格上安置一防反射塗層；及在該防反射塗層上安置一防護玻璃罩以形成一光伏打薄膜電池，其中該薄膜之該化合物係選自由以下組成之群：二硒化銅銦鎵(CuInGaSe2)、二硫化銅銦鎵(CuInGaS2)、二硒化銅鎵(CuGaSe2)、二硫化銅鎵(CuGaS2)及二硫化銅銦(CuInS2)。
- 如請求項1之方法，其中該保護層包含選自由以下組成之群的化合物：氮化矽(SiN)、二氧化矽(SiO2)、二氧化鈦(TiO2)、五氧化二鉭(Ta2O5)、氧化鋁(Al2O3)、氧化鋅(ZnO)、二氧化錫(SnO2)、氧化銦錫(ITO)、氮化鈦(TiN)、矽化物(Si)、氧化錫(SnO)、氧化銦(In2O3)、氧化 鎘(CdO)、氮化鉭(TaN)、硫化鋅(ZnS)及硫化鎘(CdS)。
- 如請求項1之方法，其中該保護層藉由選自由以下組成之群的技術塗佈：旋塗、噴塗、陽極化、電鍍及氣相沈積。
- 如請求項1之方法，其中該保護層摻雜有選自由以下組成之群的化學元素：鈉、硫、磷、硼及硒。
- 如請求項1之方法，其中該退火之溫度範圍為約100℃至約900℃。
- 如請求項1之方法，其中該保護層包含選自由以下組成之群的化合物：二氧化鈦(TiO2)、五氧化二鉭(Ta2O5)、氧化鋅(ZnO)、二氧化錫(SnO2)、氧化銦錫(ITO)、氮化鈦(TiN)、矽化物(Si)、氧化錫(SnO)、氧化銦(In2O3)、氧化鎘(CdO)、氮化鉭(TaN)、硫化鋅(ZnS)及硫化鎘(CdS)。
- 如請求項1之方法，其中將該經塗佈薄膜結構退火至300℃至600℃之間的溫度。
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| US3869322A (en) * | 1973-10-15 | 1975-03-04 | Ibm | Automatic P-N junction formation during growth of a heterojunction |
| JP2005524244A (ja) * | 2002-04-29 | 2005-08-11 | エレクトリシテ ド フランス セルビス ナショナル | Ｉ−ｉｉｉ−ｖｉ２化合物を基礎とする光起電性用途向け薄膜半導体の製造方法 |
| JP2006013028A (ja) * | 2004-06-24 | 2006-01-12 | National Institute Of Advanced Industrial & Technology | 化合物太陽電池及びその製造方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| DE112010003603B4 (de) | 2018-10-18 |
| WO2011029706A2 (en) | 2011-03-17 |
| US7923628B2 (en) | 2011-04-12 |
| GB201200871D0 (en) | 2012-02-29 |
| WO2011029706A3 (en) | 2011-09-15 |
| DE112010003603T5 (de) | 2012-08-23 |
| CN102484169A (zh) | 2012-05-30 |
| GB2485494A (en) | 2012-05-16 |
| US20100218814A1 (en) | 2010-09-02 |
| TW201123469A (en) | 2011-07-01 |
| CN102484169B (zh) | 2015-10-14 |
| GB2485494B (en) | 2014-01-15 |
| JP5791035B2 (ja) | 2015-10-07 |
| JP2013504219A (ja) | 2013-02-04 |
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