WO2017135293A1 - 太陽電池 - Google Patents
太陽電池 Download PDFInfo
- Publication number
- WO2017135293A1 WO2017135293A1 PCT/JP2017/003575 JP2017003575W WO2017135293A1 WO 2017135293 A1 WO2017135293 A1 WO 2017135293A1 JP 2017003575 W JP2017003575 W JP 2017003575W WO 2017135293 A1 WO2017135293 A1 WO 2017135293A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- photoelectric conversion
- solar cell
- layer
- titanium
- organic
- Prior art date
Links
- 238000006243 chemical reaction Methods 0.000 claims abstract description 104
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000010936 titanium Substances 0.000 claims abstract description 67
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 63
- 229910052751 metal Inorganic materials 0.000 claims abstract description 49
- 239000002184 metal Substances 0.000 claims abstract description 49
- 150000001875 compounds Chemical class 0.000 claims abstract description 48
- 239000000463 material Substances 0.000 claims abstract description 40
- 125000005843 halogen group Chemical group 0.000 claims abstract description 10
- 125000004429 atom Chemical group 0.000 claims abstract description 8
- 229910052798 chalcogen Chemical group 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 8
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 238000001782 photodegradation Methods 0.000 abstract description 25
- 230000007423 decrease Effects 0.000 abstract description 16
- 230000007797 corrosion Effects 0.000 abstract description 15
- 238000005260 corrosion Methods 0.000 abstract description 15
- 238000010030 laminating Methods 0.000 abstract description 2
- 239000010409 thin film Substances 0.000 description 51
- 239000004065 semiconductor Substances 0.000 description 35
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 20
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 19
- 230000005525 hole transport Effects 0.000 description 16
- 239000000758 substrate Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- 239000010408 film Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 230000000737 periodic effect Effects 0.000 description 8
- 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
- 239000002131 composite material Substances 0.000 description 7
- 238000010304 firing Methods 0.000 description 7
- 229910003472 fullerene Inorganic materials 0.000 description 7
- 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 7
- 238000001552 radio frequency sputter deposition Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 6
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 6
- 229910052779 Neodymium Inorganic materials 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- 229910052787 antimony Inorganic materials 0.000 description 6
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 229910052741 iridium Inorganic materials 0.000 description 6
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 6
- 229910052746 lanthanum Inorganic materials 0.000 description 6
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- -1 polyphenylene vinylene Polymers 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000000137 annealing Methods 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 150000001787 chalcogens Chemical group 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- 229910052712 strontium Inorganic materials 0.000 description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 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
- PNKUSGQVOMIXLU-UHFFFAOYSA-N Formamidine Chemical compound NC=N PNKUSGQVOMIXLU-UHFFFAOYSA-N 0.000 description 3
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-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
- 238000000576 coating method Methods 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- BWUWTXKPVKAOED-UHFFFAOYSA-N pentylcarbamic acid Chemical compound CCCCCNC(O)=O BWUWTXKPVKAOED-UHFFFAOYSA-N 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 description 3
- 238000007740 vapor deposition Methods 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
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-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
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-O Methylammonium ion Chemical compound [NH3+]C BAVYZALUXZFZLV-UHFFFAOYSA-O 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- QCOGKXLOEWLIDC-UHFFFAOYSA-N N-methylbutylamine Chemical compound CCCCNC QCOGKXLOEWLIDC-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000000333 X-ray scattering Methods 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
- 238000013459 approach Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000011248 coating agent Substances 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
- 230000006866 deterioration Effects 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
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000005530 etching Methods 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
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 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
- 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
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
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- 150000002739 metals Chemical class 0.000 description 2
- WOGVSFZYKQTBKV-UHFFFAOYSA-N methylsulfinylmethane;hydroiodide Chemical compound [I-].C[SH+](C)=O WOGVSFZYKQTBKV-UHFFFAOYSA-N 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- UOIWOHLIGKIYFE-UHFFFAOYSA-N n-methylpentan-1-amine Chemical compound CCCCCNC UOIWOHLIGKIYFE-UHFFFAOYSA-N 0.000 description 2
- GVWISOJSERXQBM-UHFFFAOYSA-N n-methylpropan-1-amine Chemical compound CCCNC GVWISOJSERXQBM-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
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- 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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- 150000004032 porphyrins Chemical group 0.000 description 2
- KBJXDTIYSSQJAI-UHFFFAOYSA-N propylcarbamic acid Chemical compound CCCNC(O)=O KBJXDTIYSSQJAI-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- GKCNVZWZCYIBPR-UHFFFAOYSA-N sulfanylideneindium Chemical compound [In]=S GKCNVZWZCYIBPR-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
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- 239000011787 zinc oxide 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
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
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- BHHGXPLMPWCGHP-UHFFFAOYSA-O 2-phenylethanaminium Chemical compound [NH3+]CCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-O 0.000 description 1
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- 101100069231 Caenorhabditis elegans gkow-1 gene Proteins 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-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
- 229910016001 MoSe Inorganic materials 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
- 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
- 229910000883 Ti6Al4V Inorganic materials 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
- 238000010306 acid treatment Methods 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
- HONIICLYMWZJFZ-UHFFFAOYSA-N azetidine Chemical compound C1CNC1 HONIICLYMWZJFZ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 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
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- 239000002041 carbon nanotube Substances 0.000 description 1
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- 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
- 239000000919 ceramic Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
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- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
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- 230000005684 electric field Effects 0.000 description 1
- KWBIXTIBYFUAGV-UHFFFAOYSA-N ethylcarbamic acid Chemical compound CCNC(O)=O KWBIXTIBYFUAGV-UHFFFAOYSA-N 0.000 description 1
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- 229910052732 germanium Inorganic materials 0.000 description 1
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- 150000004820 halides Chemical class 0.000 description 1
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- 150000002367 halogens Chemical class 0.000 description 1
- YAQPZDICKJDHTR-UHFFFAOYSA-N hexylcarbamic acid Chemical compound CCCCCCNC(O)=O YAQPZDICKJDHTR-UHFFFAOYSA-N 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
- 229910052738 indium Inorganic materials 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
- 239000011261 inert gas Substances 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
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- LLWRXQXPJMPHLR-UHFFFAOYSA-N methylazanium;iodide Chemical compound [I-].[NH3+]C LLWRXQXPJMPHLR-UHFFFAOYSA-N 0.000 description 1
- UFEJKYYYVXYMMS-UHFFFAOYSA-N methylcarbamic acid Chemical compound CNC(O)=O UFEJKYYYVXYMMS-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
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- DIAIBWNEUYXDNL-UHFFFAOYSA-N n,n-dihexylhexan-1-amine Chemical compound CCCCCCN(CCCCCC)CCCCCC DIAIBWNEUYXDNL-UHFFFAOYSA-N 0.000 description 1
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- 239000002105 nanoparticle Substances 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
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- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
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- 230000001443 photoexcitation Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 238000004544 sputter deposition 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
- 239000011135 tin Substances 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 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
- 229910001935 vanadium oxide Inorganic materials 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
Images
Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/02—Sulfones; Sulfoxides having sulfone or sulfoxide groups bound to acyclic carbon atoms
- C07C317/04—Sulfones; Sulfoxides having sulfone or sulfoxide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- 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
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
- H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- 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
- H10K30/81—Electrodes
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- 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
-
- 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 and suppresses a decrease in photoelectric conversion efficiency (photodegradation) caused by continuing to irradiate light with less corrosion of the photoelectric conversion layer.
- 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.
- Non-Patent Document 2 a photoelectric conversion material having a perovskite structure using lead, tin, or the like as a central metal, which is called an organic-inorganic hybrid semiconductor, has been discovered and shown to have high photoelectric conversion efficiency (for example, Non-Patent Document 2).
- the present inventors examined the use of an organic / inorganic perovskite compound for the photoelectric conversion layer in a solar cell having a structure in which a cathode, an electron transport layer, a photoelectric conversion layer, and an anode are laminated in this order.
- an improvement in the photoelectric conversion efficiency of the solar cell can be expected.
- a solar cell in which the photoelectric conversion layer contains an organic / inorganic perovskite compound exhibits high photoelectric conversion efficiency immediately after the start of light irradiation, but newly revealed that the photoelectric conversion efficiency decreases as light is continuously irradiated. (Light degradation).
- a solar cell including an organic / inorganic perovskite compound in the photoelectric conversion layer may be discolored and corrode in the photoelectric conversion layer during the manufacturing process of the solar cell or over time.
- the phenomenon that such corrosion occurs has been found by the present inventors as a phenomenon peculiar to solar cells in which the photoelectric conversion layer contains an organic / inorganic perovskite compound, and has been reported in other general solar cells. Not.
- the present invention provides a solar cell that is excellent in photoelectric conversion efficiency and suppresses a decrease in photoelectric conversion efficiency (photodegradation) caused by continuing to irradiate light, and has less corrosion of the photoelectric conversion layer. Objective.
- the present invention is a solar cell having a structure in which a cathode, an electron transport layer, a photoelectric conversion layer, and an anode are laminated in this order, and the photoelectric conversion layer has a general formula RMX 3 (where R is an organic compound) Molecule, M is a metal atom, X is a halogen atom or a chalcogen atom), and the cathode is made of a titanium material and has an oxide layer on at least one surface. is there.
- R is an organic compound
- the present inventors are made of a titanium material and have an oxide layer on at least one surface. It has been found that by using a cathode, the photoelectric conversion efficiency can be further improved, a decrease in photoelectric conversion efficiency (photodegradation) due to continuous irradiation with light can be suppressed, and the corrosion of the photoelectric conversion layer can be reduced. It came to complete.
- a photoelectric conversion layer containing an organic / inorganic perovskite compound has a property that reverse electron transfer is particularly likely to occur as compared with a photoelectric conversion layer using another semiconductor material.
- the electron transport layer has a high density, reverse electron transfer does not occur and photodegradation is suppressed.
- the density of the electron transport layer decreases, reverse electron transfer occurs and photodegradation is likely to occur. It is done.
- the reason why corrosion of the photoelectric conversion layer is reduced is considered to be that by using a cathode made of a titanium material, corrosion of the photoelectric conversion layer due to element diffusion of the cathode and the substrate disposed as necessary can be suppressed. . That is, although element diffusion is likely to occur depending on the type of cathode and substrate, the use of a cathode made of a titanium material makes it difficult for element diffusion at the cathode, and element diffusion at the cathode and substrate occurs. However, it is considered that an oxide layer (titanium oxide layer) generated at the interface between the cathode and the electron transport layer by natural oxidation can suppress element diffusion.
- titanium oxide layer titanium oxide layer
- the oxide layer formed at the interface between the cathode and the electron transport layer due to natural oxidation is a gradient oxide layer in which the ratio of titanium atoms to oxygen atoms in the thickness direction increases gradually in the thickness direction as it approaches the portion made of titanium material. It is preferable to have. It is considered that the corrosion of the photoelectric conversion layer can be further suppressed by making it difficult for cracks or the like to occur in the oxide layer due to this gradient composition change.
- the solar cell of the present invention has a structure in which a cathode, an electron transport layer, a photoelectric conversion layer, and an anode are laminated in this order.
- 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 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 cathode is made of a titanium material.
- a cathode made of a titanium material By using a cathode made of a titanium material, the photoelectric conversion efficiency is further improved, a decrease in photoelectric conversion efficiency (photodegradation) due to continuous irradiation with light can be suppressed, and corrosion of the photoelectric conversion layer is also reduced.
- the titanium material is not particularly limited as long as it can generate titanium oxide by oxidation.
- Metal titanium, a mixture of metal titanium and another metal, Ti-6Al-4V, Ti-4.5Al-3V- A titanium alloy such as 2Fe-2Mo and Ti-0.5Pd can be used.
- a mixture of metal titanium and another metal is preferable because it is relatively inexpensive and the resistance value of the cathode is lowered to improve the photoelectric conversion efficiency of the solar cell.
- the titanium content is preferably 50% by weight or more from the viewpoint of reliably exhibiting the effects of the present invention.
- the titanium material is a mixture of metal titanium and another metal
- the titanium material is preferably a laminate of a metal titanium thin film and another metal thin film.
- the metal titanium thin film is preferably disposed on the electron transport layer side.
- An example of the metal titanium thin film is a titanium foil.
- the other metal include aluminum, cobalt, chromium, molybdenum, tungsten, gold, silver, copper, magnesium, and nickel. Among these, aluminum and cobalt are preferable, and aluminum is more preferable because it is relatively inexpensive and has a low resistance value of the cathode and improves the photoelectric conversion efficiency of the solar cell.
- the cathode has an oxide layer on at least one surface.
- the oxide layer is a layer containing titanium oxide.
- the oxide layer is preferably disposed on the electron transport layer side of the cathode.
- the oxide layer has a graded oxide layer in which the ratio of titanium atoms to oxygen atoms is gradedly increased in the thickness direction (depth direction) as it approaches a portion made of a titanium material. It is considered that the corrosion of the photoelectric conversion layer can be further suppressed by making it difficult for cracks or the like to occur in the oxide layer due to this gradient composition change.
- the thickness of the gradient oxide layer is not particularly limited, but the preferred lower limit is 5 nm, the preferred upper limit is 150 nm, the more preferred lower limit is 10 nm, and the more preferred upper limit is 100 nm.
- a preferable lower limit of the thickness of the oxide layer is 1 nm.
- the thickness of the oxide layer is 1 nm.
- the generation of pinholes can be further prevented, and a decrease in photoelectric conversion efficiency (photodegradation) due to continued irradiation with light can be reliably suppressed.
- the thickness of the oxide layer is set to or more than the lower limit, corrosion of the photoelectric conversion layer due to element diffusion of the cathode and the substrate disposed as necessary can be surely suppressed.
- a more preferable lower limit of the thickness of the oxide layer is 5 nm, a still more preferable lower limit is 10 nm, and a particularly preferable lower limit is 20 nm.
- a preferable upper limit of the thickness of the oxide layer is 1000 nm. By setting the thickness of the oxide layer to be equal to or lower than the upper limit, the electrical resistance loss can be reduced and the photoelectric conversion efficiency can be increased.
- a more preferable upper limit of the thickness of the oxide layer is 200 nm, a still more preferable upper limit is 100 nm, and a particularly preferable upper limit is 50 nm.
- a step of heating the titanium material may be provided separately, but the heating of the titanium material is also performed by steps such as firing of the electron transport layer and thermal annealing (heat treatment) of the photoelectric conversion layer in the manufacturing process of the solar cell. It is preferable to carry out. Moreover, you may perform both of these.
- the temperature and time for heating the titanium material are not particularly limited, but it is preferably heated at 100 to 500 ° C. for about 1 to 60 minutes.
- the formation of the oxide layer can be confirmed by, for example, elemental analysis of the cross section of the solar cell with TEM-EDS.
- the thickness of the oxide layer is measured by XPS (X-ray photoelectron spectroscopy) while performing Ar etching or C60 etching in the thickness direction (depth direction) of the cathode, and signals of titanium (Ti) and oxygen (O) are obtained.
- XPS X-ray photoelectron spectroscopy
- Ar etching or C60 etching in the thickness direction (depth direction) of the cathode
- signals of titanium (Ti) and oxygen (O) are obtained.
- information in the thickness direction (depth direction) of the abundance ratio of titanium (Ti) and oxygen (O) can also be obtained.
- the cathode may be formed on the surface of the substrate.
- the substrate is not particularly limited, for example, a transparent glass substrate such as soda lime glass or non-alkali glass, a rigid type substrate such as a ceramic substrate or a transparent plastic substrate, a metal thin film made of a metal other than the titanium material, a plastic thin film, etc.
- the flexible type substrate can be used.
- the cathode since the cathode is made of a titanium material, it is preferable that light is incident from the anode side. Therefore, the substrate is not necessarily required to be transparent.
- the obtained solar cell can be a flexible solar cell, and in the process of manufacturing the solar cell.
- a process involving heating can also be performed without problems.
- the solar cell of this invention may not have a board
- the titanium material is preferably a metal titanium thin film.
- An example of the metal titanium thin film is a titanium foil.
- 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 examples include 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.
- titanium oxide is particularly preferred because of its excellent affinity with the titanium material constituting the cathode.
- the electron transport layer preferably includes a thin film electron transport layer and a porous electron transport layer laminated thereon.
- the photoelectric conversion layer is a composite film in which an organic semiconductor or an inorganic semiconductor part and an organic / inorganic perovskite compound part are combined, a more complex composite film (a more complicated and complicated structure) is obtained. Since efficiency becomes high, it is preferable that the composite film of the photoelectric converting layer is formed on the porous electron carrying layer.
- the titanium material is naturally oxidized to form an oxide layer (titanium oxide layer) at the interface between the cathode and the electron transport layer (especially a porous electron transport layer), the thin film electron transport is performed.
- a thin film electron transport layer may be formed on the oxide layer.
- the thin film electron transport layer preferably has an element ratio of titanium to oxygen of between 1: 2 and 1: 1.
- a preferred lower limit of the thickness of the thin film electron transport layer is 5 nm. By setting the thickness of the thin-film electron transport layer to the above lower limit or more, it is possible to further suppress a decrease in photoelectric conversion efficiency (photodegradation) due to continuous irradiation with light.
- a more preferable lower limit of the thickness of the thin film electron transport layer is 10 nm, and a more preferable lower limit is 20 nm.
- the upper limit of the thickness of the thin film electron transport layer is not particularly limited, but is preferably 500 nm. When the thickness of the thin-film electron transport layer is not more than the above upper limit, it becomes easy to suppress the occurrence of cracks.
- a more preferable upper limit of the thickness of the thin film electron transport layer is 400 nm, and a more preferable upper limit is 300 nm.
- the thickness of the thin film electron transport layer means an average value of the distance from the electrode to the porous electron transport layer, and can be measured by cross-sectional observation with a transmission electron microscope.
- 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.
- ions e.g., 3 NH 3
- methylamine, ethylamine, propylamine, propylcarboxyamine, butylcarboxyamine, pentylcarboxyamine, formamidinium, guanidine and their ions are preferred, and methylamine, ethylamine, pentylcarboxyamine, formamidinium, guanidine and These ions are more preferred.
- methylamine, formaminidium, and these ions are more preferable because high photoelectric conversion efficiency can be obtained.
- 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.
- lead or tin is preferable from the viewpoint of overlapping of electron orbits.
- 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. If 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. In addition, if the organic / inorganic perovskite compound is a crystalline semiconductor, it is easy to suppress a decrease in photoelectric conversion efficiency (photodegradation) caused by continuing to irradiate light on a solar cell, particularly a photodegradation due to a decrease in short-circuit current. .
- 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%. If 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.
- the said crystallinity is 30% or more, it will become easy to suppress the photodegradation resulting from the fall (photodegradation) of photoelectric conversion efficiency by continuing irradiating a solar cell with light, especially the fall of a short circuit current.
- a more preferred lower limit of the crystallinity is 50%, and a more preferred lower limit is 70%.
- Examples of a method for increasing the crystallinity of the organic / inorganic perovskite compound include thermal annealing (heat treatment), irradiation with intense light such as a laser, and plasma irradiation.
- the photoelectric conversion layer includes at least one element selected from the group consisting of Group 2 elements of the periodic table, Group 11 elements of the periodic table, antimony, manganese, neodymium, iridium, titanium, and lanthanum in addition to the organic inorganic perovskite compound. It is preferable that it is further included.
- the photoelectric conversion layer contains an organic / inorganic perovskite compound and the above elements, resulting in a decrease in photoelectric conversion efficiency (photodegradation) caused by continuing to irradiate light to the solar cell, particularly a short circuit current and a fill factor. Photodegradation is suppressed.
- At least one element selected from the group consisting of Group 2 elements of the periodic table Group 11 elements of the periodic table, antimony, manganese, neodymium, iridium, titanium and lanthanum, specifically, for example, calcium, strontium, silver, Examples thereof include copper, antimony, manganese, neodymium, iridium, titanium, and lanthanum.
- calcium, strontium, silver, copper, neodymium and iridium are preferable. From the viewpoint of increasing the initial conversion efficiency, calcium, strontium, silver, copper, manganese, and lanthanum are more preferable, and calcium, strontium, silver, and copper are particularly preferable.
- the content ratio (mole) of at least one element selected from the group consisting of Group 2 elements of the periodic table, Group 11 elements of the periodic table, antimony, manganese, neodymium, iridium, titanium and lanthanum is not particularly limited.
- a preferable lower limit for the metal element (M represented by RMX- 3 ) 100 in the organic-inorganic perovskite compound is 0.01, and a preferable upper limit is 20. If the content ratio (mole) is 0.01 or more, light resulting from a decrease in photoelectric conversion efficiency (photodegradation) caused by continuing to irradiate light to the solar cell, particularly a short circuit current density and a fill factor. Deterioration is suppressed. When the content ratio (mole) is 20 or less, it is possible to suppress a decrease in initial conversion efficiency due to the presence of the element.
- the more preferable lower limit of the content ratio (mole) is 0.1, and the more preferable upper limit is 10.
- the organic inorganic perovskite compound contains at least one element selected from the group consisting of Group 2 elements of the periodic table, Group 11 elements of the periodic table, antimony, manganese, neodymium, iridium, titanium and lanthanum in particular.
- the method of mixing the halide of the said element with the solution used when forming the layer of an organic inorganic perovskite compound is mentioned.
- 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 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.
- compounds having a porphyrin skeleton such as a phthalocyanine skeleton, a naphthalocyanine skeleton, a pentacene skeleton, or a benzoporphyrin skeleton, a spirobifluorene skeleton, etc.
- carbon-containing materials such as carbon nanotubes, graphene, and fullerene that may be surface-modified 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 includes the organic-inorganic perovskite compound and the organic semiconductor or the inorganic semiconductor
- the photoelectric conversion layer is a laminated body in which a thin-film organic semiconductor or an inorganic semiconductor portion and a thin-film organic-inorganic perovskite compound portion are stacked.
- a composite film in which an organic semiconductor or inorganic semiconductor part and an organic / inorganic perovskite compound part are combined may be used.
- a laminated body is preferable in that the production method is simple, and a composite film 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 film 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.
- the photoelectric conversion layer may be subjected to thermal annealing (heat treatment) after the photoelectric conversion layer is formed.
- thermal annealing heat treatment
- the degree of crystallinity of the organic-inorganic perovskite compound in the photoelectric conversion layer can be sufficiently increased, and the decrease in photoelectric conversion efficiency (photodegradation) due to continued irradiation with light is further increased. Can be suppressed.
- the temperature for heating the photoelectric conversion layer is not particularly limited, but is preferably 100 ° C. or higher and lower than 200 ° C. When the heating temperature is 100 ° C. or higher, the crystallinity of the organic / inorganic perovskite compound can be sufficiently increased.
- the said heating temperature is less than 200 degreeC, it can heat-process, without thermally degrading the said organic-inorganic perovskite compound.
- a more preferable heating temperature is 120 ° C. or higher and 170 ° C. or lower.
- the heating time is not particularly limited, but is preferably 3 minutes or longer and 2 hours or shorter. When the heating time is 3 minutes or longer, the crystallinity of the organic-inorganic perovskite compound can be sufficiently increased. If the heating time is within 2 hours, the organic inorganic perovskite compound can be heat-treated without causing thermal degradation.
- These heating operations are preferably performed in a vacuum or under an inert gas, and the dew point temperature is preferably 10 ° C or lower, more preferably 7.5 ° C or lower, and further preferably 5 ° C or lower.
- the material of the said anode is not specifically limited, A conventionally well-known material can be used.
- the anode is often a patterned electrode.
- Specific examples of the material for the anode include metals such as gold, CuI, ITO (indium tin oxide), SnO 2 , AZO (aluminum zinc oxide), IZO (indium zinc oxide), GZO (gallium zinc). Oxides), conductive transparent materials such as ATO (antimony-doped tin oxide), conductive transparent polymers, and the like. These materials may be used alone or in combination of two or more.
- the solar cell of the present invention may have a hole transport layer between the photoelectric conversion layer and the anode.
- 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.
- a preferable lower limit of the thickness of the hole transport layer is 100 nm. By setting the thickness of the hole transport layer to be equal to or more than the lower limit, it is possible to further suppress a decrease in photoelectric conversion efficiency (photodegradation) due to continuous irradiation with light.
- a more preferable lower limit of the thickness of the hole transport layer is 200 nm, and a more preferable lower limit is 300 nm.
- the upper limit of the thickness of the hole transport layer is not particularly limited, but is preferably 500 nm. It becomes easy to suppress generation
- a more preferable upper limit of the thickness of the hole transport layer is 400 nm.
- the thickness of the said hole transport layer means the average value of the distance from a photoelectric converting layer to an anode, and can be measured by cross-sectional observation with a transmission electron microscope.
- FIG. 2 is a cross-sectional view schematically showing an example of the solar cell of the present invention.
- a solar cell 1 shown in FIG. 2 includes an electron transport layer 3 (a thin-film electron transport layer 31 and a porous electron transport layer 32), a photoelectric conversion layer 4 containing an organic / inorganic perovskite compound, a hole transport layer on a cathode 2. 5 and the anode 6 are laminated in this order.
- the cathode 2 has an oxide layer on at least one surface.
- the anode 6 is a patterned electrode.
- the solar cell with few corrosion of a photoelectric converting layer which was excellent in photoelectric conversion efficiency, the fall (photodegradation) of the photoelectric conversion efficiency by continuing irradiating light was suppressed can be provided.
- Example 1 On the surface of a 200 nm-thick metal titanium thin film (surface is naturally oxidized) as a cathode, titanium oxide nanoparticles (average particle size 10 nm (Showa Denko, F6A) and average particle size 30 nm (Showa Denko, A titanium oxide paste in which a mixture with F4A) was dispersed in ethanol was applied by spin coating, and then irradiated with ultraviolet light of 80 mW / cm 2 for 1 minute to form a porous electron transport layer.
- titanium oxide nanoparticles average particle size 10 nm (Showa Denko, F6A) and average particle size 30 nm (Showa Denko, A titanium oxide paste in which a mixture with F4A) was dispersed in ethanol was applied by spin coating, and then irradiated with ultraviolet light of 80 mW / cm 2 for 1 minute to form a porous electron transport layer.
- lead iodide-dimethyl sulfoxide complex is prepared by previously reacting lead iodide with dimethyl sulfoxide (DMSO), and the lead iodide-dimethyl sulfoxide complex is dissolved in N, N-dimethylformamide (DMF).
- DMSO dimethyl sulfoxide
- DMF N, N-dimethylformamide
- a coating solution of 60% by weight was obtained.
- the obtained coating solution was laminated on the electron transport layer to a thickness of 200 nm by a spin coating method, and an isopropanol solution of methylammonium iodide (CH 3 NH 3 I) adjusted to 8% from the top was further spun.
- the photoelectric conversion layer containing an organic inorganic perovskite compound was formed by making it react with a lead iodide by laminating
- an ITO film having a thickness of 100 nm was formed as an anode by EB vapor deposition to obtain a solar cell in which a cathode / electron transport layer / photoelectric conversion layer / hole transport layer / anode were laminated.
- Examples 2 to 5 A solar cell was obtained in the same manner as in Example 1 except that the cathode was heated under the firing temperature conditions shown in Table 1 before forming the porous electron transport layer.
- Example 6 A solar cell was obtained in the same manner as in Example 5 except that the thickness of the metal titanium thin film as the cathode was changed to the thickness shown in Table 1.
- Example 7 The thickness of the metal titanium thin film as the cathode was changed to the thickness shown in Table 1, and before forming the porous electron transport layer, the cathode was heated under the firing temperature conditions shown in Table 1. A solar cell was obtained in the same manner as Example 1.
- Example 9 Before forming the porous electron transport layer, the same procedure as in Example 1 was performed except that a thin film electron transport layer made of titanium oxide having a thickness of 30 nm was formed on the surface of the cathode by RF sputtering. A solar cell was obtained.
- Example 10 Before forming the porous electron transport layer, the cathode is heated under the firing temperature conditions shown in Table 1, and then, on the surface of the cathode, thin film electrons made of titanium oxide having a thickness of 30 nm are formed by RF sputtering. A solar cell was obtained in the same manner as in Example 1 except that the transport layer was formed.
- Example 12 A solar cell was obtained in the same manner as in Example 1 except that the metal thin film shown in Table 1 was used instead of the metal titanium thin film as the cathode.
- Example 13 and 14 A solar cell was obtained in the same manner as in Example 12 except that the cathode was heated under the firing temperature conditions shown in Table 1 before forming the porous electron transport layer.
- Example 15 Before forming the porous electron transport layer, the cathode is heated under the firing temperature conditions shown in Table 1, and then, on the surface of the cathode, thin film electrons made of titanium oxide having a thickness of 30 nm are formed by RF sputtering. A solar cell was obtained in the same manner as in Example 12 except that the transport layer was formed.
- Example 16 to 19 A solar cell was obtained in the same manner as in Example 1 except that the metal thin film shown in Table 1 was used instead of the metal titanium thin film as the cathode.
- Example 1 A substrate having a metal titanium thin film with a thickness of 200 nm was placed in a glove box with an oxygen concentration of 10 ppm or less, and hydrofluoric acid treatment was performed in the glove box to remove the oxide film on the surface of the metal titanium thin film. Then, the solar cell was obtained like Example 1 except having operated in the glove box.
- Comparative Example 6 Before forming the porous electron transport layer, the same procedure as in Comparative Example 3 was performed except that a thin film electron transport layer made of titanium oxide having a thickness of 30 nm was formed on the surface of the cathode by RF sputtering. A solar cell was obtained.
- Example 7 Before forming the porous electron transport layer, the cathode is heated under the firing temperature conditions shown in Table 2, and then, on the surface of the cathode, thin film electrons made of titanium oxide having a thickness of 30 nm are formed by RF sputtering. A solar cell was obtained in the same manner as in Example 3 except that the transport layer was formed.
- Comparative Example 31 Before forming the porous electron transport layer, the same procedure as in Comparative Example 30 was performed except that a thin film electron transport layer made of titanium oxide having a thickness of 30 nm was formed on the surface of the cathode by RF sputtering. A solar cell was obtained.
- Comparative Example 35 Prior to forming the porous electron transport layer, the same procedure as in Comparative Example 34 was performed except that a thin film electron transport layer made of titanium oxide having a thickness of 30 nm was formed on the surface of the cathode by RF sputtering. A solar cell was obtained.
- a power source manufactured by KEITHLEY, model 2366 was connected between the electrodes of the solar cell, and light having an intensity of 100 mW / cm 2 was irradiated using a solar simulation (manufactured by Yamashita Denso Co., Ltd.) to measure the photoelectric conversion efficiency.
- the obtained photoelectric conversion efficiency was normalized with the photoelectric conversion efficiency of the solar cell obtained in Example 1 as 1.
- a power source manufactured by KEITHLEY, model 2366 was connected between the electrodes of the solar cell, and light with an intensity of 100 mW / cm 2 was irradiated using a solar simulation (manufactured by Yamashita Denso Co., Ltd.).
- the photoelectric conversion efficiency is higher than that of the solar cell obtained in Example 1, the photoelectric conversion performance maintenance rate in the light degradation test is 90% or more, and the corrosion evaluation of the photoelectric conversion layer is “ ⁇ ” ⁇ , one that did not satisfy any one was marked as x.
- the solar cell with few corrosion of a photoelectric converting layer which was excellent in photoelectric conversion efficiency, the fall (photodegradation) of the photoelectric conversion efficiency by continuing irradiating light was suppressed can be provided.
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Abstract
Description
しかしながら、光電変換層が有機無機ペロブスカイト化合物を含む太陽電池は、光照射を開始した直後は高い光電変換効率を示すものの、光を照射し続けると光電変換効率が低下していくことが新たに明らかとなった(光劣化)。また、光電変換層が有機無機ペロブスカイト化合物を含む太陽電池は、太陽電池の製造過程で又は時間の経過とともに光電変換層に変色が生じ、腐食が生じる場合があることも新たに明らかとなった。なお、このような腐食が生じるという現象は、光電変換層が有機無機ペロブスカイト化合物を含む太陽電池に特有の現象として本発明者らが見出したものであり、一般的な他の太陽電池では報告されていない。
以下に本発明を詳述する。
光劣化を抑制できる理由については必ずしも明らかではないが、本発明者らは、光電変換層が有機無機ペロブスカイト化合物を含む太陽電池の光劣化が、電子輸送層の密度に影響されることを突き止めている。有機無機ペロブスカイト化合物を含む光電変換層は、他の半導体材料を用いた光電変換層に比べて特に逆電子移動が生じやすいという性質がある。電子輸送層が高密度である場合には、逆電子移動が発生せず光劣化が抑制される一方、電子輸送層の密度が低下すると、逆電子移動が生じて光劣化が発生し易くなると考えられる。とりわけ、電子輸送層にピンホールが生じた場合には、てきめんに光劣化が発生する。これに対して、チタン材料からなる陰極を用いることにより、自然酸化により陰極と電子輸送層との界面に酸化層(酸化チタン層)が生じ、該酸化チタン層が電子輸送層の密度を向上させ、かつ、たとえ電子輸送層にピンホールが生じた場合にでも、該酸化チタン層が電子輸送層としても作用することにより、光劣化を抑制できるのではないかと考えられる。
光電変換層の腐食が少なくなる理由としては、チタン材料からなる陰極を用いることにより、陰極及び必要に応じて配置される基板の元素拡散による光電変換層の腐食を抑制できるのではないかと考えられる。即ち、陰極及び基板の種類によっては元素拡散が生じやすいものがあるが、チタン材料からなる陰極を用いることにより、陰極の元素拡散が生じにくくなり、かつ、たとえ陰極及び基板の元素拡散が生じたとしても、自然酸化により陰極と電子輸送層との界面に生じた酸化層(酸化チタン層)が元素拡散を抑制できると考えられる。更に、自然酸化により陰極と電子輸送層との界面に生じた酸化層は、チタン材料からなる部分に近づくにつれて厚み方向に酸素原子に対するチタン原子の割合が傾斜的に増加している傾斜酸化層を有することが好ましい。この傾斜的な組成の変化により酸化層にクラック等が生じにくくなることによって、光電変換層の腐食をより抑制できると考えられる。
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。
上記チタン材料としては、酸化により酸化チタンを生成し得るものであれば特に限定されず、金属チタン、金属チタンと他の金属との混合物、Ti-6Al-4V、Ti-4.5Al-3V-2Fe-2Mo、Ti-0.5Pd等のチタン合金等を用いることができる。なかでも、比較的安価であるうえ、上記陰極の抵抗値が低くなって太陽電池の光電変換効率が向上することから、金属チタンと他の金属との混合物が好ましい。なお、上記チタン材料として金属チタンと他の金属との混合物やチタン合金を用いる場合には、本発明の効果を確実に発揮する観点から、チタンの含有量が50重量%以上であることが好ましい。
上記他の金属として、例えば、アルミニウム、コバルト、クロム、モリブデン、タングステン、金、銀、銅、マグネシウム、ニッケル等が挙げられる。なかでも、比較的安価であるうえ、上記陰極の抵抗値が低くなって太陽電池の光電変換効率が向上することから、アルミニウム、コバルトが好ましく、アルミニウムがより好ましい。
上記酸化層の厚みの好ましい上限は1000nmである。上記酸化層の厚みを上記上限以下とすることにより、電気抵抗損失が低減し、光電変換効率を高くすることができる。上記酸化層の厚みのより好ましい上限は200nmであり、更に好ましい上限は100nmであり、特に好ましい上限は50nmである。
上記チタン材料を加熱する温度及び時間は特に限定されないが、100~500℃で1~60分程度加熱することが好ましい。
また、本発明の太陽電池は、基板を有しないものであってもよい。基板を有せずに、上記チタン材料からなる薄膜を陰極として用いることにより、得られる太陽電池をフレキシブル太陽電池とすることができる。その場合、上記チタン材料は金属チタン薄膜であることが好ましい。上記金属チタン薄膜としては、例えば、チタン箔が挙げられる。
なお、本発明では、上記チタン材料が自然酸化され陰極と電子輸送層(特に多孔質状の電子輸送層)との界面に酸化層(酸化チタン層)を形成するため、上記薄膜状の電子輸送層を形成しなくとも、光劣化が抑制された太陽電池を得ることができる。その場合であっても、より電子輸送層の密度を高めるために、上記酸化層上に薄膜状の電子輸送層を形成してもよい。上記薄膜状の電子輸送層の材料として酸化チタンを用いる場合、上記薄膜状の電子輸送層は、チタンと酸素との元素比が1:2から1:1の間であることが好ましい。
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、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、イミダゾリン、カルバゾール、メチルカルボキシアミン、エチルカルボキシアミン、プロピルカルボキシアミン、ブチルカルボキシアミン、ペンチルカルボキシアミン、ヘキシルカルボキシアミン、ホルムアミジニウム、グアニジン、アニリン、ピリジン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、プロピルカルボキシアミン、ブチルカルボキシアミン、ペンチルカルボキシアミン、ホルムアミジニウム、グアニジン及びこれらのイオンが好ましく、メチルアミン、エチルアミン、ペンチルカルボキシアミン、ホルムアミジニウム、グアニジン及びこれらのイオンがより好ましい。中でも高い光電変換効率が得られることから、メチルアミン、ホルムアミニジウム及びこれらのイオンが更に好ましい。
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が結晶性半導体であれば、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。また、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れば、太陽電池に光を照射し続けることによる光電変換効率の低下(光劣化)、特に短絡電流の低下に起因する光劣化が抑制されやすくなる。
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。上記結晶化度が30%以上であれば、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。また、上記結晶化度が30%以上であれば、太陽電池に光を照射し続けることによる光電変換効率の低下(光劣化)、特に短絡電流の低下に起因する光劣化が抑制されやすくなる。上記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(加熱処理)、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。
上記光電変換層が有機無機ペロブスカイト化合物と、上記の元素とを含むことにより、太陽電池に光を照射し続けることによる光電変換効率の低下(光劣化)、特に短絡電流とフィルファクターの低下に起因する光劣化が抑制される。
上記周期表2族元素、周期表11族元素、アンチモン、マンガン、ネオジム、イリジウム、チタン及びランタンからなる群より選択される少なくとも1種の元素として、具体的には例えば、カルシウム、ストロンチウム、銀、銅、アンチモン、マンガン、ネオジム、イリジウム、チタン及びランタン等が挙げられる。なかでも、カルシウム、ストロンチウム、銀、銅、ネオジム、イリジウムが好ましい。また初期変換効率も高くなるという観点からは、カルシウム、ストロンチウム、銀、銅、マンガン、ランタンがより好ましく、カルシウム、ストロンチウム、銀、銅が特に好ましい。
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。
上記熱アニール(加熱処理)を行う場合、上記光電変換層を加熱する温度は特に限定されないが、100℃以上、200℃未満であることが好ましい。上記加熱温度が100℃以上であれば、上記有機無機ペロブスカイト化合物の結晶化度を充分に上げることができる。上記加熱温度が200℃未満であれば、上記有機無機ペロブスカイト化合物を熱劣化させることなく加熱処理を行うことができる。より好ましい加熱温度は、120℃以上、170℃以下である。また、加熱時間も特に限定されないが、3分以上、2時間以内であることが好ましい。上記加熱時間が3分以上であれば、上記有機無機ペロブスカイト化合物の結晶化度を充分に上げることができる。上記加熱時間が2時間以内であれば、上記有機無機ペロブスカイト化合物を熱劣化させることなく加熱処理を行うことができる。
これらの加熱操作は真空又は不活性ガス下で行われることが好ましく、露点温度は10℃以下が好ましく、7.5℃以下がより好ましく、5℃以下が更に好ましい。
上記陽極の材料として、具体的には例えば、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)、ATO(アンチモンドープ酸化スズ)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。
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。
図2に示す太陽電池1は、陰極2上に電子輸送層3(薄膜状の電子輸送層31と多孔質状の電子輸送層32)、有機無機ペロブスカイト化合物を含む光電変換層4、ホール輸送層5及び陽極6がこの順に積層されたものである。図示しないが、陰極2は、少なくとも一方の表面に酸化層を有するものである。なお、図2に示す太陽電池1において、陽極6はパターニングされた電極である。
陰極としての厚み200nmの金属チタン薄膜(表面が自然酸化されている)の表面上に、酸化チタンナノ粒子(平均粒子径10nm(昭和電工社製、F6A)と平均粒子径30nm(昭和電工社製、F4A)との混合物)をエタノールに分散させた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、80mW/cm2の紫外線を1分間照射し、多孔質状の電子輸送層を形成した。
多孔質状の電子輸送層を形成する前に、陰極を表1に記載の焼成温度条件で加熱したこと以外は実施例1と同様にして、太陽電池を得た。
陰極としての金属チタン薄膜の厚みを表1に記載の厚みに変更したこと以外は実施例5と同様にして、太陽電池を得た。
陰極としての金属チタン薄膜の厚みを表1に記載の厚みに変更し、かつ、多孔質状の電子輸送層を形成する前に、陰極を表1に記載の焼成温度条件で加熱したこと以外は実施例1と同様にして、太陽電池を得た。
多孔質状の電子輸送層を形成する前に、陰極の表面上に、RFスパッタにて厚み30nmの酸化チタンからなる薄膜状の電子輸送層を成膜したこと以外は実施例1と同様にして、太陽電池を得た。
多孔質状の電子輸送層を形成する前に、陰極を表1に記載の焼成温度条件で加熱し、その後、陰極の表面上に、RFスパッタにて厚み30nmの酸化チタンからなる薄膜状の電子輸送層を成膜したこと以外は実施例1と同様にして、太陽電池を得た。
陰極としての金属チタン薄膜の代わりに、表1に記載の金属からなる薄膜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。
多孔質状の電子輸送層を形成する前に、陰極を表1に記載の焼成温度条件で加熱したこと以外は実施例12と同様にして、太陽電池を得た。
多孔質状の電子輸送層を形成する前に、陰極を表1に記載の焼成温度条件で加熱し、その後、陰極の表面上に、RFスパッタにて厚み30nmの酸化チタンからなる薄膜状の電子輸送層を成膜したこと以外は実施例12と同様にして、太陽電池を得た。
陰極としての金属チタン薄膜の代わりに、表1に記載の金属からなる薄膜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。
厚み200nmの金属チタン薄膜を有する基板を酸素濃度10ppm以下のグローブボックス内に入れ、グローブボックス内にてフッ酸処理を行い、金属チタン薄膜表面の酸化膜を除去した。その後、グローブボックス内にて操作を行ったこと以外は実施例1と同様にして、太陽電池を得た。
陰極としての金属チタン薄膜の代わりに、表2に記載の金属からなる薄膜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。
多孔質状の電子輸送層を形成する前に、陰極の表面上に、RFスパッタにて厚み30nmの酸化チタンからなる薄膜状の電子輸送層を成膜したこと以外は比較例3と同様にして、太陽電池を得た。
多孔質状の電子輸送層を形成する前に、陰極を表2に記載の焼成温度条件で加熱し、その後、陰極の表面上に、RFスパッタにて厚み30nmの酸化チタンからなる薄膜状の電子輸送層を成膜したこと以外は実施例3と同様にして、太陽電池を得た。
陰極としての金属チタン薄膜の代わりに、表2に記載の金属からなる薄膜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。
陰極としての金属チタン薄膜の代わりに、表2に記載の透明電極からなる薄膜を用い、かつ、ホール輸送層上に、陽極として抵抗加熱蒸着法により厚み100nmのAu膜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。
多孔質状の電子輸送層を形成する前に、陰極の表面上に、RFスパッタにて厚み30nmの酸化チタンからなる薄膜状の電子輸送層を成膜したこと以外は比較例30と同様にして、太陽電池を得た。
陰極としての金属チタン薄膜の代わりに、表2に記載の透明電極からなる薄膜を用い、かつ、ホール輸送層上に、陽極として抵抗加熱蒸着法により厚み100nmのAu膜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。
多孔質状の電子輸送層を形成する前に、陰極の表面上に、RFスパッタにて厚み30nmの酸化チタンからなる薄膜状の電子輸送層を成膜したこと以外は比較例34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。結果を表1及び2に示した。
得られた太陽電池の陰極について、Arスパッタにより厚み方向(深さ方向)へ掘りながらXPS(X線光電子分光)測定を行い、陰極の表面から、酸素(O)の信号に対するチタン(Ti)の信号の割合が増加し一定になるまでの厚みを計測し、それを酸化層の厚みとした。また、酸素(O)の信号に対するチタン(Ti)の信号の割合が傾斜的に増加している領域を傾斜酸化層の厚みとして計測した。
太陽電池の電極間に電源(KEITHLEY社製、236モデル)を接続し、ソーラーシミュレーション(山下電装社製)を用いて強度100mW/cm2の光を照射し、光電変換効率を測定した。得られた光電変換効率を、実施例1で得られた太陽電池の光電変換効率を1として規格化した。
太陽電池の電極間に電源(KEITHLEY社製、236モデル)を接続し、ソーラーシミュレーション(山下電装社製)を用いて強度100mW/cm2の光を照射した。光照射を開始した直後の光電変換効率と光照射を1時間続けた後の光電変換効率とをそれぞれ測定し、光照射後の光電変換性能維持率(光照射を1時間続けた後の光電変換効率/光照射を開始した直後の光電変換効率)を求めた。
それぞれの実施例及び比較例と同様にして、陰極上に有機無機ペロブスカイト化合物を含む光電変換層を成膜して180℃で焼成を行い、評価サンプルを作製した。評価サンプルにおいて本来の有機無機ペロブスカイト化合物の色である茶色から変色がおこったものを×、茶色のままであったものを○とした。
光電変換効率が実施例1で得られた太陽電池より高く、光劣化試験での光電変換性能維持率が90%以上であり、かつ、光電変換層の腐食評価が「○」であったものを○、いずれか一つでも満たさなかったものを×とした。
2 陰極
3 電子輸送層
31 薄膜状の電子輸送層
32 多孔質状の電子輸送層
4 有機無機ペロブスカイト化合物を含む光電変換層
5 ホール輸送層
6 陽極(パターニングされた電極)
Claims (5)
- 陰極、電子輸送層、光電変換層及び陽極がこの順に積層された構造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、
前記陰極は、チタン材料からなり、少なくとも一方の表面に酸化層を有する
ことを特徴とする太陽電池。 - チタン材料は、金属チタン、金属チタンと他の金属との混合物又はチタン合金であることを特徴とする請求項1記載の太陽電池。
- 酸化層の厚みが1nm以上、1000nm以下であることを特徴とする請求項1又は2記載の太陽電池。
- 酸化層は、チタン材料からなる部分に近づくにつれて厚み方向に酸素原子に対するチタン原子の割合が傾斜的に増加している傾斜酸化層を有することを特徴とする請求項1、2又は3記載の太陽電池。
- 傾斜酸化層の厚みが5nm以上、150nm以下であることを特徴とする請求項4記載の太陽電池。
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Cited By (2)
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20150206663A1 (en) * | 2012-08-13 | 2015-07-23 | Swansea University | Opto-electronic device |
JP2015191997A (ja) * | 2014-03-28 | 2015-11-02 | 新日鉄住金化学株式会社 | 光電変換素子 |
JP2015191913A (ja) * | 2014-03-27 | 2015-11-02 | 株式会社リコー | ペロブスカイト型太陽電池 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9741901B2 (en) * | 2006-11-07 | 2017-08-22 | Cbrite Inc. | Two-terminal electronic devices and their methods of fabrication |
US20110226320A1 (en) * | 2010-03-18 | 2011-09-22 | Patrick Little | Solar cell having a transparent conductive oxide contact layer with an oxygen gradient |
JP4993018B2 (ja) * | 2010-12-07 | 2012-08-08 | 大日本印刷株式会社 | 有機薄膜太陽電池および有機薄膜太陽電池の製造方法 |
US9982511B2 (en) * | 2014-01-03 | 2018-05-29 | Proserv Operations, Inc. | Dirty fluid pressure regulator and control valve |
CN104993061B (zh) * | 2015-06-04 | 2017-05-24 | 华东师范大学 | 一种金属空芯波导太阳能电池的制备方法 |
-
2017
- 2017-02-01 US US15/774,394 patent/US20200251674A1/en not_active Abandoned
- 2017-02-01 AU AU2017215725A patent/AU2017215725A1/en not_active Abandoned
- 2017-02-01 CN CN201780003524.8A patent/CN108140737A/zh active Pending
- 2017-02-01 JP JP2017565579A patent/JP6989391B2/ja active Active
- 2017-02-01 BR BR112018011137-6A patent/BR112018011137A2/ja not_active Application Discontinuation
- 2017-02-01 WO PCT/JP2017/003575 patent/WO2017135293A1/ja active Application Filing
- 2017-02-01 EP EP17747449.1A patent/EP3413366A4/en not_active Withdrawn
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20150206663A1 (en) * | 2012-08-13 | 2015-07-23 | Swansea University | Opto-electronic device |
JP2015191913A (ja) * | 2014-03-27 | 2015-11-02 | 株式会社リコー | ペロブスカイト型太陽電池 |
JP2015191997A (ja) * | 2014-03-28 | 2015-11-02 | 新日鉄住金化学株式会社 | 光電変換素子 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11335514B2 (en) | 2017-09-21 | 2022-05-17 | Sekisui Chemical Co., Ltd. | Solar cell |
WO2022071302A1 (ja) * | 2020-09-30 | 2022-04-07 | 株式会社カネカ | ペロブスカイト薄膜系太陽電池の製造方法 |
Also Published As
Publication number | Publication date |
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JP6989391B2 (ja) | 2022-01-05 |
US20200251674A1 (en) | 2020-08-06 |
EP3413366A1 (en) | 2018-12-12 |
AU2017215725A1 (en) | 2018-05-10 |
BR112018011137A2 (ja) | 2018-11-21 |
CN108140737A (zh) | 2018-06-08 |
JPWO2017135293A1 (ja) | 2018-12-06 |
EP3413366A4 (en) | 2019-09-04 |
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