WO2016068155A1 - 均一系塗布液及びその製造方法、太陽電池用光吸収層及びその製造方法、並びに太陽電池及びその製造方法 - Google Patents
均一系塗布液及びその製造方法、太陽電池用光吸収層及びその製造方法、並びに太陽電池及びその製造方法 Download PDFInfo
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- WO2016068155A1 WO2016068155A1 PCT/JP2015/080296 JP2015080296W WO2016068155A1 WO 2016068155 A1 WO2016068155 A1 WO 2016068155A1 JP 2015080296 W JP2015080296 W JP 2015080296W WO 2016068155 A1 WO2016068155 A1 WO 2016068155A1
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- Prior art keywords
- coating solution
- group
- uniform coating
- ammonium
- solution according
- Prior art date
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- 239000007788 liquid Substances 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 49
- 239000002904 solvent Substances 0.000 claims abstract description 110
- 239000002879 Lewis base Substances 0.000 claims abstract description 67
- 150000007527 lewis bases Chemical class 0.000 claims abstract description 67
- 229910052751 metal Inorganic materials 0.000 claims abstract description 67
- 239000002184 metal Substances 0.000 claims abstract description 67
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 64
- 239000002841 Lewis acid Substances 0.000 claims abstract description 62
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 36
- 229910021482 group 13 metal Inorganic materials 0.000 claims abstract description 15
- 150000002739 metals Chemical class 0.000 claims abstract description 10
- 238000000576 coating method Methods 0.000 claims description 158
- 239000011248 coating agent Substances 0.000 claims description 155
- 238000000034 method Methods 0.000 claims description 68
- 229910052798 chalcogen Inorganic materials 0.000 claims description 59
- 150000001875 compounds Chemical class 0.000 claims description 46
- 230000031700 light absorption Effects 0.000 claims description 45
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 42
- 239000000758 substrate Substances 0.000 claims description 42
- 238000002156 mixing Methods 0.000 claims description 29
- 229910052711 selenium Inorganic materials 0.000 claims description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 21
- -1 ammonium selenide Chemical compound 0.000 claims description 16
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 claims description 16
- 229910052951 chalcopyrite Inorganic materials 0.000 claims description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 229910052717 sulfur Inorganic materials 0.000 claims description 15
- 150000003863 ammonium salts Chemical class 0.000 claims description 13
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 11
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 239000000010 aprotic solvent Substances 0.000 claims description 10
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 239000000908 ammonium hydroxide Substances 0.000 claims description 6
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 5
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 5
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 5
- 239000005695 Ammonium acetate Substances 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 229940043376 ammonium acetate Drugs 0.000 claims description 5
- 235000019257 ammonium acetate Nutrition 0.000 claims description 5
- BVCZEBOGSOYJJT-UHFFFAOYSA-N ammonium carbamate Chemical compound [NH4+].NC([O-])=O BVCZEBOGSOYJJT-UHFFFAOYSA-N 0.000 claims description 5
- 239000001099 ammonium carbonate Substances 0.000 claims description 5
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 5
- 235000019270 ammonium chloride Nutrition 0.000 claims description 5
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims description 5
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052787 antimony Inorganic materials 0.000 claims description 5
- LDDQLRUQCUTJBB-UHFFFAOYSA-O azanium;hydrofluoride Chemical compound [NH4+].F LDDQLRUQCUTJBB-UHFFFAOYSA-O 0.000 claims description 5
- 229910052797 bismuth Inorganic materials 0.000 claims description 5
- 229910052792 caesium Inorganic materials 0.000 claims description 5
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 239000000243 solution Substances 0.000 description 139
- 239000010949 copper Substances 0.000 description 82
- 239000010410 layer Substances 0.000 description 78
- 238000002360 preparation method Methods 0.000 description 35
- 239000011669 selenium Substances 0.000 description 35
- 239000002994 raw material Substances 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 23
- 239000010408 film Substances 0.000 description 20
- 239000002243 precursor Substances 0.000 description 19
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 17
- 238000000137 annealing Methods 0.000 description 16
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 14
- 229910052733 gallium Inorganic materials 0.000 description 12
- 229910052738 indium Inorganic materials 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 229910052802 copper Inorganic materials 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- 239000012691 Cu precursor Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 150000004770 chalcogenides Chemical class 0.000 description 6
- 150000001787 chalcogens Chemical class 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 238000004528 spin coating Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000002411 thermogravimetry Methods 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 5
- 229910001195 gallium oxide Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 150000004696 coordination complex Chemical class 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 229910003437 indium oxide Inorganic materials 0.000 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 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910002531 CuTe Inorganic materials 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- ZZEMEJKDTZOXOI-UHFFFAOYSA-N digallium;selenium(2-) Chemical compound [Ga+3].[Ga+3].[Se-2].[Se-2].[Se-2] ZZEMEJKDTZOXOI-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- AKUCEXGLFUSJCD-UHFFFAOYSA-N indium(3+);selenium(2-) Chemical compound [Se-2].[Se-2].[Se-2].[In+3].[In+3] AKUCEXGLFUSJCD-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- HWJHZLJIIWOTGZ-UHFFFAOYSA-N n-(hydroxymethyl)acetamide Chemical compound CC(=O)NCO HWJHZLJIIWOTGZ-UHFFFAOYSA-N 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229910000058 selane Inorganic materials 0.000 description 2
- 229910001923 silver oxide Inorganic materials 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- GKCNVZWZCYIBPR-UHFFFAOYSA-N sulfanylideneindium Chemical compound [In]=S GKCNVZWZCYIBPR-UHFFFAOYSA-N 0.000 description 2
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052946 acanthite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- WDODWFPDZYSKIA-UHFFFAOYSA-N benzeneselenol Chemical compound [SeH]C1=CC=CC=C1 WDODWFPDZYSKIA-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- ZKIBBIKDPHAFLN-UHFFFAOYSA-N boronium Chemical class [H][B+]([H])([H])[H] ZKIBBIKDPHAFLN-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000000224 chemical solution deposition Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- KDSXXMBJKHQCAA-UHFFFAOYSA-N disilver;selenium(2-) Chemical compound [Se-2].[Ag+].[Ag+] KDSXXMBJKHQCAA-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002290 germanium Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000011817 metal compound particle Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical class OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 229940056910 silver sulfide Drugs 0.000 description 1
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 1
- VPQBLCVGUWPDHV-UHFFFAOYSA-N sodium selenide Chemical compound [Na+].[Na+].[Se-2] VPQBLCVGUWPDHV-UHFFFAOYSA-N 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Images
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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G15/00—Compounds of gallium, indium or thallium
-
- 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
-
- 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
Definitions
- the present invention relates to a uniform coating solution and a method for producing the same, a light absorption layer for solar cells and a method for producing the same, a solar cell and a method for producing the same.
- chalcopyrite solar cells which are thin-film solar cells with high photoelectric conversion efficiency
- kesterite systems in which rare metals such as indium are replaced with other environmentally friendly metals.
- Solar cells are attracting particular attention, and research and development are actively underway.
- a chalcopyrite solar cell is a solar cell formed by forming a light absorption layer made of a chalcopyrite (chalcopyrite) material on a substrate.
- chalcopyrite-based materials are copper (Cu), indium (In), gallium (Ga), selenium (Se), sulfur (S), and the like, and typical examples of the light absorption layer include Cu.
- Cu copper
- In indium
- Ga gallium
- Se sulfur
- typical examples of the light absorption layer include Cu.
- a kesterite solar cell made of, for example, copper (Cu), zinc (Zn), tin (Sn), selenium (Se), and sulfur (S), which replaces rare metal indium, has been studied.
- Typical examples of the absorption layer include Cu 2 ZnSnSe 4 , Cu 2 ZnSnS 4 and Cu 2 ZnSn (S, Se) 4 .
- FIG. 1 is a schematic cross-sectional view showing an example of a chalcopyrite solar cell or a kesterite solar cell.
- a chalcopyrite solar cell or a kesterite solar cell includes a first electrode 3 (back electrode), a CIGS or CZTS layer (light absorption layer) 4, a buffer layer 5, i- The ZnO layer 6 and the second electrode 7 are roughly configured by being stacked in this order.
- the buffer layer for example, a CdS layer, a ZnS layer, an InS layer, or the like is known.
- Terminals are joined to the first electrode 3 and the second electrode 7, respectively, and wiring is connected to the terminals.
- a chalcopyrite-based or kesterite-based solar cell 1 light incident in the direction of arrow A is absorbed by the CIGS or CZTS layer 4 to generate an electromotive force, and a current flows in the direction of arrow B.
- the surface of the second electrode 7 is protected by being covered with an antireflection film layer 8 made of, for example, an MgF 2 layer.
- Patent Document 1 discloses a method of preparing a coating solution by preparing a hydrazine coordination metal chalcogenide complex and dissolving the hydrazine coordination metal chalcogenide complex in a solvent containing a dissolution accelerator.
- Patent Document 2 discloses a method of preparing a coating solution by reacting two kinds of organic compounds containing metal and chalcogen in the presence of a thiol compound or a selenol compound.
- Patent Document 3 discloses a method of preparing a coating solution by reacting a chalcogen element-containing organic compound, a Lewis base, and a metal.
- Patent Document 4 an aqueous solution containing two or more metal salts and one or more ligands is prepared, and the aqueous solution is mixed and stirred with a chalcogen source to form a coating solution as a dispersion of metal chalcogenide nanoparticles.
- a method of preparing is disclosed.
- Patent Document 5 discloses a method of preparing a coating solution as a dispersion of metal chalcogenide nanoparticles using metal ions and / or metal complex ions.
- the metal chalcogenide nanoparticles precipitate with the passage of time, and thus a dispersant is required.
- the organic substance it is not preferable that the organic substance remain in the coating film due to the dispersant, since this causes a factor that inhibits the crystal growth of the light absorption layer.
- the present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a uniform coating solution that can form a light-absorbing layer containing high-quality crystals at a low cost and a high safety, and a method for producing the same. To do.
- the present invention employs the following configuration.
- a uniform coating solution used for forming a light absorption layer of a solar cell A homogeneous coating solution containing at least one metal or metal compound selected from the group consisting of Group 11 metals, Group 13 metals, Group 11 metal compounds and Group 13 metal compounds, a Lewis base solvent and a Lewis acid.
- the uniform coating solution according to (1), wherein the solar cell is a chalcopyrite solar cell.
- the uniform coating solution according to (1) or (2) which contains a compound represented by the following general formula (1). [Where 0 ⁇ w ⁇ 1, 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 2, and A is at least one group 16 element.
- the aprotic solvent is selected from the group consisting of dimethyl sulfoxide, pyridine, tetramethylurea, tetrahydrofuran, ethyl acetate, acetone, dimethylformamide, acetonitrile, dichloromethane, dimethylacetamide, N-methylpyrrolidone and N-methylimidazole.
- the uniform coating solution according to (4) which is at least one kind.
- (6) The uniform coating solution according to any one of (1) to (5), wherein the Lewis acid is an onium salt.
- the uniform coating solution according to (6), wherein the Lewis acid is an ammonium salt.
- the ammonium salt is ammonium hydroxide, ammonium sulfide, ammonium chloride, ammonium carbonate, ammonium selenide, ammonium thiocyanate, ammonium acetate, ammonium carbamate, ammonium formate, ammonium hexafluorophosphate, ammonium hydrogen fluoride and ammonium nitrate.
- the uniform coating solution according to (7) which is at least one selected from the group consisting of: (9) The uniform coating solution according to any one of (1) to (8), further containing a Group 16 element.
- a method for producing a uniform coating solution used for forming a light absorption layer of a solar cell Including mixing at least one metal or metal compound selected from the group consisting of Group 11 metals, Group 13 metals, Group 11 metal compounds and Group 13 metal compounds, Lewis base solvents and Lewis acids.
- a method for producing a uniform coating liquid Including mixing at least one metal or metal compound selected from the group consisting of Group 11 metals, Group 13 metals, Group 11 metal compounds and Group 13 metal compounds, Lewis base solvents and Lewis acids.
- a method for producing a uniform coating liquid (15) The method for producing a uniform coating solution according to (14), wherein the solar cell is a chalcopyrite solar cell. (16) The method for producing a uniform coating solution according to (14) or (15), wherein the uniform coating solution contains a compound represented by the following general formula (1).
- A is at least one group 16 element.
- the aprotic solvent is selected from the group consisting of dimethyl sulfoxide, pyridine, tetramethylurea, tetrahydrofuran, ethyl acetate, acetone, dimethylformamide, acetonitrile, dichloromethane, dimethylacetamide, N-methylpyrrolidone and N-methylimidazole.
- the Lewis acid is an ammonium salt.
- the ammonium salt is ammonium hydroxide, ammonium sulfide, ammonium chloride, ammonium carbonate, ammonium selenide, ammonium thiocyanate, ammonium acetate, ammonium carbamate, ammonium formate, ammonium hexafluorophosphate, ammonium hydrogen fluoride and ammonium nitrate.
- the manufacturing method of the uniform type coating liquid as described in said (20) which is at least 1 sort (s) chosen from the group which consists of.
- a solar cell characterized in that a uniform coating solution obtained by the method for producing a uniform coating solution according to any one of (14) to (24) is applied to a substrate and baked. Method for manufacturing a light absorption layer. (26) forming a first electrode on the substrate; A uniform coating solution obtained by the method for producing a uniform coating solution according to any one of (14) to (24) is applied onto the first electrode, and baked to form a light absorption layer. Forming, and Forming a buffer layer on the light absorbing layer; And a step of forming a second electrode on the buffer layer.
- the present invention it is possible to provide a uniform coating solution that can form a light absorption layer containing high-quality crystals at a low cost with high safety and a method for producing the same.
- FIG. 1 is a schematic cross-sectional view showing an example of a chalcopyrite solar cell or a kesterite solar cell.
- the uniform coating solution of the present invention is a uniform coating solution used for forming a light absorption layer of a solar cell, and includes a Group 11 metal, a Group 13 metal, a Group 11 metal compound, and a Group 13 metal compound. It contains at least one metal or metal compound selected from the group (hereinafter sometimes simply referred to as “metal and / or metal compound”), a Lewis base solvent and a Lewis acid.
- the term “homogeneous coating solution” means that the solute (metal and / or metal compound, Lewis acid, 16th element and optional component) is a solvent (Lewis base solvent and optional solvent). And a dispersion solution in which metal particles and / or metal compound particles are dispersed in a solvent.
- Examples of the Group 11 metal include a Cu element and an Ag element. Among these, Cu element is particularly preferable.
- Examples of the Group 13 metal include Al element, Ga element, and In element. Among these, Ga element and In element are particularly preferable.
- Examples of the Group 11 metal compound include Cu (OH) 2 , CuS, Cu 2 S, Cu 2 Se, CuSe, Cu 2 Te, CuTe, CuO, Cu 2 O, silver oxide, silver sulfide, and silver selenide. Etc.
- Examples of the Group 13 metal compound include In (OH) 3 , indium oxide, indium sulfide, indium selenide, indium telluride, gallium oxide, gallium sulfide, gallium selenide, gallium telluride, boric acid, and boron oxide. Etc. Among these, Cu element, Ag element, Al element, Ga element, In element, Cu (OH) 2 , CuO, Cu 2 O, silver oxide, In (OH) 3 , indium oxide, and gallium oxide are preferable, and Cu element Further, Ga element and In element are more preferable. As a metal and / or a metal compound, 1 type may be used and it may be used in combination of 2 or more type.
- the Lewis base solvent is not particularly limited as long as it is a substance that dissolves a metal and / or a metal compound, a Lewis acid, a Group 16 element, and an optional component, and donates an electron pair.
- an aprotic solvent is preferable.
- the aprotic solvent include dimethyl sulfoxide, pyridine, tetramethyl urea, tetrahydrofuran, ethyl acetate, acetone, dimethylformamide, acetonitrile, dichloromethane, dimethylacetamide, N-methylpyrrolidone and N-methylimidazole.
- dimethyl sulfoxide or tetramethyl urea is preferable, and dimethyl sulfoxide is more preferable.
- the Lewis base solvent one kind may be used, or two or more kinds may be used in combination.
- the Lewis acid is not particularly limited as long as it is a substance that can accept an electron pair.
- an onium salt is preferable.
- onium salts include ammonium salts [(NH 4 ) + ], phosphonium salts [(PH 4 ) + ], sulfonium salts [(H 3 S) + ], metanium salts [(CH 5 )] + , boronium salts [( BH 3 ) + , (BH 4 ) + , (BH 5 ) + , (BH 6 ) + ], disilanium salt [(Si 2 H 7 ) + ], germanium salt [(GeH 5 ) + ] and the like. Of these, ammonium salts are preferred.
- Ammonium salts include ammonium hydroxide, ammonium sulfide, ammonium chloride and ammonium carbonate, ammonium selenide, ammonium thiocyanate, ammonium acetate, ammonium carbamate, ammonium formate, ammonium hexafluorophosphate, ammonium hydrogen fluoride and ammonium nitrate. It is done. Among these, ammonium hydroxide, ammonium sulfide, or a combination thereof is preferable. As the Lewis acid, one kind may be used, or two or more kinds may be used in combination.
- the uniform coating solution of the present invention may contain a Group 16 element.
- the Group 16 element include O, S, Se, Te, and the like. At least one selected from S and Se is preferable, and Se is particularly preferable.
- the group 16 element one type may be used alone, or two or more types may be used in combination.
- the compound containing a 16th element can also be used among the said metal and / or a metal compound, and the said Lewis' acid.
- the uniform coating solution of the present invention may contain a solvent other than a Lewis base solvent (hereinafter referred to as “arbitrary solvent”).
- arbitrary solvent examples include water, alcohol (for example, methanol, ethanol, propanol), glycol (for example, ethylene glycol and propylene glycol), glycol ether (for example, methyl diglycol) and the like.
- 1 type may be used independently and 2 or more types may be used in combination.
- a solvent having a lower polarity than the Lewis base solvent (hereinafter sometimes referred to as “poor solvent”) may be added to the uniform coating solution.
- poor solvent a solvent having a lower polarity than the Lewis base solvent
- the uniform coating solution can be purified and impurities can be removed.
- such a purification step is not always necessary. By omitting the purification step, the entire process can be simplified, which is industrially advantageous.
- the poor solvent is not particularly limited as long as the solvent is less polar than the Lewis base solvent, but acetone and isopropanol are preferable.
- the poor solvent may be mixed with the metal and / or metal compound, Lewis base solvent, Lewis acid, and, optionally, a Group 16 element when preparing the uniform coating solution. It is preferable to mix after preparing the liquid.
- the complex can be further washed with a poor solvent. Impurities can be more reliably removed by performing the cleaning multiple times.
- the poor solvent one kind may be used alone, or two or more kinds may be used in combination.
- the uniform coating solution of the present invention can be obtained by mixing a metal and / or a metal compound, a Lewis base solvent, a Lewis acid and an optional component.
- the method of mixing is not particularly limited.
- metal precursor solution After preparing each complex solution (hereinafter sometimes referred to as “metal precursor solution”), a method of mixing each metal precursor solution (hereinafter referred to as “preparation method (I)”), and all the raw materials (Hereinafter referred to as “Preparation Method (II)”), a method of preparing a binary or ternary metal complex solution using at least two Group 11 and / or Group 13 metals (hereinafter referred to as “Preparation Method (II)”). "Preparation method (III)").
- Cu precursor is obtained, for example, by mixing Cu and / or a Cu compound, a Lewis base solvent, a Lewis acid, and, optionally, a Group 16 element.
- Cu and / or Cu compound, Lewis base solvent, Lewis acid and Group 16 element include the Cu and / or Cu compound, Lewis base solvent, Lewis acid and Group 16 element exemplified in the description of the uniform coating solution.
- Cu and / or a Cu compound Cu, Cu (OH) 2 , CuS, Cu 2 S, CuO, Cu 2 O, Cu 2 Se, CuSe, Cu 2 Te, and CuTe are preferable, and Cu is more preferable.
- Cu and / or Cu compound one kind may be used alone, or two or more kinds may be used in combination.
- the amount of the Group 16 element is preferably 0.5 to 15 mol, more preferably 1 to 10 mol, and further preferably 2 to 5 mol, relative to 1 mol of Cu.
- the Lewis acid is preferably 0.1 to 50 moles, more preferably 1 to 20 moles, and even more preferably 2.5 to 8.5 moles with respect to 1 mole of Cu.
- a method of mixing Cu and / or a Cu compound, a Lewis base solvent, a Lewis acid, and, optionally, a Group 16 element is not particularly limited.
- Cu and / or a Cu compound, a Lewis acid, and optionally a Group 16 element after adding to a Lewis base solvent, stirring, Cu and / or a Cu compound, a Lewis acid, and optionally a 16th group.
- Examples thereof include a method of adding a Lewis base solvent to a reaction solution obtained by mixing a group element, a method of adding a Lewis base solvent to a complex obtained by adding the poor solvent to a reaction solution, and the like.
- a method of adding a Lewis acid and, optionally, a Group 16 element to a Lewis base solvent and stirring, and then adding Cu and / or a Cu compound is also preferred.
- the total amount of the Lewis base solvent and the arbitrary solvent (hereinafter, simply referred to as “amount of solvent”) is preferably such that when mixed, the Cu concentration becomes 0.1 mol / L to 2.0 mol / L. -1.5 mol / L is more preferable, and 0.4-1.2 mol / L is particularly preferable.
- the reaction temperature in the preparation of the Cu precursor varies depending on the type of Cu and / or Cu compound, Lewis base solvent, Lewis acid, Group 16 element used, etc., but from the viewpoint of safety and stability of the Cu complex, Usually, 0 ° C to 200 ° C is preferable, room temperature to 150 ° C is more preferable, and room temperature to 100 ° C is still more preferable.
- the reaction time in the preparation of the Cu precursor varies depending on the type of Cu and / or Cu compound, Lewis base solvent, Lewis acid, Group 16 element used, the stirring time, and the reaction temperature, but usually from 1 hour to Two weeks are preferred, one day to one week is more preferred, and one to four days is even more preferred.
- the Cu precursor After preparing the Cu precursor, it is preferable to remove impurities by mixing the Cu precursor with a solvent (poor solvent) having a polarity lower than that of the Lewis base solvent.
- a solvent poor solvent
- isopropyl alcohol is particularly preferable.
- the mixing of the poor solvent is preferably performed a plurality of times, and specifically, it is preferably performed once to 5 times.
- the amount of the poor solvent is preferably 2 to 20 times, more preferably 5 to 20 times, and even more preferably 7 to 20 times that of the Cu precursor.
- the In precursor is obtained, for example, by mixing In and / or an In compound, a Lewis base solvent, a Lewis acid, and, optionally, a Group 16 element.
- a Lewis base solvent examples include the In and / or In compound, Lewis base solvent, Lewis acid and Group 16 element exemplified in the description of the homogeneous coating solution.
- In and / or In compounds In, In (OH) 3 , indium oxide, indium sulfide, indium selenide, and indium telluride are preferable, and In, In (OH) 3 , and indium oxide are more preferable.
- one kind may be used alone, or two or more kinds may be used in combination.
- the amount of the group 16 element is preferably 0.5 to 15 mol, more preferably 1 to 10 mol, and still more preferably 2 to 5 mol with respect to 1 mol of In.
- the Lewis acid is preferably 0.1 to 50 moles, more preferably 1 to 20 moles, and even more preferably 2.5 to 8.5 moles relative to 1 mole of In.
- the method of mixing In and / or an In compound, a Lewis base solvent, a Lewis acid, and, optionally, a Group 16 element is not particularly limited.
- a method of stirring after adding In and / or an In compound, a Lewis acid, and optionally a Group 16 element to a Lewis base solvent, an In and / or In compound, a Lewis acid, and an optional 16th group examples thereof include a method of adding a Lewis base solvent to a reaction solution obtained by mixing a group element, a method of adding a Lewis base solvent to a complex obtained by adding the poor solvent to a reaction solution, and the like.
- a Lewis acid and optionally a Group 16 element are added to a Lewis base solvent and stirred, and then In and / or an In compound are added.
- the amount of the solvent is preferably such that when mixed, the In concentration in the In precursor is 0.1 mol / L to 2.0 mol / L, more preferably 0.2 to 1.5 mol / L, 0.4 -1.2 mol / L is particularly preferred.
- the reaction temperature varies depending on the type of In and / or In compound, Lewis base solvent, Lewis acid, Group 16 element used, etc., but from the viewpoint of safety and stability of the In complex, Usually, 0 ° C to 200 ° C is preferable, room temperature to 150 ° C is more preferable, and room temperature to 100 ° C is still more preferable.
- the reaction time varies depending on the type of In and / or In compound used, Lewis base solvent, Lewis acid, Group 16 element, the stirring time, and the reaction temperature, but usually from 1 hour to Two weeks are preferred, one day to one week is more preferred, and one to four days is even more preferred.
- the In precursor After the In precursor is prepared, it is preferable to remove impurities by mixing the In precursor with a solvent (poor solvent) having a lower polarity than the Lewis base solvent.
- a solvent poor solvent
- acetone is particularly preferable.
- the mixing of the poor solvent is preferably performed a plurality of times, and specifically, it is preferably performed once to 5 times.
- the amount of the poor solvent is preferably 2 to 20 times, more preferably 5 to 20 times, still more preferably 7 to 20 times that of the In precursor.
- Ga precursor The Ga precursor is obtained, for example, by mixing Ga and / or a Ga compound, a Lewis base solvent, a Lewis acid, and, optionally, a Group 16 element.
- the Ga and / or Ga compound, Lewis base solvent, Lewis acid and Group 16 element include the Ga and / or Ga compound, Lewis base solvent, Lewis acid and Group 16 element exemplified in the description of the homogeneous coating solution.
- Ga and / or Ga compounds Ga, gallium oxide, gallium sulfide, gallium selenide, and gallium telluride are preferable, and Ga and gallium oxide are more preferable.
- Ga and / or Ga compounds one kind may be used alone, or two or more kinds may be used in combination.
- the amount of Group 16 element is preferably 0.5 to 15 moles, more preferably 1 to 10 moles, and even more preferably 2 to 5 moles relative to 1 mole of Ga.
- the Lewis acid is preferably 0.1 to 50 moles, more preferably 1 to 20 moles, and even more preferably 2.5 to 8.5 moles relative to 1 mole of Ga.
- the method of mixing Ga and / or a Ga compound, a Lewis base solvent, a Lewis acid, and, optionally, a Group 16 element is not particularly limited.
- a method of stirring after adding Ga and / or Ga compound, Lewis acid, and optionally a Group 16 element to a Lewis base solvent, Ga and / or Ga compound, Lewis acid, and optionally 16th examples thereof include a method of adding a Lewis base solvent to a reaction solution obtained by mixing a group element, a method of adding a Lewis base solvent to a complex obtained by adding the poor solvent to a reaction solution, and the like.
- a Lewis acid and optionally a Group 16 element are added to a Lewis base solvent and stirred, and then Ga and / or a Ga compound is added.
- the amount of the solvent is preferably such that when mixed, the Ga concentration in the Ga precursor is 0.1 mol / L to 2.0 mol / L, more preferably 0.2 to 1.5 mol / L, 0.4 -1.2 mol / L is particularly preferred.
- the reaction temperature varies depending on the type of Ga and / or Ga compound used, Lewis base solvent, Lewis acid, Group 16 element, etc., but from the viewpoint of safety and stability of the Ga complex, Usually, 0 ° C to 200 ° C is preferable, room temperature to 150 ° C is more preferable, and room temperature to 100 ° C is still more preferable.
- the reaction time varies depending on the type of Ga and / or Ga compound, Lewis base solvent, Lewis acid, Group 16 element, etc. used, stirring time, and reaction temperature, but usually from 1 hour to Two weeks are preferred, one day to one week is more preferred, and one to four days is even more preferred.
- the Ga precursor After the preparation of the Ga precursor, it is preferable to remove impurities by mixing the Ga precursor with a solvent (poor solvent) having a lower polarity than the Lewis base solvent.
- a solvent poor solvent
- acetone is particularly preferable.
- the mixing of the poor solvent is preferably performed a plurality of times, and specifically, it is preferably performed once to 5 times.
- the amount of the poor solvent is preferably 2 to 20 times, more preferably 5 to 20 times, and even more preferably 7 to 20 times that of the Ga precursor.
- the amount of the group 16 element is preferably 0 to 10 equivalents, more preferably 0.5 to 4 equivalents, and more preferably 1 to 2 equivalents with respect to 1 mol of the total amount of Cu, In, and Ga metals. Is more preferable.
- the Lewis acid is preferably 0.1 to 50 moles, more preferably 1 to 20 moles, and even more preferably 2.5 to 8.5 moles with respect to 1 mole of Cu.
- the method of mixing the respective raw materials is not particularly limited.
- a method of stirring after adding each raw material to the Lewis base solvent a method of adding the Lewis base solvent after mixing the respective raw materials, etc.
- a method of adding the Lewis base solvent after mixing the respective raw materials etc.
- the amount of the solvent varies depending on the type of each raw material to be used, but it should be prepared so that the solid component concentration is 1 to 30% by weight when the residual component when heated at 500 ° C. by thermogravimetry is defined as the solid component. It is preferably 5 to 20% by weight.
- the reaction temperature in the preparation method (II) varies depending on the type of each raw material used, but is usually preferably 0 ° C. to 200 ° C., more preferably room temperature to 150 ° C., and more preferably room temperature to 150 ° C. from the viewpoint of safety and complex stability. 100 degreeC is still more preferable.
- the reaction time in the preparation method (II) varies depending on the types of raw materials used and the stirring time, but is usually preferably 1 hour to 2 weeks, more preferably 1 day to 1 week, and further preferably 1 day to 4 days.
- Preparation method (III) As the metal and / or metal compound, Lewis base solvent, Lewis acid and Group 16 element in the preparation method (III), the metal and / or metal compound, Lewis base solvent and Lewis acid exemplified in the description of the homogeneous coating solution are used. In addition, Group 16 elements can be used. Preferable examples of each raw material include the same as in the preparation method (I).
- a binary or ternary metal complex is prepared by mixing at least two metals and / or metal compounds, a Lewis base solvent, a Lewis acid, and optionally a Group 16 element.
- a solution can be obtained.
- Preferable examples of each raw material include the same as in the preparation method (I).
- the amount of each raw material can be appropriately adjusted depending on the type of each raw material.
- the uniform coating solution contains a compound represented by the following general formula (1)
- Cu element and / or Cu compound, In element and / or In A compound and at least two kinds of Ga element and / or Ga compound (hereinafter, sometimes collectively referred to as “CIGS metal”) can be used.
- CIGS metal a compound and at least two kinds of Ga element and / or Ga compound
- the amount of the group 16 element is preferably 0.5 to 10 moles, more preferably 0.5 to 5 moles, still more preferably 1 to 3 moles, relative to 1 mole of the total amount of CIGS metal.
- the Lewis acid is preferably from 0.1 to 50 mol, more preferably from 1 to 20 mol, still more preferably from 2.5 to 8.5 mol, based on 1 mol of the total CIGS metal.
- the method of mixing each raw material is not particularly limited.
- a method of stirring after adding each raw material to a Lewis base solvent a method of adding a Lewis base solvent after mixing each raw material, etc.
- a method of adding a Lewis base solvent after mixing each raw material etc.
- a method in which a Lewis acid and optionally a Group 16 element are added to a Lewis base solvent and stirred, and then a metal and / or metal compound is added.
- the amount of the solvent varies depending on the type of each raw material to be used, but it should be prepared so that the solid component concentration is 1 to 30% by weight when the residual component when heated at 500 ° C. by thermogravimetry is defined as the solid component. It is preferably 5 to 20% by weight.
- the reaction temperature in the preparation method (III) varies depending on the kind of each raw material to be used, but from the viewpoint of safety and stability of the complex, it is usually preferably 0 ° C to 200 ° C, more preferably room temperature to 150 ° C, more preferably room temperature to 100 degreeC is still more preferable.
- the reaction time in the preparation method (III) varies depending on the type of each raw material used and the stirring time, but is usually preferably 1 hour to 2 weeks, more preferably 1 day to 1 week, and further preferably 1 day to 4 days.
- the uniform coating solution of the present invention is preferably used for forming a light absorption layer of a chalcopyrite solar cell.
- the uniform coating solution preferably contains a compound represented by the following general formula (1).
- A is at least one group 16 element.
- A is at least one group 16 element, preferably Se and / or S.
- the uniform coating solution of the present invention further contains at least one selected from the group consisting of Li, Na, K, Cs, Sb, and Bi (hereinafter sometimes collectively referred to as “added metal”). Also good.
- the additive metal is preferably Na and / or Sb.
- the additive metal may be dissolved in a Lewis base solvent and added as a metal solution.
- the Na solution include sodium selenide and selenium dissolved in DMSO.
- the addition amount of Na is preferably 0.1 to 10 atomic% with respect to the molar amount of CIGS metal, 0.1 to 2 atom% is more preferable.
- the amount of Sb added is preferably 0.1 to 2 atom%, more preferably 0.1 to 0.5 atom%, based on the molar amount of CIGS metal.
- the uniform coating solution of the present invention does not use hydrazine, the process safety is improved. In addition, the uniform coating solution of the present invention can be easily prepared at low cost. Furthermore, since the uniform coating solution of the present invention does not use an organic ligand, it is possible to form a light absorption layer in which the content of organic matter that is a factor that inhibits crystal growth is reduced. Furthermore, the uniform coating solution of the present invention is excellent in storage stability, and can be stored stably, for example, without precipitation of a metal compound for at least 2 months.
- the solar cell light absorption layer of the present invention is formed using the uniform coating solution of the present invention.
- the manufacturing method of the light absorption layer for solar cells of this invention is the same as the process of forming the light absorption layer in the manufacturing method of the solar cell of this invention.
- the solar cell of this invention is equipped with the light absorption layer for solar cells of this invention.
- the method for manufacturing a solar cell of the present invention includes a step of forming a first electrode on a substrate, and a uniform coating solution of the present invention is applied on the first electrode and baked to form a light absorption layer. A step of forming a buffer layer on the light absorption layer, and a step of forming a second electrode on the buffer layer.
- a method known in the art may be used except for the step of forming a light absorption layer on the first electrode.
- a Mo layer may be formed by sputtering using nitrogen as a sputtering gas.
- the buffer layer may be formed as a CdS layer, for example, and may be formed using a chemical bath deposition method, for example.
- the transparent electrode may be formed using an appropriate material.
- the uniform coating solution according to the first aspect is applied onto the first electrode (substrate).
- a coating method a spin coating method, a non-spin coating method, a dip coating method, a doctor blade (applicator) method, a curtain / slit casting method, a printing method, a spray method, or the like can be used.
- a non-spin coating method from the viewpoint of mass production.
- the application conditions may be set as appropriate according to the desired film thickness, material concentration, and the like.
- the substrate is set on a spin coater and a uniform coating solution is applied.
- the coating conditions at this time may be appropriately set according to the film thickness to be formed.
- the rotation speed is 300 to 3000 rpm and the film can be formed by maintaining for 10 to 180 seconds. Application can be repeated until a desired film thickness is obtained.
- the non-spin coating method is used, the uniform coating solution is applied by a slit nozzle having a rectangular discharge port.
- the number of coating is not particularly limited, but is preferably 1 to 10 times, and more preferably 1 to 5 times.
- a dip method when using a dip method, it can carry out by immersing a base
- substrate you may vacuum-dry.
- Firing conditions can be appropriately set according to the desired film thickness, material type, and the like. For example, it can be a two-stage process in which baking (annealing) is performed in an oven after soft baking (pre-baking) on a hot plate.
- the temperature of the hot plate is set to 100 to 500 ° C., and soft baking is performed for 1 to 300 seconds, the substrate is cooled to near room temperature, and then coated again. Do. After the desired film thickness is obtained, annealing is performed by raising the inside of the hot plate or oven to 300 to 700 ° C. and holding it for 1 to 180 minutes. Thereby, the light absorption layer is cured.
- each temperature of the said baking shows one condition, and is not restricted to this.
- the temperature of the hot plate may be increased stepwise, and these heating steps may be performed in an inert gas atmosphere in a glove box.
- hydrogen sulfide, hydrogen selenide, solid sulfur, and solid selenium may be coexisted in the atmosphere during soft baking and annealing.
- chalcopyrite A light absorption layer having a desired structure such as a structure can be formed.
- the solar cell of the present invention is preferably a chalcopyrite solar cell.
- a light absorption layer contains the compound represented by the said General formula (1).
- the first complex solution is applied to a substrate, baked to form a first layer, and then a metal composition different from that of the first complex solution is used.
- the second complex solution can be applied to the first layer and baked to form the second layer. Thereafter, by annealing the first layer and the second layer, a single light absorption layer having a desired composition or a multilayer structure light absorption layer having a desired gradation of the metal composition ratio can be formed.
- the arrangement of the metal in the light absorption layer can be surely designed, and the structure of the light absorption layer can be reliably controlled.
- the complex solutions having different compositions it is not limited to the preparation method (III). Even when the complex solution is prepared by the preparation method (I) and / or the preparation method (II), the complex solutions having different compositions can be laminated in a desired order. As described above, it is easy to flexibly design the composition distribution in the coating film.
- the solar cell of this embodiment can be manufactured. And since the solar cell manufactured by the manufacturing method of this embodiment does not contain hydrazine in the uniform coating liquid, the safety of the process is improved. Furthermore, since an organic ligand is not used in the uniform coating solution, the content of organic matter that becomes a factor inhibiting crystal growth in the light absorption layer is reduced, and good crystal growth can be obtained.
- preparation method (I), preparation method (II), and preparation method (III) were demonstrated as a preparation method of a uniform type coating liquid, this invention is not limited to these.
- a metal precursor is prepared for some metal components, the prepared metal complex, other metal components, a Lewis base solvent, a Lewis acid, a group 16 element as required, and other desired elements.
- the ingredients can also be mixed. Further, for example, in the preparation method (II), after a part of the raw materials are mixed first, the remaining raw materials can be added.
- Example 2 S1.600 g (50.00 mmol), DMSO 22.00 g, (NH 4 ) 2 S42% aqueous solution 8.095 g (50.00 mmol in terms of S) were mixed and stirred at room temperature for 6 hours.
- In 1.208 g (10.50 mmol), Ga 0.315 g (4.50 mmol), and Cu 0.4425 g (6.75 mmol) were added, and the mixture was stirred at room temperature for 1 day, and further stirred at 70 ° C. for 3 days. did. Thereafter, 0.4425 g (6.75 mmol) of Cu was added and stirred at 70 ° C. for 1 day to obtain a uniform coating solution 2.
- Example 3 S1.536 g (48.00 mmol), DMSO 22.00 g, NH 3 28% aqueous solution 6.204 g (102.00 mmol in terms of NH 3 ), (NH 4 ) 2 S42% aqueous solution 1.943 g (S in terms of 12.00 mmol) Were mixed and stirred at room temperature for 6 hours.
- In 1.208 g (10.50 mmol), Ga 0.315 g (4.50 mmol), and Cu 0.4425 g (6.75 mmol) were added, and the mixture was stirred at room temperature for 1 day, and further stirred at 70 ° C. for 3 days. did. Thereafter, 0.4425 g (6.75 mmol) of Cu was added and stirred at room temperature for 2 days to obtain a uniform coating solution 3.
- Example 4 3.948 g (50.00 mmol) of Se, 23.00 g of DMSO, and 8.095 g of (NH 4 ) 2 S42% aqueous solution (50.00 mmol in terms of S) were mixed and stirred at room temperature for 6 hours.
- 1.208 g (10.50 mmol) of In, 0.420 g (6.00 mmol) of Ga, 0.429 g (6.75 mmol) of Cu were added and stirred overnight at room temperature, and further stirred at 70 ° C. for 4 days. did. Thereafter, 0.429 g (6.75 mmol) of Cu was added and stirred at 70 ° C. for 1 day to obtain a uniform coating solution 4.
- Example 6 Se 3.790 g (48.00 mmol), DMSO 22.50 g, NH 3 28% aqueous solution 6.204 g (102.00 mmol in terms of NH 3 ), (NH 4 ) 2 S42% aqueous solution 1.943 g (S in terms of 12.00 mmol) And stirred at room temperature overnight. To the obtained reaction solution, 0.6355 g (10.0 mmol) of Cu was added and stirred at room temperature for 24 hours. Thereafter, 0.6355 g (10.0 mmol) of Cu was added and stirred at room temperature for 2 days to obtain a uniform coating solution 6.
- Example 7 3.948 g (50.00 mmol) of Se, 23.00 g of DMSO, and 1.538 g of (NH 4 ) 2 S42% aqueous solution (9.5 mmol in terms of S) were mixed and stirred at room temperature for 6 hours. To the obtained reaction solution, 1.208 g (10.50 mmol) of In and 0.315 g (4.5 mmol) of Ga were added and stirred overnight at room temperature, and further stirred at 70 ° C. for 4 days. Thereafter, 0.4425 g (6.75 mmol) of Cu was added and stirred at 70 ° C. for 1 day to obtain a uniform coating solution 7.
- Example 8 DMSO 12.00 g and (NH 4 ) 2 S42% aqueous solution 2.429 g (15.0 mmol in terms of S) were mixed and stirred at room temperature for 24 hours.
- Cu 0.086 g (1.5 mmol), In 0.345 g (3.0 mmol) and Ga 0.105 g (1.5 mmol) were added and stirred overnight at room temperature, and further stirred at 70 ° C. for 4 days. did. Thereafter, 0.086 g (1.5 mmol) of Cu was added and stirred at 70 ° C. for 1 day to obtain a uniform coating solution 8.
- Example 9 Uniform coating as in Example 4 except that the amounts of In, Ga and Cu were changed to In1.035 g (9.0 mmol), Ga0.420 g (6.0 mmol) and Cu1.082 g (16.5 mmol), respectively. A liquid 9-1 was obtained. Apart from the above, the same as Example 4 except that the amounts of In, Ga and Cu were changed to In 1.380 g (12.0 mmol), Ga 0.210 g (3.0 mmol) and Cu 0.787 g (12.0 mmol), respectively. Thus, a uniform coating solution 9-2 was obtained. Next, 6.0 g of the uniform coating solution 9-1 and 6.0 g of the uniform coating solution 9-2 were mixed and stirred at room temperature for 1 hour to obtain a uniform coating solution 9. The ICP measurement was measured in the same manner as described above for the uniform coating solution 9-1, the uniform coating solution 9-2, and the uniform coating solution 9. The results are shown in Table 2.
- Example 10 Cu 0.508 g (8.0 mmol), In 1.208 g (10.5 mmol), Ga 0.105 g (1.5 mmol), Se4.501 g (57.00 mmol), DMSO 27.00 g and NH 3 28% aqueous solution 10.4 g were mixed. And stirred at room temperature for 6 hours. Thereafter, the mixture was stirred at 70 ° C. for 1 day and sonicated for 1 hour to obtain a uniform coating solution 10. For the uniform coating solution 10, ICP measurement was measured in the same manner as described above. The results are shown in Table 2.
- a CIGS coating solution was prepared with reference to the examples of WO 2011/013657.
- a mixed solvent was prepared by mixing 4.949 g (47.1 mmol) of benzeneselenol and 3.726 g (47.1 mmol) of pyridine.
- TGA analysis The homogeneous coating liquids 4 and 7 obtained in Examples 4 and 7 were subjected to thermogravimetric analysis (TGA) using TGA 2950 (manufactured by TA Instruments) at a heating rate of 2 ° C./min. As a result, it was confirmed that excess Se or S was removed by the temperature rise.
- Example 11 to 16 The uniform coating solution 9 prepared in Example 9 was applied on a glass substrate on which Mo was vapor-deposited, and soft baking was performed at 325 ° C. for 2 minutes. After performing this process 15 times in total, annealing was performed under the conditions shown in Table 3 in the presence of a small amount of selenium to produce a CIGS substrate on which a CIGS layer was formed. When the CIGS substrate created above was observed with an SEM, the grain growth of CIGS was confirmed in all cases. It was also confirmed that a uniform single layer film was formed.
- Example 17 The uniform coating solution 9-1 prepared in Example 9 was applied on a Mo-deposited glass substrate and soft baked at 325 ° C. for 2 minutes. After performing this process 15 times in total, annealing was performed under the conditions shown in Table 3 in the presence of a small amount of selenium to produce a CIGS substrate on which a CIGS layer was formed. When the CIGS substrate created above was observed with an SEM, the grain growth of CIGS was confirmed. It was also confirmed that a uniform single layer film was formed.
- Example 18 The uniform coating solution 9-2 prepared in Example 9 was coated on a Mo-deposited glass substrate and soft baked at 325 ° C. for 2 minutes. After performing this process 15 times in total, annealing was performed under the conditions shown in Table 3 in the presence of a small amount of selenium to produce a CIGS substrate on which a CIGS layer was formed. When the CIGS substrate created above was observed with an SEM, the grain growth of CIGS was confirmed. It was also confirmed that a uniform single layer film was formed.
- Example 19 The uniform coating solution 10 prepared in Example 10 was applied on a Mo-deposited glass substrate and soft baked at 325 ° C. for 2 minutes. After performing this process 15 times in total, annealing was performed under the conditions shown in Table 3 in the presence of a small amount of selenium to produce a CIGS substrate on which a CIGS layer was formed. When the CIGS substrate created above was observed with an SEM, the grain growth of CIGS was confirmed. It was also confirmed that a uniform film in which a plurality of particles were laminated was formed.
- Example 20 A CIGS substrate on which a CIGS layer was formed was produced in the same manner as in Example 11 except that the annealing time was changed to 50 minutes and annealing was performed in the absence of selenium.
- the CIGS substrate prepared above was observed with an SEM, grain growth of CIGS was confirmed despite annealing in the absence of selenium. It was also confirmed that a uniform single layer film was formed.
- Example 21 A CIGS substrate was formed in the same manner as in Example 11 except that the uniform coating solution 4 was used instead of the uniform coating solution 9 and annealing was performed at 560 ° C. for 50 minutes in the absence of selenium.
- Example 22 A CIGS substrate was formed in the same manner as in Example 21 except that annealing was performed in the presence of a small amount of selenium.
- Comparative Example 2 The comparative uniform coating solution 1 prepared in Comparative Example 1 was applied on a Mo-deposited glass substrate and soft baked at 120 ° C. for 1 minute and at 300 ° C. for 3 minutes. Then, the CIGS board
- Comparative Example 3 The comparative uniform coating solution 1 prepared in Comparative Example 1 was applied on a Mo-deposited glass substrate and soft baked at 120 ° C. for 1 minute and at 300 ° C. for 3 minutes. After performing this process twice in total, the CIGS substrate in which the CIGS layer was formed was produced by performing 30 minutes annealing at 540 degreeC in presence of a small amount of selenium.
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Abstract
Description
本願は、2014年10月30日に日本に出願された、特願2014-221682号及び2015年6月2日に日本に出願された、特願2015-112555号に基づき優先権主張し、その内容をここに援用する。
図1に示すように、カルコパイライト系太陽電池又はケステライト系太陽電池は、基板2上に第1の電極3(裏面電極)、CIGS又はCZTS層(光吸収層)4、バッファ層5、i-ZnO層6及び第2の電極7が、この順序で積層されて概略構成されている。なお、バッファ層としては、例えばCdS層や、ZnS層や、InS層等が知られている。
なお、第2の電極7の表面は、例えばMgF2層からなる反射防止膜層8によって覆われることで保護されている。
特許文献1には、ヒドラジン配位金属カルコゲニド錯体を調製し、溶解促進剤を含む溶媒に該ヒドラジン配位金属カルコゲニド錯体を溶解して塗布液を得る方法が開示されている。
特許文献2には、チオール化合物又はセレノール化合物の存在下、金属及びカルコゲンを含む有機化合物を2種反応させて塗布液を調製する方法が開示されている。
特許文献3には、カルコゲン元素含有有機化合物、ルイス塩基及び金属を反応させて塗布液を調製する方法が開示されている。
特許文献4には、2つ以上の金属塩および1つ以上の配位子を含む水性溶液を調製し、該水性溶液をカルコゲン源と混合・撹拌して金属カルコゲニドナノ粒子の分散液として塗布液を調製する方法が開示されている。
特許文献5には、金属イオン及び/又は金属錯体イオンを用いて金属カルコゲニドナノ粒子の分散液として塗布液を調製する方法が開示されている。
カルコゲン源としてカルコゲン元素含有有機化合物を用いる方法では、ヒドラジンを用いる方法と比べてプロセスの安全性は向上しているが、塗布膜中の有機物含有量が多くなるおそれがある。塗布膜中に有機物が残存すると、光吸収層の結晶成長を阻害する要因となるため、好ましくない。
一方、金属カルコゲニドナノ粒子の分散液として塗布液を調製する方法では、時間の経過に伴って金属カルコゲニドナノ粒子が沈殿するため、分散剤が必要となる。しかし、該分散剤が塗布膜中に有機物が残存すると、光吸収層の結晶成長を阻害する要因となるため、好ましくない。
本発明は、上記事情に鑑みてなされたものであって、安全性が高く、低コストで高質結晶を含む光吸収層を形成できる均一系塗布液及びその製造方法を提供することを課題とする。
(1)太陽電池の光吸収層の形成に用いられる均一系塗布液であって、
第11族金属、第13族金属、第11族金属化合物及び第13族金属化合物からなる群より選ばれる少なくとも1種の金属または金属化合物、ルイス塩基溶媒及びルイス酸を含有する均一系塗布液。
(2)前記太陽電池がカルコパイライト系太陽電池である前記(1)に記載の均一系塗布液。
(3)下記一般式(1)で表される化合物を含有する前記(1)又は(2)に記載の均一系塗布液。
(4)前記ルイス塩基溶媒が非プロトン性溶媒である前記(1)~(3)のいずれか一項に記載の均一系塗布液。
(5)前記非プロトン性溶媒が、ジメチルスルホキシド、ピリジン、テトラメチルウレア、テトラヒドロフラン、酢酸エチル、アセトン、ジメチルホルムアミド、アセトニトリル、ジクロロメタン、ジメチルアセトアミド、N-メチルピロリドン及びN-メチルイミダゾールからなる群より選ばれる少なくとも1種である前記(4)に記載の均一系塗布液。
(6)前記ルイス酸がオニウム塩である前記(1)~(5)のいずれか一項に記載の均一系塗布液。
(7)前記ルイス酸がアンモニウム塩である前記(6)に記載の均一系塗布液。
(8)前記アンモニウム塩が、水酸化アンモニウム、硫化アンモニウム、塩化アンモニウム、炭酸アンモニウム、アンモニウムセレニド、アンモニウムチオシアネート、酢酸アンモニウム、アンモニウムカルバメート、ギ酸アンモニウム、アンモニウムヘキサフルオロホスファート、二フッ化水素アンモニウム及び硝酸アンモニウムからなる群より選ばれる少なくとも1種である前記(7)に記載の均一系塗布液。
(9)更に第16族元素を含有する前記(1)~(8)のいずれか一項に記載の均一系塗布液。
(10)前記第16元素が、S及びSeからなる群より選ばれる少なくとも1種である前記(9)に記載の均一系塗布液。
(11)更にLi、Na、K、Cs、Sb及びBiからなる群より選ばれる少なくとも1種を前記溶媒に溶解する前記(1)~(10)のいずれか一項に記載の均一系塗布液。
(12)前記(1)~(11)のいずれか一項に記載の均一系塗布液を用いて形成される、太陽電池用光吸収層。
(13)前記(12)の太陽電池用光吸収層を備えた太陽電池。
(14)太陽電池の光吸収層の形成に用いられる均一系塗布液の製造方法であって、
第11族金属、第13族金属、第11族金属化合物及び第13族金属化合物からなる群より選ばれる少なくとも1種の金属または金属化合物、ルイス塩基溶媒及びルイス酸を混合することを含むことを特徴とする均一系塗布液の製造方法。
(15)前記太陽電池がカルコパイライト系太陽電池である前記(14)に記載の均一系塗布液の製造方法。
(16)前記均一系塗布液が、下記一般式(1)で表される化合物を含有する前記(14)又は(15)に記載の均一系塗布液の製造方法。
(17)前記ルイス塩基溶媒が非プロトン性溶媒である前記(14)~(16)のいずれか一項に記載の均一系塗布液の製造方法。
(18)前記非プロトン性溶媒が、ジメチルスルホキシド、ピリジン、テトラメチルウレア、テトラヒドロフラン、酢酸エチル、アセトン、ジメチルホルムアミド、アセトニトリル、ジクロロメタン、ジメチルアセトアミド、N-メチルピロリドン及びN-メチルイミダゾールからなる群より選ばれる少なくとも1種である前記(17)に記載の均一系塗布液の製造方法。
(19)前記ルイス酸がオニウム塩である前記(14)~(18)のいずれか一項に記載の均一系塗布液の製造方法。
(20)前記ルイス酸がアンモニウム塩である前記(19)に記載の均一系塗布液の製造方法。
(21)前記アンモニウム塩が、水酸化アンモニウム、硫化アンモニウム、塩化アンモニウム、炭酸アンモニウム、アンモニウムセレニド、アンモニウムチオシアネート、酢酸アンモニウム、アンモニウムカルバメート、ギ酸アンモニウム、アンモニウムヘキサフルオロホスファート、二フッ化水素アンモニウム及び硝酸アンモニウムからなる群より選ばれる少なくとも1種である前記(20)に記載の均一系塗布液の製造方法。
(22)更に第16族元素を混合することを含む前記(14)~(21)のいずれか一項に記載の均一系塗布液の製造方法。
(23)前記第16元素が、S及びSeからなる群より選ばれる少なくとも1種である前記(22)に記載の均一系塗布液の製造方法。
(24)更にLi、Na、K、Cs、Sb及びBiからなる群より選ばれる少なくとも1種を前記溶媒に溶解する前記(14)~(23)のいずれか一項に記載の均一系塗布液の製造方法。
(25)前記(14)~(24)のいずれか一項に記載の均一系塗布液の製造方法により得られた均一系塗布液を、基体に塗布し、焼成することを特徴とする太陽電池用光吸収層の製造方法。
(26)基板上に第1の電極を形成する工程と、
前記第1の電極上に、前記(14)~(24)のいずれか一項に記載の均一系塗布液の製造方法により得られた均一系塗布液を塗布し、焼成して光吸収層を形成する工程と、
前記光吸収層上にバッファ層を形成する工程と、
前記バッファ層上に第2の電極を形成する工程と、を有することを特徴とする太陽電池の製造方法。
以下、本発明の均一系塗布液およびその製造方法について説明する。
本発明の均一系塗布液は、太陽電池の光吸収層の形成に用いられる均一系塗布液であって、第11族金属、第13族金属、第11族金属化合物及び第13族金属化合物からなる群より選ばれる少なくとも1種の金属または金属化合物(以下、単に「金属及び/又は金属化合物」という場合がある。)、ルイス塩基溶媒及びルイス酸を含有する。
なお、本明細書及び特許請求の範囲において、「均一系塗布液」とは、溶質(金属及び/又は金属化合物、ルイス酸、第16元素及び任意成分)が溶媒(ルイス塩基溶媒及び任意の溶媒)の全体に亘って均一に溶解している溶液であり、溶媒中に金属粒子及び/又は金属化合物粒子等が分散した分散系溶液は包含しないものとする。
前記第13族金属としては、例えば、Al元素、Ga元素、およびIn元素等が挙げられる。これらの中でも、Ga元素およびIn元素が特に好ましい。
前記第11族金属化合物としては、例えば、Cu(OH)2、CuS、Cu2S、Cu2Se、CuSe、Cu2Te、CuTe、CuO、Cu2O、酸化銀、硫化銀、セレン化銀等が挙げられる。
前記第13族金属化合物としては、例えば、In(OH)3、酸化インジウム、硫化インジウム、セレン化インジウム、テルル化インジウム、酸化ガリウム、硫化ガリウム、セレン化ガリウム、テルル化ガリウム、ホウ酸、酸化ホウ素等が挙げられる。
これらの中でも、Cu元素、Ag元素、Al元素、Ga元素、In元素、Cu(OH)2、CuO、Cu2O、酸化銀、In(OH)3、酸化インジウム、酸化ガリウムが好ましく、Cu元素、Ga元素、In元素、が更に好ましい。
金属及び/又は金属化合物としては、1種を用いてもよく、2種以上を組み合わせて用いてもよい。
ルイス塩基溶媒としては、非プロトン性溶媒が好ましい。非プロトン性溶媒としては、ジメチルスルホキシド、ピリジン、テトラメチルウレア、テトラヒドロフラン、酢酸エチル、アセトン、ジメチルホルムアミド、アセトニトリル、ジクロロメタン、ジメチルアセトアミド、N-メチルピロリドン及びN-メチルイミダゾールが挙げられる。
これらの中でも、ジメチルスルホキシド又はテトラメチルウレアが好ましく、ジメチルスルホキシドがより好ましい。
ルイス塩基溶媒としては、1種を用いてもよく、2種以上を組み合わせて用いてもよい。
ルイス酸としては、オニウム塩が好ましい。オニウム塩としては、アンモニウム塩[(NH4)+]、ホスホニウム塩[(PH4)+]、スルホニウム塩[(H3S)+]、メタニウム塩[(CH5)]+、ボロニウム塩[(BH3)+、(BH4)+、(BH5)+、(BH6)+]、ジシラニウム塩[(Si2H7)+]、ゲルモニウム塩[(GeH5)+]等が挙げられる。中でも、アンモニウム塩が好ましい。
アンモニウム塩としては、水酸化アンモニウム、硫化アンモニウム、塩化アンモニウム及び、炭酸アンモニウム、アンモニウムセレニド、アンモニウムチオシアネート、酢酸アンモニウム、アンモニウムカルバメート、ギ酸アンモニウム、アンモニウムヘキサフルオロホスファート、二フッ化水素アンモニウム及び硝酸アンモニウムが挙げられる。中でも、水酸化アンモニウム、硫化アンモニウム又はこれらの組み合わせが好ましい。
ルイス酸としては、1種を用いてもよく、2種以上を組み合わせて用いてもよい。
第16族元素としては、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。また、前記金属及び/又は金属化合物並びに前記ルイス酸のうち、第16元素を含む化合物を用いることもできる。
任意溶媒としては、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
前記貧溶媒は、均一系塗布液の調製の際に、前記金属および/または金属化合物と、ルイス塩基溶媒と、ルイス酸と、所望により第16族元素と共に混合してもよいが、均一系塗布液を調製した後に混合することが好ましい。均一系塗布液を調製した後に貧溶媒を混合することにより、目的物である錯体を沈殿させ、未反応S又はSe等の不純物を上清として除去できる。錯体と不純物は、例えば遠心分離、ろ過、抽出等で分離できる。
また、不純物を上清として除去した後に、更に貧溶媒で錯体を洗浄できる。洗浄を複数回行うことにより、より確実に不純物を除去することができる。
貧溶媒としては、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
(Cu前駆体)
Cu前駆体は、例えばCu及び/又はCu化合物と、ルイス塩基溶媒と、ルイス酸と、所望により第16族元素とを混合することにより得られる。
Cu及び/又はCu化合物、ルイス塩基溶媒、ルイス酸ならびに第16族元素としては、前記均一系塗布液の説明において例示した前記Cu及び/又はCu化合物、ルイス塩基溶媒、ルイス酸ならびに第16族元素を用いることができる。
Cu及び/又はCu化合物としては、Cu、Cu(OH)2、CuS、Cu2S、CuO、Cu2O、Cu2Se、CuSe、Cu2Te、CuTeが好ましく、Cuがより好ましい。
Cu及び/又はCu化合物としては、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
ルイス酸は、Cu1モルに対し、0.1~50モルが好ましく、1~20モルがより好ましく、2.5~8.5モルが更に好ましい。
ルイス塩基溶媒及び任意溶媒の合計量(以下、単に「溶媒の量」という。)は、混合した際にCu濃度が0.1mol/L~2.0mol/Lになる量が好ましく、0.2~1.5mol/Lがより好ましく、0.4~1.2mol/Lが特に好ましい。
貧溶媒の量は、Cu前駆体に対して2~20倍が好ましく、5~20倍がより好ましく、7~20倍が更に好ましい。
In前駆体は、例えばIn及び/又はIn化合物と、ルイス塩基溶媒と、ルイス酸と、所望により第16族元素とを混合することにより得られる。
In及び/又はIn化合物、ルイス塩基溶媒、ルイス酸ならびに第16族元素としては、前記均一系塗布液の説明において例示した前記In及び/又はIn化合物、ルイス塩基溶媒、ルイス酸ならびに第16族元素を用いることができる。
In及び/又はIn化合物としては、In、In(OH)3、酸化インジウム、硫化インジウム、セレン化インジウム、テルル化インジウムが好ましく、In、In(OH)3、酸化インジウムがより好ましい。
In及び/又はIn化合物としては、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
ルイス酸は、In1モルに対し、0.1~50モルが好ましく、1~20モルがより好ましく、2.5~8.5モルが更に好ましい。
溶媒の量は、混合した際にIn前駆体中のIn濃度が0.1mol/L~2.0mol/Lになる量が好ましく、0.2~1.5mol/Lがより好ましく、0.4~1.2mol/Lが特に好ましい。
貧溶媒の量は、In前駆体に対して2~20倍が好ましく、5~20倍がより好ましく、7~20倍が更に好ましい。
Ga前駆体は、例えばGa及び/又はGa化合物と、ルイス塩基溶媒と、ルイス酸と、所望により第16族元素とを混合することにより得られる。
Ga及び/又はGa化合物、ルイス塩基溶媒、ルイス酸ならびに第16族元素としては、前記均一系塗布液の説明において例示した前記Ga及び/又はGa化合物、ルイス塩基溶媒、ルイス酸ならびに第16族元素を用いることができる。
Ga及び/又はGa化合物としては、Ga、酸化ガリウム、硫化ガリウム、セレン化ガリウム、テルル化ガリウムが好ましく、Ga、酸化ガリウムがより好ましい。
Ga及び/又はGa化合物としては、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
ルイス酸は、Ga1モルに対し、0.1~50モルが好ましく、1~20モルがより好ましく、2.5~8.5モルが更に好ましい。
溶媒の量は、混合した際にGa前駆体中のGa濃度が0.1mol/L~2.0mol/Lになる量が好ましく、0.2~1.5mol/Lがより好ましく、0.4~1.2mol/Lが特に好ましい。
貧溶媒の量は、Ga前駆体に対して2~20倍が好ましく、5~20倍がより好ましく、7~20倍が更に好ましい。
調製方法(II)における金属及び/又は金属化合物、ルイス塩基溶媒、ルイス酸ならびに第16族元素としては、前記均一系塗布液の説明において例示した金属及び/又は金属化合物、ルイス塩基溶媒、ルイス酸ならびに第16族元素を用いることができる。
16族元素を用いる場合、Cu、In、Ga各金属の合計量1モルに対し、第16族元素の量は0~10当量が好ましく、0.5~4当量がより好ましく、1~2当量が更に好ましい。
ルイス酸は、Cu1モルに対し、0.1~50モルが好ましく、1~20モルがより好ましく、2.5~8.5モルが更に好ましい。
溶媒の量は、使用する各原料の種類によって異なるが、熱重量測定で500℃で加熱したときの残渣成分を固形分としたとき、固形分濃度が1~30重量%になるよう調製することが好ましく、5~20重量%がより好ましい。
調製方法(III)における金属及び/又は金属化合物、ルイス塩基溶媒、ルイス酸ならびに第16族元素としては、前記均一系塗布液の説明において例示した金属及び/又は金属化合物、ルイス塩基溶媒、ルイス酸ならびに第16族元素を用いることができる。
各原料の好ましい例としては、前記調製方法(I)と同様のものが挙げられる。
各原料の好ましい例としては、前記調製方法(I)と同様のものが挙げられる。
第16元素を用いる場合、CIGS金属の合計量1モルに対し、第16族元素の量は0.5~10モルが好ましく、0.5~5モルがより好ましく、1~3モルが更に好ましい。
ルイス酸は、CIGS金属の合計1モルに対し、0.1~50モルが好ましく、1~20モルがより好ましく、2.5~8.5モルが更に好ましい。
溶媒の量は、使用する各原料の種類によって異なるが、熱重量測定で500℃で加熱したときの残渣成分を固形分としたとき、固形分濃度が1~30重量%になるよう調製することが好ましく、5~20重量%がより好ましい。
前記添加金属としては、Na及び/又はSbが好ましい。
Na溶液としては、セレン化ナトリウム、セレンをDMSOに溶解したもの等が挙げられる。
例えば、本発明の均一系塗布液をCIGS系太陽電池の光吸収層を形成するのに用いる場合、Naの添加量は、CIGS金属のモル量に対し、0.1~10原子%が好ましく、0.1~2原子%がより好ましい。また、Sbの添加量は、CIGS金属のモル量に対し、0.1~2原子%が好ましく、0.1~0.5原子%がより好ましい。
本発明の太陽電池用光吸収層は、前記本発明の均一系塗布液を用いて形成される。
本発明の太陽電池用光吸収層の製造方法は、本発明の太陽電池の製造方法における光吸収層を形成する工程と同様である。
本発明の太陽電池は、本発明の太陽電池用光吸収層を備える。
本発明の太陽電池の製造方法は、基板上に第1の電極を形成する工程と、前記第1の電極上に、本発明の均一系塗布液を塗布し、焼成して光吸収層を形成する工程と、前記光吸収層上にバッファ層を形成する工程と、前記バッファ層上に第2の電極を形成する工程と、を有する。
塗布条件は、所望の膜厚、材料の濃度などに応じて適宜設定すればよい。
また、ノンスピンコート法を用いる場合は、矩形上の吐出口を有するスリットノズルにより均一系塗布液を塗布する。塗布回数は特に限定されないが、1~10回が好ましく、1~5回がさらに好ましい。
また、ディップ法を用いる場合には、均一系塗布液が入った容器中に、基体を浸漬させることにより行うことができ、浸漬回数は1回でもよいし、複数回行ってもよい。
なお、基体上に均一系塗布液を塗布した後に、真空乾燥を行っても構わない。
焼成条件は、所望の膜厚、材料の種類などに応じて適宜設定することができる。例えば、ホットプレート上でソフトベーク(前焼成)を行った後に、オーブン中で焼成(アニーリング)を行う2段階工程とすることができる。
これにより、光吸収層が硬化される。
しかしながら、異なる組成を有する錯体溶液を積層する場合は、前記調製方法(III)に限られるものではない。錯体溶液を前記調製方法(I)及び/又は前記調製方法(II)で調製した場合であっても、異なる組成を有する錯体溶液を所望の順序で積層することができる。上記のようにして、塗布膜中の組成分布を柔軟にデザインすることが容易となる。
上記実施形態では、均一系塗布液の調製方法として、調製方法(I)、調製方法(II)及び調製方法(III)について説明したが、本発明はこれらに限定されるものではない。例えば、一部の金属成分については金属前駆体を調製しておき、調製した金属錯体と、他の金属成分と、ルイス塩基溶媒と、ルイス酸と、所望により第16族元素と、その他所望の成分とを混合することもできる。また、例えば調製方法(II)において、一部の原料を先に混合した後に、残りの原料を添加することもできる。
(実施例1)
S(硫黄)1.536g(48.00mmol)、DMSO(ジメチルスルホキシド)22.00g、NH328%水溶液6.204g(NH3換算で102.00mmol)を混合し、室温で一晩撹拌した。
得られた反応液に、In1.208g(10.50mmol)、Ga0.315g(4.50mmol)、Cu0.4425g(6.75mmol)を加えて室温で4日間撹拌した。その後、Cu0.4425g(6.75mmol)を加えて室温で2日間撹拌し、均一系塗布液1を得た。
S1.600g(50.00mmol)、DMSO22.00g、(NH4)2S42%水溶液8.095g(S換算で50.00mmol)を混合し、室温で6時間撹拌した。
得られた反応液に、In1.208g(10.50mmol)、Ga0.315g(4.50mmol)、Cu0.4425g(6.75mmol)を加えて室温で1日間撹拌し、更に70℃で3日間撹拌した。その後、Cu0.4425g(6.75mmol)を加えて70℃で1日間撹拌し、均一系塗布液2を得た。
S1.536g(48.00mmol)、DMSO22.00g、NH328%水溶液6.204g(NH3換算で102.00mmol)、(NH4)2S42%水溶液1.943g(S換算で12.00mmol)を混合し、室温で6時間撹拌した。
得られた反応液に、In1.208g(10.50mmol)、Ga0.315g(4.50mmol)、Cu0.4425g(6.75mmol)を加えて室温で1日間撹拌し、更に70℃で3日間撹拌した。その後、Cu0.4425g(6.75mmol)を加えて室温で2日間撹拌し、均一系塗布液3を得た。
Se 3.948g(50.00mmol)、DMSO23.00g、(NH4)2S42%水溶液8.095g(S換算で50.00mmol)を混合し、室温で6時間撹拌した。
得られた反応液に、In1.208g(10.50mmol)、Ga0.420g(6.00mmol)、Cu0.429g(6.75mmol)を加えて室温で一晩撹拌し、更に70℃で4日間撹拌した。その後、Cu0.429g(6.75mmol)を加えて70℃で1日間撹拌し、均一系塗布液4を得た。
Se3.790g(48.00mmol)、DMSO22.50g、NH328%水溶液6.204g(NH3換算で102.00mmol)、(NH4)2S42%水溶液1.943g(S換算で12.00mmol)を混合し、室温で一晩撹拌した。
得られた反応液に、In1.208g(10.50mmol)、Ga 0.315g(4.500)、Cu0.297g(4.67mmol)を加えて室温で6時間撹拌し、更に70℃で2日間撹拌した。その後、Cu0.593g(9.33mmol)を加えて室温で2日間撹拌し、均一系塗布液5を得た。
Se3.790g(48.00mmol)、DMSO22.50g、NH328%水溶液6.204g(NH3換算で102.00mmol)、(NH4)2S42%水溶液1.943g(S換算で12.00mmol)を混合し、室温で一晩撹拌した。
得られた反応液に、Cu0.6355g(10.0mmol)を加えて室温で24時間撹拌した。その後、Cu0.6355g(10.0mmol)を加えて室温で2日間撹拌し、均一系塗布液6を得た。
Se3.948g(50.00mmol)、DMSO23.00g、(NH4)2S42%水溶液1.538g(S換算で9.5mmol)を混合し、室温で6時間撹拌した。
得られた反応液に、In1.208g(10.50mmol)、Ga0.315g(4.5mmol)を加えて室温で一晩撹拌し、更に70℃で4日撹拌した。その後、Cu0.4425g(6.75mmol)を加えて70℃で1日撹拌し、均一系塗布液7を得た。
DMSO12.00g、(NH4)2S42%水溶液2.429g(S換算で15.0mmol)を混合し、室温で24時間撹拌した。
得られた反応液に、Cu0.086g(1.5mmol)、In0.345g(3.0mmol)、Ga0.105g(1.5mmol)を加えて室温で一晩撹拌し、更に70℃で4日撹拌した。その後、Cu0.086g(1.5mmol)を加えて70℃で1日撹拌し、均一系塗布液8を得た。
実施例1~5で得られた均一系塗布液1~5をそれぞれ王水に溶解し、水で希釈後ICP測定を行った。ICP測定結果からCu、In、Gaのモル比を計算した。結果を表1に示す。
In、Ga及びCuの量をIn1.035g(9.0mmol)、Ga0.420g(6.0mmol)、Cu1.082g(16.5mmol)にそれぞれ変更した以外は実施例4と同様にして均一系塗布液9-1を得た。
上記とは別に、In、Ga及びCuの量をIn1.380g(12.0mmol)、Ga0.210g(3.0mmol)、Cu0.787g(12.0mmol)にそれぞれ変更した以外は実施例4と同様にして均一系塗布液9-2を得た。
ついで、均一系塗布液9-1 6.0gと均一系塗布液9-2 6.0gとを混合し、室温で1時間撹拌し、均一系塗布液9を得た。
均一系塗布液9-1、均一系塗布液9-2及び均一系塗布液9について、上記と同様にしてICP測定を測定した。結果を表2に示す。
Cu0.508g(8.0mmol)、In1.208g(10.5mmol)、Ga0.105g(1.5mmol)、Se4.501g(57.00mmol)、DMSO27.00g及びNH328%水溶液10.4gを混合し、室温で6時間撹拌した。その後、70℃で1日撹拌し、1時間音波処理し、均一系塗布液10を得た。
均一系塗布液10について、上記と同様にしてICP測定を測定した。結果を表2に示す。
国際公開第2011/013657号の実施例を参照してCIGS塗布液を調製した。
ベンゼンセレノール4.949g(47.1mmol)とピリジン3.726g(47.1mmol)とを混合して混合溶媒を調製した。この混合溶媒に、固形分濃度14%、金属比率がCu/(In+Ga)=0.78、In/(In+Ga)=0.60、Ga/(In+Ga)=0.40となるように、Cu0.230g(3.619mmol)と、In0.320g(2.787mmol)と、Ga0.130g(1.865mmol)と、Se0.720g(9.119mmol)とを混合し、室温で2週間撹拌し、比較均一系塗布液1を得た。
得られた溶液の上澄み液の金属比率をICPで確認したところ、Cu/(In+Ga)=0.93、In/(In+Ga)=0.62、Ga/(In+Ga)=0.38であった。
実施例4及び7で得られた均一系塗布液4及び7について、TGA 2950(TA Instruments社製)を用いて、昇温速度2℃/分にて熱重量分析(TGA)を行った。その結果、温度上昇により過剰Se又はSが除去されることが確認された。
(実施例11~16)
実施例9で作成した均一系塗布液9をMo蒸着したガラス基板上に塗布し、325℃で2分間のソフトベイクを行った。この工程を合計15回行った後、少量のセレン存在下で、表3に示す条件でアニーリングを行うことにより、CIGS層が成膜されたCIGS基板を作成した。
上記で作成したCIGS基板をSEMで観察したところ、いずれもCIGSのグレイン成長が確認された。また、均一な1層の膜が形成されていることが確認された。
実施例9で作成した均一系塗布液9-1をMo蒸着したガラス基板上に塗布し、325℃で2分間のソフトベイクを行った。この工程を合計15回行った後、少量のセレン存在下で、表3に示す条件でアニーリングを行うことにより、CIGS層が成膜されたCIGS基板を作成した。
上記で作成したCIGS基板をSEMで観察したところ、CIGSのグレイン成長が確認された。また、均一な1層の膜が形成されていることが確認された。
実施例9で作成した均一系塗布液9-2をMo蒸着したガラス基板上に塗布し、325℃で2分間のソフトベイクを行った。この工程を合計15回行った後、少量のセレン存在下で、表3に示す条件でアニーリングを行うことにより、CIGS層が成膜されたCIGS基板を作成した。
上記で作成したCIGS基板をSEMで観察したところ、CIGSのグレイン成長が確認された。また、均一な1層の膜が形成されていることが確認された。
実施例10で作成した均一系塗布液10をMo蒸着したガラス基板上に塗布し、325℃で2分間のソフトベイクを行った。この工程を合計15回行った後、少量のセレン存在下で、表3に示す条件でアニーリングを行うことにより、CIGS層が成膜されたCIGS基板を作成した。
上記で作成したCIGS基板をSEMで観察したところ、CIGSのグレイン成長が確認された。また、複数の粒子が積層した均一な膜が形成されていることが確認された。
アニール時間を50分に変更し、セレン非存在下でアニーリングを行った以外は、実施例11と同様にしてCIGS層が成膜されたCIGS基板を作成した。
上記で作成したCIGS基板をSEMで観察したところ、セレン非存在下でアニーリングを行ったにもかかわらず、CIGSのグレイン成長が確認された。また、均一な1層の膜が形成されていることが確認された。
均一系塗布液9に替えて均一系塗布液4を用い、セレン非存在下でアニーリングを560℃で50分行った以外は、実施例11と同様にしてCIGS基板を形成した。
少量のセレン存在下でアニーリングを行った以外は実施例21と同様にしてCIGS基板を形成した。
比較例1で調製した比較均一系塗布液1をMo蒸着したガラス基板上に塗布し、120℃で1分間、300℃で3分間ソフトベイクを行った。その後、少量のセレン存在下で、540℃で30分間アニーリングを行うことにより、CIGS層が成膜されたCIGS基板を作成した。
比較例1で調製した比較均一系塗布液1をMo蒸着したガラス基板上に塗布し、120℃で1分間、300℃で3分間ソフトベイクを行った。この工程を合計2回行った後、少量のセレン存在下で、540℃で30分間アニーリングを行うことにより、CIGS層が成膜されたCIGS基板を作成した。
実施例21、22及び比較例2、3で作成したCIGS基板について、ラマン分光分析を行った。その結果、実施例21、22のCIGS基板については、1500cm-1付近にピークは見られず、CIGS膜に炭素成分が残存していないことが確認された。一方、比較例2、3のCIGS基板については、1500cm-1付近にピークが見られ、CIGS膜に炭素成分が残存していることが確認された。
実施例11及び20で作成した各CIGS基板をXRD測定したところ、2θ=約27゜、45゜および52~53゜にそれぞれ、CIGSの(112)面、(220)/(204)面、(312)/(116)面に相当する強いピークが確認された。これらは既存のCIGS膜の結果(Souilah, M. , Lafond, A. , Guillot Deudon, C. , Harel, S. , Evain, M. J.Solid State Chem. 183 (2010) 2274)と良い一致を示すことから、CIGS膜の生成を確認した。
Claims (26)
- 太陽電池の光吸収層の形成に用いられる均一系塗布液であって、
第11族金属、第13族金属、第11族金属化合物及び第13族金属化合物からなる群より選ばれる少なくとも1種の金属または金属化合物、ルイス塩基溶媒及びルイス酸を含有する均一系塗布液。 - 前記太陽電池がカルコパイライト系太陽電池である請求項1に記載の均一系塗布液。
- 前記ルイス塩基溶媒が非プロトン性溶媒である請求項1~3のいずれか一項に記載の均一系塗布液。
- 前記非プロトン性溶媒が、ジメチルスルホキシド、ピリジン、テトラメチルウレア、テトラヒドロフラン、酢酸エチル、アセトン、ジメチルホルムアミド、アセトニトリル、ジクロロメタン、ジメチルアセトアミド、N-メチルピロリドン及びN-メチルイミダゾールからなる群より選ばれる少なくとも1種である請求項4に記載の均一系塗布液。
- 前記ルイス酸がオニウム塩である請求項1~5のいずれか一項に記載の均一系塗布液。
- 前記ルイス酸がアンモニウム塩である請求項6に記載の均一系塗布液。
- 前記アンモニウム塩が、水酸化アンモニウム、硫化アンモニウム、塩化アンモニウム、炭酸アンモニウム、アンモニウムセレニド、アンモニウムチオシアネート、酢酸アンモニウム、アンモニウムカルバメート、ギ酸アンモニウム、アンモニウムヘキサフルオロホスファート、二フッ化水素アンモニウム及び硝酸アンモニウムからなる群より選ばれる少なくとも1種である請求項7に記載の均一系塗布液。
- 更に第16族元素を含有する請求項1~8のいずれか一項に記載の均一系塗布液。
- 前記第16元素が、S及びSeからなる群より選ばれる少なくとも1種である請求項9に記載の均一系塗布液。
- 更にLi、Na、K、Cs、Sb及びBiからなる群より選ばれる少なくとも1種を含有する請求項1~10のいずれか一項に記載の均一系塗布液。
- 請求項1~11のいずれか一項に記載の均一系塗布液を用いて形成される、太陽電池用光吸収層。
- 請求項12の太陽電池用光吸収層を備えた太陽電池。
- 太陽電池の光吸収層の形成に用いられる均一系塗布液の製造方法であって、
第11族金属、第13族金属、第11族金属化合物及び第13族金属化合物からなる群より選ばれる少なくとも1種の金属または金属化合物、ルイス塩基溶媒及びルイス酸を混合することを含むことを特徴とする均一系塗布液の製造方法。 - 前記太陽電池がカルコパイライト系太陽電池である請求項14に記載の均一系塗布液の製造方法。
- 前記ルイス塩基溶媒が非プロトン性溶媒である請求項14~16のいずれか一項に記載の均一系塗布液の製造方法。
- 前記非プロトン性溶媒が、ジメチルスルホキシド、ピリジン、テトラメチルウレア、テトラヒドロフラン、酢酸エチル、アセトン、ジメチルホルムアミド、アセトニトリル、ジクロロメタン、ジメチルアセトアミド、N-メチルピロリドン及びN-メチルイミダゾールからなる群より選ばれる少なくとも1種である請求項17に記載の均一系塗布液の製造方法。
- 前記ルイス酸がオニウム塩である請求項14~18のいずれか一項に記載の均一系塗布液の製造方法。
- 前記ルイス酸がアンモニウム塩である請求項19に記載の均一系塗布液の製造方法。
- 前記アンモニウム塩が、水酸化アンモニウム、硫化アンモニウム、塩化アンモニウム、炭酸アンモニウム、アンモニウムセレニド、アンモニウムチオシアネート、酢酸アンモニウム、アンモニウムカルバメート、ギ酸アンモニウム、アンモニウムヘキサフルオロホスファート、二フッ化水素アンモニウム及び硝酸アンモニウムからなる群より選ばれる少なくとも1種である請求項20に記載の均一系塗布液の製造方法。
- 更に第16族元素を混合することを含む請求項14~21のいずれか一項に記載の均一系塗布液の製造方法。
- 前記第16元素が、S及びSeからなる群より選ばれる少なくとも1種である請求項22に記載の均一系塗布液の製造方法。
- 更にLi、Na、K、Cs、Sb及びBiからなる群より選ばれる少なくとも1種を添加することを含む請求項14~23のいずれか一項に記載の均一系塗布液の製造方法。
- 請求項14~24のいずれか一項に記載の均一系塗布液の製造方法により得られた均一系塗布液を、基体に塗布し、焼成することを特徴とする太陽電池用光吸収層の製造方法。
- 基板上に第1の電極を形成する工程と、
前記第1の電極上に、請求項14~24のいずれか一項に記載の均一系塗布液の製造方法により得られた均一系塗布液を塗布し、焼成して光吸収層を形成する工程と、
前記光吸収層上にバッファ層を形成する工程と、
前記バッファ層上に第2の電極を形成する工程と、を有することを特徴とする太陽電池の製造方法。
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