JP6876480B2 - Solar cell - Google Patents
Solar cell Download PDFInfo
- Publication number
- JP6876480B2 JP6876480B2 JP2017059351A JP2017059351A JP6876480B2 JP 6876480 B2 JP6876480 B2 JP 6876480B2 JP 2017059351 A JP2017059351 A JP 2017059351A JP 2017059351 A JP2017059351 A JP 2017059351A JP 6876480 B2 JP6876480 B2 JP 6876480B2
- Authority
- JP
- Japan
- Prior art keywords
- layer
- solar cell
- sealing layer
- photoelectric conversion
- inorganic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000007789 sealing Methods 0.000 claims description 78
- 238000006243 chemical reaction Methods 0.000 claims description 61
- 150000001875 compounds Chemical class 0.000 claims description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 32
- 229920001709 polysilazane Polymers 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 16
- 239000000377 silicon dioxide Substances 0.000 claims description 16
- 238000002835 absorbance Methods 0.000 claims description 15
- 229910018557 Si O Inorganic materials 0.000 claims description 11
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 11
- 125000005843 halogen group Chemical group 0.000 claims description 10
- 238000010521 absorption reaction Methods 0.000 claims description 8
- 125000004429 atom Chemical group 0.000 claims description 8
- 238000002329 infrared spectrum Methods 0.000 claims description 4
- 229910052798 chalcogen Chemical group 0.000 claims description 2
- 239000004065 semiconductor Substances 0.000 description 36
- 238000000034 method Methods 0.000 description 25
- 239000010408 film Substances 0.000 description 22
- 239000011135 tin Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 230000004888 barrier function Effects 0.000 description 13
- 238000004544 sputter deposition Methods 0.000 description 13
- 239000000758 substrate Substances 0.000 description 12
- 239000011701 zinc Substances 0.000 description 12
- 230000005525 hole transport Effects 0.000 description 11
- 229910044991 metal oxide Inorganic materials 0.000 description 11
- 150000004706 metal oxides Chemical class 0.000 description 11
- -1 gold Chemical class 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 239000010409 thin film Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000002131 composite material Substances 0.000 description 7
- 239000000463 material 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
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 6
- 229910052718 tin Inorganic materials 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 150000001787 chalcogens Chemical group 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 150000004767 nitrides Chemical class 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 238000004528 spin coating Methods 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 4
- 229910052710 silicon Inorganic materials 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
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 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
- 238000000333 X-ray scattering Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000011133 lead Substances 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 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 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
- 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
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 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
- 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
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 2
- 238000007606 doctor blade method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 229910001195 gallium oxide Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 229910003437 indium oxide Inorganic materials 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229940100684 pentylamine Drugs 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000004032 porphyrins Chemical group 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GKCNVZWZCYIBPR-UHFFFAOYSA-N sulfanylideneindium Chemical compound [In]=S GKCNVZWZCYIBPR-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 2
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 1
- ZHKJHQBOAJQXQR-UHFFFAOYSA-N 1H-azirine Chemical class N1C=C1 ZHKJHQBOAJQXQR-UHFFFAOYSA-N 0.000 description 1
- BHHGXPLMPWCGHP-UHFFFAOYSA-O 2-phenylethanaminium Chemical compound [NH3+]CCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-O 0.000 description 1
- UUIMDJFBHNDZOW-UHFFFAOYSA-N 2-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=CC=N1 UUIMDJFBHNDZOW-UHFFFAOYSA-N 0.000 description 1
- 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
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910001148 Al-Li alloy Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 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 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910000799 K alloy Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-O Methylammonium ion Chemical compound [NH3+]C BAVYZALUXZFZLV-UHFFFAOYSA-O 0.000 description 1
- 229910016001 MoSe Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- QCOGKXLOEWLIDC-UHFFFAOYSA-N N-methylbutylamine Chemical class CCCCNC QCOGKXLOEWLIDC-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 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
- 229910007717 ZnSnO Inorganic materials 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- JHYLKGDXMUDNEO-UHFFFAOYSA-N [Mg].[In] Chemical compound [Mg].[In] JHYLKGDXMUDNEO-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- HONIICLYMWZJFZ-UHFFFAOYSA-N azetidine Chemical compound C1CNC1 HONIICLYMWZJFZ-UHFFFAOYSA-N 0.000 description 1
- 150000001541 aziridines Chemical class 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- ILOUFDHKHFCJBC-UHFFFAOYSA-N ethanol propan-2-olate titanium(4+) Chemical compound [Ti+4].CCO.CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ILOUFDHKHFCJBC-UHFFFAOYSA-N 0.000 description 1
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical class CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- SJCKRGFTWFGHGZ-UHFFFAOYSA-N magnesium silver Chemical compound [Mg].[Ag] SJCKRGFTWFGHGZ-UHFFFAOYSA-N 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- LLWRXQXPJMPHLR-UHFFFAOYSA-N methylazanium;iodide Chemical compound [I-].[NH3+]C LLWRXQXPJMPHLR-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- DIAIBWNEUYXDNL-UHFFFAOYSA-N n,n-dihexylhexan-1-amine Chemical class CCCCCCN(CCCCCC)CCCCCC DIAIBWNEUYXDNL-UHFFFAOYSA-N 0.000 description 1
- OOHAUGDGCWURIT-UHFFFAOYSA-N n,n-dipentylpentan-1-amine Chemical class CCCCCN(CCCCC)CCCCC OOHAUGDGCWURIT-UHFFFAOYSA-N 0.000 description 1
- QHCCDDQKNUYGNC-UHFFFAOYSA-N n-ethylbutan-1-amine Chemical class CCCCNCC QHCCDDQKNUYGNC-UHFFFAOYSA-N 0.000 description 1
- XCVNDBIXFPGMIW-UHFFFAOYSA-N n-ethylpropan-1-amine Chemical class CCCNCC XCVNDBIXFPGMIW-UHFFFAOYSA-N 0.000 description 1
- PXSXRABJBXYMFT-UHFFFAOYSA-N n-hexylhexan-1-amine Chemical compound CCCCCCNCCCCCC PXSXRABJBXYMFT-UHFFFAOYSA-N 0.000 description 1
- XJINZNWPEQMMBV-UHFFFAOYSA-N n-methylhexan-1-amine Chemical class CCCCCCNC XJINZNWPEQMMBV-UHFFFAOYSA-N 0.000 description 1
- UOIWOHLIGKIYFE-UHFFFAOYSA-N n-methylpentan-1-amine Chemical class CCCCCNC UOIWOHLIGKIYFE-UHFFFAOYSA-N 0.000 description 1
- GVWISOJSERXQBM-UHFFFAOYSA-N n-methylpropan-1-amine Chemical class CCCNC GVWISOJSERXQBM-UHFFFAOYSA-N 0.000 description 1
- JACMPVXHEARCBO-UHFFFAOYSA-N n-pentylpentan-1-amine Chemical compound CCCCCNCCCCC JACMPVXHEARCBO-UHFFFAOYSA-N 0.000 description 1
- LKKPNUDVOYAOBB-UHFFFAOYSA-N naphthalocyanine Chemical group N1C(N=C2C3=CC4=CC=CC=C4C=C3C(N=C3C4=CC5=CC=CC=C5C=C4C(=N4)N3)=N2)=C(C=C2C(C=CC=C2)=C2)C2=C1N=C1C2=CC3=CC=CC=C3C=C2C4=N1 LKKPNUDVOYAOBB-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 125000005582 pentacene group Chemical group 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
- 229920000205 poly(isobutyl methacrylate) Polymers 0.000 description 1
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- WSANLGASBHUYGD-UHFFFAOYSA-N sulfidophosphanium Chemical class S=[PH3] WSANLGASBHUYGD-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine group Chemical class C(CCC)N(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
Description
本発明は、高温高湿耐久性に優れた太陽電池に関する。 The present invention relates to a solar cell having excellent high temperature and high humidity durability.
従来から、対向する電極間にＮ型半導体層とＰ型半導体層とを配置した積層体を備えた光電変換素子が開発されている。このような光電変換素子では、光励起により光キャリアが生成し、電子がＮ型半導体を、ホールがＰ型半導体を移動することで、電界が生じる。 Conventionally, a photoelectric conversion element having a laminate in which an N-type semiconductor layer and a P-type semiconductor layer are arranged between facing electrodes has been developed. In such a photoelectric conversion element, optical carriers are generated by photoexcitation, and electrons move N-type semiconductors and holes move P-type semiconductors to generate an electric field.
現在、実用化されている光電変換素子の多くは、シリコン等の無機半導体を用いて製造される無機太陽電池である。しかしながら、無機太陽電池は製造にコストがかかるうえ大型化が困難であり、利用範囲が限られてしまうことから、無機半導体の代わりに有機半導体を用いて製造される有機太陽電池、無機半導体と有機半導体とを併用して製造される有機太陽電池等が注目されている（例えば、特許文献１参照）。 Most of the photoelectric conversion elements currently in practical use are inorganic solar cells manufactured by using an inorganic semiconductor such as silicon. However, inorganic solar cells are expensive to manufacture, difficult to increase in size, and have a limited range of use. Therefore, organic solar cells manufactured using organic semiconductors instead of inorganic semiconductors, inorganic semiconductors and organics Organic solar cells and the like manufactured in combination with semiconductors are attracting attention (see, for example, Patent Document 1).
有機太陽電池においては、対向する電極間にＮ型半導体層とＰ型半導体層とを配置した積層体の陰極側又は陽極側を、樹脂層で封止することが一般的である（例えば、非特許文献１参照）。しかしながら、このような樹脂層の封止のみでは充分な耐久性は得られず、更なる耐久性の向上が求められている。 In an organic solar cell, it is common to seal the cathode side or the anode side of a laminate in which an N-type semiconductor layer and a P-type semiconductor layer are arranged between facing electrodes with a resin layer (for example, non-type). See Patent Document 1). However, sufficient durability cannot be obtained only by sealing the resin layer, and further improvement in durability is required.
本発明は、高温高湿耐久性に優れた太陽電池を提供することを目的とする。 An object of the present invention is to provide a solar cell having excellent high temperature and high humidity durability.
本発明は、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を有し、更に、前記対向電極上を覆って前記積層体を封止する封止層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、前記封止層は、ポリシラザンからなるシリカを含み、厚みが５０〜１００００ｎｍである太陽電池である。
以下、本発明を詳述する。
The present invention has a laminate having an electrode, a counter electrode, and a photoelectric conversion layer arranged between the electrode and the counter electrode, and further covers the counter electrode to seal the laminate. A solar cell having a sealing layer for stopping, the photoelectric conversion layer is of 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. ) Is contained, and the sealing layer is a solar cell containing silica made of polychalcogen and having a thickness of 50 to 10,000 nm.
Hereinafter, the present invention will be described in detail.
本発明者らは、電極と、対向電極と、上記電極と上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を有する太陽電池において、上記光電変換層に有機無機ペロブスカイト化合物を用いることを検討した。上記有機無機ペロブスカイト化合物を用いることで、高い光電変換効率が期待できる。また、本発明者らは、上記対向電極上を覆って上記積層体を封止する封止層を設けることで、太陽電池の耐久性を向上させることを検討した。
しかしながら、上記有機無機ペロブスカイト化合物は耐湿性が低いことから、上記封止層として従来のような樹脂層を用いたのでは、太陽電池の耐久性、特に高温高湿環境下での耐久性が充分には得られなかった。
本発明者らは、上記封止層にポリシラザンからなるシリカを用い、かつ、上記封止層の厚みを特定範囲に調整することにより、太陽電池の高温高湿耐久性を向上できることを見出し、本発明を完成させるに至った。即ち、ポリシラザンは熱処理されることによりシリカとなるため、上記対向電極上を覆って上記積層体を封止するようにポリシラザン含有溶液を塗工した後、熱処理することにより、シリカを含む封止層を形成することができる。このような封止層は、従来のような樹脂層に比べて水蒸気バリア性が高く、また、塗工により形成されたものであるため、上記対向電極上及び上記積層体の側面に対する表面追従性も高い。従って、このような封止層を設けるとともにその厚みを特定範囲に調整することにより、太陽電池の高温高湿耐久性を向上させることができる。
The present inventors have applied an organic-inorganic perovskite compound to the photoelectric conversion layer in a solar cell having a laminate having an electrode, a counter electrode, and a photoelectric conversion layer arranged between the electrode and the counter electrode. We considered using it. High photoelectric conversion efficiency can be expected by using the above-mentioned organic-inorganic perovskite compound. Further, the present inventors have studied to improve the durability of the solar cell by providing a sealing layer that covers the counter electrode and seals the laminated body.
However, since the organic-inorganic perovskite compound has low moisture resistance, the durability of the solar cell, particularly the durability in a high-temperature and high-humidity environment, is sufficient if a conventional resin layer is used as the sealing layer. I couldn't get it.
The present inventors have found that the high temperature and high humidity durability of a solar cell can be improved by using silica made of polysilazane for the sealing layer and adjusting the thickness of the sealing layer to a specific range. The invention was completed. That is, since polysilazane becomes silica by heat treatment, a sealing layer containing silica is applied by applying a polysilazane-containing solution so as to cover the counter electrode and seal the laminate, and then heat-treat. Can be formed. Such a sealing layer has a higher water vapor barrier property than a conventional resin layer, and is formed by coating, so that it has surface followability on the counter electrode and on the side surface of the laminated body. Is also expensive. Therefore, the high temperature and high humidity durability of the solar cell can be improved by providing such a sealing layer and adjusting the thickness thereof within a specific range.
本発明の太陽電池は、電極と、対向電極と、上記電極と上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を有する。
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。また、本明細書中、Ａ〜Ｂとは、Ａ以上、Ｂ以下を意味する。
The solar cell of the present invention has a laminate having an electrode, a counter electrode, and a photoelectric conversion layer arranged between the electrode and the counter electrode.
In the present specification, the layer means not only a layer having a clear boundary but also a layer having a concentration gradient in which the 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 elemental distribution of the specific element. Further, in the present specification, the layer means not only a flat thin film layer but also a layer capable of forming a complicated and intricate structure together with other layers. Further, in the present specification, A to B mean A or more and B or less.
上記電極及び上記対向電極は、どちらが陰極になっても陽極になってもよい。上記電極及び上記対向電極の材料は特に限定されず、従来公知の材料を用いることができる。なお、上記対向電極は、パターニングされた電極であることが多い。
電極材料として、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混合物等が挙げられる。陽極材料として、例えば、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。
Either the electrode or the counter electrode may be a cathode or an anode. The material of the electrode and the counter electrode is not particularly limited, and conventionally known materials can be used. The counter electrode is often a patterned electrode.
As the electrode material, for example, FTO (fluorine-doped tin oxide), sodium, sodium-potassium alloy, lithium, magnesium, aluminum, magnesium-silver mixture, magnesium-indium mixture, aluminum-lithium alloy, Al / Al 2 O 3 mixture, Al / LiF mixture and the like can be mentioned. Examples of the anode material include metals such as gold, and conductivity such as CuI, ITO (indium tin oxide), SnO 2 , AZO (aluminum zinc oxide), IZO (indium zinc oxide), and GZO (gallium zinc oxide). Examples thereof include sex-transparent materials and conductive transparent polymers. These materials may be used alone or in combination of two or more.
上記光電変換層は、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む。上記光電変換層が上記有機無機ペロブスカイト化合物を含む太陽電池は、有機無機ハイブリッド型太陽電池とも呼ばれる。
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。また、上記有機無機ペロブスカイト化合物は耐湿性が低いことから、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場合には、太陽電池の高温高湿耐久性の向上のために後述する封止層を上記対向電極上を覆って上記積層体を封止するように設けることがより有効となる。
The photoelectric conversion layer contains 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). A solar cell in which the photoelectric conversion layer contains the organic-inorganic perovskite compound is also called an organic-inorganic hybrid type solar cell.
By using the organic-inorganic perovskite compound in the photoelectric conversion layer, the photoelectric conversion efficiency of the solar cell can be improved. Further, since the organic-inorganic perovskite compound has low moisture resistance, when the organic-inorganic perovskite compound is used for the photoelectric conversion layer, a sealing layer described later is used to improve the high-temperature and high-humidity durability of the solar cell. It is more effective to cover the counter electrode and seal the laminated body.
上記Ｒは有機分子であり、ＣｌＮｍＨｎ（ｌ、ｍ、ｎはいずれも正の整数）で示されることが好ましい。
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、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）や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、ヘキシルアミン及びこれらのイオンや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、プロピルアミン及びこれらのイオンがより好ましい。
The above R is an organic molecule, and is preferably represented by C l N m H n (all l, m, and n are positive integers).
Specifically, the R is, for example, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, trimethylamine, triethylamine, tripropyl. Amines, tributylamines, tripentylamines, trihexylamines, ethylmethylamines, methylpropylamines, butylmethylamines, methylpentylamines, hexylmethylamines, ethylpropylamines, ethylbutylamines, imidazoles, azoles, pyrroles, aziridines, azirins, Examples thereof include azetidine, azeto, azole, imidazoline, carbazole and ions thereof (for example, methylammonium (CH 3 NH 3 )), phenethylammonium and the like. Among them, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine and their ions and phenethylammon are preferable, and methylamine, ethylamine, propylamine and these ions are more preferable.
上記Ｍは金属原子であり、例えば、鉛、スズ、亜鉛、チタン、アンチモン、ビスマス、ニッケル、鉄、コバルト、銀、銅、ガリウム、ゲルマニウム、マグネシウム、カルシウム、インジウム、アルミニウム、マンガン、クロム、モリブデン、ユーロピウム等が挙げられる。これらの金属原子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。 The above 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 and the like can be mentioned. These metal atoms may be used alone or in combination of two or more.
上記Ｘはハロゲン原子又はカルコゲン原子であり、例えば、塩素、臭素、ヨウ素、硫黄、セレン等が挙げられる。これらのハロゲン原子又はカルコゲン原子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、構造中にハロゲンを含有することで、上記有機無機ペロブスカイト化合物が有機溶媒に可溶になり、安価な印刷法等への適用が可能になることから、ハロゲン原子が好ましい。更に、上記有機無機ペロブスカイト化合物のエネルギーバンドギャップが狭くなることから、ヨウ素がより好ましい。 The 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 them, a halogen atom is preferable because the inclusion of a halogen in the structure makes the organic-inorganic perovskite compound soluble in an organic solvent and can be applied to an inexpensive printing method or the like. Further, iodine is more preferable because the energy band gap of the organic-inorganic perovskite compound is narrowed.
上記有機無機ペロブスカイト化合物は、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を有することが好ましい。
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。
The organic-inorganic perovskite compound preferably has a cubic structure in which a metal atom M is arranged at the body center, an organic molecule R is arranged at each apex, and a halogen atom or a chalcogen atom X is arranged at the face center.
FIG. 1 shows an example of the crystal structure of an organic-inorganic perovskite compound, which is a cubic structure in which a metal atom M is arranged at the body center, an organic molecule R is arranged at each apex, and a halogen atom or a chalcogen atom X is arranged at the face center. It is a schematic diagram. Although the details are not clear, the orientation of the octahedron in the crystal lattice can be easily changed by having the above structure, so that the mobility of electrons in the organic-inorganic perovskite compound is high, and the photoelectric of the solar cell is high. It is estimated that the conversion efficiency will improve.
上記有機無機ペロブスカイト化合物は、結晶性半導体であることが好ましい。結晶性半導体とは、Ｘ線散乱強度分布を測定し、散乱ピークが検出できる半導体を意味している。上記有機無機ペロブスカイト化合物が結晶性半導体であることにより、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。 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 the scattering peak. Since 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.
また、結晶化の指標として結晶化度を評価することもできる。結晶化度は、Ｘ線散乱強度分布測定により検出された結晶質由来の散乱ピークと非晶質部由来のハローとをフィッティングにより分離し、それぞれの強度積分を求めて、全体のうちの結晶部分の比を算出することにより求めることができる。
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。
It is also possible to evaluate the degree of crystallization as an index of crystallization. The crystallinity is determined by separating the scattering peak derived from the crystalline substance and the halo derived from the amorphous part detected by the X-ray scattering intensity distribution measurement by fitting, and obtaining the intensity integration of each to obtain the crystal part of the whole. It can be obtained by calculating the ratio of.
The 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 high, and the photoelectric conversion efficiency of the solar cell is improved. A more preferable lower limit of crystallinity is 50%, and a more preferable lower limit is 70%.
Further, as a method for increasing the crystallinity of the organic-inorganic perovskite compound, for example, thermal annealing, irradiation with strong light such as a laser, plasma irradiation and the like can be mentioned.
上記光電変換層が上記有機無機ペロブスカイト化合物を含む場合、上記光電変換層は、本発明の効果を損なわない範囲内であれば、上記有機無機ペロブスカイト化合物に加えて、更に、有機半導体又は無機半導体を含んでいてもよい。なお、ここでいう有機半導体又は無機半導体は、後述する電子輸送層又はホール輸送層としての役割を果たしてもよい。
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や、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。
When the photoelectric conversion layer contains the organic-inorganic perovskite compound, 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 effect of the present invention is not impaired. It may be included. The organic semiconductor or the inorganic semiconductor referred to here may play a role as an electron transport layer or a hole transport layer described later.
Examples of the organic semiconductor include compounds having a thiophene skeleton such as poly (3-alkylthiophene). Further, for example, a conductive polymer having a polyparaphenylene vinylene skeleton, a polyvinylcarbazole skeleton, a polyaniline skeleton, a polyacetylene skeleton and the like can be mentioned. Further, for example, a compound having a porphyrin skeleton such as a phthalocyanine skeleton, a naphthalocyanine skeleton, a pentacene skeleton, a benzoporphyrin skeleton, a spirobifluorene skeleton, or a carbon-containing material such as carbon nanotubes, graphene, or fullerene which may be surface-modified. Can also be mentioned.
上記無機半導体として、例えば、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、ＣｕＳＣＮ、Ｃｕ２Ｏ、ＣｕＩ、ＭｏＯ３、Ｖ２Ｏ５、ＷＯ３、ＭｏＳ２、ＭｏＳｅ２、Ｃｕ２Ｓ等が挙げられる。 Examples of the inorganic semiconductor 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 , and so on. Examples thereof include MoS 2 , MoSe 2 , Cu 2 S and the like.
上記光電変換層は、上記有機無機ペロブスカイト化合物と上記有機半導体又は上記無機半導体とを含む場合、薄膜状の有機半導体又は無機半導体部位と薄膜状の有機無機ペロブスカイト化合物部位とを積層した積層体であってもよいし、有機半導体又は無機半導体部位と有機無機ペロブスカイト化合物部位とを複合化した複合膜であってもよい。製法が簡便である点では積層体が好ましく、上記有機半導体又は上記無機半導体中の電荷分離効率を向上させることができる点では複合膜が好ましい。 When the organic-inorganic perovskite compound and the organic semiconductor or the inorganic semiconductor are contained, the photoelectric conversion layer is a laminate in which a thin-film organic semiconductor or an inorganic semiconductor moiety and a thin-film organic-inorganic perovskite compound moiety are laminated. It may be a composite film in which an organic semiconductor or an inorganic semiconductor moiety and an organic-inorganic perovskite compound moiety are composited. A laminated body is preferable in terms of simple manufacturing method, and a composite film is preferable in that the charge separation efficiency in the organic semiconductor or the inorganic semiconductor can be improved.
上記薄膜状の有機無機ペロブスカイト化合物部位の厚みは、好ましい下限が５ｎｍ、好ましい上限が５０００ｎｍである。上記厚みが５ｎｍ以上であれば、充分に光を吸収することができるようになり、光電変換効率が高くなる。上記厚みが５０００ｎｍ以下であれば、電荷分離できない領域が発生することを抑制できるため、光電変換効率の向上につながる。上記厚みのより好ましい下限は１０ｎｍ、より好ましい上限は１０００ｎｍであり、更に好ましい下限は２０ｎｍ、更に好ましい上限は５００ｎｍである。 The thickness of the thin-film organic-inorganic perovskite compound moiety has a preferable lower limit of 5 nm and a preferable upper limit of 5000 nm. When the thickness is 5 nm or more, light can be sufficiently absorbed and the photoelectric conversion efficiency becomes high. When the thickness is 5000 nm or less, it is possible to suppress the occurrence of a region where charge separation is not possible, which leads to an improvement in photoelectric conversion efficiency. The more preferable lower limit of the thickness is 10 nm, the more preferable upper limit is 1000 nm, the further preferable lower limit is 20 nm, and the further preferable upper limit is 500 nm.
上記光電変換層が、有機半導体又は無機半導体部位と有機無機ペロブスカイト化合物部位とを複合化した複合膜である場合、上記複合膜の厚みの好ましい下限は３０ｎｍ、好ましい上限は３０００ｎｍである。上記厚みが３０ｎｍ以上であれば、充分に光を吸収することができるようになり、光電変換効率が高くなる。上記厚みが３０００ｎｍ以下であれば、電荷が電極に到達しやすくなるため、光電変換効率が高くなる。上記厚みのより好ましい下限は４０ｎｍ、より好ましい上限は２０００ｎｍであり、更に好ましい下限は５０ｎｍ、更に好ましい上限は１０００ｎｍである。 When the photoelectric conversion layer is a composite film in which an organic semiconductor or an inorganic semiconductor moiety and an organic-inorganic perovskite compound moiety are composited, the preferable lower limit of the thickness of the composite film is 30 nm, and the preferable upper limit is 3000 nm. When the thickness is 30 nm or more, light can be sufficiently absorbed and the photoelectric conversion efficiency becomes high. When the thickness is 3000 nm or less, the electric charge easily reaches the electrode, so that the photoelectric conversion efficiency is high. The more preferable lower limit of the thickness is 40 nm, the more preferable upper limit is 2000 nm, the further preferable lower limit is 50 nm, and the further preferable upper limit is 1000 nm.
本発明の太陽電池においては、上記電極及び上記対向電極のうちの陰極となる側と、上記光電変換層との間に、電子輸送層が配置されていてもよい。
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。
In the solar cell of the present invention, an electron transport layer may be arranged between the cathode side of the electrode and the counter electrode and the photoelectric conversion layer.
The material of the electron transport layer is not particularly limited, and for example, N-type conductive polymer, N-type low-molecular-weight organic semiconductor, N-type metal oxide, N-type metal sulfide, alkali metal halide, alkali metal, and surface activity. Examples thereof include cyano group-containing polyphenylene vinylene, boron-containing polymer, vasocuproin, vasophenanthrene, hydroxyquinolinatoaluminum, oxadiazole compound, benzoimidazole compound, naphthalenetetracarboxylic acid compound, perylene derivative, and the like. Examples thereof include phosphine oxide compounds, phosphine sulfide compounds, fluorogroup-containing phthalocyanine, titanium oxide, zinc oxide, indium oxide, tin oxide, gallium oxide, tin sulfide, indium sulfide, and zinc sulfide.
上記電子輸送層は、薄膜状の電子輸送層のみからなっていてもよいが、多孔質状の電子輸送層を含むことが好ましい。特に、上記光電変換層が、有機半導体又は無機半導体部位と有機無機ペロブスカイト化合物部位とを複合化した複合膜である場合、より複雑な複合膜（より複雑に入り組んだ構造）が得られ、光電変換効率が高くなることから、多孔質状の電子輸送層上に複合膜が製膜されていることが好ましい。 The electron transport layer may be composed of only a thin-film electron transport layer, but preferably includes a porous electron transport layer. In particular, when the photoelectric conversion layer is a composite film in which an organic semiconductor or an inorganic semiconductor moiety and an organic-inorganic perovskite compound moiety are composited, a more complicated composite film (more complicated structure) can be obtained, and photoelectric conversion can be obtained. Since the efficiency is high, it is preferable that the composite film is formed on the porous electron transport layer.
上記電子輸送層の厚みは、好ましい下限が１ｎｍ、好ましい上限が２０００ｎｍである。上記厚みが１ｎｍ以上であれば、充分にホールをブロックできるようになる。上記厚みが２０００ｎｍ以下であれば、電子輸送の際の抵抗になり難く、光電変換効率が高くなる。上記電子輸送層の厚みのより好ましい下限は３ｎｍ、より好ましい上限は１０００ｎｍであり、更に好ましい下限は５ｎｍ、更に好ましい上限は５００ｎｍである。 The preferred lower limit of the thickness of the electron transport layer is 1 nm, and the preferred upper limit is 2000 nm. When the thickness is 1 nm or more, holes can be sufficiently blocked. When the thickness is 2000 nm or less, it is unlikely to become a resistance during electron transport, and the photoelectric conversion efficiency becomes 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 further preferable lower limit is 5 nm, and the further preferable upper limit is 500 nm.
本発明の太陽電池においては、上記電極及び上記対向電極のうちの陽極となる側と、上記光電変換層との間に、ホール輸送層が配置されていてもよい。
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。
In the solar cell of the present invention, a hole transport layer may be arranged between the anode side of the electrode and the counter electrode and the photoelectric conversion layer.
The material of the hole transport layer is not particularly limited, and examples thereof include P-type conductive polymers, P-type low-molecular-weight organic semiconductors, P-type metal oxides, P-type metal sulfides, and surfactants. For example, polystyrene sulfonic acid adduct of polyethylene dioxythiophene, carboxyl group-containing polythiophene, phthalocyanine, porphyrin, molybdenum oxide, vanadium oxide, tungsten oxide, nickel oxide, copper oxide, tin oxide, molybdenum sulfide, tungsten sulfide, copper sulfide. , Fluoro group-containing phosphonic acid such as tin sulfide, carbonyl group-containing phosphonic acid, copper compounds such as CuSCN and CuI, carbon nanotubes which may be surface-modified, carbon-containing materials such as graphene and the like.
上記ホール輸送層の厚みは、好ましい下限は１ｎｍ、好ましい上限は２０００ｎｍである。上記厚みが１ｎｍ以上であれば、充分に電子をブロックできるようになる。上記厚みが２０００ｎｍ以下であれば、ホール輸送の際の抵抗になり難く、光電変換効率が高くなる。上記厚みのより好ましい下限は３ｎｍ、より好ましい上限は１０００ｎｍであり、更に好ましい下限は５ｎｍ、更に好ましい上限は５００ｎｍである。 The preferred lower limit of the thickness of the hole transport layer is 1 nm, and the preferred upper limit is 2000 nm. When the thickness is 1 nm or more, electrons can be sufficiently blocked. When the thickness is 2000 nm or less, it is unlikely to become a resistance during hole transportation, and the photoelectric conversion efficiency becomes high. The more preferable lower limit of the thickness is 3 nm, the more preferable upper limit is 1000 nm, the further preferable lower limit is 5 nm, and the further preferable upper limit is 500 nm.
本発明の太陽電池は、更に、基板等を有していてもよい。上記基板は特に限定されず、例えば、ソーダライムガラス、無アルカリガラス等の透明ガラス基板、セラミック基板、透明プラスチック基板、金属箔等が挙げられる。 The solar cell of the present invention may further have a substrate or the like. The substrate is not particularly limited, and examples thereof include a transparent glass substrate such as soda lime glass and non-alkali glass, a ceramic substrate, a transparent plastic substrate, and a metal foil.
本発明の太陽電池は、更に、上記対向電極上を覆って上記積層体を封止する封止層を有する。
上記対向電極上を覆って上記積層体を封止する封止層を設けることにより、太陽電池の高温高湿耐久性を向上させることができる。これは、上記封止層を設けることにより、水分が太陽電池の内部に浸透することを抑制できるためと考えられる。ここで、上記封止層は、その端部を閉じるようにして、上記積層体全体を覆うことが好ましい。これにより、水分が太陽電池の内部に浸透することを確実に防止することができる。
The solar cell of the present invention further has a sealing layer that covers the counter electrode and seals the laminate.
By providing a sealing layer that covers the counter electrode and seals the laminated body, the high temperature and high humidity durability of the solar cell can be improved. It is considered that this is because by providing the sealing layer, it is possible to suppress the permeation of water into the inside of the solar cell. Here, it is preferable that the sealing layer covers the entire laminated body so as to close the end portion thereof. As a result, it is possible to reliably prevent moisture from penetrating into the inside of the solar cell.
上記封止層は、上記対向電極上に直接形成されて（上記対向電極と接して）いてもよいし、上記対向電極との間に他の層を介して形成されていてもよい。なかでも、太陽電池の高温高湿耐久性を向上させる観点からは、上記対向電極上に直接形成されていることが好ましい。 The sealing layer may be formed directly on the counter electrode (in contact with the counter electrode), or may be formed between the sealing layer and the counter electrode via another layer. Above all, from the viewpoint of improving the high temperature and high humidity durability of the solar cell, it is preferably formed directly on the counter electrode.
上記封止層は、ポリシラザンからなるシリカを含み、厚みが５０〜１００００ｎｍである。
上記封止層にポリシラザンからなるシリカを用い、かつ、上記封止層の厚みを上記範囲に調整することにより、太陽電池の高温高湿耐久性を向上させることができる。即ち、ポリシラザンは熱処理されることによりシリカとなるため、上記対向電極上を覆って上記積層体を封止するようにポリシラザン含有溶液を塗工した後、熱処理することにより、シリカを含む封止層を形成することができる。このような封止層は、従来のような樹脂層に比べて水蒸気バリア性が高く、また、塗工により形成されたものであるため、上記対向電極上及び上記積層体の側面に対する表面追従性も高い。従って、このような封止層を設けるとともにその厚みを上記範囲に調整することにより、太陽電池の高温高湿耐久性を向上させることができる。
The sealing layer contains silica made of polysilazane and has a thickness of 50 to 10000 nm.
By using silica made of polysilazane for the sealing layer and adjusting the thickness of the sealing layer within the above range, the high temperature and high humidity durability of the solar cell can be improved. That is, since polysilazane becomes silica by heat treatment, a sealing layer containing silica is applied by applying a polysilazane-containing solution so as to cover the counter electrode and seal the laminate, and then heat-treat. Can be formed. Such a sealing layer has a higher water vapor barrier property than a conventional resin layer, and is formed by coating, so that it has surface followability on the counter electrode and on the side surface of the laminated body. Is also expensive. Therefore, by providing such a sealing layer and adjusting the thickness within the above range, the high temperature and high humidity durability of the solar cell can be improved.
上記ポリシラザンは、シラザン骨格を有する化合物であれば特に限定されないが、例えば、パーヒドロポリシラザン、オルガノポリシラザン等が挙げられる。なかでも、低温でシリカに転化できることから、パーヒドロポリシラザンが好ましい。 The polysilazane is not particularly limited as long as it is a compound having a silazane skeleton, and examples thereof include perhydropolysilazane and organopolysilazane. Of these, perhydropolysilazane is preferable because it can be converted to silica at a low temperature.
上記ポリシラザンの重量平均分子量は特に限定されないが、好ましい下限は１５０、好ましい上限は１０００００である。上記重量平均分子量が１５０以上であれば、上記封止層が充分な水蒸気バリア性を有することができ、太陽電池の高温高湿耐久性が向上する。上記重量平均分子量が１０００００以下であれば、上記封止層が充分な表面追従性を有することができる。上記重量平均分子量のより好ましい下限は１０００、より好ましい上限は５００００である。 The weight average molecular weight of the polysilazane is not particularly limited, but the preferred lower limit is 150 and the preferred upper limit is 100,000. When the weight average molecular weight is 150 or more, the sealing layer can have a sufficient water vapor barrier property, and the high temperature and high humidity durability of the solar cell is improved. When the weight average molecular weight is 100,000 or less, the sealing layer can have sufficient surface followability. The more preferable lower limit of the weight average molecular weight is 1000, and the more preferable upper limit is 50,000.
上記封止層は、非晶質であることが好ましい。非晶質であることにより、上記封止層が緻密な層となり、水蒸気バリア性が向上する。 The sealing layer is preferably amorphous. Since it is amorphous, the sealing layer becomes a dense layer, and the water vapor barrier property is improved.
また、結晶化の指標として結晶化度を評価することもできる。結晶化度は、Ｘ線散乱強度分布測定により検出された結晶質由来の散乱ピークと非晶質部由来のハローとをフィッティングにより分離し、それぞれの強度積分を求めて、全体のうちの結晶部分の比を算出することにより求めることができる。
上記封止層の結晶化度の好ましい上限は１０％である。上記結晶化度が１０％以下であると、上記封止層が緻密な層となり、水蒸気バリア性が向上する。
なお、上記封止層は、ポリシラザンからなるシリカを含むものであるため、非晶質となったり上記範囲の結晶化度を有したりすることができる。
It is also possible to evaluate the degree of crystallization as an index of crystallization. The crystallinity is determined by separating the scattering peak derived from the crystalline substance and the halo derived from the amorphous part detected by the X-ray scattering intensity distribution measurement by fitting, and obtaining the intensity integration of each to obtain the crystal part of the whole. It can be obtained by calculating the ratio of.
The preferable upper limit of the crystallinity of the sealing layer is 10%. When the crystallinity is 10% or less, the sealing layer becomes a dense layer and the water vapor barrier property is improved.
Since the sealing layer contains silica made of polysilazane, it can be amorphous or have a crystallinity in the above range.
上記封止層は、ポリシラザンからシリカへの転化が進んだものであることが好ましい。ポリシラザンからシリカへの転化が進んでいることにより、上記封止層は、欠陥が少なく、水蒸気バリア性の高い膜となる。 The sealing layer is preferably one in which the conversion from polysilazane to silica has progressed. Due to the progress of conversion from polysilazane to silica, the sealing layer becomes a film having few defects and a high water vapor barrier property.
ポリシラザンからシリカへの転化率の指標として、赤外スペクトルでの吸光度を評価することができる。
赤外スペクトルでは、Ｓｉ−Ｈ結合に由来する吸収が２０５０〜２４００ｃｍ−１に、Ｓｉ−Ｏ結合に由来する吸収が５００〜１５００ｃｍ−１にある。Ｓｉ−Ｈ結合に由来する吸収を示す領域の最大の吸光度と、Ｓｉ−Ｏ結合に由来する吸収を示す領域の最大の吸光度との比（以下、「Ｓｉ−Ｈ／Ｓｉ−Ｏ吸光度比」とも称する）を求めることによって、ポリシラザンからシリカへの転化率を評価することができる。
上記封止層は、Ｓｉ−Ｈ／Ｓｉ−Ｏ吸光度比の好ましい下限が０．０１、好ましい上限が０．３である。上記封止層のＳｉ−Ｈ／Ｓｉ−Ｏ吸光度比が上記範囲内であれば、上記封止層は、ポリシラザンからシリカへの転化が充分に進んでおり、水蒸気バリア性が向上する。上記封止層のＳｉ−Ｈ／Ｓｉ−Ｏ吸光度比のより好ましい上限は０．１、更に好ましい上限は０．０５である。
As an index of the conversion rate from polysilazane to silica, the absorbance in the infrared spectrum can be evaluated.
The infrared spectrum, absorption derived from Si-H bond to 2050～2400Cm -1, absorption derived from Si-O bond is 500~1500cm -1. The ratio of the maximum absorbance of the region showing absorption derived from the Si—H bond to the maximum absorbance of the region showing absorption derived from the Si—O bond (hereinafter, also referred to as “Si—H / Si—O absorbance ratio”). The conversion rate from polysilazane to silica can be evaluated by obtaining (referred to as).
In the sealing layer, the preferable lower limit of the Si—H / Si—O absorbance ratio is 0.01, and the preferable upper limit is 0.3. When the Si—H / Si—O absorbance ratio of the sealing layer is within the above range, the conversion of polysilazane to silica is sufficiently advanced in the sealing layer, and the water vapor barrier property is improved. The more preferable upper limit of the Si—H / Si—O absorbance ratio of the sealing layer is 0.1, and the more preferable upper limit is 0.05.
上記封止層の厚みは、下限が５０ｎｍ、上限が１００００ｎｍである。上記厚みが５０ｎｍ以上であれば、上記封止層が充分な水蒸気バリア性を有することができ、太陽電池の高温高湿耐久性が向上する。上記厚みが１００００ｎｍ以下であれば、上記封止層の厚みが増した場合であっても、発生する応力が小さいため、上記封止層及び各層の剥離を抑制することができる。上記封止層の厚みの好ましい下限は５００ｎｍ、好ましい上限は１０００ｎｍである。
なお、上記封止層の厚みは、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。
The lower limit of the thickness of the sealing layer is 50 nm, and the upper limit is 10000 nm. When the thickness is 50 nm or more, the sealing layer can have a sufficient water vapor barrier property, and the high temperature and high humidity durability of the solar cell is improved. When the thickness is 10,000 nm or less, even when the thickness of the sealing layer is increased, the stress generated is small, so that peeling of the sealing layer and each layer can be suppressed. The preferable lower limit of the thickness of the sealing layer is 500 nm, and the preferable upper limit is 1000 nm.
The thickness of the sealing layer can be measured using an optical interference type film thickness measuring device (for example, FE-3000 manufactured by Otsuka Electronics Co., Ltd.).
上記封止層を形成する方法として、上記対向電極上を覆って上記積層体を封止するようにポリシラザン含有溶液を塗工した後、熱処理する方法が好ましい。
上記ポリシラザン含有溶液を塗工する方法は特に限定されず、例えば、ドクターブレード法、ダイコート法、スプレーコーティング法等が挙げられる。上記ポリシラザン含有溶液に対して熱処理する際の加熱温度は特に限定されないが、好ましい下限が６０℃、好ましい上限が１５０℃である。上記加熱温度が６０℃以上であれば、充分な水蒸気バリア性を有する封止層を得ることができる。上記加熱温度が１５０℃以下であれば、加熱による太陽電池の性能劣化を抑制することができる。上記加熱温度のより好ましい下限は８０℃、より好ましい上限は１２０℃である。上記ポリシラザン含有溶液に対して熱処理する際の加熱時間も特に限定されず、好ましい下限が５分、好ましい上限が６０分である。
As a method for forming the sealing layer, a method of applying a polysilazane-containing solution so as to cover the counter electrode and seal the laminated body and then heat-treating is preferable.
The method for applying the polysilazane-containing solution is not particularly limited, and examples thereof include a doctor blade method, a die coating method, and a spray coating method. The heating temperature when heat-treating the polysilazane-containing solution is not particularly limited, but the preferable lower limit is 60 ° C. and the preferable upper limit is 150 ° C. When the heating temperature is 60 ° C. or higher, a sealing layer having sufficient water vapor barrier property can be obtained. When the heating temperature is 150 ° C. or lower, deterioration of the performance of the solar cell due to heating can be suppressed. The more preferable lower limit of the heating temperature is 80 ° C., and the more preferable upper limit is 120 ° C. The heating time for heat-treating the polysilazane-containing solution is also not particularly limited, and the preferable lower limit is 5 minutes and the preferable upper limit is 60 minutes.
本発明の太陽電池は、更に、上記封止層の外側を封止する無機層を有することが好ましい。
上記封止層の外側を封止する無機層を設けることにより、太陽電池の高温高湿耐久性を更に向上させることができる。上記封止層と同様に、上記無機層もその端部を閉じるようにして、上記積層体全体を覆うことが好ましい。
The solar cell of the present invention preferably further has an inorganic layer that seals the outside of the sealing layer.
By providing the inorganic layer that seals the outside of the sealing layer, the high temperature and high humidity durability of the solar cell can be further improved. Like the sealing layer, it is preferable that the inorganic layer also closes its end to cover the entire laminate.
上記無機層は、金属酸化物、金属窒化物又は金属酸窒化物を含むことが好ましい。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、上記無機層に水蒸気バリア性及び柔軟性を付与するために、Ｚｎ、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好ましい。 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, and is, for example, Si, Al, Zn, Sn, In, Ti, Mg, Zr, Ni, Ta. , W, Cu or oxides, nitrides or oxynitrides of alloys containing two or more of them. Of these, oxides, nitrides or oxynitrides of metal elements containing both Zn and Sn metal elements are preferable in order to impart water vapor barrier properties and flexibility to the inorganic layer.
なかでも、上記金属酸化物、金属窒化物又は金属酸窒化物は、一般式ＺｎａＳｎｂＯｃで表される金属酸化物であることが特に好ましい。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、太陽電池の高温高湿耐久性をより向上させることができる。 Among them, 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. By using a metal oxide represented in the inorganic layer by the above general formula Zn a Sn b O c, since the metal oxide comprises tin (Sn) atom, impart suitable flexibility to the inorganic layer Therefore, even when the thickness of the inorganic layer is increased, the stress is reduced, so that peeling of the inorganic layer, electrodes, semiconductor layer and the like can be suppressed. Thereby, the water vapor barrier property of the inorganic layer can be enhanced, and the high temperature and high humidity durability of the solar cell can be further improved.
上記一般式ＺｎａＳｎｂＯｃで表される金属酸化物においては、ＺｎとＳｎとの総和に対するＳｎの比Ｘｓ（重量％）が７０＞Ｘｓ＞０を満たすことが好ましい。
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。
In the metal oxide represented by the general formula Zn a Sn b O c, it is preferable that the ratio of Sn to the sum of Zn and Sn Xs (wt%) satisfies 70>Xs> 0.
Incidentally, the element ratio of zinc contained in the metal oxide represented by the general formula Zn a Sn b O c of the inorganic layer (Zn), tin (Sn) and oxygen (O) is, X-rays photoelectron spectroscopy ( XPS) The measurement can be performed using a surface analyzer (for example, ESCALAB-200R manufactured by VG Scientific Co., Ltd.).
上記無機層は、上記一般式ＺｎａＳｎｂＯｃで表される金属酸化物を含む場合、更に、ケイ素（Ｓｉ）及び／又はアルミニウム（Ａｌ）を含むことが好ましい。
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。
When the inorganic layer contains a metal oxide represented by the general formula Zn a Sn b Occ , it is preferable that the inorganic layer further contains 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 enhanced and the photoelectric conversion efficiency of the solar cell can be improved.
上記無機層の厚みは、好ましい下限が３０ｎｍ、好ましい上限が３０００ｎｍである。上記厚みが３０ｎｍ以上であれば、上記無機層が充分な水蒸気バリア性を有することができ、太陽電池の高温高湿耐久性が向上する。上記厚みが３０００ｎｍ以下であれば、上記無機層の厚みが増した場合であっても、発生する応力が小さいため、上記無機層及び各層の剥離を抑制することができる。上記厚みのより好ましい下限は５０ｎｍ、より好ましい上限は１０００ｎｍであり、更に好ましい下限は１００ｎｍ、更に好ましい上限は５００ｎｍである。
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。
The preferable lower limit of the thickness of the inorganic layer is 30 nm, and the preferable upper limit is 3000 nm. When the thickness is 30 nm or more, the inorganic layer can have a sufficient water vapor barrier property, and the high temperature and high humidity durability of the solar cell is improved. When the thickness is 3000 nm or less, even when the thickness of the inorganic layer is increased, the stress generated is small, so that peeling of the inorganic layer and each layer can be suppressed. The more preferable lower limit of the thickness is 50 nm, the more preferable upper limit is 1000 nm, the further preferable lower limit is 100 nm, and the further preferable upper limit is 500 nm.
The thickness of the inorganic layer can be measured using an optical interference type film thickness measuring device (for example, FE-3000 manufactured by Otsuka Electronics Co., Ltd.).
図２は、本発明の太陽電池の一例を模式的に示す断面図である。
図２に示す太陽電池１は、基板７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とを有し、対向電極３上に封止層５が配置され、封止層５上に無機層６が配置されたものである。ここで封止層５の端部は、基板７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。
FIG. 2 is a cross-sectional view schematically showing an example of the solar cell of the present invention.
The solar cell 1 shown in FIG. 2 has an
本発明の太陽電池を製造する方法は特に限定されず、例えば、上記基板上に上記電極、上記光電変換層、上記対向電極をこの順で形成した後、上記対向電極上を覆って上記積層体を封止するように上記封止層を形成し、上記封止層の外側を封止するように上記無機層を形成する方法等が挙げられる。 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, the laminated body is covered on the counter electrode. Examples thereof include a method of forming the sealing layer so as to seal the sealing layer and forming the inorganic layer so as to seal the outside of the sealing layer.
上記光電変換層を形成する方法は特に限定されず、真空蒸着法、スパッタリング法、気相反応法（ＣＶＤ）、電気化学沈積法、印刷法等が挙げられる。なかでも、印刷法を採用することで、高い光電変換効率を発揮できる太陽電池を大面積で簡易に形成することができる。印刷法として、例えば、スピンコート法、キャスト法等が挙げられ、印刷法を用いた方法としてロールｔｏロール法等が挙げられる。 The method for forming the photoelectric conversion layer is not particularly limited, and examples thereof include a vacuum deposition method, a sputtering method, a vapor phase reaction method (CVD), an electrochemical deposition method, and a printing method. In particular, by adopting the printing method, it is possible to easily form a solar cell capable of exhibiting high photoelectric conversion efficiency in a large area. Examples of the printing method include a spin coating method and a casting method, and examples of the method using the printing method include a roll-to-roll method.
上記無機層を形成する方法として、真空蒸着法、スパッタリング法、気相反応法（ＣＶＤ）、イオンプレーティング法が好ましい。なかでも、緻密な層を形成するためにはスパッタリング法が好ましく、スパッタリング法のなかでもＤＣマグネトロンスパッタリング法がより好ましい。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、上記封止層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。 As a method for forming the inorganic layer, a vacuum vapor deposition method, a sputtering method, a vapor phase reaction method (CVD), and an ion plating method are preferable. Among them, the sputtering method is preferable for forming a dense layer, and the DC magnetron sputtering method is more preferable among the sputtering methods. In the sputtering method, an inorganic layer can be formed by using a metal target and oxygen gas or nitrogen gas as raw materials and depositing the raw materials on the sealing layer to form a film.
本発明によれば、高温高湿耐久性に優れた太陽電池を提供することができる。 According to the present invention, it is possible to provide a solar cell having excellent high temperature and high humidity durability.
以下に実施例を掲げて本発明を更に詳しく説明するが、本発明はこれら実施例のみに限定されない。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
（実施例１）
（１）電極／電子輸送層／光電変換層／ホール輸送層／対向電極が積層された積層体の作製
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、ハロゲン化金属化合物としてヨウ化鉛をＮ，Ｎ−ジメチルホルムアミド（ＤＭＦ）に溶解させて１Ｍの溶液を調製し、多孔質状の電子輸送層上にスピンコート法によって製膜した。更に、アミン化合物としてヨウ化メチルアンモニウムを２−プロパノールに溶解させて１Ｍの溶液を調製した。この溶液内に上記のヨウ化鉛を製膜したサンプルを浸漬させることによって、有機無機ペロブスカイト化合物であるＣＨ３ＮＨ３ＰｂＩ３（表１中、ＭＡＰｂＩ３）を含む層を形成した。その後、得られたサンプルに対して１２０℃で３０分間アニール処理を行った。
次いで、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、ｔ−ブチルピリジンを５５ｍＭ、ビス（トリフルオロメチルスルホニル）イミド・銀塩を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塗布し、厚み１５０ｎｍの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、電極／電子輸送層／光電変換層／ホール輸送層／対向電極が積層された積層体を得た。
(Example 1)
(1) Preparation of a laminated body in which electrodes / electron transport layers / photoelectric conversion layers / hole transport layers / counter electrodes are laminated A 1000 nm-thick FTO film is formed as electrodes on a glass substrate, and pure water, acetone, and methanol are added. It was ultrasonically washed for 10 minutes each using this order, and then dried.
A titanium isopropoxide ethanol solution adjusted to 2% was applied on the surface of the FTO film by a spin coating method, and then calcined at 400 ° C. for 10 minutes to form a thin-film electron transport layer having a thickness of 20 nm. Further, 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 coating method, and then at 500 ° C. Was fired for 10 minutes to form a porous electron transport layer having a thickness of 500 nm.
Next, lead iodide as a metal halide compound was dissolved in N, N-dimethylformamide (DMF) to prepare a 1M solution, and a film was formed on the porous electron transport layer by the spin coating method. Further, methylammonium iodide as an amine compound was dissolved in 2-propanol to prepare a 1M solution. Within this solution by immersing the sample was formed of the above lead iodide, (In Table 1, MAPbI 3) CH 3 NH 3
Next, a solution was prepared in which 25 μL of chlorobenzene was dissolved with 68 mM of Spiro-OMeTAD (having a spirobifluorene skeleton), 55 mM of t-butylpyridine, and 9 mM of bis (trifluoromethylsulfonyl) imide / silver salt. This solution was applied onto the photoelectric conversion layer by a spin coating method to form a hole transport layer having a thickness of 150 nm.
A gold film having a thickness of 100 nm was formed on the hole transport layer by vacuum vapor deposition as a counter electrode, and a laminate in which the electrode / electron transport layer / photoelectric conversion layer / hole transport layer / counter electrode was laminated was obtained.
（２）封止層の形成
得られた電極／電子輸送層／光電変換層／ホール輸送層／対向電極が積層された積層体の対向電極上に、ポリシラザンキシレン溶液（ＮＬ１１０Ａ−２０、クラリアント社製、濃度２０％）をドクターブレード法により１００ｎｍの厚みで塗工し、１２０℃で３０分間ホットプレートで加熱して封止層を形成し、太陽電池を得た。
得られた封止層について、ＦＴ−ＩＲ測定装置ＦＴ／ＩＲ−４６００（日本分光社製）を用いて赤外スペクトル測定を行った。Ｓｉ−Ｈ結合に由来する吸収を示す領域の最大の吸光度（Ｓｉ−Ｈ吸光度）と、Ｓｉ−Ｏ結合に由来する吸収を示す領域の最大の吸光度（Ｓｉ−Ｏ吸光度）とから、Ｓｉ−Ｈ／Ｓｉ−Ｏ吸光度比を評価した。
(2) Formation of Sealing Layer Polysilazane xylene solution (NL110A-20, manufactured by Clariant Co., Ltd.) is placed on the counter electrode of the laminated body in which the obtained electrode / electron transport layer / photoelectric conversion layer / hole transport layer / counter electrode is laminated. , Concentration 20%) was applied to a thickness of 100 nm by the doctor blade method, and heated at 120 ° C. for 30 minutes on a hot plate to form a sealing layer to obtain a solar cell.
The obtained sealing layer was subjected to infrared spectrum measurement using an FT-IR measuring device FT / IR-4600 (manufactured by JASCO Corporation). From the maximum absorbance of the region showing absorption derived from the Si—H bond (Si—H absorbance) and the maximum absorbance of the region showing absorption derived from the Si—O bond (Si—O absorbance), Si—H The / Si—O absorbance ratio was evaluated.
（実施例２〜６）
封止層の厚みを表１に示すよう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。
(Examples 2 to 6)
A solar cell was obtained in the same manner as in Example 1 except that the thickness of the sealing layer was changed as shown in Table 1.
（実施例７）
封止層のポリシラザンとしてＮＬ１１０Ａ−２０（クラリアント社製）の代わりにＮＰ−１１０（クラリアント社製）を用いたこと以外は実施例１と同様にして、太陽電池を得た。
(Example 7)
A solar cell was obtained in the same manner as in Example 1 except that NP-110 (manufactured by Clariant) was used instead of NL110A-20 (manufactured by Clariant) as the polysilazane of the sealing layer.
（実施例８）
封止層のポリシラザンの加熱温度、加熱時間を表１に示すよう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。
(Example 8)
A solar cell was obtained in the same manner as in Example 1 except that the heating temperature and heating time of polysilazane in the sealing layer were changed as shown in Table 1.
（実施例９）
封止層を形成した後、下記のようにして封止層の外側を封止する無機層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。
(Example 9)
After forming the sealing layer, a solar cell was obtained in the same manner as in Example 1 except that an inorganic layer for sealing the outside of the sealing layer was formed as described below.
封止層を形成したサンプル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、成膜条件Ａに示す条件でスパッタリングし、封止層上に無機層としてＺｎＳｎＯ（Ｓｉ）薄膜を１００ｎｍ形成し、太陽電池を得た。
（成膜条件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
The sample on which the sealing layer was formed was attached to the substrate holder of the sputtering apparatus, and a ZnSn alloy (Zn: Sn = 95: 5% by weight) target was attached to the cathode A of the sputtering apparatus, and a Si target was attached to the cathode B. The film forming chamber of the sputtering apparatus was exhausted by a vacuum pump, and the pressure was reduced to 5.0 × 10 -4 Pa. Then, the film was sputtered under the conditions shown in the film forming condition A to form a ZnSnO (Si) thin film as an inorganic layer at 100 nm on the sealing layer to obtain a solar cell.
(Film formation condition A)
Argon gas flow rate: 50 sccm, oxygen gas flow rate: 50 sccm
Power output: Cathode A = 500W, Cathode B = 1500W
（比較例１〜２）
封止層の厚みを表１に示すよう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。
(Comparative Examples 1-2)
A solar cell was obtained in the same manner as in Example 1 except that the thickness of the sealing layer was changed as shown in Table 1.
（比較例３）
下記のようにして封止層をスパッタリング法により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。
(Comparative Example 3)
A solar cell was obtained in the same manner as in Example 1 except that the sealing layer was formed by a sputtering method as described below.
電極／電子輸送層／光電変換層／ホール輸送層／対向電極が積層さ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にＳｉＯ２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、成膜条件Ａに示す条件でスパッタリングし、電極／電子輸送層／光電変換層／ホール輸送層／対向電極が積層された積層体上に封止層としてＳｉＯ２薄膜を１００ｎｍ形成し、太陽電池を得た。
（成膜条件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
A laminate in which electrodes / electron transport layers / photoelectric conversion layers / hole transport layers / counter electrodes were laminated was attached to a substrate holder of a sputtering apparatus, and a SiO 2 target was attached to the cathode of the sputtering apparatus. The film forming chamber of the sputtering apparatus was exhausted by a vacuum pump, and the pressure was reduced to 5.0 × 10 -4 Pa. After that, sputtering was performed under the conditions shown in the film forming condition A to form a SiO 2 thin film of 100 nm as a sealing layer on the laminated body in which the electrode / electron transport layer / photoelectric conversion layer / hole transport layer / counter electrode was laminated, and the sun was formed. I got a battery.
(Film formation condition A)
Argon gas flow rate: 50 sccm, oxygen gas flow rate: 50 sccm
Power output: Cathode A = 500W, Cathode B = 1500W
＜評価＞
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。結果を表１に示した。
<Evaluation>
The solar cells obtained in Examples and Comparative Examples were evaluated as follows. The results are shown in Table 1.
（高温高湿耐久性）
太陽電池を湿度８７％、温度６０℃の条件下に２４時間置いて高温高湿耐久試験を行った。作製直後（封止直後）の太陽電池、及び、高温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、高温高湿耐久試験後の光電変換効率／作製直後（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／作製直後（封止直後）の光電変換効率の値が０．９以上
○：高湿耐久試験後の光電変換効率／作製直後（封止直後）の光電変換効率の値が０．７以上、０．９未満
×：高湿耐久試験後の光電変換効率／作製直後（封止直後）の光電変換効率の値が０．７未満
(High temperature and high humidity durability)
The solar cell was placed under the conditions of a humidity of 87% and a temperature of 60 ° C. for 24 hours to perform a high temperature and high humidity durability test. A solar simulation (Yamashita Denso ) with a strength of 100 mW / cm 2 is connected by connecting a power supply (236 model manufactured by KEITHLEY) between the electrodes of the solar cell immediately after production (immediately after sealing) and the solar cell after the high temperature and high humidity durability test. The photoelectric conversion efficiency was measured using (manufactured by the same company), and the value of the photoelectric conversion efficiency after the high temperature and high humidity durability test / the photoelectric conversion efficiency immediately after production (immediately after sealing) was determined.
⊚: Photoelectric conversion efficiency after high humidity durability test / photoelectric conversion efficiency immediately after fabrication (immediately after sealing) is 0.9 or more ○: Photoelectric conversion efficiency after high humidity durability test / immediately after fabrication (immediately after sealing) Photoelectric conversion efficiency value is 0.7 or more and less than 0.9 ×: Photoelectric conversion efficiency after high humidity durability test / Photoelectric conversion efficiency value immediately after fabrication (immediately after sealing) is less than 0.7
本発明によれば、高温高湿耐久性に優れた太陽電池を提供することができる。 According to the present invention, it is possible to provide a solar cell having excellent high temperature and high humidity durability.
１ 太陽電池
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 封止層
６ 無機層
７ 基板
1
4
Claims (4)
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、
前記封止層は、ポリシラザンからなるシリカを含み、厚みが５０〜１００００ｎｍであり、
結晶化度が１０％以下である
ことを特徴とする太陽電池。 A seal having a laminate having an electrode, a counter electrode, and a photoelectric conversion layer arranged between the electrode and the counter electrode, and further covering the counter electrode to seal the laminate. A solar cell with layers
The photoelectric conversion layer contains 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 sealing layer comprises a silica consisting of polysilazane, Ri thickness 50~10000nm der,
A solar cell having a crystallinity of 10% or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017059351A JP6876480B2 (en) | 2017-03-24 | 2017-03-24 | Solar cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017059351A JP6876480B2 (en) | 2017-03-24 | 2017-03-24 | Solar cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2018163938A JP2018163938A (en) | 2018-10-18 |
| JP6876480B2 true JP6876480B2 (en) | 2021-05-26 |
Family
ID=63860345
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2017059351A Active JP6876480B2 (en) | 2017-03-24 | 2017-03-24 | Solar cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6876480B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020088316A (en) * | 2018-11-30 | 2020-06-04 | 国立大学法人東京工業大学 | Laminate, solar cell, and method of manufacturing solar cell |
| CN113016091A (en) | 2019-10-18 | 2021-06-22 | 株式会社安能科多科技 | Component |
| CN113272987A (en) | 2019-12-12 | 2021-08-17 | 株式会社安能科多科技 | Method for manufacturing element |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090301560A1 (en) * | 2008-06-05 | 2009-12-10 | Sanyo Electric Co., Ltd. | Photovoltaic element, photovoltaic module and method of manufacturing photovoltaic element |
| WO2015012404A1 (en) * | 2013-07-26 | 2015-01-29 | コニカミノルタ株式会社 | Electronic device and method for manufacturing same |
| EP3273496A4 (en) * | 2015-03-16 | 2018-10-31 | Sekisui Chemical Co., Ltd. | Solar cell |
-
2017
- 2017-03-24 JP JP2017059351A patent/JP6876480B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2018163938A (en) | 2018-10-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6745214B2 (en) | Solar cell and method of manufacturing solar cell | |
| JP6138968B2 (en) | Solar cell | |
| JP6151378B2 (en) | Solar cell | |
| JP6286106B2 (en) | Solar cell and organic semiconductor materials | |
| EP3518302A1 (en) | Solar cell | |
| JP6755678B2 (en) | Solar cell | |
| JP6876480B2 (en) | Solar cell | |
| JP7016806B2 (en) | Flexible solar cell | |
| JP2016178295A (en) | Solar battery | |
| JP6572039B2 (en) | Thin film solar cell and method for manufacturing thin film solar cell | |
| JP6921582B2 (en) | Solar cell | |
| JP2017034089A (en) | Thin film solar cell | |
| JP2016082003A (en) | Method for manufacturing thin-film solar battery | |
| JP6078662B2 (en) | Solar cell | |
| JP5926466B1 (en) | Solar cell | |
| EP3522245B1 (en) | Flexible solar cell | |
| JP2016082006A (en) | Method for manufacturing solar battery | |
| JP2016015409A (en) | Thin film solar cell | |
| JP2016025330A (en) | Thin film solar cell and manufacturing method therefor | |
| JP2018056233A (en) | Solar battery | |
| JP2018046056A (en) | Solar cell and method of manufacturing the same | |
| JP7112225B2 (en) | FLEXIBLE SOLAR CELL AND METHOD FOR MANUFACTURING FLEXIBLE SOLAR CELL | |
| JP2018046055A (en) | Solar cell | |
| JP6835644B2 (en) | Solar cell | |
| JP2016082004A (en) | solar battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20191017 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20201027 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20201104 |
|
| A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20201225 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20210128 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20210406 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20210426 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 6876480 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE Ref document number: 6876480 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |