WO2016060185A1 - 太陽電池 - Google Patents
太陽電池 Download PDFInfo
- Publication number
- WO2016060185A1 WO2016060185A1 PCT/JP2015/079095 JP2015079095W WO2016060185A1 WO 2016060185 A1 WO2016060185 A1 WO 2016060185A1 JP 2015079095 W JP2015079095 W JP 2015079095W WO 2016060185 A1 WO2016060185 A1 WO 2016060185A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- photoelectric conversion
- solar cell
- organic
- sealing material
- atom
- Prior art date
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 95
- 239000003566 sealing material Substances 0.000 claims abstract description 62
- 150000001875 compounds Chemical class 0.000 claims abstract description 43
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 24
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 23
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 23
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 21
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 19
- 125000004429 atom Chemical group 0.000 claims abstract description 10
- 125000005843 halogen group Chemical group 0.000 claims abstract description 10
- 229910044991 metal oxide Inorganic materials 0.000 claims description 14
- 150000004706 metal oxides Chemical class 0.000 claims description 14
- 150000004767 nitrides Chemical class 0.000 claims description 9
- 229910052798 chalcogen Chemical group 0.000 claims description 3
- 238000007789 sealing Methods 0.000 abstract description 47
- 230000006866 deterioration Effects 0.000 abstract description 17
- 150000001787 chalcogens Chemical group 0.000 abstract description 5
- 239000004065 semiconductor Substances 0.000 description 40
- 125000000524 functional group Chemical group 0.000 description 30
- 238000000034 method Methods 0.000 description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 23
- 229920001577 copolymer Polymers 0.000 description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 20
- 238000004544 sputter deposition Methods 0.000 description 19
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 description 18
- 239000011347 resin Substances 0.000 description 18
- 229920005989 resin Polymers 0.000 description 18
- 239000011135 tin Substances 0.000 description 18
- 239000000178 monomer Substances 0.000 description 17
- -1 polyparaphenylene vinylene skeleton Polymers 0.000 description 17
- 239000000463 material Substances 0.000 description 16
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 13
- 239000011701 zinc Substances 0.000 description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 11
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- 230000000052 comparative effect Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
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- 239000010409 thin film Substances 0.000 description 8
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- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 7
- IEQWWMKDFZUMMU-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethyl)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)CCOC(=O)C=C IEQWWMKDFZUMMU-UHFFFAOYSA-N 0.000 description 7
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 7
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- 230000005525 hole transport Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 6
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- 239000008393 encapsulating agent Substances 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
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- 238000004088 simulation Methods 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
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- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 4
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- 125000003700 epoxy group Chemical group 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
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- 238000004528 spin coating Methods 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- 229910001887 tin oxide Inorganic materials 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- PNKUSGQVOMIXLU-UHFFFAOYSA-N Formamidine Chemical compound NC=N PNKUSGQVOMIXLU-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- 229920002367 Polyisobutene Polymers 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000565 sealant Substances 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 description 3
- 238000001771 vacuum deposition Methods 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- ICPSWZFVWAPUKF-UHFFFAOYSA-N 1,1'-spirobi[fluorene] Chemical group C1=CC=C2C=C3C4(C=5C(C6=CC=CC=C6C=5)=CC=C4)C=CC=C3C2=C1 ICPSWZFVWAPUKF-UHFFFAOYSA-N 0.000 description 2
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 2
- BHHGXPLMPWCGHP-UHFFFAOYSA-O 2-phenylethanaminium Chemical compound [NH3+]CCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-O 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
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- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
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- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
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- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 238000000333 X-ray scattering Methods 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
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- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 125000000609 carbazolyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 2
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- 230000015556 catabolic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- PDZKZMQQDCHTNF-UHFFFAOYSA-M copper(1+);thiocyanate Chemical compound [Cu+].[S-]C#N PDZKZMQQDCHTNF-UHFFFAOYSA-M 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- JAONJTDQXUSBGG-UHFFFAOYSA-N dialuminum;dizinc;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Zn+2].[Zn+2] JAONJTDQXUSBGG-UHFFFAOYSA-N 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
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- 125000001153 fluoro group Chemical group F* 0.000 description 2
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- 238000010574 gas phase reaction Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
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- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- UOIWOHLIGKIYFE-UHFFFAOYSA-N n-methylpentan-1-amine Chemical compound CCCCCNC UOIWOHLIGKIYFE-UHFFFAOYSA-N 0.000 description 2
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- 239000003960 organic solvent Substances 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 229940100684 pentylamine Drugs 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical group N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
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- 238000000926 separation method Methods 0.000 description 2
- GKCNVZWZCYIBPR-UHFFFAOYSA-N sulfanylideneindium Chemical compound [In]=S GKCNVZWZCYIBPR-UHFFFAOYSA-N 0.000 description 2
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical group [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 2
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- 239000010936 titanium Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
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- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 2
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- XDXWNHPWWKGTKO-UHFFFAOYSA-N 207739-72-8 Chemical compound C1=CC(OC)=CC=C1N(C=1C=C2C3(C4=CC(=CC=C4C2=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC(=CC=C1C1=CC=C(C=C13)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 XDXWNHPWWKGTKO-UHFFFAOYSA-N 0.000 description 1
- MHIITNFQDPFSES-UHFFFAOYSA-N 25,26,27,28-tetrazahexacyclo[16.6.1.13,6.18,11.113,16.019,24]octacosa-1(25),2,4,6,8(27),9,11,13,15,17,19,21,23-tridecaene Chemical group N1C(C=C2C3=CC=CC=C3C(C=C3NC(=C4)C=C3)=N2)=CC=C1C=C1C=CC4=N1 MHIITNFQDPFSES-UHFFFAOYSA-N 0.000 description 1
- SKKHNUKNMQLBTJ-UHFFFAOYSA-N 3-bicyclo[2.2.1]heptanyl 2-methylprop-2-enoate Chemical compound C1CC2C(OC(=O)C(=C)C)CC1C2 SKKHNUKNMQLBTJ-UHFFFAOYSA-N 0.000 description 1
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- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
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- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- H—ELECTRICITY
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
- H01G9/2009—Solid electrolytes
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- C07C211/62—Quaternary ammonium compounds
- C07C211/63—Quaternary ammonium compounds having quaternised nitrogen atoms bound to acyclic carbon atoms
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3464—Sputtering using more than one target
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/141—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
- C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C211/03—Monoamines
- C07C211/04—Mono-, di- or tri-methylamine
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/24—Lead compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/50—Photovoltaic [PV] devices
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/84—Layers having high charge carrier mobility
- H10K30/85—Layers having high electron mobility, e.g. electron-transporting layers or hole-blocking layers
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- H—ELECTRICITY
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Definitions
- the present invention relates to a solar cell that has excellent photoelectric conversion efficiency, little deterioration during sealing (initial deterioration), high-temperature durability, and excellent temperature cycle resistance.
- a photoelectric conversion element including a stacked body in which an N-type semiconductor layer and a P-type semiconductor layer are arranged between opposing electrodes.
- photocarriers are generated by photoexcitation, and an electric field is generated by electrons moving through an N-type semiconductor and holes moving through a P-type semiconductor.
- inorganic solar cells manufactured using an inorganic semiconductor such as silicon.
- inorganic solar cells are expensive to manufacture and difficult to increase in size, and the range of use is limited, organic solar cells manufactured using organic semiconductors instead of inorganic semiconductors are attracting attention. .
- Fullerene In organic solar cells, fullerene is almost always used. Fullerenes are known to work mainly as N-type semiconductors.
- Patent Document 1 describes a semiconductor heterojunction film formed using an organic compound that becomes a P-type semiconductor and fullerenes.
- the cause of deterioration is fullerenes (see, for example, Non-Patent Document 1), and materials that replace fullerenes are required.
- an organic solar cell it is general to seal a laminated body in which an N-type semiconductor layer and a P-type semiconductor layer are arranged between opposing electrodes using a sealing resin such as a sealing material (for example, refer nonpatent literature 2).
- a sealing resin such as a sealing material
- the semiconductor material deteriorates during sealing and the photoelectric conversion efficiency decreases. (Initial deterioration).
- An object of the present invention is to provide a solar cell that has excellent photoelectric conversion efficiency, little deterioration during sealing (initial deterioration), high-temperature durability, and excellent temperature cycle resistance.
- the present invention provides a laminate having an electrode, a counter electrode, and a photoelectric conversion layer disposed between the electrode and the counter electrode, and sealing for covering the counter electrode and sealing the laminate.
- the photoelectric conversion layer is represented by the general formula R-MX 3 (where R is an organic molecule, M is a metal atom, and X is a halogen atom or a chalcogen atom).
- R is an organic molecule
- M is a metal atom
- X is a halogen atom or a chalcogen atom
- the organic inorganic perovskite compound is included, and the sealing material is a solar cell including a (meth) acrylic resin having 4 or more C atoms / O atoms in the molecule.
- the present invention is described in detail below.
- the present inventor has disclosed a photoelectric conversion in a solar cell in which a laminated body having an electrode, a counter electrode, and a photoelectric conversion layer disposed between the electrode and the counter electrode is sealed with a sealing material.
- the use of a specific organic / inorganic perovskite compound in the layer was studied.
- an improvement in the photoelectric conversion efficiency of the solar cell can be expected.
- a laminated body including a photoelectric conversion layer using an organic / inorganic perovskite compound was sealed with a conventional sealing material, it was found that the photoelectric conversion efficiency was lowered at the time of sealing (initial deterioration).
- the present inventors have examined in detail the cause of deterioration when a laminate including a photoelectric conversion layer using an organic / inorganic perovskite compound is sealed with a sealing material. As a result, it has been found that the organic component in the organic / inorganic perovskite compound is dissolved in the sealing material at the time of sealing and the organic / inorganic perovskite compound is deteriorated. As a result of intensive studies, the present inventors have used a (meth) acrylic resin having 4 or more C atoms / O atoms in the molecule as a sealing material, so that the organic component in the organic / inorganic perovskite compound can be reduced during sealing.
- the solar cell according to the present invention includes an electrode, a counter electrode, a laminate having a photoelectric conversion layer disposed between the electrode and the counter electrode, and encapsulates the laminate so as to cover the counter electrode. And a sealing material.
- the term “layer” means not only a layer having a clear boundary but also a layer having a concentration gradient in which contained elements gradually change.
- the elemental analysis of the layer can be performed, for example, by performing FE-TEM / EDS line analysis measurement of the cross section of the solar cell and confirming the element distribution of the specific element.
- a layer means not only a flat thin film-like layer but also a layer that can form a complicated and complicated structure together with other layers.
- the material of the said electrode and the said counter electrode is not specifically limited, A conventionally well-known material can be used.
- the counter electrode is often a patterned electrode.
- the material for the electrode and the counter electrode include FTO (fluorine-doped tin oxide), sodium, sodium-potassium alloy, lithium, magnesium, aluminum, magnesium-silver mixture, magnesium-indium mixture, aluminum-lithium alloy, Al / lithium Al 2 O 3 mixture, Al / LiF mixture, metal such as gold, CuI, ITO (indium tin oxide), SnO 2 , AZO (aluminum zinc oxide), IZO (indium zinc oxide), GZO (gallium zinc oxide) Conductive transparent materials, conductive transparent polymers, and the like. These materials may be used alone or in combination of two or more. Further, the electrode and the counter electrode may be a cathode or an anode, respectively.
- the photoelectric conversion layer includes an organic / inorganic perovskite compound represented by the general formula R-MX 3 (where R is an organic molecule, M is a metal atom, and X is a halogen atom or a chalcogen atom).
- R-MX 3 an organic / inorganic perovskite compound represented by the general formula R-MX 3 (where R is an organic molecule, M is a metal atom, and X is a halogen atom or a chalcogen atom).
- the R is an organic molecule, and is preferably represented by C 1 N m H n (l, m, and n are all positive integers). Specifically, R is, for example, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, trimethylamine, triethylamine, tripropyl.
- methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, formamidine and their ions and phenethylammonium are preferred, and methylamine, ethylamine, propylamine, formamidine and these ions are more preferred.
- M is a metal atom, for example, lead, tin, zinc, titanium, antimony, bismuth, nickel, iron, cobalt, silver, copper, gallium, germanium, magnesium, calcium, indium, aluminum, manganese, chromium, molybdenum, Europium etc. are mentioned. These metal atoms may be used independently and 2 or more types may be used together.
- X is a halogen atom or a chalcogen atom, and examples thereof include chlorine, bromine, iodine, sulfur, and selenium. These halogen atoms or chalcogen atoms may be used alone or in combination of two or more. Among these, the halogen atom is preferable because the organic / inorganic perovskite compound becomes soluble in an organic solvent and can be applied to an inexpensive printing method by containing halogen in the structure. Furthermore, iodine is more preferable because the energy band gap of the organic-inorganic perovskite compound becomes narrow.
- the organic / inorganic perovskite compound preferably has a cubic structure in which a metal atom M is disposed at the body center, an organic molecule R is disposed at each vertex, and a halogen atom or a chalcogen atom X is disposed at the face center.
- FIG. 1 shows an example of a crystal structure of an organic / inorganic perovskite compound having a cubic structure in which a metal atom M is arranged at the body center, an organic molecule R is arranged at each vertex, and a halogen atom or a chalcogen atom X is arranged at the face center. It is a schematic diagram.
- the organic / inorganic perovskite compound is preferably a crystalline semiconductor.
- the crystalline semiconductor means a semiconductor capable of measuring the X-ray scattering intensity distribution and detecting a scattering peak.
- the organic / inorganic perovskite compound is a crystalline semiconductor, the mobility of electrons in the organic / inorganic perovskite compound is increased, and the photoelectric conversion efficiency of the solar cell is improved.
- the degree of crystallization can be evaluated as an index of crystallization.
- the degree of crystallinity is determined by separating the crystalline-derived scattering peak detected by the X-ray scattering intensity distribution measurement and the halo derived from the amorphous part by fitting, obtaining the respective intensity integrals, Can be obtained by calculating the ratio.
- a preferable lower limit of the crystallinity of the organic-inorganic perovskite compound is 30%. When the crystallinity is 30% or more, the mobility of electrons in the organic / inorganic perovskite compound is increased, and the photoelectric conversion efficiency of the solar cell is improved.
- a more preferred lower limit of the crystallinity is 50%, and a more preferred lower limit is 70%. Examples of the method for increasing the crystallinity of the organic / inorganic perovskite compound include thermal annealing, irradiation with intense light such as laser, and plasma irradiation.
- the photoelectric conversion layer may further contain an organic semiconductor or an inorganic semiconductor in addition to the organic / inorganic perovskite compound as long as the effects of the present invention are not impaired.
- the organic semiconductor or inorganic semiconductor referred to here may serve as an electron transport layer or a hole transport layer described later.
- the organic semiconductor include compounds having a thiophene skeleton such as poly (3-alkylthiophene).
- conductive polymers having a polyparaphenylene vinylene skeleton, a polyvinyl carbazole skeleton, a polyaniline skeleton, a polyacetylene skeleton, and the like can be given.
- a compound having a porphyrin skeleton such as a phthalocyanine skeleton, a naphthalocyanine skeleton, a pentacene skeleton, or a benzoporphyrin skeleton, a spirobifluorene skeleton, etc., and a carbon-containing material such as carbon nanotubes, graphene, and fullerene that may be surface-modified. Materials are also mentioned.
- the inorganic semiconductor examples include titanium oxide, zinc oxide, indium oxide, tin oxide, gallium oxide, tin sulfide, indium sulfide, zinc sulfide, CuSCN, Cu 2 O, CuI, MoO 3 , V 2 O 5 , WO 3 , MoS 2, MoSe 2, Cu 2 S , and the like.
- the photoelectric conversion layer may be a laminated structure in which a thin-film organic semiconductor or an inorganic semiconductor portion and a thin-film organic-inorganic perovskite compound portion are laminated, or an organic A composite structure in which a semiconductor or inorganic semiconductor portion and an organic / inorganic perovskite compound portion are combined may be used.
- a laminated structure is preferable in that the production method is simple, and a composite structure is preferable in that the charge separation efficiency in the organic semiconductor or the inorganic semiconductor can be improved.
- the preferable lower limit of the thickness of the thin-film organic / inorganic perovskite compound site is 5 nm, and the preferable upper limit is 5000 nm. If the thickness is 5 nm or more, light can be sufficiently absorbed, and the photoelectric conversion efficiency is increased. If the said thickness is 5000 nm or less, since it can suppress that the area
- the more preferable lower limit of the thickness is 10 nm, the more preferable upper limit is 1000 nm, the still more preferable lower limit is 20 nm, and the still more preferable upper limit is 500 nm.
- a preferable lower limit of the thickness of the composite structure is 30 nm, and a preferable upper limit is 3000 nm. If the thickness is 30 nm or more, light can be sufficiently absorbed, and the photoelectric conversion efficiency is increased. If the said thickness is 3000 nm or less, since it becomes easy to reach
- the more preferable lower limit of the thickness is 40 nm, the more preferable upper limit is 2000 nm, the still more preferable lower limit is 50 nm, and the still more preferable upper limit is 1000 nm.
- an electron transport layer may be disposed between the electrode and the photoelectric conversion layer.
- the material of the electron transport layer is not particularly limited.
- N-type conductive polymer, N-type low molecular organic semiconductor, N-type metal oxide, N-type metal sulfide, alkali metal halide, alkali metal, surface activity Specific examples include, for example, cyano group-containing polyphenylene vinylene, boron-containing polymer, bathocuproine, bathophenanthrene, hydroxyquinolinato aluminum, oxadiazole compound, benzimidazole compound, naphthalene tetracarboxylic acid compound, perylene derivative, Examples include phosphine oxide compounds, phosphine sulfide compounds, fluoro group-containing phthalocyanines, titanium oxide, zinc oxide, indium oxide, tin oxide, gallium oxide, tin sulfide, indium sulfide, and zinc sulfide.
- the electron transport layer may consist of only a thin film electron transport layer, but preferably includes a porous electron transport layer.
- the photoelectric conversion layer is a composite structure in which an organic semiconductor or inorganic semiconductor portion and an organic inorganic perovskite compound portion are combined, a more complex composite structure (a more complicated and complicated structure) is obtained. Since the photoelectric conversion efficiency becomes high, it is preferable that the composite structure is formed on the porous electron transport layer.
- the preferable lower limit of the thickness of the electron transport layer is 1 nm, and the preferable upper limit is 2000 nm. If the thickness is 1 nm or more, holes can be sufficiently blocked. If the said thickness is 2000 nm or less, it will become difficult to become resistance at the time of electron transport, and photoelectric conversion efficiency will become high.
- the more preferable lower limit of the thickness of the electron transport layer is 3 nm, the more preferable upper limit is 1000 nm, the still more preferable lower limit is 5 nm, and the still more preferable upper limit is 500 nm.
- a hole transport layer may be disposed between the counter electrode and the photoelectric conversion layer.
- the material of the hole transport layer is not particularly limited, and examples thereof include a P-type conductive polymer, a P-type low molecular organic semiconductor, a P-type metal oxide, a P-type metal sulfide, and a surfactant.
- Examples include polystyrene sulfonate adduct of polyethylenedioxythiophene, carboxyl group-containing polythiophene, phthalocyanine, porphyrin, molybdenum oxide, vanadium oxide, tungsten oxide, nickel oxide, copper oxide, tin oxide, molybdenum sulfide, tungsten sulfide, copper sulfide. , Tin sulfide and the like, fluoro group-containing phosphonic acid, carbonyl group-containing phosphonic acid, copper compounds such as CuSCN and CuI, surface-modified carbon nanotubes, carbon-containing materials such as graphene, and the like.
- the preferable lower limit of the thickness of the hole transport layer is 1 nm, and the preferable upper limit is 2000 nm. If the thickness is 1 nm or more, electrons can be sufficiently blocked. If the said thickness is 2000 nm or less, it will become difficult to become resistance at the time of hole transport, and a photoelectric conversion efficiency will become high.
- the more preferable lower limit of the thickness is 3 nm, the more preferable upper limit is 1000 nm, the still more preferable lower limit is 5 nm, and the still more preferable upper limit is 500 nm.
- the laminate may further include a substrate or the like.
- substrate is not specifically limited, For example, transparent glass substrates, such as soda-lime glass and an alkali free glass, a ceramic substrate, a transparent plastic substrate, etc. are mentioned.
- the laminate is sealed with a sealing material.
- the durability of the solar cell can be improved by sealing the laminate with the sealing material. This is considered to be because moisture can be prevented from penetrating into the inside by sealing with the sealing material.
- the sealing material covers the entire laminated body so as to close an end portion thereof. This can reliably prevent moisture from penetrating into the interior.
- either the electrode side or the counter electrode side of the said laminated body may be covered with the sealing material.
- the sealing material includes a (meth) acrylic resin (hereinafter, also simply referred to as “(meth) acrylic resin”) having 4 or more C atoms / O atoms in the molecule.
- (meth) acrylic resin hereinafter, also simply referred to as “(meth) acrylic resin”.
- the solar cell of the present invention by using the (meth) acrylic resin, even if the organic / inorganic perovskite compound is used in the photoelectric conversion layer, The elution of the organic component can be suppressed and the photoelectric conversion layer can be prevented from deteriorating. This is probably because the (meth) acrylic resin has relatively high hydrophobicity and low affinity for the organic / inorganic perovskite compound. Furthermore, by using the (meth) acrylic resin for the sealing material, molecular diffusion over time can be suppressed, so that the heat resistance and durability of the solar cell can be improved.
- the (meth) acrylic resin preferably has 5 or more C atoms / O atoms in the molecule, and more preferably 6 or more.
- the (meth) acrylic resin preferably has 30 or less C atoms / O atoms in the molecule, and more preferably 20 or less.
- the value of the C atom / O atom in the molecule of the (meth) acrylic resin is, for example, CHN / O elemental analysis using an organic trace element analyzer (for example, 2400II manufactured by Perkin Elmer) or an NMR apparatus ( For example, it can be measured by solution NMR using JEOL, ECA II).
- the value of C atom / O atom in the molecule of the (meth) acrylic polymer can be easily controlled by adjusting the kind and composition of the (meth) acrylic monomer used as a raw material.
- the (meth) acrylic polymer can be obtained by homopolymerizing or copolymerizing a (meth) acrylic monomer having 4 or more C atoms / O atoms in the molecule.
- Examples of the (meth) acrylic monomer having 4 or more C atoms / O atoms in the molecule include alkyl groups having 8 or more carbon atoms such as ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and the like.
- These (meth) acrylic monomers may be used alone or in combination of two or more.
- (meth) alkyl acrylate having an alkyl group having 8 or more carbon atoms, alicyclic skeleton-containing (meth) acrylate, and a group to which a reactive functional group can be added for example, a hydroxyl group, a carboxyl group, an epoxy group, etc.
- (Meth) acrylate and the like are preferable, and alicyclic skeleton-containing (meth) acrylate is preferable.
- a (meth) acrylate having a group capable of adding a reactive functional group for example, a hydroxyl group, a carboxyl group, an epoxy group, etc.
- the reactive functional group is added.
- the sealing material may be covered with an inorganic layer as described later.
- the (meth) acrylic resin by using a homopolymerized or copolymerized monomer containing the alicyclic skeleton-containing (meth) acrylate, the encapsulant may be made of other materials such as polyisobutylene resin. Compared with the sealing material containing this resin, the sputtering resistance required when the inorganic layer is formed by the sputtering method is also excellent.
- the (meth) acrylic resin may be a resin obtained by forming a copolymer having a reactive functional group and then crosslinking the reactive functional group with a crosslinking agent.
- a crosslinking agent for example.
- the said crosslinking agent is not specifically limited, The crosslinking reaction of the said reactive functional group can be started using a catalyst etc.
- the (meth) acrylic resin may be a resin obtained by forming the (meth) acrylic monomer as a monomer and then crosslinking or polymerizing the (meth) acrylic monomer with heat or UV.
- the (meth) acrylic resin is, for example, a copolymer of isobornyl acrylate, ethylhexyl acrylate, and hydroxybutyl acrylate ((meth) acrylate having a hydroxyl group as a group to which a reactive functional group can be added).
- -Methacryloyloxyethyl isocyanate adduct (having a methacryloyloxy group as a reactive functional group), isobornyl acrylate, ethylhexyl acrylate, and acryloyloxyethyl-succinic acid (having a carboxyl group as a group to which a reactive functional group can be added) (Meth) acrylate) and 2-methacryloyloxyethyl isocyanate adduct (having a methacryloyloxy group as a reactive functional group).
- the lower limit of the solubility parameter (SP value) of the (meth) acrylic resin is 7.0, and the preferable upper limit is 10.0. If the solubility parameter (SP value) of the (meth) acrylic resin is 7.0 or more, the choice of resin is widened and molding becomes easy. If the solubility parameter (SP value) of the (meth) acrylic resin is 10.0 or less, elution of the organic component in the organic / inorganic perovskite compound at the time of sealing is further suppressed, and the photoelectric conversion layer is deteriorated. Can be further suppressed.
- the more preferable lower limit of the solubility parameter (SP value) of the (meth) acrylic resin is 7.5, and the more preferable lower limit is 8.0. From the viewpoint of increasing the high temperature durability of the solar cell, the upper limit of the solubility parameter (SP value) of the sealing resin is more preferably 9.5, and further preferably 9.0.
- the SP value is called a solubility parameter, and is an index that can express the ease of dissolution.
- the SP value is calculated by using a method proposed by Fedors (R. F. Fedors, Polym. Eng. Sci., 14 (2), 147-154 (1974)). It can be calculated according to the following formula (1) from the evaporation energy ( ⁇ ecoh) (cal / mol) and the molar volume ( ⁇ v) (cm 3 / mol) with respect to the atomic group.
- ⁇ represents an SP value (cal / mol) 1/2 .
- the SP value of the copolymer can be calculated by the following formula (2) by calculating the SP value of each repeating unit alone in the copolymer and using the volume fraction thereof.
- ⁇ cop represents the SP value of the copolymer
- ⁇ 1, ⁇ 2 represents the volume fraction of the repeating units 1 and 2
- ⁇ 1, ⁇ 2 represents the SP value of the repeating units 1 and 2 alone.
- the preferable lower limit of the thickness of the sealing material is 100 nm, and the preferable upper limit is 100000 nm.
- a more preferable lower limit of the thickness is 500 nm, a more preferable upper limit is 50000 nm, a still more preferable lower limit is 1000 nm, and a still more preferable upper limit is 20000 nm.
- the solar cell of the present invention it is further preferable to have an inorganic layer on the sealing material.
- the said inorganic layer has water vapor
- the solar cell of this invention it is also preferable to have an inorganic layer between the said laminated body and the said sealing material. Also in this case, since the said inorganic layer has water vapor
- the inorganic layer preferably contains a metal oxide, a metal nitride, or a metal oxynitride.
- the metal oxide, metal nitride or metal oxynitride is not particularly limited as long as it has a water vapor barrier property.
- oxides, nitrides or oxynitrides of Si, Al, Zn or Sn are preferable, oxides, nitrides or oxynitrides of Zn or Sn are more preferable. Since flexibility can be imparted, an oxide, nitride, or oxynitride of a metal element containing both Zn and Sn metal elements is more preferable.
- the metal oxide, metal nitride, or metal oxynitride is particularly preferably a metal oxide represented by the general formula Zn a Sn b O c .
- a, b, and c represent positive integers.
- the metal oxide represented by the general formula Zn a Sn b O c for the inorganic layer, the metal oxide contains tin (Sn) atoms, and thus gives the inorganic layer appropriate flexibility. Even when the thickness of the inorganic layer is increased, the stress is reduced, so that peeling of the inorganic layer, the electrode, the semiconductor layer, and the like can be suppressed.
- steam barrier property of the said inorganic layer can be improved, and the durability of a solar cell can be improved more.
- the metal oxide contains zinc (Zn) atoms, the inorganic layer can exhibit particularly high barrier properties.
- the ratio Xs (wt%) of Sn to the sum of Zn and Sn satisfies 70>Xs> 0.
- the value Y represented by Y c / (a + 2b) satisfies 1.5>Y> 0.5.
- the element ratio of zinc (Zn), tin (Sn), and oxygen (O) contained in the metal oxide represented by the general formula Zn a Sn b O c in the inorganic layer is determined by X-ray photoelectron spectroscopy ( It can be measured using an XPS) surface analyzer (for example, ESCALAB-200R manufactured by VG Scientific).
- the inorganic layer when containing a metal oxide represented by the general formula Zn a Sn b O c, preferably further contains silicon (Si) and / or aluminum (Al).
- silicon (Si) and / or aluminum (Al) By adding silicon (Si) and / or aluminum (Al) to the inorganic layer, the transparency of the inorganic layer can be increased and the photoelectric conversion efficiency of the solar cell can be improved.
- the preferable lower limit of the thickness of the inorganic layer is 30 nm, and the preferable upper limit is 3000 nm.
- the inorganic layer can have a sufficient water vapor barrier property, and the durability of the solar cell is improved.
- the thickness is 3000 nm or less, even if the thickness of the inorganic layer is increased, the generated stress is small, and thus the peeling of the inorganic layer, the electrode, the semiconductor layer, and the like can be suppressed.
- the more preferable lower limit of the thickness is 50 nm, the more preferable upper limit is 1000 nm, the still more preferable lower limit is 100 nm, and the still more preferable upper limit is 500 nm.
- the thickness of the inorganic layer can be measured using an optical interference film thickness measuring device (for example, FE-3000 manufactured by Otsuka Electronics Co., Ltd.).
- the sealing material may be further covered with other materials such as a glass plate, a resin film, a resin film coated with an inorganic material, and a metal foil such as aluminum. . That is, the solar cell of the present invention may have a configuration in which the laminate and the other materials are sealed, filled, or bonded with the sealing material. Thereby, even if there is a pinhole in the sealing material, water vapor can be sufficiently blocked, and the high humidity durability of the solar cell can be further improved. Among these, it is more preferable to dispose a resin film coated with an inorganic material.
- FIG. 2 is a cross-sectional view schematically showing an example of the solar cell of the present invention.
- a laminate having an electrode 2, a counter electrode 3, and a photoelectric conversion layer 4 disposed between the electrode 2 and the counter electrode 3 on a substrate 6 is a counter electrode.
- 3 is sealed with a sealing material 5 covering the top.
- the end of the sealing material 5 is closed by being in close contact with the substrate 6.
- the counter electrode 3 is a patterned electrode.
- an inorganic layer may be disposed between the laminate and the sealing material 5 or on the sealing material 5.
- the method for producing the solar cell of the present invention is not particularly limited. For example, after forming the electrode, the photoelectric conversion layer, and the counter electrode in this order on the substrate in this order, the encapsulant is formed. And a method of sealing the laminate and further covering the sealing material with an inorganic layer.
- the method for forming the photoelectric conversion layer is not particularly limited, and examples thereof include a vacuum deposition method, a sputtering method, a gas phase reaction method (CVD), an electrochemical deposition method, and a printing method.
- the solar cell which can exhibit high photoelectric conversion efficiency can be simply formed in a large area by employ
- the printing method include a spin coating method and a casting method, and examples of a method using the printing method include a roll-to-roll method.
- the method for sealing the laminate with the sealant is not particularly limited.
- the method for sealing the laminate using a sheet-like sealant, or the sealing in which the sealant is dissolved in an organic solvent A method of applying a material solution to the laminate, a method of crosslinking or polymerizing a compound having a reactive functional group with heat or UV after applying a compound having a reactive functional group to be a sealing material to the laminate and a method of cooling the sealing material after applying heat to the sealing material.
- a vacuum deposition method As a method of covering the sealing material with the inorganic layer, a vacuum deposition method, a sputtering method, a gas phase reaction method (CVD), or an ion plating method is preferable.
- the sputtering method is preferable for forming a dense layer, and the DC magnetron sputtering method is more preferable among the sputtering methods.
- the said sealing material is a sealing material containing other resins, such as polyisobutylene resin, for example
- the sputtering resistance required when the inorganic layer is formed by the sputtering method is also excellent.
- the (meth) acrylic resin is a resin obtained by forming a copolymer having a reactive functional group and then crosslinking the reactive functional group with a crosslinking agent, the sputtering resistance is improved. be able to.
- an inorganic layer can be formed by using a metal target and oxygen gas or nitrogen gas as raw materials and depositing the raw material on the sealing material to form a film.
- the present invention it is possible to provide a solar cell that is excellent in photoelectric conversion efficiency, has little deterioration during sealing (initial deterioration), has high-temperature durability, and has excellent temperature cycle resistance.
- Example 1 (Production of laminate) An FTO film having a thickness of 1000 nm was formed as an electrode on a glass substrate, and ultrasonic cleaning was performed for 10 minutes each using pure water, acetone, and methanol in this order, followed by drying. A titanium isopropoxide ethanol solution adjusted to 2% was applied on the surface of the FTO film by a spin coating method, followed by baking at 400 ° C. for 10 minutes to form a thin-film electron transport layer having a thickness of 20 nm.
- a titanium oxide paste containing polyisobutyl methacrylate as an organic binder and titanium oxide (a mixture of an average particle size of 10 nm and 30 nm) is applied onto the thin film electron transport layer by a spin coat method, and then heated to 500 ° C. Was fired for 10 minutes to form a porous electron transport layer having a thickness of 500 nm.
- CH 3 NH 3 I and PbI 2 were dissolved at a molar ratio of 1: 1 using N, N-dimethylformamide (DMF) as a solvent as a solution for forming an organic inorganic perovskite compound, and the total weight of CH 3 NH 3 I and PbI 2 The concentration was adjusted to 20%.
- This solution was laminated on the electron transport layer by a spin coating method to form a photoelectric conversion layer. Furthermore, a solution was prepared by dissolving Spiro-OMeTAD (having a spirobifluorene skeleton) 68 mM, Tert-butylpyridine 55 mM, and Lithium Bis (trifluoromethylsulfonyl) imide 9 mM in 25 ⁇ L of chlorobenzene. This solution was laminated on the photoelectric conversion layer to a thickness of 300 nm by spin coating to form a hole transport layer. On the hole transport layer, a gold film having a thickness of 100 nm was formed as a counter electrode by vacuum deposition to obtain a laminate.
- Spiro-OMeTAD having a spirobifluorene skeleton
- Tert-butylpyridine 55 mM Tert-butylpyridine 55 mM
- the monomer ratio of iB, EH, and MOI added is 4.5: 4.5: 1 in terms of molar ratio. Further, when measured by CHN / O elemental analysis, the C atom / O atom in the obtained copolymer molecule was 6.
- the film formation chamber of the sputtering apparatus was evacuated by a vacuum pump, and the pressure was reduced to 5.0 ⁇ 10 ⁇ 4 Pa.
- Example 2 In the production of the laminate, a solar cell was obtained in the same manner as in Example 1 except that the photoelectric conversion layer (organic inorganic perovskite compound) shown in Table 1 was formed by changing the compounding components of the organic / inorganic perovskite compound forming solution.
- the photoelectric conversion layer organic inorganic perovskite compound shown in Table 1 was formed by changing the compounding components of the organic / inorganic perovskite compound forming solution.
- CH 3 NH 3 Br, CH 3 NH 3 I, PbBr 2 and PbI 2 were dissolved at a molar ratio of 1: 2: 1: 2 using N, N-dimethylformamide (DMF) as a solvent.
- DMF N-dimethylformamide
- Example 3 CH 3 NH 3 I and PbCl 2 were dissolved at a molar ratio of 3: 1 using N, N-dimethylformamide (DMF) as a solvent.
- Example 4 CH 3 NH 3 Br and PbBr 2 were dissolved at a molar ratio of 1: 1 using N, N-dimethylformamide (DMF) as a solvent.
- Example 5 CH 3 (NH 3 ) 2 I and PbI 2 were dissolved at a molar ratio of 1: 1 using N, N-dimethylformamide (DMF) as a solvent.
- Example 6 In the sealing of the laminated body, a solar cell was obtained in the same manner as in Example 1 except that the thickness was changed to the sealing material thickness shown in Table 1.
- Example 7 In the sealing of the laminate, a solar cell was obtained in the same manner as in Example 1 except that the sealing material shown in Table 1 was changed.
- Example 7 a copolymer of isobornyl acrylate (iB) and ethylhexyl acrylate (EH) was used.
- the C atom / O atom in the obtained copolymer molecule was 6.
- the monomer ratio of iB and EH added is 5: 5 in molar ratio.
- 2-methacryloyloxyethyl which is a copolymer of isobornyl acrylate (iB) and acryloyloxyethyl-succinic acid ((meth) acrylate having a carboxyl group as a group to which a reactive functional group can be added).
- An isocyanate (MOI) adduct (having a methacryloyloxy group as a reactive functional group) was used.
- the C atom / O atom in the obtained copolymer molecule was 6.5.
- the monomer ratio of iB and MOI added is 9: 1 in terms of mol ratio.
- Example 9 a copolymer of ethylhexyl acrylate (EH) and acryloyloxyethyl-succinic acid ((meth) acrylate having a carboxyl group as a group to which a reactive functional group can be added), 2-methacryloyloxyethyl isocyanate ( MOI) Adduct (having a methacryloyloxy group as a reactive functional group) was used. The C atom / O atom in the obtained copolymer molecule was 5.5. The monomer ratio of EH and MOI added is 9: 1 in terms of mol ratio.
- EH ethylhexyl acrylate
- MOI 2-methacryloyloxyethyl isocyanate
- Example 10 instead of forming the inorganic layer on the encapsulant, the inorganic layer was formed on the laminate, and then the encapsulant was laminated, except that the inorganic layer shown in Table 1 was changed. A solar cell was obtained.
- a Si target was used as the metal target.
- a Sn target was used as the metal target.
- Example 13 A solar cell was obtained in the same manner as in Example 1 except that the inorganic layer was not formed on the sealing material.
- Example 14 In the sealing of the laminate, a solar cell was obtained in the same manner as in Example 1 except that the sealing material shown in Table 1 was changed.
- Example 14 a copolymer 2-cyclohexyl acrylate (CH, manufactured by Tokyo Chemical Industry Co., Ltd.) and acryloyloxyethyl-succinic acid ((meth) acrylate having a carboxyl group as a group to which a reactive functional group can be added) was prepared.
- a methacryloyloxyethyl isocyanate (MOI) adduct (having a methacryloyloxy group as a reactive functional group) was used.
- the C atom / O atom in the obtained copolymer molecule was 4.5.
- the monomer ratio of CH and MOI added is 9: 1 in terms of mol ratio.
- a copolymer of t-butyl methacrylate (tB, manufactured by Tokyo Chemical Industry Co., Ltd.) and acryloyloxyethyl-succinic acid ((meth) acrylate having a carboxyl group as a group to which a reactive functional group can be added) was prepared.
- 2-Methacryloyloxyethyl isocyanate (MOI) adduct (having a methacryloyloxy group as a reactive functional group) was used.
- the C atom / O atom in the obtained copolymer molecule was 4.
- the monomer ratio of tB and MOI added is 9: 1 in terms of mol ratio.
- methyl acrylate (Me, manufactured by Mitsubishi Chemical Corporation) was used in place of ethylhexyl acrylate (EH, manufactured by Mitsubishi Chemical Corporation).
- the C atom / O atom in the obtained copolymer molecule was 4.5.
- Comparative Examples 1 to 5 In the sealing of the laminate, a solar cell was obtained in the same manner as in Example 1 except that the sealing material shown in Table 1 was changed.
- a solution of polyvinyl alcohol (PVA) (manufactured by Wako Pure Chemical Industries, Ltd.) was applied on the laminate with a doctor blade and dried to obtain a sealing material.
- PVA polyvinyl alcohol
- Comparative Example 2 a mixture containing 4 mol% of imidazole compound 2MZA (manufactured by Shikoku Kasei Co., Ltd.) as a curing agent and bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation) as a curing agent was applied to the laminate. It was cured by heating for 1 hour to obtain a sealing material.
- Comparative Example 3 a solution of polyisobutylene resin (OPPANOL B 50, manufactured by BASF) was applied onto the laminate with a doctor blade and dried to obtain a sealing material.
- OPPANOL B 50 a solution of polyisobutylene resin
- Comparative Example 4 a solution of norbornene resin (manufactured by Polyplastics) was applied onto the laminate with a doctor blade and dried to obtain a sealing material.
- a solution of polymethyl methacrylate resin manufactured by Wako Pure Chemical Industries, Ltd. was applied onto the laminate with a doctor blade and dried to obtain a sealing material.
- Comparative Example 5 a copolymer of t-butyl acrylate (tB, manufactured by Osaka Organic Chemical Co., Ltd.) and acryloyloxyethyl-succinic acid ((meth) acrylate having a carboxyl group as a group to which a reactive functional group can be added) 2-methacryloyloxyethyl isocyanate (MOI) adduct (having a methacryloyloxy group as a reactive functional group) was used. The C atom / O atom in the obtained copolymer molecule was 3.5. The monomer ratio of tB and MOI added is 9: 1 in terms of mol ratio.
- tB t-butyl acrylate
- MOI 2-methacryloyloxyethyl isocyanate
- a power source (manufactured by KEITHLEY, 236 model) is connected between the electrodes of the laminate before sealing, and photoelectric conversion efficiency is measured using a solar simulation (manufactured by Yamashita Denso Co., Ltd.) with an intensity of 100 mW / cm 2 , and initial conversion is performed. The efficiency.
- a power source (made by KEITHLEY, 236 model) is connected between the electrodes of the solar cell immediately after sealing, and the photoelectric conversion efficiency is measured using a solar simulation (manufactured by Yamashita Denso Co., Ltd.) having an intensity of 100 mW / cm 2.
- a high temperature durability solar cell was heated on a hot plate at 150 ° C. for 30 minutes, and a high temperature durability test was conducted.
- a power source (manufactured by KEITHLEY, 236 model) is connected between the electrodes of the solar cell after the high temperature endurance test, and the photoelectric conversion efficiency is measured using a solar simulation (manufactured by Yamashita Denso Co., Ltd.) having an intensity of 100 mW / cm 2.
- the value of photoelectric conversion efficiency after the durability test / photoelectric conversion efficiency immediately after sealing was determined.
- A: Photoelectric conversion efficiency after high-temperature durability test / photoelectric conversion efficiency immediately after sealing is 0.9 or more.
- Photoelectric conversion efficiency after high-temperature durability test / photoelectric conversion efficiency immediately after sealing is 0.7 or more and less than 0.9.
- ⁇ photoelectric conversion efficiency after high-temperature durability test / photoelectric conversion efficiency immediately after sealing is 0.5 or more and less than 0.7
- ⁇ photoelectric conversion efficiency after high-temperature durability test / photoelectric conversion efficiency immediately after sealing is less than 0.5
- the temperature cycle test was performed on the temperature cycle resistant solar cell by performing 300 cycles from ⁇ 55 ° C. to 125 ° C.
- a power source (manufactured by KEITHLEY, 236 model) is connected between the electrodes of the solar cell after the temperature cycle test, and the photoelectric conversion efficiency is measured using a solar simulation (manufactured by Yamashita Denso Co., Ltd.) having an intensity of 100 mW / cm 2.
- the value of photoelectric conversion efficiency after cycle test / photoelectric conversion efficiency immediately after sealing was determined.
- the present invention it is possible to provide a solar cell that is excellent in photoelectric conversion efficiency, has little deterioration during sealing (initial deterioration), has high-temperature durability, and has excellent temperature cycle resistance.
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Abstract
Description
以下、本発明を詳述する。
しかしながら、有機無機ペロブスカイト化合物を用いた光電変換層を含む積層体を、従来の封止材で封止したところ、封止時に光電変換効率が低下してしまうことがわかった(初期劣化)。
そこで本発明者らは、有機無機ペロブスカイト化合物を用いた光電変換層を含む積層体を、封止材により封止したときの劣化の原因について詳しく検討した。その結果、封止時に、有機無機ペロブスカイト化合物中の有機成分が封止材に溶け込んでしまい、有機無機ペロブスカイト化合物が劣化してしまうことが原因であることを見出した。
本発明者らは、鋭意検討の結果、封止材として分子中のC原子/O原子が4以上である(メタ)アクリル樹脂を用いることにより、封止時に有機無機ペロブスカイト化合物中の有機成分が溶出してしまうのを抑制できることを見出した。更に、本発明者は、封止材に比較的疎水性の高い特定の(メタ)アクリル樹脂を用いることにより、太陽電池の高温耐久性及び温度サイクル耐性をも向上できることを見出し、本発明を完成させるに至った。
なお、本明細書中、層とは、明確な境界を有する層だけではなく、含有元素が徐々に変化する濃度勾配のある層をも意味する。なお、層の元素分析は、例えば、太陽電池の断面のFE-TEM/EDS線分析測定を行い、特定元素の元素分布を確認する等によって行うことができる。また、本明細書中、層とは、平坦な薄膜状の層だけではなく、他の層と一緒になって複雑に入り組んだ構造を形成しうる層をも意味する。
上記電極及び上記対向電極の材料として、例えば、FTO(フッ素ドープ酸化スズ)、ナトリウム、ナトリウム-カリウム合金、リチウム、マグネシウム、アルミニウム、マグネシウム-銀混合物、マグネシウム-インジウム混合物、アルミニウム-リチウム合金、Al/Al2O3混合物、Al/LiF混合物、金等の金属、CuI、ITO(インジウムスズ酸化物)、SnO2、AZO(アルミニウム亜鉛酸化物)、IZO(インジウム亜鉛酸化物)、GZO(ガリウム亜鉛酸化物)等の導電性透明材料、導電性透明ポリマー等が挙げられる。これらの材料は単独で用いられてもよく、2種以上が併用されてもよい。
また、上記電極及び上記対向電極は、それぞれ陰極になっても、陽極になってもよい。
上記光電変換層に上記有機無機ペロブスカイト化合物を用いることにより、太陽電池の光電変換効率を向上させることができる。
上記Rは、具体的には例えば、メチルアミン、エチルアミン、プロピルアミン、ブチルアミン、ペンチルアミン、ヘキシルアミン、ジメチルアミン、ジエチルアミン、ジプロピルアミン、ジブチルアミン、ジペンチルアミン、ジヘキシルアミン、トリメチルアミン、トリエチルアミン、トリプロピルアミン、トリブチルアミン、トリペンチルアミン、トリヘキシルアミン、エチルメチルアミン、メチルプロピルアミン、ブチルメチルアミン、メチルペンチルアミン、ヘキシルメチルアミン、エチルプロピルアミン、エチルブチルアミン、ホルムアミジン、グアニジン、イミダゾール、アゾール、ピロール、アジリジン、アジリン、アゼチジン、アゼト、アゾール、イミダゾリン、カルバゾール及びこれらのイオン(例えば、メチルアンモニウム(CH3NH3)等)、及び、フェネチルアンモニウム等が挙げられる。なかでも、メチルアミン、エチルアミン、プロピルアミン、ブチルアミン、ペンチルアミン、ヘキシルアミン、ホルムアミジン及びこれらのイオン、及び、フェネチルアンモニウムが好ましく、メチルアミン、エチルアミン、プロピルアミン、ホルムアミジン及びこれらのイオンがより好ましい。
図1は、体心に金属原子M、各頂点に有機分子R、面心にハロゲン原子又はカルコゲン原子Xが配置された立方晶系の構造である、有機無機ペロブスカイト化合物の結晶構造の一例を示す模式図である。詳細は明らかではないが、上記構造を有することにより、結晶格子内の八面体の向きが容易に変わることができるため、上記有機無機ペロブスカイト化合物中の電子の移動度が高くなり、太陽電池の光電変換効率が向上すると推定される。
上記有機無機ペロブスカイト化合物の結晶化度の好ましい下限は30%である。結晶化度が30%以上であると、上記有機無機ペロブスカイト化合物中の電子の移動度が高くなり、太陽電池の光電変換効率が向上する。結晶化度のより好ましい下限は50%、更に好ましい下限は70%である。
また、上記有機無機ペロブスカイト化合物の結晶化度を上げる方法として、例えば、熱アニール、レーザー等の強度の強い光の照射、プラズマ照射等が挙げられる。
上記有機半導体として、例えば、ポリ(3-アルキルチオフェン)等のチオフェン骨格を有する化合物等が挙げられる。また、例えば、ポリパラフェニレンビニレン骨格、ポリビニルカルバゾール骨格、ポリアニリン骨格、ポリアセチレン骨格等を有する導電性高分子等も挙げられる。更に、例えば、フタロシアニン骨格、ナフタロシアニン骨格、ペンタセン骨格、ベンゾポルフィリン骨格等のポルフィリン骨格、スピロビフルオレン骨格等を有する化合物、及び、表面修飾されていてもよいカーボンナノチューブ、グラフェン、フラーレン等のカーボン含有材料も挙げられる。
上記電子輸送層の材料は特に限定されず、例えば、N型導電性高分子、N型低分子有機半導体、N型金属酸化物、N型金属硫化物、ハロゲン化アルカリ金属、アルカリ金属、界面活性剤等が挙げられ、具体的には例えば、シアノ基含有ポリフェニレンビニレン、ホウ素含有ポリマー、バソキュプロイン、バソフェナントレン、ヒドロキシキノリナトアルミニウム、オキサジアゾール化合物、ベンゾイミダゾール化合物、ナフタレンテトラカルボン酸化合物、ペリレン誘導体、ホスフィンオキサイド化合物、ホスフィンスルフィド化合物、フルオロ基含有フタロシアニン、酸化チタン、酸化亜鉛、酸化インジウム、酸化スズ、酸化ガリウム、硫化スズ、硫化インジウム、硫化亜鉛等が挙げられる。
上記ホール輸送層の材料は特に限定されず、例えば、P型導電性高分子、P型低分子有機半導体、P型金属酸化物、P型金属硫化物、界面活性剤等が挙げられ、具体的には例えば、ポリエチレンジオキシチオフェンのポリスチレンスルホン酸付加物、カルボキシル基含有ポリチオフェン、フタロシアニン、ポルフィリン、酸化モリブデン、酸化バナジウム、酸化タングステン、酸化ニッケル、酸化銅、酸化スズ、硫化モリブデン、硫化タングステン、硫化銅、硫化スズ等、フルオロ基含有ホスホン酸、カルボニル基含有ホスホン酸、CuSCN、CuI等の銅化合物、表面修飾されていてもよいカーボンナノチューブ、グラフェン等のカーボン含有材料等が挙げられる。
なお、上記積層体が封止材で封止されていれば、上記積層体の電極側又は対向電極側のいずれが封止材で覆われていてもよい。
上記光電変換層に上記有機無機ペロブスカイト化合物を用いた場合、封止時に上記有機無機ペロブスカイト化合物中の有機成分が上記封止材に溶け込んでしまい、上記有機無機ペロブスカイト化合物が劣化する(初期劣化)。これに対して、本発明の太陽電池においては、上記(メタ)アクリル樹脂を用いることにより、上記光電変換層に上記有機無機ペロブスカイト化合物を用いていても、封止時に上記有機無機ペロブスカイト化合物中の有機成分の溶出を抑えて、光電変換層が劣化してしまうのを防止することができる。これは、上記(メタ)アクリル樹脂は比較的疎水性が高く、上記有機無機ペロブスカイト化合物に対する親和性が低いためではないかと考えられる。更に、上記封止材に上記(メタ)アクリル樹脂を用いることにより、経時での分子拡散を抑えることができるため、太陽電池の耐熱耐久性を向上させることができる。
上記(メタ)アクリル樹脂は、分子中のC原子/O原子が5以上であることが好ましく、6以上であることがより好ましい。また、樹脂の溶剤溶解性の観点より、上記(メタ)アクリル樹脂は、分子中のC原子/O原子が30以下であることが好ましく、20以下であることがより好ましい。
なお、(メタ)アクリル樹脂の分子中のC原子/O原子の値は、例えば、有機微量元素分析装置(例えば、Perkin Elmer社製、2400II)を用いたCHN/O元素分析や、NMR装置(例えば、JEOL社製、ECA II)を用いた溶液NMR等により測定することができる。
具体的には例えば、分子中のC原子/O原子が4以上である(メタ)アクリルモノマーを単独重合又は共重合することにより上記(メタ)アクリル重合体を得ることができる。
上記分子中のC原子/O原子が4以上である(メタ)アクリルモノマーとしては、例えば、エチルヘキシル(メタ)アクリレート、ラウリル(メタ)アクリレート、ステアリル(メタ)アクリレート等の炭素数8以上のアルキル基を有する(メタ)アルキルアクリレート;フェニル(メタ)アクリレート、ナフチル(メタ)アクリレート等の芳香族骨格含有(メタ)アクリレート;イソボルニル(メタ)アクリレート、ノルボルニル(メタ)アクリレート、アダマンチル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート等の脂環式骨格含有(メタ)アクリレート;ヒドロキシルエチルヘキシル(メタ)アクリレート等の反応性官能基を付加できる基(例えば、水酸基、カルボキシル基、エポキシ基等)を有する(メタ)アクリレート等が挙げられる。これらの(メタ)アクリルモノマーは単独で用いられてもよく、2種以上が併用されてもよい。なかでも、炭素数8以上のアルキル基を有する(メタ)アルキルアクリレート、脂環式骨格含有(メタ)アクリレート、反応性官能基を付加できる基(例えば、水酸基、カルボキシル基、エポキシ基等)を有する(メタ)アクリレート等が好ましく、脂環式骨格含有(メタ)アクリレートが好適である。
更に、原料となる(メタ)アクリルモノマーの種類及び組成を調整することにより、上記封止材の広い温度域における被着体に対する密着性を制御することが容易であるため、太陽電池の温度サイクル耐性をも向上させることができる。
この場合、上記(メタ)アクリル樹脂として、上記脂環式骨格含有(メタ)アクリレートを含むモノマーを単独重合又は共重合したものを用いることにより、上記封止材は、例えばポリイソブチレン樹脂等のその他の樹脂を含む封止材と比較して、スパッタリング法により無機層を形成する際に要求されるスパッタリング耐性にも優れたものとなる。
上記架橋剤は特に限定されず、触媒等を用いて上記反応性官能基の架橋反応を開始させることができる。
また、上記(メタ)アクリル樹脂は、上記(メタ)アクリルモノマーをモノマーのままで製膜した後、熱又はUV等で上記(メタ)アクリルモノマーを架橋又は重合させた樹脂であってもよい。
また、Tg≧25℃の場合、主鎖骨格原子数をnとして、n≧3の時は2n、n<3の時は4nをΔvに加えて計算する。
上記金属酸化物、金属窒化物又は金属酸窒化物は、水蒸気バリア性を有するものであれば特に限定されないが、例えば、Si、Al、Zn、Sn、In、Ti、Mg、Zr、Ni、Ta、W、Cu若しくはこれらを2種以上含む合金の酸化物、窒化物又は酸窒化物が挙げられる。なかでも、Si、Al、Zn又はSnの酸化物、窒化物又は酸窒化物が好ましく、Zn又はSnの酸化物、窒化物又は酸窒化物がより好ましく、上記無機層に特に高い水蒸気バリア性及び柔軟性を付与できることから、Zn及びSnの両金属元素を含む金属元素の酸化物、窒化物又は酸窒化物が更に好ましい。
上記無機層に上記一般式ZnaSnbOcで表される金属酸化物を用いることにより、上記金属酸化物がスズ(Sn)原子を含むため、上記無機層に適度な可撓性を付与することができ、上記無機層の厚みが増した場合であっても応力が小さくなるため、上記無機層、電極、半導体層等の剥離を抑えることができる。これにより、上記無機層の水蒸気バリア性を高め、太陽電池の耐久性をより向上させることができる。一方、上記金属酸化物が亜鉛(Zn)原子を含むため、上記無機層は特に高いバリア性を発揮することができる。
なお、上記無機層中の上記一般式ZnaSnbOcで表される金属酸化物に含まれる亜鉛(Zn)、スズ(Sn)及び酸素(O)の元素比率は、X線光電子分光(XPS)表面分析装置(例えば、VGサイエンティフィックス社製のESCALAB-200R等)を用いて測定することができる。
上記無機層にケイ素(Si)及び/又はアルミニウム(Al)を添加することにより、上記無機層の透明性を高め、太陽電池の光電変換効率を向上させることができる。
なお、上記無機層の厚みは、光学干渉式膜厚測定装置(例えば、大塚電子社製のFE-3000等)を用いて測定することができる。
図2に示す太陽電池1においては、基板6上に電極2と、対向電極3と、この電極2と対向電極3との間に配置された光電変換層4とを有する積層体が、対向電極3上を覆う封止材5で封止されている。ここで封止材5の端部は、基板6に密着することにより閉じている。なお、図2に示す太陽電池1において、対向電極3はパターニングされた電極である。図示はしないが、積層体と封止材5の間、又は、封止材5上に無機層が配置されていてもよい。
上記スパッタリング法においては、金属ターゲット、及び、酸素ガス又は窒素ガスを原料とし、上記封止材上に原料を堆積して製膜することにより、無機層を形成することができる。
(積層体の作製)
ガラス基板上に、電極として厚み1000nmのFTO膜を形成し、純水、アセトン、メタノールをこの順に用いて各10分間超音波洗浄した後、乾燥させた。
FTO膜の表面上に、2%に調整したチタンイソプロポキシドエタノール溶液をスピンコート法により塗布した後、400℃で10分間焼成し、厚み20nmの薄膜状の電子輸送層を形成した。更に、薄膜状の電子輸送層上に、有機バインダとしてのポリイソブチルメタクリレートと酸化チタン(平均粒子径10nmと30nmとの混合物)とを含有する酸化チタンペーストをスピンコート法により塗布した後、500℃で10分間焼成し、厚み500nmの多孔質状の電子輸送層を形成した。
次いで、有機無機ペロブスカイト化合物形成用溶液として、N,N-Dimethylformamide(DMF)を溶媒としてCH3NH3IとPbI2をモル比1:1で溶かし、CH3NH3IとPbI2の合計重量濃度を20%に調製した。この溶液を電子輸送層上にスピンコート法によって積層して、光電変換層を形成した。
更に、クロロベンゼン25μLにSpiro-OMeTAD(スピロビフルオレン骨格を有する)を68mM、Tert-butylpyridineを55mM、Lithium Bis(trifluoromethylsufonyl)imide塩を9mM溶解させた溶液を調製した。この溶液を光電変換層上にスピンコート法によって300nmの厚みに積層し、ホール輸送層を形成した。
ホール輸送層上に、対向電極として真空蒸着により厚み100nmの金膜を形成し、積層体を得た。
得られた積層体上に、イソボルニルアクリレート(iB、共栄社化学社製)とエチルヘキシルアクリレート(EH、三菱化学社製)とアクリロイロキシエチル-コハク酸(反応性官能基を付加できる基としてカルボキシル基を有する(メタ)アクリレート、共栄社化学社製)との共重合体の2-メタクリロイルオキシエチルイソシアネート(MOI、昭和電工社製)付加物(反応性官能基としてメタクリロイルオキシ基を有する)と、反応触媒としての過酸化物(パークミルD、日油社製)とを含有する混合物をドクターブレードにより厚み10μmに積層し、150℃10分で上記共重合体を架橋反応させて封止材とした。
なお、iBとEHとMOIの添加したモノマー比率はmol比で4.5:4.5:1である。また、CHN/O元素分析により測定したところ、得られた共重合体分子中のC原子/O原子は6であった。
得られた積層体をスパッタリング装置の基板ホルダーに取り付け、更に、スパッタリング装置のカソードAにZnSn合金(Zn:Sn=95:5重量%)ターゲットを、カソードBにSiターゲットを取り付けた。スパッタリング装置の成膜室を真空ポンプにより排気し、5.0×10-4Paまで減圧した。その後、スパッタ条件Aに示す条件でスパッタリングし、積層体に無機膜(封止層)としてZnSnO(Si)薄膜を100nm形成し、薄膜太陽電池を得た。
<スパッタ条件A>
アルゴンガス流量:50sccm、酸素ガス流量:50sccm
電源出力:カソードA=500W、カソードB=1500W
積層体の作製において、有機無機ペロブスカイト化合物形成用溶液の配合成分を変更することによって表1に示す光電変換層(有機無機ペロブスカイト化合物)を形成したこと以外は実施例1と同様にして、太陽電池を得た。
なお、実施例2では、N,N-Dimethylformamide(DMF)を溶媒としてCH3NH3Br、CH3NH3I、PbBr2、PbI2をモル比1:2:1:2で溶かした。実施例3では、N,N-Dimethylformamide(DMF)を溶媒としてCH3NH3IとPbCl2をモル比3:1で溶かした。実施例4では、N,N-Dimethylformamide(DMF)を溶媒としてCH3NH3BrとPbBr2をモル比1:1で溶かした。実施例5では、N,N-Dimethylformamide(DMF)を溶媒としてCH3(NH3)2IとPbI2をモル比1:1で溶かした。
積層体の封止において、表1に示す封止材厚みに変更したこと以外は実施例1と同様にして、太陽電池を得た。
積層体の封止において、表1に示す封止材に変更したこと以外は実施例1と同様にして、太陽電池を得た。
実施例7では、イソボルニルアクリレート(iB)とエチルヘキシルアクリレート(EH)との共重合体を用いた。得られた共重合体分子中のC原子/O原子は6であった。なお、iBとEHの添加したモノマー比率はmol比で5:5である。
実施例8では、イソボルニルアクリレート(iB)とアクリロイロキシエチル-コハク酸(反応性官能基を付加できる基としてカルボキシル基を有する(メタ)アクリレート)との共重合体の2-メタクリロイルオキシエチルイソシアネート(MOI)付加物(反応性官能基としてメタクリロイルオキシ基を有する)を用いた。得られた共重合体分子中のC原子/O原子は6.5であった。なお、iBとMOIの添加したモノマー比率はmol比で9:1である。
実施例9では、エチルヘキシルアクリレート(EH)とアクリロイロキシエチル-コハク酸(反応性官能基を付加できる基としてカルボキシル基を有する(メタ)アクリレート)との共重合体の2-メタクリロイルオキシエチルイソシアネート(MOI)付加物(反応性官能基としてメタクリロイルオキシ基を有する)を用いた。得られた共重合体分子中のC原子/O原子は5.5であった。なお、EHとMOIの添加したモノマー比率はmol比で9:1である。
封止材上に無機層を形成する代わりに積層体上に無機層を形成してから封止材を積層したこと、表1に示す無機層に変更したこと以外は実施例1と同様にして、太陽電池を得た。
なお、実施例11では、金属ターゲットとして、Siターゲットを用いた。実施例12では、金属ターゲットとして、Snターゲットを用いた。
封止材上に無機層を形成しないこと以外は実施例1と同様にして、太陽電池を得た。
積層体の封止において、表1に示す封止材に変更したこと以外は実施例1と同様にして、太陽電池を得た。
実施例14では、シクロヘキシルアクリレート(CH、東京化成社製)とアクリロイロキシエチル-コハク酸(反応性官能基を付加できる基としてカルボキシル基を有する(メタ)アクリレート)との共重合体の2-メタクリロイルオキシエチルイソシアネート(MOI)付加物(反応性官能基としてメタクリロイルオキシ基を有する)を用いた。得られた共重合体分子中のC原子/O原子は4.5であった。なお、CHとMOIの添加したモノマー比率はmol比で9:1である。
実施例15では、t-ブチルメタクリレート(tB、東京化成社製)とアクリロイロキシエチル-コハク酸(反応性官能基を付加できる基としてカルボキシル基を有する(メタ)アクリレート)との共重合体の2-メタクリロイルオキシエチルイソシアネート(MOI)付加物(反応性官能基としてメタクリロイルオキシ基を有する)を用いた。得られた共重合体分子中のC原子/O原子は4であった。なお、tBとMOIの添加したモノマー比率はmol比で9:1である。
実施例16ではエチルヘキシルアクリレート(EH、三菱化学社製)の代わりにメチルアクリレート(Me、三菱化学社製)を使用した。得られた共重合体分子中のC原子/O原子は4.5であった。
積層体の封止において、表1に示す封止材に変更したこと以外は実施例1と同様にして、太陽電池を得た。
比較例1では、積層体上に、ポリビニルアルコール(PVA)(和光純薬工業社製)の溶液をドクターブレードにより塗布し、乾燥させて封止材とした。
比較例2では、積層体上に、硬化剤としての4mol%のイミダゾール化合物2MZA(四国化成社製)と、ビスフェノールA型エポキシ樹脂(三菱化学社製)とを含有する混合物を塗布し、120℃1時間加熱して硬化させて封止材とした。
比較例3では、積層体上に、ポリイソブチレン樹脂(OPPANOL B 50、BASF社製)の溶液をドクターブレードにより塗布し、乾燥させて封止材とした。
比較例4では、積層体上に、ノルボルネン樹脂(Polyplastics社製)の溶液をドクターブレードにより塗布し、乾燥させて封止材とした。比較例5では、積層体上に、ポリメチルメタクリレート樹脂(和光純薬工業社製)の溶液をドクターブレードにより塗布し、乾燥させて封止材とした。
比較例5ではt-ブチルアクリレート(tB、大阪有機化学工業社製)とアクリロイロキシエチル-コハク酸(反応性官能基を付加できる基としてカルボキシル基を有する(メタ)アクリレート)との共重合体の2-メタクリロイルオキシエチルイソシアネート(MOI)付加物(反応性官能基としてメタクリロイルオキシ基を有する)を用いた。得られた共重合体分子中のC原子/O原子は3.5であった。なお、tBとMOIの添加したモノマー比率はmol比で9:1である。
積層体の封止を行わなかったこと以外は実施例1と同様にして、太陽電池を得た。
実施例及び比較例で得られた太陽電池について、以下の評価を行った。
封止前の積層体の電極間に、電源(KEITHLEY社製、236モデル)を接続し、強度100mW/cm2のソーラーシミュレーション(山下電装社製)を用いて光電変換効率を測定し、初期変換効率とした。
封止直後の太陽電池の電極間に、電源(KEITHLEY社製、236モデル)を接続し、強度100mW/cm2のソーラーシミュレーション(山下電装社製)を用いて光電変換効率を測定し、封止直後の光電変換効率/初期変換効率の値を求めた。
○:封止直後の光電変換効率/初期変換効率の値が0.5以上
×:封止直後の光電変換効率/初期変換効率の値が0.5未満
太陽電池を70%30℃の条件下に24時間置いて高湿耐久試験を行った。高湿耐久試験後の太陽電池の電極間に、電源(KEITHLEY社製、236モデル)を接続し、強度100mW/cm2のソーラーシミュレーション(山下電装社製)を用いて光電変換効率を測定し、高湿耐久試験後の光電変換効率/封止直後の光電変換効率の値を求めた。
◎:高湿耐久試験後の光電変換効率/封止直後の光電変換効率が0.9以上
○:高湿耐久試験後の光電変換効率/封止直後の光電変換効率が0.5以上0.9未満
×:高湿耐久試験後の光電変換効率/封止直後の光電変換効率が0.5未満
太陽電池を150℃のホットプレートに30分加熱し、高温耐久試験を行った。高温耐久試験後の太陽電池の電極間に、電源(KEITHLEY社製、236モデル)を接続し、強度100mW/cm2のソーラーシミュレーション(山下電装社製)を用いて光電変換効率を測定し、高温耐久試験後の光電変換効率/封止直後の光電変換効率の値を求めた。
◎:高温耐久試験後の光電変換効率/封止直後の光電変換効率が0.9以上
○:高温耐久試験後の光電変換効率/封止直後の光電変換効率が0.7以上0.9未満
△:高温耐久試験後の光電変換効率/封止直後の光電変換効率が0.5以上0.7未満
×:高温耐久試験後の光電変換効率/封止直後の光電変換効率が0.5未満
太陽電池に対して-55℃から125℃までのサイクルを300サイクル行い、温度サイクル試験を行った。温度サイクル試験後の太陽電池の電極間に、電源(KEITHLEY社製、236モデル)を接続し、強度100mW/cm2のソーラーシミュレーション(山下電装社製)を用いて光電変換効率を測定し、温度サイクル試験後の光電変換効率/封止直後の光電変換効率の値を求めた。
○:温度サイクル試験後の光電変換効率/封止直後の光電変換効率の値が0.5以上
×:温度サイクル試験後の光電変換効率/封止直後の光電変換効率の値が0.5未満
(5)スパッタリング耐性
太陽電池の製造工程において封止材上にスパッタリング法により無機層を形成する際に、封止材の表面を目視観察した。
○:変化なし
△:封止材にわずかな白化が見られる
×:封止材に白化が見られる
2 電極
3 対向電極(パターニングされた電極)
4 光電変換層
5 封止材
6 基板
Claims (3)
- 電極と、対向電極と、前記電極と前記対向電極との間に配置された光電変換層とを有する積層体と、前記対向電極上を覆って前記積層体を封止する封止材とを有する太陽電池であって、
前記光電変換層は、一般式R-M-X3(但し、Rは有機分子、Mは金属原子、Xはハロゲン原子又はカルコゲン原子である。)で表される有機無機ペロブスカイト化合物を含み、
前記封止材は、分子中のC原子/O原子が4以上である(メタ)アクリル樹脂を含む
ことを特徴とする太陽電池。 - 封止材上に無機層を有し、前記無機層は、金属酸化物、金属窒化物又は金属酸窒化物を含むことを特徴とする請求項1記載の太陽電池。
- 積層体と封止材との間に無機層を有し、前記無機層は、金属酸化物、金属窒化物又は金属酸窒化物を含むことを特徴とする請求項1記載の太陽電池。
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Also Published As
Publication number | Publication date |
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CN107078220A (zh) | 2017-08-18 |
BR112017006760A2 (pt) | 2017-12-12 |
EP3208859B1 (en) | 2019-05-22 |
BR112017006760B1 (pt) | 2022-09-06 |
CN107078220B (zh) | 2019-07-26 |
AU2015331367A1 (en) | 2017-03-09 |
TR201911104T4 (tr) | 2019-08-21 |
AU2015331367B2 (en) | 2020-08-27 |
JP5926466B1 (ja) | 2016-05-25 |
EP3208859A4 (en) | 2018-06-20 |
US20170278640A1 (en) | 2017-09-28 |
EP3208859A1 (en) | 2017-08-23 |
JPWO2016060185A1 (ja) | 2017-04-27 |
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