JP4291973B2 - Photoelectric conversion material and photovoltaic cell - Google Patents
Photoelectric conversion material and photovoltaic cell Download PDFInfo
- Publication number
- JP4291973B2 JP4291973B2 JP2002029524A JP2002029524A JP4291973B2 JP 4291973 B2 JP4291973 B2 JP 4291973B2 JP 2002029524 A JP2002029524 A JP 2002029524A JP 2002029524 A JP2002029524 A JP 2002029524A JP 4291973 B2 JP4291973 B2 JP 4291973B2
- Authority
- JP
- Japan
- Prior art keywords
- carbon
- photoelectric conversion
- electron
- solar cell
- layer
- 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.)
- Expired - Fee Related
Links
- 238000006243 chemical reaction Methods 0.000 title claims description 84
- 239000000463 material Substances 0.000 title claims description 48
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 115
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class 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 claims description 54
- 229910003472 fullerene Inorganic materials 0.000 claims description 51
- 239000003504 photosensitizing agent Substances 0.000 claims description 48
- 229910052799 carbon Inorganic materials 0.000 claims description 44
- 229920005989 resin Polymers 0.000 claims description 44
- 239000011347 resin Substances 0.000 claims description 44
- 239000002041 carbon nanotube Substances 0.000 claims description 30
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 30
- -1 fullerenes fullerenes Chemical class 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 28
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 239000011159 matrix material Substances 0.000 claims description 17
- 230000004048 modification Effects 0.000 claims description 11
- 238000012986 modification Methods 0.000 claims description 11
- 150000004032 porphyrins Chemical class 0.000 claims description 9
- 229920003026 Acene Polymers 0.000 claims description 7
- 229920000767 polyaniline Polymers 0.000 claims description 5
- 239000013522 chelant Substances 0.000 claims description 4
- 239000000370 acceptor Substances 0.000 description 35
- 229920001940 conductive polymer Polymers 0.000 description 22
- 238000004611 spectroscopical analysis Methods 0.000 description 17
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 17
- 229910052721 tungsten Inorganic materials 0.000 description 17
- 239000010937 tungsten Substances 0.000 description 17
- 239000011248 coating agent Substances 0.000 description 16
- 239000010439 graphite Substances 0.000 description 15
- 229910002804 graphite Inorganic materials 0.000 description 15
- 230000006870 function Effects 0.000 description 14
- 230000003287 optical effect Effects 0.000 description 13
- 238000000926 separation method Methods 0.000 description 12
- 239000000758 substrate Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 9
- 230000004044 response Effects 0.000 description 9
- 239000000969 carrier Substances 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 8
- 230000002165 photosensitisation Effects 0.000 description 8
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- 239000010408 film Substances 0.000 description 7
- 239000012212 insulator Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 230000001443 photoexcitation Effects 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 5
- 229920000265 Polyparaphenylene Polymers 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 125000005647 linker group Chemical group 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- HCIIFBHDBOCSAF-UHFFFAOYSA-N octaethylporphyrin Chemical compound N1C(C=C2C(=C(CC)C(C=C3C(=C(CC)C(=C4)N3)CC)=N2)CC)=C(CC)C(CC)=C1C=C1C(CC)=C(CC)C4=N1 HCIIFBHDBOCSAF-UHFFFAOYSA-N 0.000 description 4
- 229920001197 polyacetylene Polymers 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 229920003067 (meth)acrylic acid ester copolymer Polymers 0.000 description 3
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 3
- 150000004696 coordination complex Chemical class 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 238000002715 modification method Methods 0.000 description 3
- 238000005325 percolation Methods 0.000 description 3
- 108091008695 photoreceptors Proteins 0.000 description 3
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound 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
- 238000005240 physical vapour deposition Methods 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 238000001771 vacuum deposition Methods 0.000 description 3
- GZEFZLXJPGMRSP-UHFFFAOYSA-N 37,38,39,40-tetrazanonacyclo[28.6.1.13,10.112,19.121,28.04,9.013,18.022,27.031,36]tetraconta-1(37),2,4,6,8,10,12(39),13,15,17,19,21,23,25,27,29,31,33,35-nonadecaene Chemical compound c1ccc2c3cc4[nH]c(cc5nc(cc6[nH]c(cc(n3)c2c1)c1ccccc61)c1ccccc51)c1ccccc41 GZEFZLXJPGMRSP-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
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 2
- 239000004985 Discotic Liquid Crystal Substance Substances 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical class NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 206010034972 Photosensitivity reaction Diseases 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical class CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical compound CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical class 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- ZQBFAOFFOQMSGJ-UHFFFAOYSA-N hexafluorobenzene Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1F ZQBFAOFFOQMSGJ-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002121 nanofiber Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- JZRYQZJSTWVBBD-UHFFFAOYSA-N pentaporphyrin i Chemical compound N1C(C=C2NC(=CC3=NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 JZRYQZJSTWVBBD-UHFFFAOYSA-N 0.000 description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 2
- 229920006380 polyphenylene oxide Polymers 0.000 description 2
- 229920000123 polythiophene Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- GUEIZVNYDFNHJU-UHFFFAOYSA-N quinizarin Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(O)=CC=C2O GUEIZVNYDFNHJU-UHFFFAOYSA-N 0.000 description 2
- 238000005063 solubilization Methods 0.000 description 2
- 230000007928 solubilization Effects 0.000 description 2
- 229920003066 styrene-(meth)acrylic acid ester copolymer Polymers 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- BTRWUZQEZSPCPS-UHFFFAOYSA-N 1,2,3,4,5,6,7,8,9,10-decafluorophenanthrene Chemical compound FC1=C(F)C(F)=C2C3=C(F)C(F)=C(F)C(F)=C3C(F)=C(F)C2=C1F BTRWUZQEZSPCPS-UHFFFAOYSA-N 0.000 description 1
- ZRQXDCFMDRAOSA-UHFFFAOYSA-N 1,2,3,4,5,6,7,8,9,10-decafluoropyrene Chemical compound FC1=C(F)C(F)=C2C(F)=C(F)C3=C(F)C(F)=C(F)C4=C(F)C(F)=C1C2=C43 ZRQXDCFMDRAOSA-UHFFFAOYSA-N 0.000 description 1
- JDCMOHAFGDQQJX-UHFFFAOYSA-N 1,2,3,4,5,6,7,8-octafluoronaphthalene Chemical compound FC1=C(F)C(F)=C(F)C2=C(F)C(F)=C(F)C(F)=C21 JDCMOHAFGDQQJX-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical group C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- UOFGSWVZMUXXIY-UHFFFAOYSA-N 1,5-Diphenyl-3-thiocarbazone Chemical class C=1C=CC=CC=1N=NC(=S)NNC1=CC=CC=C1 UOFGSWVZMUXXIY-UHFFFAOYSA-N 0.000 description 1
- KMHSUNDEGHRBNV-UHFFFAOYSA-N 2,4-dichloropyrimidine-5-carbonitrile Chemical compound ClC1=NC=C(C#N)C(Cl)=N1 KMHSUNDEGHRBNV-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- UZVMVUUAAXJDIL-UHFFFAOYSA-N 37,38,39,40-tetrazanonacyclo[28.6.1.13,10.112,19.121,28.04,9.013,18.022,27.031,36]tetraconta-1(37),2,4,6,8,10,12(39),13,15,17,19,21,23,25,27,29,31,33,35-nonadecaene zinc Chemical compound [Zn].N1C(C=C2C3=CC=CC=C3C(C=C3C4=CC=CC=C4C(=C4)N3)=N2)=C(C=CC=C2)C2=C1C=C1C2=CC=CC=C2C4=N1 UZVMVUUAAXJDIL-UHFFFAOYSA-N 0.000 description 1
- FXPOCCDGHHTZAO-UHFFFAOYSA-N 4-methyl-1h-pyrrole-3-carboxylic acid Chemical compound CC1=CNC=C1C(O)=O FXPOCCDGHHTZAO-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 101710158075 Bucky ball Proteins 0.000 description 1
- 125000003184 C60 fullerene group Chemical group 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004471 Glycine Chemical class 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- HKESYQYIAZTIFI-UHFFFAOYSA-N [Mg].N1C(C=C2C3=CC=CC=C3C(C=C3C4=CC=CC=C4C(=C4)N3)=N2)=C(C=CC=C2)C2=C1C=C1C2=CC=CC=C2C4=N1 Chemical compound [Mg].N1C(C=C2C3=CC=CC=C3C(C=C3C4=CC=CC=C4C(=C4)N3)=N2)=C(C=CC=C2)C2=C1C=C1C2=CC=CC=C2C4=N1 HKESYQYIAZTIFI-UHFFFAOYSA-N 0.000 description 1
- 239000011354 acetal resin Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000006208 butylation Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 239000000412 dendrimer Substances 0.000 description 1
- 229920000736 dendritic polymer Polymers 0.000 description 1
- JGUQDUKBUKFFRO-CIIODKQPSA-N dimethylglyoxime Chemical class O/N=C(/C)\C(\C)=N\O JGUQDUKBUKFFRO-CIIODKQPSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- QGEOKXWFGANCJL-UHFFFAOYSA-N ethenyl acetate;hydrochloride Chemical compound Cl.CC(=O)OC=C QGEOKXWFGANCJL-UHFFFAOYSA-N 0.000 description 1
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000004525 petroleum distillation Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920000414 polyfuran Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical class C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- WHRNULOCNSKMGB-UHFFFAOYSA-N tetrahydrofuran thf Chemical compound C1CCOC1.C1CCOC1 WHRNULOCNSKMGB-UHFFFAOYSA-N 0.000 description 1
- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- HEPBQSXQJMTVFI-UHFFFAOYSA-N zinc;butane Chemical compound [Zn+2].CCC[CH2-].CCC[CH2-] HEPBQSXQJMTVFI-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Theoretical Computer Science (AREA)
- Mathematical Physics (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Hybrid Cells (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Photovoltaic Devices (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、電子供与体、電子受容体、電子輸送体及び必要により光増感剤で構成された光電変換材料およびそれを用いた光電池（太陽電池など）に関する。
【０００２】
【従来の技術】
現在実用化されている太陽電池には、シリコン系光電変換材料と化合物半導体系光電変換材料が主に使用されており、有機系光電変換材料は余り使用されていない。一方、1977年に導電性ポリアセチレンが発見されて以来、有機薄膜を利用した太陽電池の研究も盛んに行われている。しかし、有機系材料を用いた太陽電池は、一般に、安定性が低く、しかもエネルギー変換率が低い。
【０００３】
特開平１０−８１７５４号公報には、ビピリジル単位を有する金属錯体で構成され、可視光領域および近赤外領域でも感光性を有する金属錯体ポリマーが開示されている。しかし、この金属錯体ポリマーは構造が複雑であるとともにビピリジル単位に対して配位する特殊な配位子を用いる必要がある。
【０００４】
特開平９−７３１８０号公報には、炭素数７０以上の基本骨格を有するカーボンクラスターなどの非晶質フラーレンおよびその誘導体の少なくとも一種と、この非晶質フラーレンが分散したマトリックスポリマーとで構成された光導電体が開示されている。この文献には、導電性支持体と、この導電性支持体上に形成された電荷輸送層および前記光導電体からなる電荷発生層とを備えた感光体も開示されている。これらの光電変換材料は、太陽電池などの光電池、感光体などの感光材料として有用である。しかし、この材料に対しても、さらに高い光電変換効率が求められている。
【０００５】
特開２０００−２６１０１６号公報には、Ｃ60，Ｃ70などの球殻状炭素分子を電子受容体として内包した化合物（例えば、フェロセンなどの有機金属錯体単位と、ポルフィリン単位と、フラーレン単位とが順次リンカーで結合した化合物）で構成された光電荷分離材料が開示されている。この文献には、電子供与体、光増感剤および電子受容体を三次元的に配置し、光励起による電荷分離状態に方向性を付与した光電荷分離材料と、この光電荷分離材料で構成された光電池も開示されている。しかし、前記光電荷分離材料は、フラーレンなどの球殻状炭素分子を電子受容体として内包させる必要があるため、構造が複雑化し、光電荷分離材料や光電池を高い生産性で工業的に有利に製造することが困難である。
【０００６】
【発明が解決しようとする課題】
従って、本発明の目的は、高い光電変換機能を有し、大面積化、薄膜化、軽量化やコストダウンが可能な光電変換材料およびそれを用いた光電池を提供することにある。
【０００７】
本発明の他の目的は、構造が簡単であり、かつ高い安定性および変換効率を有する光電変換材料およびそれを用いた光電池を提供することにある。
【０００８】
【課題を解決するための手段】
本発明者らは、前記課題を達成するため鋭意検討した結果、フラーレン類などの球殻状炭素が電子受容体として有効に機能するとともに、カーボンナノチューブ類などの線状又は筒状炭素が電荷輸送体として有効に機能すること、また、平面的（又は二次元的構造）かつ線状の炭素（例えば、グラファイトリボンなど）が、電子受容体と電荷輸送体としての両機能を有することを見いだし、本発明を完成した。
【０００９】
すなわち、本発明の光電変換材料は、電子供与体と、球殻状炭素と、線状又は筒状炭素とを含む。光電変換材料は、さらに光増感剤を含んでいてもよい。光電変換材料において、前記各成分（電子供与体、球殻状炭素、線状又は筒状炭素および必要により光増感剤）の配置又は配列状態は、電子供与体からのキャリア（電子又は正孔）が電子輸送体に効率よく輸送される限り特に制限されず、例えば、電子供与体と電子輸送体との間に光増感剤が介在し、かつ電子受容体がキャリア（電子、正孔）を電荷輸送体に付与可能な形態で、それぞれの成分が二次元的又は三次元的に配置又は配向していてもよい。より具体的には、二次元的構造の光電変換材料は、例えば、電子供与体を含む電子供与層と、この電子供与層上に形成され、かつ電子受容体と電子輸送体（又は電荷輸送体）とを含む電荷輸送層とで構成してもよい。また、電子供与体を含む電子供与層と、この電子供与層上に形成され、かつ光増感剤を含む光増感層と、この光増感層上に形成され、かつ電子受容体と電子輸送体（又は電荷輸送体）とを含む電荷輸送層とで構成してもよい。このような二次元的構造の光電変換材料において、電子供与層および電荷輸送層は球殻状の炭素を含んでいてもよく、電子供与層と電荷輸送層との間には球殻状炭素の濃度差を形成してもよい。例えば、電子供与層における球殻状炭素の濃度は電荷輸送層よりも小さくてもよい。
【００１０】
前記球殻状の炭素としては、フラーレン類、その修飾体、金属内包物などが例示でき、線状又は筒状炭素としては、チューブ状、繊維状またはリボン状の形態の炭素、例えば、カーボンナノチューブ、グラファイトナノファイバー、グラファイトリボン、フィブリル、グラファイト層間化合物、それらの修飾体などが例示できる。さらに、光増感剤としては、π電子系化合物、例えば、ポルフィリン類、金属キレート化合物、ポリアニリン類、芳香族多環化合物、ポリアセン系骨格構造を有する化合物などが例示できる。
【００１１】
前記光電変換材料は、高い光電変換効率を有しており、安定性も高い。そのため、本発明は、前記光電変換材料で構成された種々の素子又はユニット、例えば、光電池（太陽電池など）も包含する。
【００１２】
【発明の実施の形態】
本発明の光電変換材料の特色は、球殻状炭素と線状又は筒状炭素とを組み合わせている点にある。前記球殻状炭素は電子受容体として機能させることができ、線状又は筒状炭素は電荷輸送体として機能させることができる。また、平面的（又は二次元的構造）で、しかも線状の炭素（例えば、グラファイトリボンなど）は、電子受容体と電荷輸送体との両機能を兼ね備える。
【００１３】
球殻状炭素には、フラーレン類、その修飾体、金属内包物などが挙げられる。これらの球殻状炭素は、単独で又は二種以上組み合わせて使用できる。フラーレン類としては、種々の立体構造を有するカーボンクラスター、例えば、Ｃ60、Ｃ70、Ｃ74、Ｃ76、Ｃ78、Ｃ82、Ｃ84、Ｃ720、Ｃ860などのフラーレン類などが挙げられる。フラーレン類の形態は、例えば、サッカーボール状、バッキーボール状などであってもよい。
【００１４】
フラーレン類は置換基の導入などにより修飾されていてもよい。修飾方法は、特に限定されず、例えば、フラーレン類の反応性に富む炭素５員環部を化学的に修飾できる。置換基の種類は、特に限定されず、例えば、アルキル基（メチル基、ｔ−ブチル基などのＣ1-10アルキル基など）、アリール基（フェニル基など）、アラルキル基（ベンジル基など）、ジオキソラン単位、ハロゲン又は酸素原子などが例示でき、液晶ポリマー、色素類、ポリエチレンオキシドなどの導入により修飾してもよい。フラーレン類の修飾により、溶媒、高分子への可溶化や親和性の改善、フラーレン類の配列又は配向を可能にする。
【００１５】
金属を内包したフラーレン類としては、種々の金属、例えば、周期表第１Ａ族元素（Ｋ、Ｎａ、Ｒｂなど）、周期表第２Ａ族元素、ランタノイド族元素（Ｌａなど）などの金属がドープされたフラーレン類が例示できる。ドーパントとしての金属は単独で又は二種以上組み合わせてドープとしてもよい。これらの金属内包フラーレン類は、単独で又は二種以上組み合わせて使用してもよい。
【００１６】
線状又は筒状炭素には、チューブ状、繊維状またはリボン状の形態の炭素が含まれる。このような炭素としては、例えば、カーボンナノチューブ、カーボンナノコイル、グラファイトナノファイバー（又はカーボンナノファイバー）、グラファイトリボン、フィブリル、グラファイト層間化合物などが例示できる。これらの炭素材は単独で又は二種以上組み合わせて使用できる。
【００１７】
好ましい線状又は筒状炭素は、チューブ状又はリボン状、例えば、カーボンナノチューブ類、グラファイトリボン類である。カーボンナノチューブ類は、単層カーボンナノチューブ、多層カーボンナノチューブであってもよく、バッキーオニオン（bucky-onion）構造を有していてもよい。
【００１８】
カーボンナノチューブ類などの線状又は筒状炭素の平均直径は、例えば、０．７〜３００ｎｍ、好ましくは０．７〜２５０ｎｍ、さらに好ましくは１〜２５０ｎｍ、特に５〜２５０ｎｍ程度であってもよい。なお、前記平均直径は、リボン状の形態の炭素では、平均厚み又は平均幅を意味する。
【００１９】
溶媒、高分子への可溶化や親和性の改善、線状又は筒状炭素の配列又は配向を制御するため、カーボンナノチューブ類などの炭素は、前記フラーレン類と同様に、置換基の導入などにより修飾してもよい。修飾方法および置換基の種類は、前記フラーレン類と同様である。なお、カーボンナノチューブ類には、金属内包フラーレン類と同じく、金属をドープしてもよい。グラファイトリボンなどの平面的（二次元的構造）でしかも線状の炭素は構造的にエッジ部分を多く含むため、置換基の導入、修飾や金属内包が容易である。
【００２０】
電子供与体（正孔受容体又は電子発生剤）としては、特に限定されないが、導電性高分子であり、かつｐ型半導体としての機能を有する高分子が望ましい。このような電子供与体としては、ＰＴ［ポリ（３−アルキルチオフェン）］などのポリチオフェン系樹脂、ＰＰＶ［ポリ（Ｐ−フェニレンビニレン）］，ＯＯＰＶ［ポリ（２，５−ジオクチルオキシ−Ｐ−フェニレンビニレン）］，ＰＥＤＯＴ［ポリ（２，３−ジヒドロチエノ）［３，４−ｂ］-１，４−ジオキン］，ＰＳＳ［ポリ（スチレンスルホネート）］などのポリフェニレンビニレン系樹脂、ポリフェニレン系樹脂（例えば、ポリ（ｐ−フェニレン）系樹脂、ポリ（ｍ−フェニレン）系樹脂）やそれらの置換体などが挙げられる。
【００２１】
光増感剤としては、例えば、アンテナ分子、すなわち光を有効に吸収して他の物質に電子、正孔をトランスファーする化合物であればよく、例えば、π電子系化合物（ポルフィリン類、金属キレート化合物、ポリアニリン、芳香族多環化合物、ポリアセン系骨格構造を有する化合物など）、異種元素を含むπ電子系化合物（カルバゾールなど）、ハロゲン化されたπ電子系化合物、キニザリン又はその誘導体などが例示できる。ポルフィリン類としては、ポルフィリン骨格を有する種々の化合物、例えば、ポルフィリン、フタロシアニン、金属フタロシアニン（鉄フタロシアニンなどの遷移金属を含むフタロシアニン）、テトラベンゾポルフィリン又はテトラフェニルポルフィリン又はその誘導体〔金属テトラベンゾポルフィリン（亜鉛−テトラベンゾポルフィリン、マグネシウム−テトラベンゾポルフィリンなど）、テトラキスペンタフルオロフェニルポルフィリンなど〕などが例示される。金属キレート化合物としては、例えば、ジメチルグリオキシム、ジチゾン、オキシン、アセチルアセトン、グリシン、ＥＤＴＡ（エチレンジアミン四酢酸）、ＮＴＡなどの金属塩（例えば、遷移金属塩）などが例示できる。
【００２２】
芳香族多環化合物としては、石油蒸留残渣、ナフサ熱分解残渣、エチレンボトム油、石炭液化油、コールタールなどの石油系又は石炭系重質油、ナフタレンなどの縮合によって合成された多環式炭化水素類、これら炭化水素類の構造中にヘテロ原子（窒素原子、イオウ原子、ホウ素原子、リン原子、酸素原子など）が導入された多環式炭化水素類、さらに前記残渣からの溶剤抽出などにより得られる多環式炭化水素類などが例示される。
【００２３】
ポリアセン系骨格構造を有する化合物は、特開昭６０−１７０１６３号公報に記載されている芳香族炭化水素化合物とアルデヒド類との縮合物の熱処理物であって、水素原子／炭素原子の原子比が０．０５〜０．５である。
【００２４】
ハロゲン原子を有する化合物としては、特に限定されず、例えば、フッ化炭化水素類、フッ化芳香族多環化合物（フッ化ピッチなど）、重質油フッ化物、六フッ化ベンゼン、オクタフルオロナフタレン、デカフルオロフェナンスレン、デカフルオロピレンなど）、これらに対応する塩化炭化水素類、臭化炭化水素類、ヨウ素化炭化水素類などが例示できる。これらのハロゲン化物のうちフッ化ピッチが好ましい。これらのハロゲン化物は単独で又は二種以上組み合わせて使用できる。
【００２５】
なお、ポルフィリン類は、ポルフィリンデンドリマーとして使用でき、ポリアニリンも化学結合により電子供与体、電子受容体、電子輸送体に結合させて使用できる。
【００２６】
前記成分で構成された光電変換材料は、高安定性および高エネルギー変換率を実現する。すなわち、光励起により電子供与体から電子受容体へ電子が移動するとともに、電子供与体へ正孔が移動し、電荷分離状態が効率よく生成する。例えば、光増感剤の光励起により光増感剤から電子受容体へ電子が移動するとともに、光増感剤から電子供与体へ正孔が移動し、電荷分離状態を効率よく形成できる。しかも、線状又は筒状炭素の電子輸送体により、電荷分離状態に方向性を与えることができる。そのため、失活することなく、電荷を輸送でき、高い安定性および光電変換効率が得られるものと思われる。
【００２７】
このような光電変換材料では、フラーレン類、カーボンナノチューブ類などの炭素材には構造的特異性とともに多くのπ電子系が存在するためか、光との強い相互作用、分子間電荷移動、電子輸送現象などが生じ、高い効率で光電変換機能が発現するものと思われる。例えば、光増感剤は、光励起によりキャリア又は電荷（電子と正孔）を生成し、電子受容体へ電子を与えるとともに、電子供与体へ正孔を与える。そのため、光増感剤は、キャリア又は電荷（電子と正孔）を分離する機能を有しており、後続反応に利用可能な電荷分離状態を効率よく生成させる。このように、光増感剤により、生成した電荷（電子と正孔）を分離して輸送できるため、ｐｎ接合面での電荷発生によるシリコン系半導体と比較して、高い光電変換効率が得られる。しかも、カーボンナノチューブ類などの線状または筒状炭素は少量の添加で方向性のあるパーコレーション伝導路を形成する。そのため、電子輸送体は、電荷輸送に極めて有効であり、電荷を失活させることなく輸送できるものと思われる。
【００２８】
前記各成分は、物理的又は化学的蒸着法、リソグラフィ技術などを利用して光電変換材料又は光電変換素子を形成してもよく、マトリックス樹脂と複合化して光電変換材料又は光電変換素子を形成してもよい。マトリックス樹脂としては、例えば、ポリオレフィン系樹脂（ポリエチレン系樹脂、ポリプロピレン系樹脂、エチレン−酢酸ビニル共重合体、エチレン−（メタ）アクリル酸エステル共重合体など）、酢酸ビニル系樹脂（酢酸ビニル−塩化ビニル共重合体、酢酸ビニル−（メタ）アクリル酸エステル共重合体など）、（メタ）アクリル系樹脂（ポリメタクリル酸メチル、メタクリル酸メチル−（メタ）アクリル酸エステル共重合体、メタクリル酸メチル−スチレン−（メタ）アクリル酸エステル共重合体など）、ポリスチレン系樹脂（ポリスチレン、スチレン−（メタ）アクリル酸エステル共重合体、スチレン−（メタ）アクリル酸共重合体、スチレン−無水マレイン酸共重合体など）、塩化ビニル系樹脂、ポリエステル系樹脂（ポリアリレート系樹脂を含む）、ポリアミド系樹脂、ポリカーボネート系樹脂、ポリビニルアルコール系樹脂、ポリビニルアセタール系樹脂（ポリビニルブチラール系樹脂など）、ポリスルホン系樹脂、ポリフェニレンオキシド系樹脂などが例示できる。これらのマトリックス樹脂は単独で又は二種以上組み合わせて使用できる。
【００２９】
マトリックス樹脂としては、導電性高分子、ポリアセン系骨格構造を有する化合物などが好ましい。導電性高分子としては、例えば、ポリアセチレン系高分子（ポリアセチレンなどの溶媒不溶性樹脂、フェニルアセチレンなどを用いた溶媒可溶性ポリアセチレン系樹脂など）、ポリフェニレン系高分子（例えば、ポリ（ｐ−フェニレン）系樹脂、ポリ（ｍ−フェニレン）系樹脂、ポリ（ｐ−フェニレンビニレン）などのポリフェニレンビニレン系樹脂、ポリフェニレンスルフィド系樹脂、ポリフェニレンオキシド系樹脂など）、複素環式高分子（ポリピロール、ポリ（３−アルキルチオフェン）などのポリチオフェン系樹脂、ポリフラン系樹脂、ポリセレノフェン系樹脂、ポリテルロフェン系樹脂など）、イオン性高分子（ポリアニリン系樹脂、ポリ（３−メチル−４−カルボキシピロール）などのピロール系樹脂など）、はしご型高分子などが例示できる。導電性高分子としては、通常、溶媒可溶性樹脂が使用される。なお、マトリックス樹脂の種類は特に制限されず、電子供与層や電荷輸送層などの層の機能に応じて選択でき、電子供与層としてはｐ型導電性高分子を用いる場合が多く、電荷輸送層としてはｎ型導電性高分子を用いる場合が多い。
【００３０】
ポリアセン系骨格構造を有する化合物には、例えば、光増感剤の項で記載した前記ポリアセン系骨格構造を有する化合物が含まれる。
【００３１】
なお、ディスコティック液晶を電子供与体に用いると、カラム構造に配列し、正孔や電子の輸送に効果的である。
【００３２】
マトリックス樹脂として、ｐ型半導体的性質を有する導電性高分子を用いると、フラーレン類は電子供与体を取り込んでｎ型半導体的性質を有する電荷移動型物質となりやすい。さらに、フラーレン類と導電性高分子との複合体は、特に光に対して大きな応答を示す。このことは、シリコン系半導体のｐｎ接合素子とは異なる光誘起電荷移動で説明されるドナー−アクセプター型素子を形成していることに起因すると思われ、光照射により複合体全体で励起子が発生する。そのため、導電性高分子との組合せにおいて、電子供与体としてフラーレン類などを用いることにより、効率よくキャリア（電子、正孔）を生成する。
【００３３】
本発明の光電変換材料において、電子供与体、電子受容体および電子輸送体で構成されていればよく、光増感剤を含有していてもよい。このような光電変換材料は各成分の複合体（又は混合組成物）であってもよい。好ましい態様において、各成分は、互いに関連付けて、二次元的（層状）又は三次元的に配置できる。例えば、それぞれの成分が二次元的又は三次元的に配置、結合又は配向した構造において、電子供与体と電子輸送体との間に、電子受容体がキャリア（電子）を電荷輸送体に付与可能な形態で配置、結合又は配向していてもよく、電子供与体と電子輸送体との間に光増感剤が介在し、かつ電子受容体はキャリア（電子）を電荷輸送体に付与可能な形態で配置、結合又は配向していてもよい。
【００３４】
好ましい態様では、光増感剤の光励起により生成したキャリア又は電荷（電子又は正孔）を分離して効率よく移動させるため、光増感剤には、キャリアを輸送可能な形態で、電子供与体が結合又は近接（又は配向）しているとともに、電子受容体（球殻状炭素）も結合又は近接（又は配向）している。さらに、電荷輸送体（線状又は筒状炭素）は、キャリアを輸送可能な形態で、少なくとも前記電子受容体（球殻状炭素）と結合又は近接（又は配向）しており、電荷輸送体（線状又は筒状炭素）は、光増感剤を介して、キャリアを輸送可能な形態で、前記電子供与体および前記電子受容体（球殻状炭素）と結合又は近接（又は配向）していてもよい。このような光電変換材料としては、例えば、下記式で表される複合体が例示できる。
【００３５】
Ｅd−Ｌ1−Ｐ−Ｌ2−Ｅａ−（Ｃt）
（式中、Ｅdは電子供与体、Ｐは光増感剤、Ｅａは電子受容体、Ｃtは電荷輸送体を示し、Ｅａ−（Ｃt）は電子受容体Ｅａと電荷輸送体Ｃｔとが結合、近接又は配向していることを示す。Ｌ1およびＬ2はそれぞれ同一又は異なって、電子供与体Ｅd、光増感剤Ｐ、電子受容体Ｅａを連結するリンカーを示す）
なお、前記各成分を結合させるためのリンカーとしては、慣用の反応を利用して形成される結合、例えば、直接結合、アミド結合、エステル結合、ウレタン結合、エーテル結合などが利用できる。なお、これらのリンカーの一例としては、例えば、特開２０００−２６１０１６号公報などを参照できる。
【００３６】
好ましい態様において、光電変換材料（又は光電変換素子）は、二次元的な層構造（積層構造）を有している。このような積層構造は、例えば、電子供与体を含む電子供与層と、この電子供与層上に形成された電子輸送層とで構成された積層構造を有している。この電子輸送層は、通常、電子受容体（球殻状炭素など）と電子輸送体（線状又は筒状炭素など）とを含んでいる。特に、電子供与体を含む電子供与層と、この電子供与層上に形成され、かつ光増感剤を含む光増感層と、この光増感層上に形成され、かつ電子受容体と電子輸送体とを含む電荷輸送層とで構成された構造を含む。なお、光増感層の光増感剤は、電子供与層と電荷輸送層との界面近傍に分散していてもよい。
【００３７】
このような層構造の光電変換材料において、電子供与層および電荷輸送層は、球殻状の炭素を含んでいてもよい。また、電子供与層および電荷輸送層での球殻状の炭素の濃度は異なっていてもよい。例えば、電子供与層における球殻状炭素の濃度は、電荷輸送層での球殻状炭素の濃度より小さくてもよい。例えば、電子供与層と電荷輸送層との球殻状炭素の含有量の差は、例えば、１〜８０重量％、好ましくは５〜７０重量％（例えば、１０〜５０重量％）程度であってもよい。電子供与層中の球殻状炭素の含有量は１０重量％以下（例えば、０〜１０重量％、特に０〜７重量％程度）、電荷輸送層中の球殻状炭素の含有量は１０重量％以上（例えば、１０〜７０重量％程度）であってもよい。
【００３８】
前記層構造の光電変換材料又は素子において、種々の製膜法、例えば、スパッタリング、蒸着などの化学的又は物理的蒸着法、前記マトリックス樹脂（導電性高分子など）を利用するコーティング法、これらの方法を組み合わせた方法などにより各層を形成してもよい。例えば、基板上に、電子供与体と必要により球殻状炭素とマトリックス樹脂とを含む塗布液をコーティングして電子供与層を形成し、光増感剤とマトリックス樹脂とを含む塗布液をコーティングして光増感層を形成し、電子受容体と電子輸送体とマトリックス樹脂とを含む塗布剤をコーティングすることにより電荷輸送層を形成できる。また、所望の層（例えば、光増感層など）は必要により化学的又は物理的蒸着法により形成してもよい。
【００３９】
電子供与層における球殻状炭素の割合は、マトリックス樹脂１００重量部に対して、例えば、０．０１〜１０重量部、好ましくは０．１〜９重量部、さらに好ましくは１〜８重量部程度である。
【００４０】
光増感層において、全体１００重量部に対する光増感剤の割合は、例えば、１〜１００重量部、好ましくは２〜１００重量部、さらに好ましくは５〜１００重量部程度である。
【００４１】
電荷輸送層において、全体１００重量部に対する電子受容体（球殻状炭素）の割合は、例えば、１０重量部以上（例えば、１０〜２００重量部程度）、好ましくは１５重量部以上（例えば、１５〜１５０重量部程度）、さらに好ましくは２０重量部以上（例えば、２０〜１２０重量部程度）であり、電子輸送体（線状又は筒状炭素）の割合は、例えば、０．１重量部以上（例えば、０．５〜１００重量部程度）、好ましくは１重量部以上（例えば、１〜５０重量部程度）、さらに好ましくは２重量部以上（例えば、２〜３０重量部程度）である。
【００４２】
さらに、電子供与層の厚みは、例えば、５ｎｍ〜３００μｍ（例えば、５ｎｍ〜３０μｍ）、好ましくは５０ｎｍ〜５０μｍ、さらに好ましくは５０ｎｍ〜３０μｍ程度である。光増感層の厚みは、例えば、５ｎｍ〜５０μｍ、好ましくは５ｎｍ〜５μｍ、さらに好ましくは５ｎｍ〜１μｍ程度である。電荷輸送層の厚みは、例えば、５ｎｍ〜３００μｍ（例えば、５ｎｍ〜３０μｍ）、好ましくは５０ｎｍ〜５０μｍ、さらに好ましくは５０ｎｍ〜３０μｍ程度である。
【００４３】
前記基板は、光電変換材料の種類や用途に応じて、前記成分や層が吸着や化学結合などにより物理的又は化学的に結合できる基板、例えば、導電体、半導体、絶縁体（例えば、金、銀、銅、アルミニウムなどの導電性金属、酸化スズ、酸化インジウム、酸化亜鉛、ＩＴＯなどの透明導電体又は半導電体、シリコンなどの半導電体又は絶縁体、ガラス、プラスチックフィルムなどの透明絶縁体、導電性、半導電性又は絶縁性セラミックスなど）などから適当に選択できる。
【００４４】
なお、基板は、光電変換素子（例えば、太陽電池などの光電池）の電極として使用することもできる。この場合には、光の入射側の電極には透明導電体又は半導電体が使用でき、反対側の電極には金属などの導電性金属などが使用できる。また、光の入射側の透明導電体は透明基板（ガラス板など）で保護してもよい。
【００４５】
前記塗布液の溶媒としては、例えば、アルコール類、エステル類、ケトン類、エーテル類、アミド類、硫黄含有化合物（スルホキシド類を含む）、ハロゲン化炭化水素類、炭化水素類などが挙げられ、溶媒は混合溶媒として使用してもよい。なお、芳香族炭化水素類（ベンゼン、トルエン）、脂環族炭化水素類（シクロヘキサンなど）、脂肪族炭化水素類（ノルマルヘキサンなど）、ハロゲン化炭化水素類（塩化メチレン、クロロホルム、トリクロロエチレンなど）、二硫化炭素などは、フラーレン類、ナノチューブ類に対する溶解量が多いために好適である。
【００４６】
なお、コーティングには、例えば、スピンコーティング法、スプレーコーティング法、ロールコーティング法、蒸着法などの慣用の方法が採用でき、塗布液をコーティングした後、乾燥することにより層構造を有する光電変換材料を得ることができる。
【００４７】
より具体的には、層状構造の光電変換素子において、電子供与層は、低濃度（例えば、１０重量％以下）のフラーレン類（Ｃ60など）と、マトリックス樹脂（チオフェン系樹脂、フェニレン系樹脂などの導電性高分子、特にｐ型導電性高分子）とで形成できる。この電子供与層は、電荷輸送性化合物（例えば、正孔を輸送可能なディスコティック液晶など）をパーコレーション濃度前後で含んでいてもよい。
【００４８】
光増感層は、電荷分離を生成させるため、電子供与層と電荷輸送層との間に介在していればよく、電子供与層と電荷輸送層との界面において光増感剤が分散していてもよい。また、光増感剤の種類や層又は分散形態などにより、光電変換素子のスペクトル特性を改善できる。
【００４９】
電子輸送層は、例えば、フラーレン類（Ｃ60など）と、カーボンナノチューブ類と、マトリックス樹脂（導電性高分子、特にｎ型導電性高分子）とで形成できる。この電子輸送層には、カーボンナノチューブ類と同様に電荷輸送性化合物をパ−コレーション閾値以上の濃度で含んでいてもよい。この場合、フラーレン類（Ｃ60フラーレンなど）とともに、導電性高分子との間で光誘起電荷移動を生じる化合物を用いてもよい。
【００５０】
本発明の光電変換材料および光電変換素子又はデバイスは、光電変換機能、増幅機能、光整流機能などを利用した種々の光電変換デバイス、電光変換デバイス又はオプトエレクトロニクスデバイスへの幅広い応用が可能である。例えば、電子素子又は光電変換素子（ダイオード、整流素子、フォトダイオード、光センサ、光スイッチ、トランジスタ、ＦＥＴ、ホログラフィック素子など）、光電池（太陽電池など）、光起電力素子、光記録材（電子写真方式での感光体、光導電性トナー、光メモリなど）などとして有用である。特に、光電変換効率が高く、しかも安定しているため、光電池の光電変換素子として適している。しかも、光電変換デバイスは、大面積化、薄膜化、軽量化やコストダウンが可能であるため、壁や窓などにも適用でき、次世代の太陽電池の光電変換素子として利用できる。
【００５１】
【発明の効果】
本発明では、球殻状炭素と線状又は筒状炭素とを組み合わせているため、光電変換機能が高い。また、大面積化、薄膜化、軽量化やコストダウンが可能である。しかも、簡単な構造で、高い安定性および変換効率を示す。そのため、光電変換材料又はその素子は光電池（特に太陽電池）に適している。
【００５２】
【実施例】
以下に、実施例に基づいて本発明をより詳細に説明するが、本発明はこれらの実施例によって限定されるものではない。
【００５３】
なお、以下の実施例において、分子修飾方法（ブチル化方法）としては、以下の２方法を用いて分子修飾物を調製した。（１）Ｃ60フラーレン、カーボンナノチューブ又はグラファイトリボン（５ｇ）、ジブチル亜鉛（１０５ｇ）、ヨウ化ブチル（５０ｍｌ）をフラスコに入れ、１８０℃で４時間攪拌した。反応終了後、エタノール、希塩酸で洗浄し、ブチル化物を調製した。（２）Ｃ60フラーレン、カーボンナノチューブ又はグラファイトリボン（５ｇ）、カリウムＫ（７ｇ）、テトラヒドロフランＴＨＦ（１００ｍｌ）を三口フラスコに入れ、超音波照射下、６０℃で５時間攪拌した。続いて、９０ｍｌのヨウ化ブチルを加え、室温で一晩攪拌した。溶媒を留去後、残さを水−エタノールで洗浄し、ブチル化物を調製した。
【００５４】
実施例１
導電性高分子ＯＯＰＰＶ（ポリ（２，５−ジオクチルオキシ−ｐ−フェニレンビニレン））をクロロホルム中に溶解させ、この溶液中に、電子供与体として分子修飾したＣ60フラーレン５重量部（前記導電性高分子１００重量部に対して）を加え、超音波処理した。得られた塗布剤を、透明電極としてＩＴＯ膜を形成した石英ガラス基板上にスピンコートして薄膜（厚み１２０ｎｍの電子供与層）を形成した。
【００５５】
また、導電性高分子ＣＮＰＰＶ（ＣＮ ポリ（ｐ−フェニレンビニレン））をトリクロロエチレン中に溶解させ、この溶液中に、電子受容体としてＣ60フラーレン２０重量部と、電荷輸送体としてポリエチレンオキシドで分子修飾したカーボンナノチューブ（平均直径４０〜２００ｎｍ、平均長さ２０〜３０μｍ）２重量部を加え、超音波処理した。得られた塗布剤を、電子供与層上にスピンコートし、電荷輸送層（厚み５０ｎｍ）を形成した。さらに、電荷輸送層上にアルミニウムを蒸着して上部電極を形成し、素子を作製した。
【００５６】
なお、上記Ｃ60フラーレンは、黒鉛電極を用い、１００ｍｍＨｇのヘリウム雰囲気でアーク放電し、得られたススをベンゼンで抽出し、得られたＣ60混合物を、塩基性活性アルミナを担体とし、ヘキサンを展開溶媒として、カラム分離精製することにより調製した。また、カーボンナノチューブは、ＣＶＤ法を用い、７００℃で、Ｎｉ−フタロシアニンを原料として調製した。
【００５７】
作製した素子に直流電源を接続して、光導電性を調べた。光を照射しない場合、素子は絶縁体であった。この素子に可視光領域の光を透明電極側から照射したところ、光電流が観測された。タングステンランプを分光し、光電流強度の波長依存性を測定した結果、７００ｎｍ以下の波長に対して光応答が観測された。
【００５８】
この太陽電池は、整流性を示し、透明電極側から波長６３５ｎｍの単色光を照射したところ、過電力が発生し、良好な太陽電池であることが判った。この太陽電池のエネルギー変換効率は４％であった。
【００５９】
実施例２
光増感剤としてのポルフィン類（オクタエチルポルフィリン）を真空蒸着することにより、電子供与層と電荷輸送層との間に光増感層（厚み４０ｎｍ）を形成する以外は、実施例１と同様の素子を作製した。この素子に可視光領域の光を透明電極側から照射したところ、光電流が観測された。タングステンランプを分光し、光電流強度の波長依存性も測定した結果、８００ｎｍ以下の波長に対して光応答が観測された。また、実施例１と比較して、光電流値が増加した。
【００６０】
この太陽電池は、整流性を、透明電極側から波長６３５ｎｍの単色光を照射したところ、過電力が発生し、良好な太陽電池であることが判った。この太陽電池のエネルギー変換効率は５％であった。
【００６１】
実施例３
素子は、マトリックス樹脂（ＯＯＰＶポリ（２，５−ジオクチルオキシ−ｐ−フェニレンビニレン）６０重量％，ＣＮＰＰＶ（ＣＮ ポリ（ｐ−フェニレンビニレン））３０重量％）に、電子受容体としてのＣ60フラーレン５重量％と、電荷輸送物体としてポリエチレンオキシドで分子修飾したカーボンナノチューブ２重量％、光増感剤としてポルフィン類（オクタエチルポルフィン）３重量％とを分子分散させた光導電体を形成した。なお、フラーレンおよびカーボンナノチューブは、実施例１と同様のフラーレンおよびカーボンナノチューブを用いた。
【００６２】
すなわち、上記成分をクロロホルム／トリクロロエチレン混合溶媒に溶解し、得られた塗布剤を、透明電極としてＩＴＯ膜を形成した石英ガラス基板上にスピンコートして光導電層の薄膜（厚み０．３μｍ）を形成した。さらに、光導電層上にアルミニウムを蒸着して上部電極を形成し、素子を作製した。
【００６３】
作製した素子に直接電源を接続して、光導電性を調べた。光を照射しない場合、感光体は絶縁体であった。この素子に可視光領域の光を透明電極側から照射したところ、光電流が観測された。タングステンランプを分光し、光電流強度の波長依存性を測定した結果、８００ｎｍ以下の波長に対して光応答が観測された。
【００６４】
この太陽電池は、整流性を示し、透明電極側から波長６３５ｎｍの単色光を照射したところ、過電力が発生し、良好な太陽電池であることが判った。この太陽電池のエネルギー変換効率は３．５％であった。
【００６５】
実施例４
導電性高分子ＯＯＰＰＶ（ポリ（２，５−ジオクチルオキシ−ｐ−フェニレンビニレン））をクロロベンゼン中に溶解させ、この溶液を超音波処理した。得られた塗布剤を、透明電極としてＩＴＯ膜を形成した石英ガラス基板上にスピンコートして薄膜（厚み１２０ｎｍの電子供与層）を形成した。
【００６６】
また、導電性高分子ＣＮＰＰＶ（ＣＮ ポリ（ｐ−フェニレンビニレン））をトリクロロエチレン中に溶解させ、この溶液中に、電子受容体としてＣ60フラーレン２０重量部と、電荷輸送体としてカーボンナノチューブ（平均直径４０〜２００ｎｍ、平均長さ２０〜３０μｍ）２重量部を加え、超音波処理した。得られた塗布剤を、電子供与層上にスピンコートし、電荷輸送層（厚み５０ｎｍ）を形成した。さらに、電荷輸送層上にアルミニウムを蒸着して上部電極を形成し、素子を作製した。
【００６７】
作製した素子に直流電源を接続して、光導電性を調べた。光を照射しない場合、素子は絶縁体であった。この素子に可視光領域の光を透明電極側から照射したところ、光電流が観測された。タングステンランプを分光し、光電流強度の波長依存性を測定した結果、７００ｎｍ以下の波長に対して光応答が観測された。
【００６８】
この太陽電池は、整流性を示し、透明電極側から波長６３５ｎｍの単色光を照射したところ、過電圧が発生し、良好な太陽電池であることが判った。この太陽電池のエネルギー変換効率は０．８％であった。
【００６９】
実施例５
カーボンナノチューブに代えて、グラファイトリボンを使用する以外は、実施例４と同様の素子を作製した。この素子の可視光域の光を透明電極側から照射したところ、光電流が観測された。タングステンランプを分光し、光電流強度の波長依存性を測定した結果、７００ｎｍ以下の波長に対して光応答が観測された。
【００７０】
この太陽電池は、整流性を示し、透明電極側から波長６３５ｎｍの単色光を照射したところ、過電圧が発生し、良好な太陽電池であることが判った。この太陽電池の変換効率は０．７％であった。
【００７１】
実施例６
Ｃ60フラーレン、カーボンナノチューブに代えて、グラファイトリボンを使用する以外は、実施例４と同様の素子を作製した。この素子に可視光域の光を透明電極側から照射したところ、光電流が観測された。タングステンランプを分光し、光電流強度の波長依存性を測定した結果、７００ｎｍ以下の波長に対して光応答が観測された。
【００７２】
この太陽電池は、整流性を示し、透明電極側から波長６３５ｎｍの単色光を照射したところ、過電圧が発生し、良好な太陽電池であることが判った。この太陽電池の変換効率は０．５％であった。
【００７３】
実施例７
光増感剤としてのポルフィン類（オクタエチルポルフィリン）を真空蒸着することにより、電子供与層と電荷輸送層との間に光増感層（厚み４０ｎｍ）を形成する以外は、実施例４と同様の素子を作製した。この素子に可視光領域の光を透明電極側から照射したところ、光電流が観測された。タングステンランプを分光し、光電流強度の波長依存性も測定した結果、８００ｎｍ以下の波長に対して光応答が観測された。また、実施例４と比較して、光電流値が増加した。
【００７４】
この太陽電池は、整流性を、透明電極側から波長６３５ｎｍの単色光を照射したところ、過電圧が発生し、良好な太陽電池であることが判った。この太陽電池のエネルギー変換効率は１．５％であった。
【００７５】
実施例８
導電性高分子ＯＯＰＰＶをクロロベンゼン中に溶解させ、この溶液中に、電子供与体としてＣ60フラーレン５重量部（ＯＯＰＰＶ １００重量部に対して）を加え、超音波処理した。得られた塗布剤を、透明電極としてＩＴＯ膜を形成した石英ガラス基板上にスピンコートして薄膜（厚み１２０ｎｍの電子供与層）を形成した。
【００７６】
また、導電性高分子ＣＮＰＰＶをトリクロロエチレン中に溶解させ、この溶液中に、電子受容体としてＣ60フラーレン２０重量部と、電荷輸送体としてカーボンナノチューブ（平均直径４０〜２００ｎｍ、平均長さ２０〜３０μｍ）２重量部を加え、超音波処理した。得られた塗布剤を、電子供給層上にスピンコートし、電荷輸送層（厚み５０ｎｍ）を形成した。さらに、電荷輸送層上にアルミニウムを蒸着して上部電極を形成し、素子を作製した。
【００７７】
作製した素子に直接電源を接続して、光導電性を調べた。光を照射しない場合、素子は絶縁体であった。この素子に可視光領域の光を透明電極側から照射したところ、光電流が観測された。タングステンランプを分光し、光電流強度の波長依存性を測定した結果、７００ｎｍ以下の波長に対して光応答が観測された。
【００７８】
この太陽電池は、整流性を示し、透明電極側から波長６３５ｎｍの単色光を照射したところ、過電圧が発生し、良好な太陽電池であることが判った。この太陽電池のエネルギー変換効率は２％であった。
【００７９】
実施例９
光増感剤としてのポルフィン類（オクタエチルポルフィリン）を真空蒸着することにより、電子供与層と電荷輸送層との間に光増感層（厚み４０ｎｍ）を形成する以外は、実施例８と同様の素子を作製した。この素子に可視光域の光を透明電極側から照射したところ、光電流が観測された。タングステンランプを分光し、光電流強度の波長依存症を測定した結果、８００ｎｍ以下の波長に対して光応答が観察された。
【００８０】
この太陽電池は、整流性を示し、透明電極側から波長６３５ｎｍの単色光を照射したところ、過電圧が発生し、良好な太陽電池であることが判った。この太陽電池の変換効率は３％であった。
【００８１】
実施例１０
Ｃ60フラーレン及びカーボンナノチューブに代えて、分子修飾Ｃ60フラーレン、分子修飾カーボンナノチューブを使用する以外は、実施例８と同様の素子を作製した。この素子に可視光域の光を透明電極側から照射したところ、光電流が観測された。タングステンランプを分光し、光電流強度の波長依存性を測定した結果、８００ｎｍ以下の波長に対して光応答が観察された。
【００８２】
この太陽電池は、整流性を示し、透明電極側から波長６３５ｎｍの単色光を照射したところ、過電圧が発生し、良好な太陽電池であることが判った。この太陽電池の変換効率は４％であった。
【００８３】
実施例１１
Ｃ60フラーレン及びカーボンナノチューブの代わりに、分子修飾Ｃ60フラーレン、分子修飾カーボンナノチューブを使用する以外は、実施例９と同様の素子を作製した。この素子に可視光域の光を透明電極側から照射したところ、光電流が観測された。タングステンランプを分光し、光電流強度の波長依存性を測定した結果、８００ｎｍ以下の波長に対して光応答が観察された。
【００８４】
この太陽電池は、整流性を示し、透明電極側から波長６３５ｎｍの単色光を照射したところ、過電圧が発生し、良好な太陽電池であることが判った。この太陽電池の変換効率は５％であった。
【００８５】
実施例１２
Ｃ60フラーレン及びカーボンナノチューブの代わりに、分子修飾Ｃ60フラーレン、分子修飾グラファイトリボンを使用する以外は、実施例８と同様の素子を作製した。この素子に可視光域の光を透明電極側から照射したところ、光電流が観測された。タングステンランプを分光し、光電流強度の波長依存性を測定した結果、８００ｎｍ以下の波長に対して光応答が観察された。
【００８６】
この太陽電池は、整流性を示し、透明電極側から波長６３５ｎｍの単色光を照射したところ、過電圧が発生し、良好な太陽電池であることが判った。この太陽電池の変換効率は４．５％であった。
【００８７】
実施例１３
Ｃ60フラーレン及びカーボンナノチューブの代わりに、分子修飾Ｃ60フラーレン、分子修飾グラファイトリボンを使用する以外は、実施例９と同様の素子を作製した。この素子に可視光域の光を透明電極側から照射したところ、光電流が観測された。タングステンランプを分光し、光電流強度の波長依存性を測定した結果、８００ｎｍ以下の波長に対して光応答が観察された。
【００８８】
この太陽電池は、整流性を示し、透明電極側から波長６３５ｎｍの単色光を照射したところ、過電圧が発生し、良好な太陽電池であることが判った。この太陽電池の変換効率は５．３％であった。
【００８９】
実施例１４
Ｃ60フラーレン及びカーボンナノチューブの代わりに、分子修飾グラファイトリボンを使用する以外は、実施例８と同様の素子を作製した。この素子に可視光域の光を透明電極側から照射したところ、光電流が観測された。タングステンランプを分光し、光電流強度の波長依存性を測定した結果、８００ｎｍ以下の波長に対して光応答が観察された。
【００９０】
この太陽電池は、整流性を示し、透明電極側から波長６３５ｎｍの単色光を照射したところ、過電圧が発生し、良好な太陽電池であることが判った。この太陽電池の変換効率は３．５％であった。
【００９１】
実施例１５
Ｃ60フラーレン及びカーボンナノチューブの代わりに、分子修飾グラファイトリボンを使用する以外は、実施例９と同様の素子を作製した。この素子に可視光域の光を透明電極側から照射したところ、光電流が観測された。タングステンランプを分光し、光電流強度の波長依存性を測定した結果、８００ｎｍ以下の波長に対して光応答が観察された。
【００９２】
この太陽電池は、整流性を示し、透明電極側から波長６３５ｎｍの単色光を照射したところ、過電圧が発生し、良好な太陽電池であることが判った。この太陽電池の変換効率は４．６％であった。
【００９３】
実施例１６
素子として、マトリックス樹脂ＯＯＰＰＶ６０重量部及びＣＮＰＰＶ３０重量部に、電子受容体としての分子修飾Ｃ60フラーレン５重量部と、電荷輸送体としての分子修飾カーボンナノチューブ２重量部、光増感剤として前記ポルフィン類３重量部とを分散させた光導電体を作製した。すなわち、上記成分をクロロベンゼン／トリクロロエチレン混合溶媒と混合し、得られた塗布剤を、透明電極としてＩＴＯ膜を形成した石英ガラス基板上にスピンコートして光導電層の薄膜（厚み０．３μｍ）を形成した。さらに、光導電層上にアルミニウムを蒸着して上部電極を形成し，素子を作製した。この素子に可視光域の光を透明電極側から照射したところ、光電流が観測された。タングステンランプを分光し、光電流強度の波長依存性を測定した結果、８００ｎｍ以下の波長に対して光応答が観察された。
【００９４】
この太陽電池は、整流性を示し、透明電極側から波長６３５ｎｍの単色光を照射したところ、過電圧が発生し、良好な太陽電池であることが判った。この太陽電池の変換効率は３．５％であった。
【００９５】
実施例１７
Ｃ60フラーレン及びカーボンナノチューブの代わりに、分子修飾グラファイトリボンを使用する以外は、実施例１６と同様の素子を作製した。この素子に可視光域の光を透明電極側から照射したところ、光電流が観測された。タングステンランプを分光し、光電流強度の波長依存性を測定した結果、８００ｎｍ以下の波長に対して光応答が観察された。
【００９６】
この太陽電池は、整流性を示し、透明電極側から波長６３５ｎｍの単色光を照射したところ、過電圧が発生し、良好な太陽電池であることが判った。この太陽電池の変換効率は３．９％であった。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a photoelectric conversion material composed of an electron donor, an electron acceptor, an electron transporter and, if necessary, a photosensitizer, and a photovoltaic cell (solar cell or the like) using the photoelectric conversion material.
[0002]
[Prior art]
In solar cells currently in practical use, silicon-based photoelectric conversion materials and compound semiconductor-based photoelectric conversion materials are mainly used, and organic-based photoelectric conversion materials are not so much used. On the other hand, since the discovery of conductive polyacetylene in 1977, research on solar cells using organic thin films has been actively conducted. However, solar cells using organic materials generally have low stability and low energy conversion rate.
[0003]
Japanese Patent Application Laid-Open No. 10-81754 discloses a metal complex polymer composed of a metal complex having a bipyridyl unit and having photosensitivity in the visible light region and the near infrared region. However, this metal complex polymer has a complicated structure and requires the use of a special ligand that coordinates to the bipyridyl unit.
[0004]
Japanese Patent Application Laid-Open No. 9-73180 is composed of at least one kind of amorphous fullerene such as a carbon cluster having a basic skeleton having 70 or more carbon atoms and derivatives thereof, and a matrix polymer in which the amorphous fullerene is dispersed. A photoconductor is disclosed. This document also discloses a photoconductor including a conductive support, a charge transport layer formed on the conductive support, and a charge generation layer made of the photoconductor. These photoelectric conversion materials are useful as photovoltaic materials such as solar cells and photosensitive materials such as photoreceptors. However, even higher photoelectric conversion efficiency is required for this material.
[0005]
Japanese Patent Laid-Open No. 2000-261016 discloses C 60 , C 70 Photoelectric charge separation materials composed of compounds containing spherical shell carbon molecules such as ferrocene as electron acceptors (for example, compounds in which organometallic complex units such as ferrocene, porphyrin units, and fullerene units are sequentially linked by a linker) Is disclosed. This document is composed of a photocharge separation material in which an electron donor, a photosensitizer and an electron acceptor are arranged three-dimensionally to give direction to the charge separation state by photoexcitation, and the photocharge separation material. A photovoltaic cell is also disclosed. However, since the photocharge separation material needs to enclose spherical shell carbon molecules such as fullerene as an electron acceptor, the structure is complicated, and the photocharge separation material and the photovoltaic cell are industrially advantageous with high productivity. It is difficult to manufacture.
[0006]
[Problems to be solved by the invention]
Accordingly, an object of the present invention is to provide a photoelectric conversion material having a high photoelectric conversion function and capable of increasing the area, reducing the thickness, reducing the weight, and reducing the cost, and a photovoltaic cell using the photoelectric conversion material.
[0007]
Another object of the present invention is to provide a photoelectric conversion material having a simple structure and high stability and conversion efficiency, and a photovoltaic cell using the photoelectric conversion material.
[0008]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that spherical shell carbon such as fullerenes functions effectively as an electron acceptor, and linear or cylindrical carbon such as carbon nanotubes is charge transported. Found to function effectively as a body, and that planar (or two-dimensional structure) and linear carbon (eg, graphite ribbon) has both functions as an electron acceptor and a charge transporter, The present invention has been completed.
[0009]
That is, the photoelectric conversion material of the present invention includes an electron donor, spherical shell carbon, and linear or cylindrical carbon. The photoelectric conversion material may further contain a photosensitizer. In the photoelectric conversion material, the arrangement or arrangement of each of the above components (electron donor, spherical shell carbon, linear or cylindrical carbon, and photosensitizer if necessary) depends on the carrier (electron or hole) from the electron donor. ) Is efficiently transported to the electron transporter, for example, a photosensitizer is interposed between the electron donor and the electron transporter, and the electron acceptor is a carrier (electron, hole). Each component may be arranged or oriented two-dimensionally or three-dimensionally. More specifically, the photoelectric conversion material having a two-dimensional structure includes, for example, an electron donor layer including an electron donor, and an electron acceptor and an electron transporter (or charge transporter) formed on the electron donor layer. And a charge transport layer containing An electron donor layer containing an electron donor; a photosensitizer layer formed on the electron donor layer and containing a photosensitizer; and an electron acceptor and an electron formed on the photosensitizer layer. You may comprise with the charge transport layer containing a transport body (or charge transport body). In the photoelectric conversion material having such a two-dimensional structure, the electron donor layer and the charge transport layer may contain spherical shell-like carbon, and the spherical shell-like carbon is interposed between the electron donor layer and the charge transport layer. A density difference may be formed. For example, the concentration of spherical shell carbon in the electron donor layer may be smaller than that in the charge transport layer.
[0010]
Examples of the spherical shell-like carbon include fullerenes, modified products thereof, and metal inclusions. Examples of the linear or cylindrical carbon include carbon in a tube-like, fibrous, or ribbon-like form, such as carbon nanotubes. And graphite nanofibers, graphite ribbons, fibrils, graphite intercalation compounds, and modifications thereof. Furthermore, examples of the photosensitizer include π-electron compounds such as porphyrins, metal chelate compounds, polyanilines, aromatic polycyclic compounds, and compounds having a polyacene skeleton structure.
[0011]
The photoelectric conversion material has high photoelectric conversion efficiency and high stability. Therefore, the present invention also includes various elements or units composed of the photoelectric conversion material, for example, a photovoltaic cell (such as a solar cell).
[0012]
DETAILED DESCRIPTION OF THE INVENTION
The feature of the photoelectric conversion material of the present invention resides in the combination of spherical shell carbon and linear or cylindrical carbon. The spherical shell carbon can function as an electron acceptor, and the linear or cylindrical carbon can function as a charge transporter. In addition, planar (or two-dimensional structure) and linear carbon (for example, a graphite ribbon) has both functions of an electron acceptor and a charge transporter.
[0013]
Examples of the spherical shell carbon include fullerenes, modified products thereof, and metal inclusions. These spherical shell-like carbons can be used alone or in combination of two or more. Fullerenes include carbon clusters having various steric structures, such as C 60 , C 70 , C 74 , C 76 , C 78 , C 82 , C 84 , C 720 , C 860 And fullerenes. The form of fullerenes may be, for example, a soccer ball shape or a bucky ball shape.
[0014]
Fullerenes may be modified by introduction of substituents. The modification method is not particularly limited, and for example, a carbon 5-membered ring portion rich in the reactivity of fullerenes can be chemically modified. The type of the substituent is not particularly limited, and examples thereof include alkyl groups (C groups such as methyl group and t-butyl group 1-10 Alkyl groups, etc.), aryl groups (phenyl groups, etc.), aralkyl groups (benzyl groups, etc.), dioxolane units, halogens or oxygen atoms, etc., and may be modified by introducing liquid crystal polymers, dyes, polyethylene oxide, etc. . Modification of fullerenes enables solubilization in solvents and polymers, improved affinity, and alignment or orientation of fullerenes.
[0015]
The metal-encapsulated fullerenes are doped with various metals such as 1A group elements (K, Na, Rb, etc.), 2A group elements, lanthanoid elements (La, etc.) of the periodic table. And fullerenes. The metal as the dopant may be doped alone or in combination of two or more. These metal-encapsulated fullerenes may be used alone or in combination of two or more.
[0016]
Linear or tubular carbon includes carbon in the form of tubes, fibers or ribbons. Examples of such carbon include carbon nanotubes, carbon nanocoils, graphite nanofibers (or carbon nanofibers), graphite ribbons, fibrils, and graphite intercalation compounds. These carbon materials can be used alone or in combination of two or more.
[0017]
Preferred linear or cylindrical carbon is a tube or ribbon, such as carbon nanotubes or graphite ribbons. The carbon nanotubes may be single-walled carbon nanotubes or multi-walled carbon nanotubes, and may have a bucky-onion structure.
[0018]
The average diameter of linear or cylindrical carbon such as carbon nanotubes may be, for example, 0.7 to 300 nm, preferably 0.7 to 250 nm, more preferably 1 to 250 nm, and particularly about 5 to 250 nm. In addition, the said average diameter means average thickness or average width in carbon of a ribbon form.
[0019]
In order to control solubilization and affinity to solvents and polymers, and to control the alignment or orientation of linear or cylindrical carbon, carbon such as carbon nanotubes can be obtained by introducing substituents, as in the case of fullerenes. It may be modified. The modification method and the kind of the substituent are the same as those of the fullerenes. The carbon nanotubes may be doped with a metal like the metal-encapsulated fullerenes. A planar (two-dimensional structure) and linear carbon such as a graphite ribbon structurally includes many edge portions, so that introduction, modification, and metal inclusion of substituents are easy.
[0020]
The electron donor (hole acceptor or electron generator) is not particularly limited, but is preferably a conductive polymer and a polymer having a function as a p-type semiconductor. Examples of such electron donors include polythiophene resins such as PT [poly (3-alkylthiophene)], PPV [poly (P-phenylenevinylene)], OOPV [poly (2,5-dioctyloxy-P-phenylene). Vinylene)], PEDOT [poly (2,3-dihydrothieno) [3,4-b] -1,4-dioquine], PSS [poly (styrene sulfonate)], and other polyphenylene vinylene resins, polyphenylene resins (for example, And poly (p-phenylene) resin, poly (m-phenylene) resin) and substituted products thereof.
[0021]
The photosensitizer may be any antenna molecule, that is, a compound that effectively absorbs light and transfers electrons and holes to other substances. For example, a π-electron compound (porphyrins, metal chelate compound) , Polyaniline, aromatic polycyclic compounds, compounds having a polyacene skeleton structure, etc.), π-electron compounds containing different elements (carbazole, etc.), halogenated π-electron compounds, quinizarin, or derivatives thereof. Examples of the porphyrins include various compounds having a porphyrin skeleton, such as porphyrin, phthalocyanine, metal phthalocyanine (phthalocyanine containing a transition metal such as iron phthalocyanine), tetrabenzoporphyrin, tetraphenylporphyrin or a derivative thereof [metal tetrabenzoporphyrin (zinc -Tetrabenzoporphyrin, magnesium-tetrabenzoporphyrin etc.), tetrakispentafluorophenylporphyrin etc.] and the like. Examples of the metal chelate compound include dimethylglyoxime, dithizone, oxine, acetylacetone, glycine, EDTA (ethylenediaminetetraacetic acid), metal salts such as NTA (for example, transition metal salts), and the like.
[0022]
Examples of aromatic polycyclic compounds include petroleum distillation residues, naphtha pyrolysis residues, ethylene bottom oil, coal liquefied oil, coal-based heavy oil such as coal tar, and polycyclic carbon synthesized by condensation of naphthalene. Hydrogen, polycyclic hydrocarbons in which heteroatoms (nitrogen atoms, sulfur atoms, boron atoms, phosphorus atoms, oxygen atoms, etc.) are introduced into the structure of these hydrocarbons, and solvent extraction from the residue Examples thereof include polycyclic hydrocarbons obtained.
[0023]
A compound having a polyacene skeleton structure is a heat-treated product of a condensate of an aromatic hydrocarbon compound and an aldehyde described in JP-A-60-170163, and has an atomic ratio of hydrogen atom / carbon atom. 0.05 to 0.5.
[0024]
The compound having a halogen atom is not particularly limited, and examples thereof include fluorinated hydrocarbons, fluorinated aromatic polycyclic compounds (fluorinated pitch, etc.), heavy oil fluoride, hexafluorobenzene, octafluoronaphthalene, Decafluorophenanthrene, decafluoropyrene, etc.), chlorinated hydrocarbons, brominated hydrocarbons, iodinated hydrocarbons and the like corresponding to these. Of these halides, fluoride pitch is preferred. These halides can be used alone or in combination of two or more.
[0025]
Porphyrins can be used as porphyrin dendrimers, and polyaniline can also be used by being bonded to an electron donor, electron acceptor, or electron transporter by a chemical bond.
[0026]
The photoelectric conversion material comprised with the said component implement | achieves high stability and a high energy conversion rate. That is, electrons move from the electron donor to the electron acceptor by photoexcitation and holes move to the electron donor, so that a charge separation state is efficiently generated. For example, electrons move from the photosensitizer to the electron acceptor by photoexcitation of the photosensitizer, and holes move from the photosensitizer to the electron donor, so that a charge separation state can be efficiently formed. Moreover, directivity can be given to the charge separation state by the electron transporter of linear or cylindrical carbon. Therefore, it is considered that charges can be transported without deactivation, and high stability and photoelectric conversion efficiency can be obtained.
[0027]
In such photoelectric conversion materials, carbon materials such as fullerenes and carbon nanotubes have many π-electron systems as well as structural specificity, which may cause strong interaction with light, intermolecular charge transfer, and electron transport. Phenomenon occurs, and it seems that the photoelectric conversion function is expressed with high efficiency. For example, the photosensitizer generates carriers or charges (electrons and holes) by photoexcitation, gives electrons to the electron acceptor, and gives holes to the electron donor. Therefore, the photosensitizer has a function of separating carriers or charges (electrons and holes), and efficiently generates a charge separation state that can be used for subsequent reactions. Thus, since the generated charges (electrons and holes) can be separated and transported by the photosensitizer, a higher photoelectric conversion efficiency can be obtained as compared with a silicon-based semiconductor by charge generation at the pn junction surface. . Moreover, linear or cylindrical carbon such as carbon nanotubes forms a directional percolation conduction path with a small addition. For this reason, the electron transporter is extremely effective for charge transport and can be transported without deactivating the charge.
[0028]
Each of the above components may form a photoelectric conversion material or a photoelectric conversion element using physical or chemical vapor deposition, lithography technology, etc., and may be combined with a matrix resin to form a photoelectric conversion material or a photoelectric conversion element. May be. Examples of matrix resins include polyolefin resins (polyethylene resins, polypropylene resins, ethylene-vinyl acetate copolymers, ethylene- (meth) acrylic acid ester copolymers, etc.), vinyl acetate resins (vinyl acetate-chloride). Vinyl copolymers, vinyl acetate- (meth) acrylic acid ester copolymers, etc.), (meth) acrylic resins (polymethyl methacrylate, methyl methacrylate- (meth) acrylic acid ester copolymers, methyl methacrylate- Styrene- (meth) acrylic acid ester copolymer), polystyrene resin (polystyrene, styrene- (meth) acrylic acid ester copolymer, styrene- (meth) acrylic acid copolymer, styrene-maleic anhydride copolymer) Coalesce), vinyl chloride resin, polyester resin (polyaryle) Including preparative resin), polyamide resins, polycarbonate resins, polyvinyl alcohol resins, polyvinyl acetal resins (polyvinyl butyral resin), polysulfone resins, and polyphenylene oxide resin can be exemplified. These matrix resins can be used alone or in combination of two or more.
[0029]
As the matrix resin, a conductive polymer, a compound having a polyacene skeleton structure, and the like are preferable. Examples of the conductive polymer include polyacetylene polymers (solvent insoluble resins such as polyacetylene, solvent soluble polyacetylene resins using phenylacetylene, etc.), polyphenylene polymers (for example, poly (p-phenylene) resins, and the like. , Poly (m-phenylene) resins, polyphenylene vinylene resins such as poly (p-phenylene vinylene), polyphenylene sulfide resins, polyphenylene oxide resins, etc., heterocyclic polymers (polypyrrole, poly (3-alkylthiophene) ) Such as polythiophene resins, polyfuran resins, polyselenophene resins, polytellurophene resins), ionic polymers (polyaniline resins, poly (3-methyl-4-carboxypyrrole), etc. Etc.), a ladder-type polymer There can be exemplified. As the conductive polymer, a solvent-soluble resin is usually used. The type of the matrix resin is not particularly limited, and can be selected according to the function of the layer such as an electron donating layer or a charge transport layer. As the electron donating layer, a p-type conductive polymer is often used. In many cases, an n-type conductive polymer is used.
[0030]
The compound having a polyacene skeleton structure includes, for example, the compound having the polyacene skeleton structure described in the section of the photosensitizer.
[0031]
Note that when a discotic liquid crystal is used as an electron donor, it is arranged in a column structure and is effective for transporting holes and electrons.
[0032]
When a conductive polymer having p-type semiconducting properties is used as the matrix resin, fullerenes tend to take in an electron donor and become a charge transfer material having n-type semiconducting properties. Furthermore, a complex of fullerenes and a conductive polymer exhibits a particularly large response to light. This is thought to be due to the formation of a donor-acceptor type element explained by photoinduced charge transfer, which is different from that of a silicon-based semiconductor pn junction element, and excitons are generated in the entire complex by light irradiation. To do. Therefore, carriers (electrons, holes) are efficiently generated by using fullerenes as an electron donor in combination with a conductive polymer.
[0033]
The photoelectric conversion material of this invention should just be comprised with the electron donor, the electron acceptor, and the electron transporter, and may contain the photosensitizer. Such a photoelectric conversion material may be a composite (or mixed composition) of each component. In a preferred embodiment, the components can be arranged two-dimensionally (layered) or three-dimensionally in relation to one another. For example, in a structure where each component is arranged, bonded or oriented two-dimensionally or three-dimensionally, the electron acceptor can give a carrier (electron) to the charge transporter between the electron donor and the electron transporter. May be arranged, bonded or oriented in any form, a photosensitizer is interposed between the electron donor and the electron transporter, and the electron acceptor can impart carriers (electrons) to the charge transporter. It may be arranged, bonded or oriented in a form.
[0034]
In a preferred embodiment, in order to separate and efficiently move carriers or charges (electrons or holes) generated by photoexcitation of the photosensitizer, the photosensitizer has an electron donor in a form capable of transporting carriers. Are bonded or close (or oriented), and the electron acceptor (spherical carbon) is also bonded or close (or oriented). Further, the charge transporter (linear or cylindrical carbon) is in a form capable of transporting carriers, and is bound or close (or oriented) to at least the electron acceptor (spherical carbon), and the charge transporter ( (Linear or cylindrical carbon) is in a form capable of transporting carriers via a photosensitizer, and is bonded or close (or oriented) to the electron donor and the electron acceptor (spherical carbon). May be. As such a photoelectric conversion material, the complex represented by a following formula can be illustrated, for example.
[0035]
Ed-L1-P-L2-Ea- (Ct)
(In the formula, Ed represents an electron donor, P represents a photosensitizer, Ea represents an electron acceptor, Ct represents a charge transporter, Ea- (Ct) represents a bond between the electron acceptor Ea and the charge transporter Ct, L1 and L2 are the same or different and each represents a linker that connects the electron donor Ed, the photosensitizer P, and the electron acceptor Ea)
In addition, as a linker for coupling | bonding each said component, the coupling | bonding formed using a normal reaction, for example, a direct coupling | bonding, an amide bond, an ester bond, a urethane bond, an ether bond etc. can be utilized. As an example of these linkers, for example, JP-A No. 2000-261016 can be referred to.
[0036]
In a preferred embodiment, the photoelectric conversion material (or photoelectric conversion element) has a two-dimensional layer structure (laminated structure). Such a laminated structure has, for example, a laminated structure including an electron donor layer containing an electron donor and an electron transport layer formed on the electron donor layer. This electron transport layer usually contains an electron acceptor (such as spherical shell carbon) and an electron transporter (such as linear or cylindrical carbon). In particular, an electron donor layer containing an electron donor, a photosensitizer layer formed on the electron donor layer and containing a photosensitizer, an electron acceptor and an electron formed on the photosensitizer layer. A structure including a charge transport layer including a transporter. Note that the photosensitizer of the photosensitizing layer may be dispersed in the vicinity of the interface between the electron donating layer and the charge transporting layer.
[0037]
In the photoelectric conversion material having such a layer structure, the electron donating layer and the charge transporting layer may contain spherical shell-like carbon. Further, the concentration of the spherical shell-like carbon in the electron donor layer and the charge transport layer may be different. For example, the concentration of spherical shell carbon in the electron donor layer may be smaller than the concentration of spherical shell carbon in the charge transport layer. For example, the difference in the spherical carbon content between the electron donor layer and the charge transport layer is, for example, about 1 to 80% by weight, preferably about 5 to 70% by weight (for example, 10 to 50% by weight). Also good. The content of spherical shell carbon in the electron donor layer is 10% by weight or less (for example, about 0 to 10% by weight, particularly about 0 to 7% by weight), and the content of spherical shell carbon in the charge transport layer is 10% by weight. % Or more (for example, about 10 to 70% by weight).
[0038]
In the photoelectric conversion material or element having the layer structure, various film forming methods, for example, chemical or physical vapor deposition methods such as sputtering and vapor deposition, coating methods using the matrix resin (conductive polymer, etc.), Each layer may be formed by a combination of methods. For example, a coating solution containing an electron donor and, if necessary, spherical shell carbon and a matrix resin is coated on a substrate to form an electron donating layer, and a coating solution containing a photosensitizer and a matrix resin is coated. The charge transport layer can be formed by forming a photosensitizing layer and coating a coating agent containing an electron acceptor, an electron transporter and a matrix resin. Further, a desired layer (for example, a photosensitizing layer) may be formed by chemical or physical vapor deposition if necessary.
[0039]
The ratio of the spherical shell-like carbon in the electron donor layer is, for example, 0.01 to 10 parts by weight, preferably 0.1 to 9 parts by weight, more preferably about 1 to 8 parts by weight with respect to 100 parts by weight of the matrix resin. It is.
[0040]
In the photosensitized layer, the ratio of the photosensitizer to 100 parts by weight as a whole is, for example, 1 to 100 parts by weight, preferably 2 to 100 parts by weight, and more preferably about 5 to 100 parts by weight.
[0041]
In the charge transport layer, the ratio of the electron acceptor (spherical carbon) to 100 parts by weight of the whole is, for example, 10 parts by weight or more (for example, about 10 to 200 parts by weight), preferably 15 parts by weight or more (for example, 15 About 150 parts by weight), more preferably 20 parts by weight or more (for example, about 20 to 120 parts by weight), and the ratio of the electron transporter (linear or cylindrical carbon) is, for example, 0.1 parts by weight or more. (For example, about 0.5 to 100 parts by weight), preferably 1 part by weight or more (for example, about 1 to 50 parts by weight), more preferably 2 parts by weight or more (for example, about 2 to 30 parts by weight).
[0042]
Furthermore, the thickness of the electron donor layer is, for example, about 5 nm to 300 μm (for example, 5 nm to 30 μm), preferably about 50 nm to 50 μm, and more preferably about 50 nm to 30 μm. The thickness of the photosensitizing layer is, for example, about 5 nm to 50 μm, preferably about 5 nm to 5 μm, and more preferably about 5 nm to 1 μm. The thickness of the charge transport layer is, for example, about 5 nm to 300 μm (for example, 5 nm to 30 μm), preferably about 50 nm to 50 μm, and more preferably about 50 nm to 30 μm.
[0043]
The substrate is a substrate on which the components and layers can be physically or chemically bonded by adsorption or chemical bonding, depending on the type and use of the photoelectric conversion material, such as a conductor, a semiconductor, an insulator (for example, gold, Conductive metals such as silver, copper and aluminum, transparent conductors or semiconductors such as tin oxide, indium oxide, zinc oxide and ITO, semiconductors or insulators such as silicon, transparent insulators such as glass and plastic films , Conductive, semiconductive or insulating ceramics).
[0044]
In addition, a board | substrate can also be used as an electrode of a photoelectric conversion element (for example, photovoltaic cells, such as a solar cell). In this case, a transparent conductor or a semiconductor can be used for the light incident side electrode, and a conductive metal such as a metal can be used for the opposite electrode. The transparent conductor on the light incident side may be protected with a transparent substrate (such as a glass plate).
[0045]
Examples of the solvent for the coating solution include alcohols, esters, ketones, ethers, amides, sulfur-containing compounds (including sulfoxides), halogenated hydrocarbons, hydrocarbons, and the like. May be used as a mixed solvent. In addition, aromatic hydrocarbons (benzene, toluene), alicyclic hydrocarbons (such as cyclohexane), aliphatic hydrocarbons (such as normal hexane), halogenated hydrocarbons (such as methylene chloride, chloroform, trichloroethylene), Carbon disulfide is suitable because it has a large amount of dissolution in fullerenes and nanotubes.
[0046]
For coating, for example, a conventional method such as a spin coating method, a spray coating method, a roll coating method, or a vapor deposition method can be adopted. After coating the coating liquid, the photoelectric conversion material having a layer structure is dried. Obtainable.
[0047]
More specifically, in the photoelectric conversion element having a layered structure, the electron donating layer has a low concentration (for example, 10% by weight or less) of fullerenes (C 60 And a matrix resin (a conductive polymer such as a thiophene resin or a phenylene resin, particularly a p-type conductive polymer). This electron donating layer may contain a charge transporting compound (for example, a discotic liquid crystal capable of transporting holes) around the percolation concentration.
[0048]
The photosensitizing layer may be interposed between the electron donating layer and the charge transport layer in order to generate charge separation, and the photosensitizer is dispersed at the interface between the electron donating layer and the charge transport layer. May be. Further, the spectral characteristics of the photoelectric conversion element can be improved by the type, layer, or dispersion form of the photosensitizer.
[0049]
The electron transport layer may be, for example, fullerenes (C 60 Etc.), carbon nanotubes, and a matrix resin (conductive polymer, particularly n-type conductive polymer). This electron transport layer may contain a charge transporting compound at a concentration equal to or higher than the percolation threshold as in the case of carbon nanotubes. In this case, fullerenes (C 60 A compound that causes photoinduced charge transfer with a conductive polymer may be used together with fullerene or the like.
[0050]
The photoelectric conversion material and photoelectric conversion element or device of the present invention can be widely applied to various photoelectric conversion devices, electro-optical conversion devices, or optoelectronic devices utilizing a photoelectric conversion function, an amplification function, an optical rectification function, and the like. For example, electronic elements or photoelectric conversion elements (diodes, rectifier elements, photodiodes, optical sensors, optical switches, transistors, FETs, holographic elements, etc.), photovoltaic cells (solar cells, etc.), photovoltaic elements, optical recording materials (electronics) It is useful as a photographic photoreceptor, photoconductive toner, optical memory, and the like. In particular, since the photoelectric conversion efficiency is high and stable, it is suitable as a photoelectric conversion element for a photovoltaic cell. In addition, since the photoelectric conversion device can be increased in area, thinned, reduced in weight, and reduced in cost, it can be applied to walls and windows, and can be used as a photoelectric conversion element for the next generation solar cell.
[0051]
【The invention's effect】
In the present invention, since spherical shell carbon and linear or cylindrical carbon are combined, the photoelectric conversion function is high. Further, the area can be increased, the film thickness can be reduced, the weight can be reduced, and the cost can be reduced. Moreover, it has a simple structure and exhibits high stability and conversion efficiency. Therefore, the photoelectric conversion material or the element thereof is suitable for a photovoltaic cell (particularly a solar cell).
[0052]
【Example】
Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.
[0053]
In the following examples, molecular modifications were prepared using the following two methods as the molecular modification method (butylation method). (1) C 60 Fullerene, carbon nanotube or graphite ribbon (5 g), dibutyl zinc (105 g) and butyl iodide (50 ml) were placed in a flask and stirred at 180 ° C. for 4 hours. After completion of the reaction, the product was washed with ethanol and dilute hydrochloric acid to prepare a butylated product. (2) C 60 Fullerene, carbon nanotube or graphite ribbon (5 g), potassium K (7 g) and tetrahydrofuran THF (100 ml) were placed in a three-necked flask and stirred at 60 ° C. for 5 hours under ultrasonic irradiation. Subsequently, 90 ml of butyl iodide was added and stirred overnight at room temperature. After distilling off the solvent, the residue was washed with water-ethanol to prepare a butylated product.
[0054]
Example 1
Conductive polymer OOPPV (poly (2,5-dioctyloxy-p-phenylene vinylene)) was dissolved in chloroform, and this solution was subjected to molecular modification as an electron donor. 60 5 parts by weight of fullerene (based on 100 parts by weight of the conductive polymer) was added and sonicated. The obtained coating agent was spin-coated on a quartz glass substrate on which an ITO film was formed as a transparent electrode to form a thin film (electron donating layer having a thickness of 120 nm).
[0055]
In addition, a conductive polymer CNPPV (CN poly (p-phenylene vinylene)) is dissolved in trichloroethylene, and C as an electron acceptor is dissolved in this solution. 60 20 parts by weight of fullerene and 2 parts by weight of carbon nanotubes (average diameter 40 to 200 nm, average length 20 to 30 μm) molecularly modified with polyethylene oxide as a charge transporter were added and subjected to ultrasonic treatment. The obtained coating agent was spin-coated on the electron donating layer to form a charge transport layer (thickness 50 nm). Furthermore, aluminum was vapor-deposited on the charge transport layer to form an upper electrode, thereby producing a device.
[0056]
The above C 60 Fullerenes were arc-discharged in a 100 mmHg helium atmosphere using a graphite electrode, and the resulting soot was extracted with benzene, and the resulting C 60 The mixture was prepared by column separation and purification using basic activated alumina as a carrier and hexane as a developing solvent. Carbon nanotubes were prepared using Ni-phthalocyanine as a raw material at 700 ° C. using a CVD method.
[0057]
A DC power source was connected to the fabricated element, and the photoconductivity was examined. When light was not irradiated, the element was an insulator. When this element was irradiated with light in the visible light region from the transparent electrode side, a photocurrent was observed. As a result of spectroscopy of the tungsten lamp and measuring the wavelength dependence of the photocurrent intensity, an optical response was observed for a wavelength of 700 nm or less.
[0058]
This solar cell showed a rectifying property, and when irradiated with monochromatic light having a wavelength of 635 nm from the transparent electrode side, it was found that an overpower was generated and the solar cell was a good solar cell. The energy conversion efficiency of this solar cell was 4%.
[0059]
Example 2
Except for forming a photosensitizing layer (thickness: 40 nm) between the electron donating layer and the charge transporting layer by vacuum deposition of porphins (octaethylporphyrin) as a photosensitizer, the same as in Example 1. The device was fabricated. When this element was irradiated with light in the visible light region from the transparent electrode side, a photocurrent was observed. As a result of measuring the wavelength dependence of the photocurrent intensity by spectroscopic analysis of a tungsten lamp, an optical response was observed for a wavelength of 800 nm or less. In addition, the photocurrent value increased as compared with Example 1.
[0060]
When this solar cell was irradiated with monochromatic light having a wavelength of 635 nm from the transparent electrode side, overpower was generated and it was found that this solar cell was a good solar cell. The energy conversion efficiency of this solar cell was 5%.
[0061]
Example 3
The element is composed of a matrix resin (60% by weight of OOPV poly (2,5-dioctyloxy-p-phenylene vinylene), 30% by weight of CNPPV (CN poly (p-phenylene vinylene))) and C as an electron acceptor. 60 A photoconductor was formed by molecularly dispersing 5% by weight of fullerene, 2% by weight of carbon nanotubes modified with polyethylene oxide as a charge transporting substance, and 3% by weight of porphine (octaethylporphine) as a photosensitizer. In addition, the fullerene and the carbon nanotube similar to Example 1 were used for the fullerene and the carbon nanotube.
[0062]
That is, the above components are dissolved in a chloroform / trichloroethylene mixed solvent, and the obtained coating agent is spin-coated on a quartz glass substrate on which an ITO film is formed as a transparent electrode to form a thin photoconductive layer (thickness 0.3 μm). Formed. Furthermore, aluminum was vapor-deposited on the photoconductive layer to form an upper electrode, thereby producing a device.
[0063]
A power source was directly connected to the fabricated device, and the photoconductivity was examined. When light was not irradiated, the photoreceptor was an insulator. When this element was irradiated with light in the visible light region from the transparent electrode side, a photocurrent was observed. As a result of spectroscopy of the tungsten lamp and measuring the wavelength dependence of the photocurrent intensity, an optical response was observed for wavelengths of 800 nm or less.
[0064]
This solar cell showed a rectifying property, and when irradiated with monochromatic light having a wavelength of 635 nm from the transparent electrode side, it was found that an overpower was generated and the solar cell was a good solar cell. The energy conversion efficiency of this solar cell was 3.5%.
[0065]
Example 4
The conductive polymer OOPPV (poly (2,5-dioctyloxy-p-phenylene vinylene)) was dissolved in chlorobenzene, and this solution was sonicated. The obtained coating agent was spin-coated on a quartz glass substrate on which an ITO film was formed as a transparent electrode to form a thin film (electron donating layer having a thickness of 120 nm).
[0066]
In addition, a conductive polymer CNPPV (CN poly (p-phenylene vinylene)) is dissolved in trichloroethylene, and C as an electron acceptor is dissolved in this solution. 60 20 parts by weight of fullerene and 2 parts by weight of carbon nanotubes (average diameter of 40 to 200 nm, average length of 20 to 30 μm) as a charge transporter were added and subjected to ultrasonic treatment. The obtained coating agent was spin-coated on the electron donating layer to form a charge transport layer (thickness 50 nm). Furthermore, aluminum was vapor-deposited on the charge transport layer to form an upper electrode, thereby producing a device.
[0067]
A DC power source was connected to the fabricated element, and the photoconductivity was examined. When light was not irradiated, the element was an insulator. When this element was irradiated with light in the visible light region from the transparent electrode side, a photocurrent was observed. As a result of spectroscopy of the tungsten lamp and measuring the wavelength dependence of the photocurrent intensity, an optical response was observed for a wavelength of 700 nm or less.
[0068]
This solar cell showed rectifying properties, and when irradiated with monochromatic light having a wavelength of 635 nm from the transparent electrode side, it was found that an overvoltage was generated and the solar cell was a good solar cell. The energy conversion efficiency of this solar cell was 0.8%.
[0069]
Example 5
An element similar to that of Example 4 was produced except that a graphite ribbon was used instead of the carbon nanotube. When light in the visible light range of this device was irradiated from the transparent electrode side, a photocurrent was observed. As a result of spectroscopy of the tungsten lamp and measuring the wavelength dependence of the photocurrent intensity, an optical response was observed for a wavelength of 700 nm or less.
[0070]
This solar cell showed rectifying properties, and when irradiated with monochromatic light having a wavelength of 635 nm from the transparent electrode side, it was found that an overvoltage was generated and the solar cell was a good solar cell. The conversion efficiency of this solar cell was 0.7%.
[0071]
Example 6
C 60 A device similar to that of Example 4 was produced except that graphite ribbon was used instead of fullerene and carbon nanotube. When this element was irradiated with light in the visible light region from the transparent electrode side, a photocurrent was observed. As a result of spectroscopy of the tungsten lamp and measuring the wavelength dependence of the photocurrent intensity, an optical response was observed for a wavelength of 700 nm or less.
[0072]
This solar cell showed rectifying properties, and when irradiated with monochromatic light having a wavelength of 635 nm from the transparent electrode side, it was found that an overvoltage was generated and the solar cell was a good solar cell. The conversion efficiency of this solar cell was 0.5%.
[0073]
Example 7
Except for forming a photosensitizing layer (thickness 40 nm) between the electron donating layer and the charge transporting layer by vacuum deposition of porphins (octaethylporphyrin) as a photosensitizer, as in Example 4. The device was fabricated. When this element was irradiated with light in the visible light region from the transparent electrode side, a photocurrent was observed. As a result of measuring the wavelength dependence of the photocurrent intensity by spectroscopic analysis of a tungsten lamp, an optical response was observed for a wavelength of 800 nm or less. In addition, the photocurrent value increased as compared with Example 4.
[0074]
When this solar cell was irradiated with monochromatic light having a wavelength of 635 nm from the transparent electrode side, it was found that an overvoltage was generated and the solar cell was a good solar cell. The energy conversion efficiency of this solar cell was 1.5%.
[0075]
Example 8
The conductive polymer OOPPV is dissolved in chlorobenzene, and C as an electron donor is added to this solution. 60 5 parts by weight of fullerene (based on 100 parts by weight of OOPPV) was added and sonicated. The obtained coating agent was spin-coated on a quartz glass substrate on which an ITO film was formed as a transparent electrode to form a thin film (electron donating layer having a thickness of 120 nm).
[0076]
In addition, the conductive polymer CNPPV is dissolved in trichlorethylene, and C as an electron acceptor is dissolved in this solution. 60 20 parts by weight of fullerene and 2 parts by weight of carbon nanotubes (average diameter of 40 to 200 nm, average length of 20 to 30 μm) as a charge transporter were added and subjected to ultrasonic treatment. The obtained coating agent was spin coated on the electron supply layer to form a charge transport layer (thickness 50 nm). Furthermore, aluminum was vapor-deposited on the charge transport layer to form an upper electrode, thereby producing a device.
[0077]
A power source was directly connected to the fabricated device, and the photoconductivity was examined. When light was not irradiated, the element was an insulator. When this element was irradiated with light in the visible light region from the transparent electrode side, a photocurrent was observed. As a result of spectroscopy of the tungsten lamp and measuring the wavelength dependence of the photocurrent intensity, an optical response was observed for a wavelength of 700 nm or less.
[0078]
This solar cell showed rectifying properties, and when irradiated with monochromatic light having a wavelength of 635 nm from the transparent electrode side, it was found that an overvoltage was generated and the solar cell was a good solar cell. The energy conversion efficiency of this solar cell was 2%.
[0079]
Example 9
Except for forming a photosensitizing layer (thickness 40 nm) between the electron donating layer and the charge transporting layer by vacuum deposition of porphins (octaethylporphyrin) as a photosensitizer, as in Example 8. The device was fabricated. When this element was irradiated with light in the visible light region from the transparent electrode side, a photocurrent was observed. As a result of spectroscopy of the tungsten lamp and measuring the wavelength dependence of the photocurrent intensity, a photoresponse was observed for wavelengths of 800 nm or less.
[0080]
This solar cell showed rectifying properties, and when irradiated with monochromatic light having a wavelength of 635 nm from the transparent electrode side, it was found that an overvoltage was generated and the solar cell was a good solar cell. The conversion efficiency of this solar cell was 3%.
[0081]
Example 10
C 60 Instead of fullerenes and carbon nanotubes, molecular modification C 60 A device similar to that of Example 8 was produced except that fullerene and molecularly modified carbon nanotubes were used. When this element was irradiated with light in the visible light region from the transparent electrode side, a photocurrent was observed. As a result of spectroscopy of the tungsten lamp and measuring the wavelength dependence of the photocurrent intensity, a photoresponse was observed for wavelengths of 800 nm or less.
[0082]
This solar cell showed rectifying properties, and when irradiated with monochromatic light having a wavelength of 635 nm from the transparent electrode side, it was found that an overvoltage was generated and the solar cell was a good solar cell. The conversion efficiency of this solar cell was 4%.
[0083]
Example 11
C 60 Instead of fullerenes and carbon nanotubes, molecular modification C 60 A device similar to that of Example 9 was produced except that fullerene and molecularly modified carbon nanotubes were used. When this element was irradiated with light in the visible light region from the transparent electrode side, a photocurrent was observed. As a result of spectroscopy of the tungsten lamp and measuring the wavelength dependence of the photocurrent intensity, a photoresponse was observed for wavelengths of 800 nm or less.
[0084]
This solar cell showed rectifying properties, and when irradiated with monochromatic light having a wavelength of 635 nm from the transparent electrode side, it was found that an overvoltage was generated and the solar cell was a good solar cell. The conversion efficiency of this solar cell was 5%.
[0085]
Example 12
C 60 Instead of fullerenes and carbon nanotubes, molecular modification C 60 A device similar to that of Example 8 was produced except that fullerene and a molecularly modified graphite ribbon were used. When this element was irradiated with light in the visible light region from the transparent electrode side, a photocurrent was observed. As a result of spectroscopy of the tungsten lamp and measuring the wavelength dependence of the photocurrent intensity, a photoresponse was observed for wavelengths of 800 nm or less.
[0086]
This solar cell showed rectifying properties, and when irradiated with monochromatic light having a wavelength of 635 nm from the transparent electrode side, it was found that an overvoltage was generated and the solar cell was a good solar cell. The conversion efficiency of this solar cell was 4.5%.
[0087]
Example 13
C 60 Instead of fullerenes and carbon nanotubes, molecular modification C 60 A device similar to that of Example 9 was produced except that fullerene and a molecularly modified graphite ribbon were used. When this element was irradiated with light in the visible light region from the transparent electrode side, a photocurrent was observed. As a result of spectroscopy of the tungsten lamp and measuring the wavelength dependence of the photocurrent intensity, a photoresponse was observed for wavelengths of 800 nm or less.
[0088]
This solar cell showed rectifying properties, and when irradiated with monochromatic light having a wavelength of 635 nm from the transparent electrode side, it was found that an overvoltage was generated and the solar cell was a good solar cell. The conversion efficiency of this solar cell was 5.3%.
[0089]
Example 14
C 60 A device similar to that of Example 8 was produced except that a molecularly modified graphite ribbon was used instead of fullerene and carbon nanotube. When this element was irradiated with light in the visible light region from the transparent electrode side, a photocurrent was observed. As a result of spectroscopy of the tungsten lamp and measuring the wavelength dependence of the photocurrent intensity, a photoresponse was observed for wavelengths of 800 nm or less.
[0090]
This solar cell showed rectifying properties, and when irradiated with monochromatic light having a wavelength of 635 nm from the transparent electrode side, it was found that an overvoltage was generated and the solar cell was a good solar cell. The conversion efficiency of this solar cell was 3.5%.
[0091]
Example 15
C 60 A device similar to that of Example 9 was produced except that a molecularly modified graphite ribbon was used instead of fullerene and carbon nanotube. When this element was irradiated with light in the visible light region from the transparent electrode side, a photocurrent was observed. As a result of spectroscopy of the tungsten lamp and measuring the wavelength dependence of the photocurrent intensity, a photoresponse was observed for wavelengths of 800 nm or less.
[0092]
This solar cell showed rectifying properties, and when irradiated with monochromatic light having a wavelength of 635 nm from the transparent electrode side, it was found that an overvoltage was generated and the solar cell was a good solar cell. The conversion efficiency of this solar cell was 4.6%.
[0093]
Example 16
As an element, a matrix resin OOPPV 60 parts by weight and CNPPV 30 parts by weight are combined with a molecular modification C as an electron acceptor. 60 A photoconductor was prepared by dispersing 5 parts by weight of fullerene, 2 parts by weight of molecularly modified carbon nanotubes as a charge transporter, and 3 parts by weight of the porphine as a photosensitizer. That is, the above components are mixed with a chlorobenzene / trichloroethylene mixed solvent, and the obtained coating agent is spin-coated on a quartz glass substrate on which an ITO film is formed as a transparent electrode to form a thin photoconductive layer (thickness 0.3 μm). Formed. Furthermore, aluminum was vapor-deposited on the photoconductive layer to form an upper electrode, thereby fabricating a device. When this element was irradiated with light in the visible light region from the transparent electrode side, a photocurrent was observed. As a result of spectroscopy of the tungsten lamp and measuring the wavelength dependence of the photocurrent intensity, a photoresponse was observed for wavelengths of 800 nm or less.
[0094]
This solar cell showed rectifying properties, and when irradiated with monochromatic light having a wavelength of 635 nm from the transparent electrode side, it was found that an overvoltage was generated and the solar cell was a good solar cell. The conversion efficiency of this solar cell was 3.5%.
[0095]
Example 17
C 60 A device similar to that of Example 16 was produced except that a molecularly modified graphite ribbon was used instead of fullerene and carbon nanotube. When this element was irradiated with light in the visible light region from the transparent electrode side, a photocurrent was observed. As a result of spectroscopy of the tungsten lamp and measuring the wavelength dependence of the photocurrent intensity, a photoresponse was observed for wavelengths of 800 nm or less.
[0096]
This solar cell showed rectifying properties, and when irradiated with monochromatic light having a wavelength of 635 nm from the transparent electrode side, it was found that an overvoltage was generated and the solar cell was a good solar cell. The conversion efficiency of this solar cell was 3.9%.
Claims (4)
マトリックス樹脂としての電子供与体に、電子受容体と、電荷輸送体と、光増感剤とを分散させた光電変換材料であって、
球殻状炭素が、フラーレン類、その修飾体およびその金属内包物から選択された少なくとも一種であり、
線状又は筒状炭素が、カーボンナノチューブおよびその修飾体から選択された少なくとも一種である光電変換材料。 Seen containing an electron donor, and a spherical shell-like carbon as an electron acceptor, and a linear or tubular carbon and photosensitizer as a charge transporter,
A photoelectric conversion material in which an electron acceptor, a charge transporter, and a photosensitizer are dispersed in an electron donor as a matrix resin,
The spherical shell carbon is at least one selected from fullerenes, modified products thereof, and metal inclusions thereof,
A photoelectric conversion material in which the linear or cylindrical carbon is at least one selected from carbon nanotubes and modified products thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002029524A JP4291973B2 (en) | 2001-02-08 | 2002-02-06 | Photoelectric conversion material and photovoltaic cell |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001-32652 | 2001-02-08 | ||
| JP2001032652 | 2001-02-08 | ||
| JP2002029524A JP4291973B2 (en) | 2001-02-08 | 2002-02-06 | Photoelectric conversion material and photovoltaic cell |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2008319724A Division JP4928533B2 (en) | 2001-02-08 | 2008-12-16 | Photoelectric conversion material and photovoltaic cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002335004A JP2002335004A (en) | 2002-11-22 |
| JP4291973B2 true JP4291973B2 (en) | 2009-07-08 |
Family
ID=26609145
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002029524A Expired - Fee Related JP4291973B2 (en) | 2001-02-08 | 2002-02-06 | Photoelectric conversion material and photovoltaic cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4291973B2 (en) |
Families Citing this family (37)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4211289B2 (en) * | 2002-05-29 | 2009-01-21 | 東レ株式会社 | Photovoltaic element |
| JP4189199B2 (en) * | 2002-10-29 | 2008-12-03 | 三井化学株式会社 | Organic solar cells |
| JPWO2004049458A1 (en) * | 2002-11-28 | 2006-03-30 | 新日本石油株式会社 | Photoelectric conversion element |
| FR2849539B1 (en) * | 2002-12-30 | 2005-04-15 | Nanoledge | DEVICE COMPRISING AT LEAST ONE TYPE OF TUBULAR NANOSTRUCTURE HAVING AT ITS SURFACE AT LEAST ONE COMPLEX PIGMENT |
| WO2004089822A1 (en) * | 2003-04-07 | 2004-10-21 | Ideal Star Inc. | Method and apparatus for producing gas atom containing fullerene, and gas atom containing fullerene |
| FR2856197B1 (en) * | 2003-06-11 | 2005-09-16 | Nanoledge | DEVICE COMPRISING AT LEAST ONE TYPE OF TUBULAR NANOSTRUCTURE IN FIBER FORM |
| ES2537515T3 (en) * | 2003-06-11 | 2015-06-09 | Axson Services Gmbh | Photovoltaic cell comprising carbon nanotubes that have a pigment on their surfaces |
| DE10326546A1 (en) * | 2003-06-12 | 2005-01-05 | Siemens Ag | Organic solar cell with an intermediate layer with asymmetric transport properties |
| JP4619660B2 (en) * | 2004-02-04 | 2011-01-26 | 信越ポリマー株式会社 | Photoelectric conversion element and manufacturing method thereof |
| JP4875837B2 (en) * | 2003-06-30 | 2012-02-15 | 株式会社イデアルスター | Solid-type dye-sensitized element and method for producing the same |
| JP2005032793A (en) * | 2003-07-08 | 2005-02-03 | Matsushita Electric Ind Co Ltd | Organic photoelectric converter |
| JP4221499B2 (en) * | 2003-08-27 | 2009-02-12 | 独立行政法人産業技術総合研究所 | Solar cell and manufacturing method thereof |
| JP4639336B2 (en) * | 2003-09-02 | 2011-02-23 | 国立大学法人信州大学 | Conductive polymer thin film composite |
| JP2005093307A (en) * | 2003-09-19 | 2005-04-07 | Konica Minolta Medical & Graphic Inc | Photoelectric conversion element |
| JP2005203659A (en) | 2004-01-19 | 2005-07-28 | Sony Corp | Photoelectric converting material and its manufacturing method, photoelectric converting element and its manufacturing method, and electronic device and its manufacturing method |
| JP4767498B2 (en) * | 2004-02-04 | 2011-09-07 | 信越ポリマー株式会社 | Photoelectric conversion element and manufacturing method thereof |
| JP5244287B2 (en) * | 2004-03-19 | 2013-07-24 | 富士フイルム株式会社 | Image sensor and method for applying electric field to image sensor |
| JP2005294042A (en) * | 2004-03-31 | 2005-10-20 | Nippon Sheet Glass Co Ltd | Photoelectric transducer and its manufacturing method |
| JP2007131536A (en) * | 2004-07-27 | 2007-05-31 | Vitamin C60 Bioresearch Kk | Skin melanin-controlling agent |
| JP2006073201A (en) * | 2004-08-31 | 2006-03-16 | Ideal Star Inc | Photoelectric conversion material, photoelectric conversion device and manufacturing method of photoelectric conversion material |
| KR101001744B1 (en) * | 2004-12-27 | 2010-12-15 | 삼성전자주식회사 | Photovoltaic electrode using carbon nanotube and photovoltaic cell comprising the same |
| JP2006190729A (en) * | 2005-01-04 | 2006-07-20 | Shinshu Univ | Optical sensor and its manufacturing method |
| WO2006112361A1 (en) * | 2005-04-18 | 2006-10-26 | Hiroshi Maeda | Polymeric pharmaceutical agent for treatment of cancer and process for production of the same |
| JP2007180190A (en) * | 2005-12-27 | 2007-07-12 | Toyota Central Res & Dev Lab Inc | Organic solar cell |
| JP4729708B2 (en) * | 2006-03-17 | 2011-07-20 | 国立大学法人信州大学 | Carbon fiber-conductive polymer composite film and method for producing the same |
| JP4817428B2 (en) * | 2006-03-24 | 2011-11-16 | 国立大学法人九州大学 | Photoresponsive electrode and organic solar cell using the same |
| DE102006031300A1 (en) * | 2006-06-29 | 2008-01-03 | Schmid Technology Systems Gmbh | Method for doping silicon material for solar cells, correspondingly doped silicon material and solar cell |
| JP2008091467A (en) * | 2006-09-29 | 2008-04-17 | Dainippon Printing Co Ltd | Organic thin film solar cell element and coating liquid for forming photoelectric conversion layer |
| JP2008091575A (en) * | 2006-09-29 | 2008-04-17 | Dainippon Printing Co Ltd | Organic thin film solar cell element and coating liquid for forming photoelectric conversion layer |
| JP2008243841A (en) * | 2007-03-23 | 2008-10-09 | Univ Of Yamanashi | Composition, optical conductor thin film, and optical conductor element |
| EP2154690A4 (en) * | 2007-04-27 | 2015-04-01 | Kuraray Co | Transparent conductive film and method for producing transparent conductive film |
| JP5127329B2 (en) * | 2007-07-12 | 2013-01-23 | 日立造船株式会社 | Photoelectric conversion element and manufacturing method thereof |
| JP5127330B2 (en) * | 2007-07-12 | 2013-01-23 | 日立造船株式会社 | Photoelectric conversion element and manufacturing method thereof |
| JP5093673B2 (en) * | 2008-04-17 | 2012-12-12 | 独立行政法人産業技術総合研究所 | Organic thin film solar cell |
| WO2010045308A2 (en) * | 2008-10-14 | 2010-04-22 | Drexel University | Polymer dispersed liquid crystal photovoltaic device and method for making |
| JP5381748B2 (en) * | 2010-01-27 | 2014-01-08 | コニカミノルタ株式会社 | Organic photoelectric conversion element, solar cell, and optical sensor array |
| JP5704563B2 (en) * | 2011-03-30 | 2015-04-22 | 独立行政法人産業技術総合研究所 | Photoelectric conversion element and solar cell |
-
2002
- 2002-02-06 JP JP2002029524A patent/JP4291973B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2002335004A (en) | 2002-11-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4291973B2 (en) | Photoelectric conversion material and photovoltaic cell | |
| Yang et al. | Functionalized methanofullerenes used as n-type materials in bulk-heterojunction polymer solar cells and in field-effect transistors | |
| US8017863B2 (en) | Polymer wrapped carbon nanotube near-infrared photoactive devices | |
| JP5566890B2 (en) | Organic photoelectric conversion element, solar cell, and optical sensor array | |
| US20090107539A1 (en) | Photoelectric device | |
| JP5583809B2 (en) | Organic solar cell | |
| JP5360197B2 (en) | Organic photoelectric conversion element, solar cell using the same, and optical sensor array | |
| JP2008109097A (en) | Material for photovolatic element and the photovolatic element | |
| KR20120038505A (en) | Methanofullerene derivatives and photoelectric conversion elements using same | |
| CN102203972A (en) | Merocyanines for producing photoactive layers for organic solar cells and organic photodetectors | |
| JP5098957B2 (en) | Organic photoelectric conversion element | |
| US20070295395A1 (en) | Photovoltaic Device With Trimetaspheres | |
| JP5712769B2 (en) | Organic photoelectric conversion element and solar cell | |
| JP5375066B2 (en) | Method for producing organic photoelectric conversion element, and organic photoelectric conversion element | |
| Yamamoto et al. | Extension of light-harvesting area of bulk-heterojunction solar cells by cosensitization with ring-expanded metallophthalocyanines fused with fluorene skeletons | |
| JP2010093099A (en) | Organic photoelectric converting element and method of manufacturing the same | |
| JP2010283003A (en) | Organic photoelectric conversion element, solar battery using the same, and photosensor array | |
| JP4928533B2 (en) | Photoelectric conversion material and photovoltaic cell | |
| JP5098956B2 (en) | Manufacturing method of organic photoelectric conversion element | |
| Zhen et al. | Benzo [c] thiophene–C60 Diadduct: An Electron Acceptor for p–n Junction Organic Solar Cells Harvesting Visible to Near‐IR Light | |
| JP2012209496A (en) | Photoelectric conversion element and solar cell | |
| Ma et al. | Efficient D1: D2: A Ternary Polymer Solar Cells with Low Voltage Loss and Unblocked Hole Transport Channel Characterized by Kelvin Probe Force Microscopy | |
| JP5413055B2 (en) | Organic photoelectric conversion element, solar cell using the same, and optical sensor array | |
| JP2014154653A (en) | Organic photoelectric conversion element, manufacturing method of the same and solar cell | |
| US9520564B2 (en) | Photoelectric conversion material, method for producing the same, and organic photovoltaic cell containing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20050131 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20080715 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20080715 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20080911 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20081021 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20081216 |
|
| 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: 20090310 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20090406 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120410 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150410 Year of fee payment: 6 |
|
| LAPS | Cancellation because of no payment of annual fees |