JP2013251485A - Photoelectric conversion element - Google Patents
Photoelectric conversion element Download PDFInfo
- Publication number
- JP2013251485A JP2013251485A JP2012126978A JP2012126978A JP2013251485A JP 2013251485 A JP2013251485 A JP 2013251485A JP 2012126978 A JP2012126978 A JP 2012126978A JP 2012126978 A JP2012126978 A JP 2012126978A JP 2013251485 A JP2013251485 A JP 2013251485A
- Authority
- JP
- Japan
- Prior art keywords
- photoelectric conversion
- ring
- group
- conversion element
- formula
- 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.)
- Granted
Links
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 74
- 150000001875 compounds Chemical class 0.000 claims abstract description 71
- 239000012044 organic layer Substances 0.000 claims abstract description 28
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical group 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 47
- 125000001424 substituent group Chemical group 0.000 claims description 46
- 125000004432 carbon atom Chemical group C* 0.000 claims description 31
- 229910003472 fullerene Inorganic materials 0.000 claims description 20
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 125000000623 heterocyclic group Chemical group 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 125000004429 atom Chemical group 0.000 claims description 4
- 125000005329 tetralinyl group Chemical group C1(CCCC2=CC=CC=C12)* 0.000 claims description 3
- -1 2-ethylhexyl group Chemical group 0.000 description 23
- 239000010409 thin film Substances 0.000 description 19
- 238000000034 method Methods 0.000 description 18
- 125000000217 alkyl group Chemical group 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 125000003118 aryl group Chemical group 0.000 description 14
- 239000010410 layer Substances 0.000 description 14
- 125000005843 halogen group Chemical group 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- 125000003545 alkoxy group Chemical group 0.000 description 9
- 229910052731 fluorine Inorganic materials 0.000 description 9
- 125000001153 fluoro group Chemical group F* 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 229920000144 PEDOT:PSS Polymers 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 239000000872 buffer Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- 230000032258 transport Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229910000846 In alloy Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000005036 alkoxyphenyl group Chemical group 0.000 description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 description 2
- 238000007611 bar coating method Methods 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000007756 gravure coating Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 238000007641 inkjet printing Methods 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- XURVRZSODRHRNK-UHFFFAOYSA-N o-quinodimethane Chemical compound C=C1C=CC=CC1=C XURVRZSODRHRNK-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 229920000123 polythiophene Polymers 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- ARGOTHVUUGQGPD-UHFFFAOYSA-N 1,2-bis(bromomethyl)-4,5-dimethoxybenzene Chemical compound COC1=CC(CBr)=C(CBr)C=C1OC ARGOTHVUUGQGPD-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 1
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 description 1
- YZWKKMVJZFACSU-UHFFFAOYSA-N 1-bromopentane Chemical compound CCCCCBr YZWKKMVJZFACSU-UHFFFAOYSA-N 0.000 description 1
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- MLRVZFYXUZQSRU-UHFFFAOYSA-N 1-chlorohexane Chemical compound CCCCCCCl MLRVZFYXUZQSRU-UHFFFAOYSA-N 0.000 description 1
- SQCZQTSHSZLZIQ-UHFFFAOYSA-N 1-chloropentane Chemical compound CCCCCCl SQCZQTSHSZLZIQ-UHFFFAOYSA-N 0.000 description 1
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- CMSGUKVDXXTJDQ-UHFFFAOYSA-N 4-(2-naphthalen-1-ylethylamino)-4-oxobutanoic acid Chemical compound C1=CC=C2C(CCNC(=O)CCC(=O)O)=CC=CC2=C1 CMSGUKVDXXTJDQ-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 125000003184 C60 fullerene group Chemical group 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- LFZAGIJXANFPFN-UHFFFAOYSA-N N-[3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-thiophen-2-ylpropyl]acetamide Chemical compound C(C)(C)C1=NN=C(N1C1CCN(CC1)CCC(C=1SC=CC=1)NC(C)=O)C LFZAGIJXANFPFN-UHFFFAOYSA-N 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- ULGYAEQHFNJYML-UHFFFAOYSA-N [AlH3].[Ca] Chemical compound [AlH3].[Ca] ULGYAEQHFNJYML-UHFFFAOYSA-N 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- JHYLKGDXMUDNEO-UHFFFAOYSA-N [Mg].[In] Chemical compound [Mg].[In] JHYLKGDXMUDNEO-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000005577 anthracene group Chemical group 0.000 description 1
- 150000004982 aromatic amines Chemical group 0.000 description 1
- 150000001601 aromatic carbocyclic compounds Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- UMIVXZPTRXBADB-UHFFFAOYSA-N benzocyclobutene Chemical class C1=CC=C2CCC2=C1 UMIVXZPTRXBADB-UHFFFAOYSA-N 0.000 description 1
- BFAKENXZKHGIGE-UHFFFAOYSA-N bis(2,3,5,6-tetrafluoro-4-iodophenyl)diazene Chemical compound FC1=C(C(=C(C(=C1F)I)F)F)N=NC1=C(C(=C(C(=C1F)F)I)F)F BFAKENXZKHGIGE-UHFFFAOYSA-N 0.000 description 1
- AQNQQHJNRPDOQV-UHFFFAOYSA-N bromocyclohexane Chemical compound BrC1CCCCC1 AQNQQHJNRPDOQV-UHFFFAOYSA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004744 butyloxycarbonyl group Chemical group 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 125000000000 cycloalkoxy group Chemical group 0.000 description 1
- 125000005170 cycloalkyloxycarbonyl group Chemical group 0.000 description 1
- WVIIMZNLDWSIRH-UHFFFAOYSA-N cyclohexylcyclohexane Chemical group C1CCCCC1C1CCCCC1 WVIIMZNLDWSIRH-UHFFFAOYSA-N 0.000 description 1
- 125000002933 cyclohexyloxy group Chemical group C1(CCCCC1)O* 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000006612 decyloxy group Chemical group 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 125000006371 dihalo methyl group Chemical group 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005446 heptyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000005935 hexyloxycarbonyl group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- LHJOPRPDWDXEIY-UHFFFAOYSA-N indium lithium Chemical compound [Li].[In] LHJOPRPDWDXEIY-UHFFFAOYSA-N 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- YZASAXHKAQYPEH-UHFFFAOYSA-N indium silver Chemical compound [Ag].[In] YZASAXHKAQYPEH-UHFFFAOYSA-N 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
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000005929 isobutyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])OC(*)=O 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000005928 isopropyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(OC(*)=O)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- SJCKRGFTWFGHGZ-UHFFFAOYSA-N magnesium silver Chemical compound [Mg].[Ag] SJCKRGFTWFGHGZ-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- UNFUYWDGSFDHCW-UHFFFAOYSA-N monochlorocyclohexane Chemical compound ClC1CCCCC1 UNFUYWDGSFDHCW-UHFFFAOYSA-N 0.000 description 1
- 125000006372 monohalo methyl group Chemical group 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006611 nonyloxy group Chemical group 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005447 octyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001148 pentyloxycarbonyl group Chemical group 0.000 description 1
- 125000005003 perfluorobutyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 125000005005 perfluorohexyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 125000005007 perfluorooctyl group Chemical group FC(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)* 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 1
- 229920000548 poly(silane) polymer Polymers 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229920002098 polyfluorene Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- IVFPNVDGWGXPMZ-YUMYIRISSA-N potamogetonol Chemical compound C([C@H]1[C@]2(CO)CCC[C@@]([C@H]2CCC1=C)(C)COC(=O)C)CC=1C=COC=1 IVFPNVDGWGXPMZ-YUMYIRISSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004742 propyloxycarbonyl group Chemical group 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 125000005920 sec-butoxy group Chemical group 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000005930 sec-butyloxycarbonyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(OC(*)=O)C([H])([H])[H] 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 125000005415 substituted alkoxy group Chemical group 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 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
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000004953 trihalomethyl group Chemical group 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Photovoltaic Devices (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
本発明は、フラーレン誘導体を用いた光電変換素子に関する。 The present invention relates to a photoelectric conversion element using a fullerene derivative.
光電変換素子は、陽極及び陰極からなる一対の電極と、該一対の電極間に設けられる活性層とを備える素子である。光電変換素子の一態様である有機層を含む有機薄膜太陽電池は、シリコン等の無機化合物からなる活性層を有する無機太陽電池に比べ、製造コストを大幅に低減できる可能性があり、より安価な太陽光発電素子として注目を集めている。
有機薄膜太陽電池の有機層に含まれる電荷(電子及びホール)輸送性を有する有機半導体材料としては、フラーレン誘導体が注目されており、例えば、2個の官能基で修飾されたフラーレンが検討されている。2個の官能基で修飾されたフラーレンとしては、例えば、1,2−ビス(ブロモメチル)−4,5−ジメトキシベンゼンから誘導した4,5−ジメトキシ−o−キノジメタンとC60フラーレンとを反応させて製造した、7種類の異性体からなる下記化合物が提案されている(非特許文献1)。
As an organic semiconductor material having a charge (electron and hole) transport property contained in an organic layer of an organic thin film solar cell, a fullerene derivative has attracted attention. For example, fullerene modified with two functional groups has been studied. Yes. As the fullerene modified with two functional groups, for example, 4,5-dimethoxy-o-quinodimethane derived from 1,2-bis (bromomethyl) -4,5-dimethoxybenzene and C 60 fullerene are reacted. The following compound consisting of seven types of isomers produced by the above method has been proposed (Non-patent Document 1).
しかし、上記7種類の異性体からなるフラーレン誘導体を含む有機光電変換素子は、光電変換効率が必ずしも十分でないという問題がある。 However, the organic photoelectric conversion element including the fullerene derivative composed of the seven types of isomers has a problem that the photoelectric conversion efficiency is not always sufficient.
本発明は、光電変換効率が高い有機光電変換素子を提供することを目的とする。 An object of this invention is to provide an organic photoelectric conversion element with high photoelectric conversion efficiency.
本発明は、下記[1]〜[13]を提供する。
[1] 陽極と、陰極と、該陽極と該陰極との間に設けられた式(I)で表される化合物を含む有機層とを有し、該有機層に含まれる式(I)で表される化合物の全重量に対する式(I)で表される化合物の1種の異性体の重量が50%以上である光電変換素子。
[2] B環がテトラリン環である[1]に記載の光電変換素子。
[3] 式(I)で表される化合物が式(II)で表される化合物である[1]に記載の光電変換素子を提供する。
[4] Ar1及びAr2が置換基を有していてもよいベンゼン環である[3]に記載の光電変換素子。
[5] A環が炭素原子数60のフラーレンである[1]又は[2]に記載の光電変換素子。
[6] nが2である[1]又は[2]に記載の光電変換素子。
[7] A環が炭素原子数60のフラーレンであり、nが2である[6]に記載の光電変換素子。
[8] 前記1種の異性体がtrans−2体、trans−4体、又はe体である[7]に記載の光電変換素子。
[9] A環が炭素原子数60のフラーレンである[3]又は[4]に記載の光電変換素子。
[10] 前記1種の異性体がtrans−2体、trans−4体、又はe体である[9]に記載の光電変換素子。
[11] 有機層に含まれる式(I)で表される化合物の全重量に対する式(I)で表される化合物の1種の異性体の重量が90%以上である[1]〜[10]のいずれか一項に記載の光電変換素子。
[12] [1]〜[11]のいずれか一項に記載の光電変換素子を含む太陽電池モジュール。
[13] [1]〜[11]のいずれか一項に記載の光電変換素子を含むイメージセンサー。
The present invention provides the following [1] to [13].
[1] An anode, a cathode, and an organic layer containing a compound represented by the formula (I) provided between the anode and the cathode, and the formula (I) contained in the organic layer The photoelectric conversion element whose weight of the 1 type isomer of the compound represented by Formula (I) with respect to the total weight of the represented compound is 50% or more.
[2] The photoelectric conversion device according to [1], wherein the B ring is a tetralin ring.
[3] The photoelectric conversion device according to [1], wherein the compound represented by the formula (I) is a compound represented by the formula (II).
[4] The photoelectric conversion device according to [3], wherein Ar1 and Ar2 are benzene rings which may have a substituent.
[5] The photoelectric conversion device according to [1] or [2], wherein the A ring is a fullerene having 60 carbon atoms.
[6] The photoelectric conversion element according to [1] or [2], wherein n is 2.
[7] The photoelectric conversion device according to [6], wherein the A ring is a fullerene having 60 carbon atoms and n is 2.
[8] The photoelectric conversion element according to [7], wherein the one kind of isomer is trans-2 isomer, trans-4 isomer, or e-isomer.
[9] The photoelectric conversion device according to [3] or [4], wherein the A ring is a fullerene having 60 carbon atoms.
[10] The photoelectric conversion element according to [9], wherein the one kind of isomer is trans-2 isomer, trans-4 isomer, or e-isomer.
[11] The weight of one isomer of the compound represented by the formula (I) with respect to the total weight of the compound represented by the formula (I) contained in the organic layer is 90% or more [1] to [10 ] The photoelectric conversion element as described in any one of.
[12] A solar cell module including the photoelectric conversion element according to any one of [1] to [11].
[13] An image sensor including the photoelectric conversion element according to any one of [1] to [11].
本発明によれば、変換効率が高い有機光電変換素子を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, an organic photoelectric conversion element with high conversion efficiency can be provided.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
<フラーレン誘導体>
本発明の有機光電変換素子は、前記式(I)で表される化合物(フラーレン誘導体)を含む有機層を有する。
<Fullerene derivative>
The organic photoelectric conversion element of this invention has an organic layer containing the compound (fullerene derivative) represented by the said Formula (I).
式(I)中、A環はフラーレン環を表す。フラーレン環としては、例えば、炭素原子数60のフラーレン(C60フラーレン)、炭素原子数70のフラーレン(C70フラーレン)、及び炭素原子数84のフラーレン(C84フラーレン)が挙げられる。中でも、A環としては、C70フラーレン、及びC60フラーレンが好ましく、C60フラーレンがより好ましい。 In formula (I), A ring represents a fullerene ring. Examples of the fullerene ring include fullerene having 60 carbon atoms (C 60 fullerene) , fullerene having 70 carbon atoms (C 70 fullerene) , and fullerene having 84 carbon atoms (C 84 fullerene). Specially, as the ring A, C 70 fullerene, and C 60 fullerenes are preferred, C 60 fullerene is more preferable.
式(I)中、B環は、環を構成する原子数が3以上の環を表す。中でも、環を構成する炭素原子数が3以上の環が好ましく、環を構成する炭素原子数が6以上の環がより好ましい。中でも、B環としては、テトラリン環が好ましい。 In formula (I), ring B represents a ring having 3 or more atoms constituting the ring. Among them, a ring having 3 or more carbon atoms constituting the ring is preferable, and a ring having 6 or more carbon atoms constituting the ring is more preferable. Among these, as the B ring, a tetralin ring is preferable.
式(I)中、C1及びC2はA環を構成する炭素原子であり、それらは互いに単結合で結合している。C1及びC2はまた、B環を構成する原子である。 In the formula (I), C1 and C2 are carbon atoms constituting the A ring, and they are bonded to each other by a single bond. C1 and C2 are also atoms constituting the B ring.
式(I)中、nは、2〜6の整数を表し、2であることが好ましい。mは、0〜8の整数を表し、2であることが好ましい。 In formula (I), n represents an integer of 2 to 6 and is preferably 2. m represents an integer of 0 to 8, and is preferably 2.
式(I)中、R1は置換基を表す。R1で表される置換基としては、例えば、ハロゲン原子、置換基を有していてもよいアルキル基、置換基を有していてもよいアルコキシ基、置換基を有していてもよいアリール基、及び置換基を有していてもよいアルコキシカルボニル基が挙げられる。R1が複数個ある場合、それらは同一でも異なっていてもよい。 In formula (I), R 1 represents a substituent. Examples of the substituent represented by R 1 include a halogen atom, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, and an aryl that may have a substituent. And an alkoxycarbonyl group which may have a substituent. When there are a plurality of R 1 s , they may be the same or different.
R1で表されるハロゲン原子としては、フッ素原子、塩素原子、臭素原子、及びヨウ素原子が挙げられる。光電変換素子の光電変換効率を高める観点から、ハロゲン原子としては、フッ素原子が好ましい。 Examples of the halogen atom represented by R 1 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. From the viewpoint of increasing the photoelectric conversion efficiency of the photoelectric conversion element, the halogen atom is preferably a fluorine atom.
R1で表されるアルキル基は、炭素原子数が通常1〜20であり、直鎖状でも分岐状でもよく、シクロアルキル基であってもよい。アルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、tert−ブチル基、sec−ブチル基、3−メチルブチル基、ペンチル基、ヘキシル基、2−エチルヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、及びラウリル基が挙げられる。前記アルキル基中の水素原子は置換基で置換されていてもよく、該置換基としてはハロゲン原子が挙げられる。ハロゲン原子で置換されたアルキル基としては、例えば、モノハロメチル基、ジハロメチル基、トリハロメチル基、及びペンタハロエチル基が挙げられる。アルキル基の置換基として用いられるハロゲン原子としては、フッ素原子が好ましい。フッ素原子で置換されたアルキル基としては、例えば、トリフルオロメチル基、ペンタフルオロエチル基、パーフルオロブチル基、パーフルオロヘキシル基、及びパーフルオロオクチル基が挙げられる。 The alkyl group represented by R 1 usually has 1 to 20 carbon atoms, may be linear or branched, and may be a cycloalkyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a sec-butyl group, a 3-methylbutyl group, a pentyl group, a hexyl group, and a 2-ethylhexyl group. , Heptyl group, octyl group, nonyl group, decyl group, and lauryl group. The hydrogen atom in the alkyl group may be substituted with a substituent, and examples of the substituent include a halogen atom. Examples of the alkyl group substituted with a halogen atom include a monohalomethyl group, a dihalomethyl group, a trihalomethyl group, and a pentahaloethyl group. As a halogen atom used as a substituent of an alkyl group, a fluorine atom is preferable. Examples of the alkyl group substituted with a fluorine atom include a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group, a perfluorohexyl group, and a perfluorooctyl group.
R1で表されるアルコキシ基は、炭素原子数が通常1〜20であり、直鎖状でも分岐状でもよく、シクロアルキルオキシ基であってもよい。アルコキシ基としては、例えば、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基、イソブトキシ基、sec−ブトキシ基、tert−ブトキシ基、ペンチルオキシ基、ヘキシルオキシ基、シクロヘキシルオキシ基、ヘプチルオキシ基、オクチルオキシ基、2−エチルヘキシルオキシ基、ノニルオキシ基、デシルオキシ基、3,7−ジメチルオクチルオキシ基、及びラウリルオキシ基が挙げられる。前記アルコキシ基中の水素原子は置換基で置換されていてもよく、該置換基としてはハロゲン原子が挙げられる。アルコキシ基の置換基として用いられるハロゲン原子としては、フッ素原子が好ましい。フッ素原子で置換されたアルコキシ基としては、例えば、トリフルオロメトキシ基、ペンタフルオロエトキシ基、パーフルオロブトキシ基、パーフルオロヘキシルオキシ基、及びパーフルオロオクチルオキシ基が挙げられる。 The alkoxy group represented by R 1 usually has 1 to 20 carbon atoms, may be linear or branched, and may be a cycloalkyloxy group. Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy Group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, and lauryloxy group. The hydrogen atom in the alkoxy group may be substituted with a substituent, and examples of the substituent include a halogen atom. The halogen atom used as a substituent for the alkoxy group is preferably a fluorine atom. Examples of the alkoxy group substituted with a fluorine atom include a trifluoromethoxy group, a pentafluoroethoxy group, a perfluorobutoxy group, a perfluorohexyloxy group, and a perfluorooctyloxy group.
R1で表されるアリール基は、無置換の芳香族炭素環化合物から芳香環上の水素原子1個を取り除いた基を意味する。アリール基の炭素原子数は通常6〜60であり、6〜20が好ましい。アリール基は、置換基を有していてもよい。アリール基が有していてもよい置換基としては、ハロゲン原子、炭素原子数1〜20の直鎖状又は分岐状のアルキル基、炭素原子数3〜20のシクロアルキル基、及び炭素原子数1〜20の直鎖状若しくは分岐状のアルキル基又は炭素原子数3〜20のシクロアルキル基をその構造中に含むアルコキシ基が挙げられる。アリール基の置換基として用いられるハロゲン原子としては、フッ素原子が好ましい。置換基を有していてもよいアリール基としては、例えば、フェニル基、C1〜C12アルコキシフェニル基(「C1〜C12」は、炭素原子数1〜12であることを示す。以下も同様である。)、C1〜C12アルキルフェニル基、1−ナフチル基、及び2−ナフチル基が挙げられ、C1〜C12アルコキシフェニル基、及びC1〜C12アルキルフェニル基がより好ましく、これらはハロゲン原子でさらに置換されていてもよい。 The aryl group represented by R 1 means a group obtained by removing one hydrogen atom on an aromatic ring from an unsubstituted aromatic carbocyclic compound. The number of carbon atoms of the aryl group is usually 6 to 60, and 6 to 20 is preferable. The aryl group may have a substituent. Examples of the substituent that the aryl group may have include a halogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and 1 carbon atom. Examples include an alkoxy group having -20 linear or branched alkyl groups or a cycloalkyl group having 3 to 20 carbon atoms in its structure. The halogen atom used as the substituent for the aryl group is preferably a fluorine atom. The aryl group which may have a substituent, for example, a phenyl group, C 1 -C 12 alkoxyphenyl group ( "C 1 -C 12" indicates that the 1 to 12 carbon atoms. The following And C 1 -C 12 alkylphenyl group, 1-naphthyl group, and 2-naphthyl group are mentioned, and C 1 -C 12 alkoxyphenyl group and C 1 -C 12 alkylphenyl group are more preferable. Preferably, these may be further substituted with a halogen atom.
R1で表されるアルコキシカルボニル基は、炭素原子数が通常1〜20であり、直鎖状でも分岐状でもよく、シクロアルキルオキシカルボニル基であってもよい。アルコキシカルボニル基としては、例えば、メトキシカルボニル基、エトキシカルボニル基、プロポキシカルボニル基、イソプロポキシカルボニル基、ブトキシカルボニル基、イソブトキシカルボニル基、sec−ブトキシカルボニル基、tert−ブトキシカルボニル基、ペンチルオキシカルボニル基、ヘキシルオキシカルボニル基、シクロヘキシルオキシカルボニル基、ヘプチルオキシカルボニル基、オクチルオキシカルボニル基、2−エチルヘキシルオキシカルボニル基、ノニルオキシカルボニル基、デシルオキシカルボニル基、3,7−ジメチルオクチルオキシカルボニル基、及びラウリルオキシカルボニル基が挙げられる。アルコキシカルボニル基は置換基を有していてもよく、該置換基としてはハロゲン原子が挙げられる。アルコキシカルボニル基の置換基として用いられるハロゲン原子としては、フッ素原子が好ましい。フッ素原子で置換されたアルコキシカルボニル基としては、例えば、トリフルオロメトキシカルボニル基、ペンタフルオロエトキシカルボニル基、パーフルオロブトキシカルボニル基、パーフルオロヘキシルオキシカルボニル基、及びパーフルオロオクチルオキシカルボニル基が挙げられる。 The alkoxycarbonyl group represented by R 1 usually has 1 to 20 carbon atoms, may be linear or branched, and may be a cycloalkyloxycarbonyl group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, an isobutoxycarbonyl group, a sec-butoxycarbonyl group, a tert-butoxycarbonyl group, and a pentyloxycarbonyl group. Hexyloxycarbonyl group, cyclohexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, 3,7-dimethyloctyloxycarbonyl group, and lauryl An oxycarbonyl group is mentioned. The alkoxycarbonyl group may have a substituent, and examples of the substituent include a halogen atom. The halogen atom used as a substituent for the alkoxycarbonyl group is preferably a fluorine atom. Examples of the alkoxycarbonyl group substituted with a fluorine atom include a trifluoromethoxycarbonyl group, a pentafluoroethoxycarbonyl group, a perfluorobutoxycarbonyl group, a perfluorohexyloxycarbonyl group, and a perfluorooctyloxycarbonyl group.
一実施形態において、式(I)で表される化合物としては、A環がC60フラーレン又はC70フラーレンであり、nが2である化合物が好ましく、A環がC60フラーレンであり、nが2である化合物がより好ましい。 In one embodiment, the compound represented by formula (I) is preferably a compound in which A ring is C 60 fullerene or C 70 fullerene, and n is 2, and A ring is C 60 fullerene, and n is The compound which is 2 is more preferable.
本発明の光電変換素子は、有機層に含まれる式(I)で表される化合物の全重量に対する式(I)で表される化合物の1種の異性体の重量が50%以上であることを特徴とする(「異性体」に関しては後述する)。式(I)で表される化合物として、A環がC60フラーレンであり、nが2である化合物を用いる場合、光電変換素子の光電変換効率を高める観点から、上記1種の異性体は、trans−2体、trans−4体、又はe体であることが好ましい。 In the photoelectric conversion element of the present invention, the weight of one isomer of the compound represented by the formula (I) with respect to the total weight of the compound represented by the formula (I) contained in the organic layer is 50% or more. ("Isomer" will be described later). As the compound represented by the formula (I), when a compound in which the A ring is C 60 fullerene and n is 2 is used, from the viewpoint of increasing the photoelectric conversion efficiency of the photoelectric conversion element, the one isomer is It is preferable that it is trans-2 body, trans-4 body, or e body.
式(I)で表される化合物としては、前記式(II)で表される化合物が好ましい。 As the compound represented by the formula (I), the compound represented by the formula (II) is preferable.
式(II)中、A環はフラーレン環を表す。フラーレン環の具体例は、式(I)について説明したとおりである。中でも、フラーレン環としては、C60フラーレン又はC70フラーレンが好ましく、C60フラーレンがより好ましい。 In formula (II), A ring represents a fullerene ring. Specific examples of the fullerene ring are as described for the formula (I). Among them, as the fullerene rings, preferably C 60 fullerene or C 70 fullerene, C 60 fullerene is more preferable.
式(II)中、R11、R12、R13、R14、R21、R22、R23、及びR24は、それぞれ独立に、水素原子又は置換基を表す。R11、R12、R13、R14、R21、R22、R23、及びR24で表される置換基の定義及び具体例は、前述のR1で表される置換基の定義及び具体例と同じである。 In formula (II), R 11 , R 12 , R 13, R 14 , R 21 , R 22 , R 23 , and R 24 each independently represent a hydrogen atom or a substituent. Definitions and specific examples of the substituent represented by R 11 , R 12 , R 13, R 14 , R 21 , R 22 , R 23 , and R 24 include the definition of the substituent represented by the aforementioned R 1 and It is the same as a specific example.
式(II)中、Ar1及びAr2は、それぞれ独立に、置換基を有していてもよい芳香族炭素環又は置換基を有していてもよい複素環を表す。芳香族炭素環としては、例えば、ベンゼン環、ナフタレン環、及びアントラセン環が挙げられる。複素環としては、例えば、チオフェン環、フラン環及びピロール環が挙げられる。芳香族炭素環及び複素環が有していてもよい置換基の定義及び具体例は、前述のR1で表される置換基の定義及び具体例と同じである。中でも、Ar1及びAr2としては、置換基を有していてもよい芳香族炭素環が好ましく、置換基を有していてもよいベンゼン環がより好ましい。 In formula (II), Ar1 and Ar2 each independently represent an aromatic carbocyclic ring which may have a substituent or a heterocyclic ring which may have a substituent. Examples of the aromatic carbocycle include a benzene ring, a naphthalene ring, and an anthracene ring. Examples of the heterocyclic ring include a thiophene ring, a furan ring, and a pyrrole ring. The definition and specific examples of the substituent that the aromatic carbocycle and the heterocyclic ring may have are the same as the definition and specific example of the substituent represented by R 1 described above. Especially, as Ar1 and Ar2, the aromatic carbocyclic ring which may have a substituent is preferable, and the benzene ring which may have a substituent is more preferable.
式(II)中、C1、C2、C3及びC4は、A環を構成する炭素原子であり、C1とC2は互いに単結合で結合しており、C3とC4は互いに単結合で結合している。 In the formula (II), C1, C2, C3 and C4 are carbon atoms constituting the A ring, C1 and C2 are bonded to each other by a single bond, and C3 and C4 are bonded to each other by a single bond. .
式(II)で表される化合物としては、A環がC60フラーレンである化合物が好ましく、この場合、上記1種の異性体としてはtrans−2体、trans−4体、又はe体が好ましい。 Examples of the compound represented by Formula (II), preferably Compound A ring is C 60 fullerene, in this case, the one trans-2-body as isomers, trans-4-body, or e are preferred .
式(II)で表される化合物としては、例えば、下記化合物が挙げられる。 Examples of the compound represented by the formula (II) include the following compounds.
中でも、A環がC60フラーレンである化合物が好ましく、trans−2体、trans−4体、又はe体の重量割合が50%以上の化合物が好適である。 Of these, compounds A ring is C 60 fullerene is preferred, trans-2-body, trans-4-body, or e Compounds weight ratio is more than 50% of are preferred.
式(I)で表される化合物の合成方法としては、例えば、ベンゾシクロブタン誘導体からo−キノジメタンを合成し、該o−キノジメタンとC60フラーレン等のフラーレンとをディールスアルダー反応させて合成する方法が挙げられる。得られた反応混合物をカラムクロマトグラフィーや分取ゲル浸透クロマトグラフィー(分取GPC)などを用いて精製し、位置異性体全成分に対し一種類の位置異性体成分の重量を50%以上に高める。 As a method for synthesizing the compound represented by the formula (I), for example, a method of synthesizing o-quinodimethane from a benzocyclobutane derivative and synthesizing the o-quinodimethane with a fullerene such as C 60 fullerene is synthesized. Can be mentioned. The obtained reaction mixture is purified using column chromatography, preparative gel permeation chromatography (preparative GPC), etc., and the weight of one regioisomer component is increased to 50% or more with respect to all regioisomer components. .
<光電変換素子>
本発明の光電変換素子は、陽極と、陰極と、該陽極と該陰極との間に設けられた式(I)で表される化合物を含む有機層とを有し、該有機層に含まれる式(I)で表される化合物の全重量に対する式(I)で表される化合物の1種の異性体の重量が50%以上であることを特徴とする。
<Photoelectric conversion element>
The photoelectric conversion element of the present invention has an anode, a cathode, and an organic layer containing a compound represented by the formula (I) provided between the anode and the cathode, and is included in the organic layer. The weight of one isomer of the compound represented by the formula (I) with respect to the total weight of the compound represented by the formula (I) is 50% or more.
本発明において、「異性体」とは、位置異性体をいう。例えば、式(I)で表される化合物が第1の異性体と第2の異性体とを含む場合、第1の異性体と第2の異性体とは、B環を含む付加分子のフラーレン環への結合位置が互いに異なる位置異性の関係にある。本発明の光電変換素子では、有機層に含まれる式(I)で表される化合物のうち1種の位置異性体の重量割合を50%以上に高めることによって、高い光電変換効率を実現したものである。 In the present invention, “isomer” refers to a positional isomer. For example, when the compound represented by the formula (I) includes a first isomer and a second isomer, the first isomer and the second isomer are fullerenes of an addition molecule including a B ring. The positions of bonding to the ring are different from each other in positional isomerism. In the photoelectric conversion element of the present invention, high photoelectric conversion efficiency is realized by increasing the weight ratio of one kind of positional isomer among compounds represented by formula (I) contained in the organic layer to 50% or more. It is.
光電変換素子の光電変換効率を高める観点から、有機層に含まれる式(I)で表される化合物の全重量に対する式(I)で表される化合物の1種の異性体の重量は、50%以上であり、好ましくは60%以上、70%以上、80%以上であり、より好ましくは90%以上であり、さらに好ましくは91%以上、92%以上、93%以上、94%以上、95%以上、96%以上、97%以上、98%以上、99%以上である。 From the viewpoint of increasing the photoelectric conversion efficiency of the photoelectric conversion element, the weight of one isomer of the compound represented by the formula (I) with respect to the total weight of the compound represented by the formula (I) contained in the organic layer is 50 % Or more, preferably 60% or more, 70% or more, 80% or more, more preferably 90% or more, still more preferably 91% or more, 92% or more, 93% or more, 94% or more, 95 % Or more, 96% or more, 97% or more, 98% or more, or 99% or more.
本発明の光電変換素子において、陽極と陰極の少なくとも一方は透明又は半透明であることが好ましい。 In the photoelectric conversion element of the present invention, it is preferable that at least one of the anode and the cathode is transparent or translucent.
有機層に含まれる式(I)で表される化合物は、電子受容性化合物として用いられても電子供与性化合物として用いられてもよいが、電子受容性化合物として用いられることが好ましい。 The compound represented by the formula (I) contained in the organic layer may be used as an electron accepting compound or an electron donating compound, but is preferably used as an electron accepting compound.
本発明の光電変換素子としては、下記1.又は2.の光電変換素子が好ましい。
1.少なくとも一方が透明又は半透明である陽極及び陰極と、該電極間に設けられた式(I)で表される化合物を含む第一の有機層と、該第一の有機層に隣接して設けられた電子供与性化合物を含む第二の有機層とを有する光電変換素子;
2.少なくとも一方が透明又は半透明である陽極及び陰極と、該電極間に設けられた式(I)で表される化合物及び電子供与性化合物を含む有機層を有する光電変換素子
As the photoelectric conversion element of the present invention, the following 1. Or 2. The photoelectric conversion element is preferable.
1. An anode and a cathode, at least one of which is transparent or translucent, a first organic layer containing a compound represented by the formula (I) provided between the electrodes, and provided adjacent to the first organic layer A photoelectric conversion element having a second organic layer containing the obtained electron donating compound;
2. A photoelectric conversion element comprising an anode and a cathode, at least one of which is transparent or translucent, and an organic layer containing a compound represented by formula (I) and an electron donating compound provided between the electrodes
ヘテロ接合界面を多く含むという観点から、前記2.の光電変換素子が好ましい。 From the viewpoint of including many heterojunction interfaces, 2. The photoelectric conversion element is preferable.
本発明の光電変換素子には、少なくとも一方の電極と式(I)で表される化合物を含む有機層との間に付加的な層を設けてもよい。付加的な層としては、例えば、ホール又は電子を輸送する電荷輸送層、及びバッファ層が挙げられる。 In the photoelectric conversion element of the present invention, an additional layer may be provided between at least one electrode and the organic layer containing the compound represented by the formula (I). Examples of the additional layer include a charge transport layer that transports holes or electrons, and a buffer layer.
バッファ層に用いられる材料としては、例えば、アルカリ金属のハロゲン化物(例えば、フッ化リチウム等)、アルカリ土類金属のハロゲン化物、アルカリ金属の酸化物、及びアルカリ土類金属の酸化物が挙げられる。また、酸化チタン等の無機半導体の微粒子をバッファ層に用いてもよい。 Examples of the material used for the buffer layer include alkali metal halides (for example, lithium fluoride), alkaline earth metal halides, alkali metal oxides, and alkaline earth metal oxides. . In addition, fine particles of inorganic semiconductor such as titanium oxide may be used for the buffer layer.
前記2.の光電変換素子において、式(I)で表される化合物及び電子供与性化合物を含む有機層中の式(I)で表される化合物の重量は、電子供与性化合物100重量部に対して、10〜1000重量部が好ましく、50〜500重量部がより好ましい。 2. In the photoelectric conversion element, the weight of the compound represented by the formula (I) in the organic layer containing the compound represented by the formula (I) and the electron donating compound is based on 100 parts by weight of the electron donating compound. 10-1000 weight part is preferable and 50-500 weight part is more preferable.
本発明の光電変換素子に用いられる式(I)で表される化合物を含む有機層は、式(I)で表される化合物を含む有機薄膜から形成されることが好ましい。該有機薄膜の厚さは、通常、1nm〜100μmであり、好ましくは2nm〜1000nmであり、より好ましくは5nm〜500nmであり、さらに好ましくは20nm〜200nmである。 The organic layer containing the compound represented by the formula (I) used in the photoelectric conversion element of the present invention is preferably formed from an organic thin film containing the compound represented by the formula (I). The thickness of the organic thin film is usually 1 nm to 100 μm, preferably 2 nm to 1000 nm, more preferably 5 nm to 500 nm, and further preferably 20 nm to 200 nm.
前記電子供与性化合物は、塗布法により簡便に有機層を形成できる観点から、高分子化合物が好ましい。電子供与性化合物として用い得る高分子化合物としては、例えば、ポリビニルカルバゾール及びその誘導体、ポリシラン及びその誘導体、側鎖又は主鎖に芳香族アミン構造を有するポリシロキサン誘導体、ポリアニリン及びその誘導体、ポリチオフェン及びその誘導体、ポリピロール及びその誘導体、ポリフェニレンビニレン及びその誘導体、ポリチエニレンビニレン及びその誘導体、ポリフルオレン及びその誘導体が挙げられる。 The electron donating compound is preferably a polymer compound from the viewpoint that an organic layer can be easily formed by a coating method. Examples of the polymer compound that can be used as the electron donating compound include polyvinyl carbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having an aromatic amine structure in the side chain or main chain, polyaniline and derivatives thereof, polythiophene and derivatives thereof. Derivatives, polypyrrole and its derivatives, polyphenylene vinylene and its derivatives, polythienylene vinylene and its derivatives, polyfluorene and its derivatives.
電子供与性化合物は、光電変換素子の光電変換効率を高める観点から、式(10)で表される繰り返し単位、及び式(11)で表される繰り返し単位からなる群から選ばれる1種以上の繰り返し単位を有する高分子化合物が好ましく、式(10)で表される繰り返し単位を有する高分子化合物がより好ましい。 The electron donating compound is one or more selected from the group consisting of the repeating unit represented by the formula (10) and the repeating unit represented by the formula (11) from the viewpoint of increasing the photoelectric conversion efficiency of the photoelectric conversion element. A polymer compound having a repeating unit is preferred, and a polymer compound having a repeating unit represented by formula (10) is more preferred.
R2、R3、R4、R5、R6、R7、R8、R9、R10、及びR15で表される置換基を有していてもよいアルキル基、置換基を有していてもよいアルコキシ基及び置換基を有していてもよいアリール基の定義及び具体例は、前述のR1で表される置換基を有していてもよいアルキル基、置換基を有していてもよいアルコキシ基及び置換基を有していてもよいアリール基の定義及び具体例と同じである。 R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , and an alkyl group that may have a substituent represented by R 15 , having a substituent The definition and specific examples of the optionally substituted alkoxy group and the optionally substituted aryl group include an alkyl group optionally having a substituent represented by the aforementioned R 1 and a substituent. The definition and specific examples of the alkoxy group which may be substituted and the aryl group which may have a substituent are the same.
光電変換素子の光電変換効率を高める観点から、R2とR3の少なくとも一方は、炭素原子数1〜20のアルキル基が好ましく、炭素原子数4〜8のアルキル基がより好ましい。 From the viewpoint of increasing the photoelectric conversion efficiency of the photoelectric conversion element, at least one of R 2 and R 3 is preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 4 to 8 carbon atoms.
原料モノマーの合成が容易であるため、R6、R7、R8、R9、R10、及びR15は水素原子が好ましい。光電変換素子の光電変換効率を高める観点から、R4及びR5は炭素原子数1〜20のアルキル基、又は炭素原子数6〜20のアリール基が好ましく、炭素原子数5〜8のアルキル基、又は炭素原子数6〜15のアリール基がより好ましい。 Since it is easy to synthesize raw material monomers, R 6 , R 7 , R 8 , R 9 , R 10 , and R 15 are preferably hydrogen atoms. From the viewpoint of increasing the photoelectric conversion efficiency of the photoelectric conversion element, R 4 and R 5 are preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and an alkyl group having 5 to 8 carbon atoms. Or an aryl group having 6 to 15 carbon atoms is more preferred.
本発明の光電変換素子は、通常、基板上に形成される。該基板は、電極を形成し、有機層を形成する際に化学的に変化しないものであればよい。基板の材料としては、例えば、ガラス、プラスチック、高分子フィルム、及びシリコンが挙げられる。不透明な基板の場合には、反対の電極(即ち、基板から遠い方の電極)が透明又は半透明であることが好ましい。 The photoelectric conversion element of the present invention is usually formed on a substrate. The substrate may be any substrate that does not chemically change when an electrode is formed and an organic layer is formed. Examples of the material for the substrate include glass, plastic, polymer film, and silicon. In the case of an opaque substrate, the opposite electrode (that is, the electrode far from the substrate) is preferably transparent or translucent.
電極の材料としては、例えば、金属、及び導電性高分子が挙げられる。一対の電極のうち一方の電極は仕事関数の小さい材料から形成されることが好ましい。仕事関数の小さい材料としては、例えば、リチウム、ナトリウム、カリウム、ルビジウム、セシウム、マグネシウム、カルシウム、ストロンチウム、バリウム、アルミニウム、スカンジウム、バナジウム、亜鉛、イットリウム、インジウム、セリウム、サマリウム、ユーロピウム、テルビウム、イッテルビウム等の金属;これらの金属のうちの2つ以上の金属の合金;これらの金属うちの1つ以上の金属と、金、銀、白金、銅、マンガン、チタン、コバルト、ニッケル、タングステン、錫のうちの1つ以上の金属との合金;グラファイト;及びグラファイト層間化合物が挙げられる。合金としては、例えば、マグネシウム−銀合金、マグネシウム−インジウム合金、マグネシウム−アルミニウム合金、インジウム−銀合金、リチウム−アルミニウム合金、リチウム−マグネシウム合金、リチウム−インジウム合金、及びカルシウム−アルミニウム合金が挙げられる。 Examples of the material of the electrode include metals and conductive polymers. One of the pair of electrodes is preferably formed of a material having a low work function. Examples of materials having a low work function include lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, and the like. An alloy of two or more of these metals; one or more of these metals and gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin And alloys with one or more metals; graphite; and graphite intercalation compounds. Examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, and calcium-aluminum alloy.
透明又は半透明の電極としては、導電性の金属酸化物膜、及び半透明の金属薄膜が挙げられる。透明又は半透明の電極の材料としては、例えば、酸化インジウム、酸化亜鉛、酸化スズ、それらの複合体(例えば、インジウム・スズ・オキサイド(ITO)、インジウム・亜鉛・オキサイド(IZO)、NESA等)、金、白金、銀、及び銅が挙げられ、ITO、IZO、及び酸化スズが好ましい。また、透明又は半透明の電極として、ポリアニリン及びその誘導体、ポリチオフェン及びその誘導体等の有機の透明導電膜を用いてもよい。 Examples of the transparent or translucent electrode include a conductive metal oxide film and a translucent metal thin film. Examples of the material of the transparent or translucent electrode include indium oxide, zinc oxide, tin oxide, and composites thereof (for example, indium tin oxide (ITO), indium zinc oxide (IZO), NESA, etc.) , Gold, platinum, silver, and copper, and ITO, IZO, and tin oxide are preferred. Moreover, you may use organic transparent electrically conductive films, such as a polyaniline and its derivative (s), polythiophene, and its derivative (s) as a transparent or translucent electrode.
電極の作製方法としては、例えば、真空蒸着法、スパッタリング法、イオンプレーティング法、及びメッキ法が挙げられる。 Examples of the electrode manufacturing method include a vacuum deposition method, a sputtering method, an ion plating method, and a plating method.
<有機層の製造方法>
有機層の製造方法は、特に制限されず、例えば、式(I)で表される化合物を含む溶液からの成膜による方法が挙げられる。
<Method for producing organic layer>
The method for producing the organic layer is not particularly limited, and examples thereof include a method by film formation from a solution containing the compound represented by formula (I).
溶液からの成膜に用いる溶媒は、式(I)で表される化合物を溶解させる溶媒であれば特に制限はない。該溶媒としては、例えば、トルエン、キシレン、メシチレン、テトラリン、デカリン、ビシクロヘキシル、ブチルベンゼン、sec−ブチルベゼン、tert−ブチルベンゼン等の炭化水素溶媒、四塩化炭素、クロロホルム、ジクロロメタン、ジクロロエタン、クロロブタン、ブロモブタン、クロロペンタン、ブロモペンタン、クロロヘキサン、ブロモヘキサン、クロロシクロヘキサン、ブロモシクロヘキサン、クロロベンゼン、ジクロロベンゼン、トリクロロベンゼン等のハロゲン化炭化水素溶媒、テトラヒドロフラン、テトラヒドロピラン等のエーテル溶媒が挙げられる。式(I)で表される化合物は、通常、前記溶媒に0.1重量%以上溶解させることができる。 The solvent used for film formation from a solution is not particularly limited as long as it is a solvent that dissolves the compound represented by formula (I). Examples of the solvent include hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decalin, bicyclohexyl, butylbenzene, sec-butylbesen, and tert-butylbenzene, carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, and bromobutane. And halogenated hydrocarbon solvents such as chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane, chlorobenzene, dichlorobenzene and trichlorobenzene, and ether solvents such as tetrahydrofuran and tetrahydropyran. The compound represented by the formula (I) can usually be dissolved in the solvent in an amount of 0.1% by weight or more.
式(I)で表される化合物を含む溶液は、さらに高分子化合物を含んでいてもよい。高分子化合物を含む場合、高分子化合物の溶解性の観点から、溶媒は、芳香族炭化水素溶媒が好ましく、トルエン、キシレン、及びメシチレンがより好ましい。 The solution containing the compound represented by formula (I) may further contain a polymer compound. When the polymer compound is included, from the viewpoint of solubility of the polymer compound, the solvent is preferably an aromatic hydrocarbon solvent, and more preferably toluene, xylene, and mesitylene.
溶液からの成膜には、スピンコート法、キャスティング法、マイクログラビアコート法、グラビアコート法、バーコート法、ロールコート法、ワイアーバーコート法、ディップコート法、スプレーコート法、スクリーン印刷法、フレキソ印刷法、オフセット印刷法、インクジェット印刷法、ディスペンサー印刷法、ノズルコート法、及びキャピラリーコート法等の塗布法を用いることができ、スピンコート法、フレキソ印刷法、インクジェット印刷法、及びディスペンサー印刷法が好ましい。 For film formation from solution, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen printing method, flexographic method Printing methods, offset printing methods, inkjet printing methods, dispenser printing methods, nozzle coating methods, capillary coating methods, and other coating methods can be used, and spin coating methods, flexographic printing methods, inkjet printing methods, and dispenser printing methods preferable.
光電変換素子は、透明又は半透明の電極から太陽光等の光を照射することにより、電極間に光起電力が発生し、有機薄膜太陽電池として動作させることができる。有機薄膜太陽電池を複数集積することにより有機薄膜太陽電池モジュールとして用いることもできる。 The photoelectric conversion element can be operated as an organic thin film solar cell by generating a photovoltaic force between the electrodes by irradiating light such as sunlight from a transparent or translucent electrode. It can also be used as an organic thin film solar cell module by integrating a plurality of organic thin film solar cells.
また、電極間に電圧を印加した状態で、透明又は半透明の電極から光を照射することにより、光電流が流れ、有機光センサーとして動作させることができる。有機光センサーを複数集積することにより有機イメージセンサーとして用いることもできる。 In addition, by applying light from a transparent or translucent electrode in a state where a voltage is applied between the electrodes, a photocurrent flows and it can be operated as an organic photosensor. It can also be used as an organic image sensor by integrating a plurality of organic photosensors.
以下、本発明をさらに詳細に説明するために実施例を示すが、本発明はこれらに限定されるものではない。 Examples will be shown below for illustrating the present invention in more detail, but the present invention is not limited to these examples.
<分析方法>
1H NMRスペクトルは、NMRスペクトロメーター(JNM−EX400、JEOL製)を用いて測定した。
高解像度マススペクトルは、MStationスペクトロメーター(ESI)(JMS−700、JEOL製)を用いて測定した。
元素分析は、京都大学元素分析センターにてヤナコ分析工業社製 MT−6を用いて実施した。
紫外可視吸収スペクトルは、紫外可視近赤外分光光度計(Lambda 900、Perkin Elmer製)にて測定した。
光電変換素子の光電変換効率は、標準的な2電極を有し、100mWcm−2、AM1.5の条件で、PEC−L11を付属したI−V特性計測装置(PECK2400−N、ペクセル・テクノロジーズ株式会社製)を用いて測定した。
NC60BAの異性体の分離は、分取カラムとしてNacalaiTesque cosmosil buckyprepを備えたリサイクル分取ゲル浸透クロマトグラフィー(LC−908、日本分析工業株式会社製)を用いて実施した。
<Analysis method>
1 H NMR spectrum was measured using an NMR spectrometer (JNM-EX400, manufactured by JEOL).
The high-resolution mass spectrum was measured using a MStation spectrometer (ESI) (JMS-700, manufactured by JEOL).
Elemental analysis was carried out using MT-6 manufactured by Yanaco Analytical Industries, Ltd. at Kyoto University Elemental Analysis Center.
The ultraviolet-visible absorption spectrum was measured with an ultraviolet-visible near-infrared spectrophotometer (Lambda 900, manufactured by Perkin Elmer).
The photoelectric conversion efficiency of the photoelectric conversion element has two standard electrodes, 100 mWcm −2 , AM1.5, and an IV characteristic measurement apparatus (PECK2400-N, Pexel Technologies Inc.) with PEC-L11 attached. (Made by company).
Separation of isomers of NC60BA was performed using recycle preparative gel permeation chromatography (LC-908, manufactured by Nihon Analytical Industries, Ltd.) equipped with a Nacalai Tesque cosmosil buckyprep as a preparative column.
<合成に用いた材料>
C60フラーレンは、MTR社製(純度99.98%)のフラーレンC60を購入し、精製を行わずに使用した。全ての溶媒及び有機化合物は、試薬グレードの溶媒及び有機化合物を購入し、特に記載のない場合を除き、精製を行わずに使用した。カラムクロマトグラフィーの充填剤には、SiliaFlash F60(230−400mesh、SiliCycle社製)を用いた。
<Materials used for synthesis>
C 60 fullerene, purchased fullerene C 60 of MTR Corp. (purity 99.98%) was used without purification. All solvents and organic compounds were purchased reagent-grade solvents and organic compounds and used without purification unless otherwise noted. SilicaFlash F60 (230-400 mesh, manufactured by SiliCycle) was used as a packing material for column chromatography.
製造例1
(化合物2の合成)
(Synthesis of Compound 2)
1.43gの化合物1(6.5mmol)、6.75mLのn−ヘキサノール(52.5mmol)、及び0.15mLの硫酸を、9mLのトルエンに加え、攪拌した。次いで、得られた溶液を18時間還流させた。反応生成物を、飽和炭酸水素ナトリウム水溶液、水、及び飽和食塩水で順次洗浄し、無水硫酸ナトリウムで乾燥させ、溶媒を留去した。得られた固体を、溶離液としてヘキサンと酢酸エチルとの混合液(ヘキサン:酢酸エチル(容積比)=20:1)を用いたシリカゲルクロマトグラフィーで精製し、無色オイル状の化合物2を2.17g(6.01mmol)得た。化合物2の収率は92%であった。 1.43 g of compound 1 (6.5 mmol), 6.75 mL of n-hexanol (52.5 mmol), and 0.15 mL of sulfuric acid were added to 9 mL of toluene and stirred. The resulting solution was then refluxed for 18 hours. The reaction product was washed successively with saturated aqueous sodium hydrogen carbonate solution, water and saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated. The obtained solid was purified by silica gel chromatography using a mixed solution of hexane and ethyl acetate (hexane: ethyl acetate (volume ratio) = 20: 1) as an eluent. 17 g (6.01 mmol) were obtained. The yield of compound 2 was 92%.
1H NMR(CDCl3、400MHz): δ 7.38(s, 2H), 4.26(t, 4H, J=6.59 Hz), 3.23(s, 4H), 1.71(m, 4H), 1.40-131(m, 12H), 0.89(t, 6H, J=5.21 Hz). 1 H NMR (CDCl 3 , 400 MHz): δ 7.38 (s, 2H), 4.26 (t, 4H, J = 6.59 Hz), 3.23 (s, 4H), 1.71 (m, 4H), 1.40-131 (m, 12H), 0.89 (t, 6H, J = 5.21 Hz).
Anal. Calcd for C22H32O4: C, 73.30%; H, 8.95%; O, 17.75%.
Found: C, 73.54%; H, 9.00%; O, 17.74%.
Anal.Calcd for C22H32O4: C, 73.30%; H, 8.95%; O, 17.75%.
Found: C, 73.54%; H, 9.00%; O, 17.74%.
IR (ATR): νmax/cm−1 2956, 2932, 2858, 1724, 1587, 1467, 1407, 1388, 1338, 1262, 1190, 1176, 1103, 998, 893, 782. IR (ATR): νmax / cm -1 2956, 2932, 2858, 1724, 1587, 1467, 1407, 1388, 1338, 1262, 1190, 1176, 1103, 998, 893, 782.
HRMS (ESI): calcd for C22H33O4[M+H] 361.2373, found 361.2368. HRMS (ESI): calcd for C22H33O4 [M + H] 361.2373, found 361.2368.
製造例2
(NC60BAの合成)
(Synthesis of NC60BA)
2.17gの化合物2(6.01mmol)、及び2.16gのフラーレンC60(3.0mmol)を216mLのo−ジクロロベンゼンに溶解させ、得られた溶液を220℃に加熱し、48時間還流させた。次いで、溶媒を留去した反応生成物を、トルエンを用いたシリカゲルクロマトグラフィーで精製することにより、未反応のフラーレンC60及びNC60MAを分離した。次いで、精製後の反応生成物を、トルエンを用いたリサイクル分取ゲル浸透クロマトグラフィーにより精製し、NC60BAを1.87g得た。NC60BAは、複数の異性体を含む混合物であり、収率は43%であった。なお、NC60BA(混合物)中の各異性体の割合は、trans−1体:3%、trans−2体:18%、trans−3体:31%、trans−4体:11%、e体:29%、cis−2体及びcis−3体の合計:7%、cis−1体:1%以下であった。 2.17 g of compound 2 (6.01 mmol) and 2.16 g of fullerene C 60 (3.0 mmol) were dissolved in 216 mL of o-dichlorobenzene, and the resulting solution was heated to 220 ° C. and refluxed for 48 hours. I let you. Then, the reaction product and the solvent was distilled off, purified by silica gel chromatography using toluene, to separate the fullerene C 60 and NC60MA unreacted. Subsequently, the purified reaction product was purified by recycle preparative gel permeation chromatography using toluene to obtain 1.87 g of NC60BA. NC60BA was a mixture containing a plurality of isomers, and the yield was 43%. In addition, the ratio of each isomer in NC60BA (mixture) is as follows: trans-1 form: 3%, trans-2 form: 18%, trans-3 form: 31%, trans-4 form: 11%, e form: The total of 29%, cis-2 body and cis-3 body: 7%, cis-1 body: 1% or less.
1H NMR(CDCl3、400MHz): δ 8.22-7.51(m, 4H), 5.01-3.91(m, 16H), 1.82(m, 8H), 1.42-1.25(m, 24H), 0.90(m, 12H). 1 H NMR (CDCl 3 , 400 MHz): δ 8.22-7.51 (m, 4H), 5.01-3.91 (m, 16H), 1.82 (m, 8H), 1.42-1.25 (m, 24H), 0.90 (m, 12H ).
Anal. Calcd for C104H64O8: C, 86.65%; H, 4.47%; O, 8.88%.
Found: C, 84.21%; H, 4.43%; O, 8.64%.
Anal.Calcd for C104H64O8: C, 86.65%; H, 4.47%; O, 8.88%.
Found: C, 84.21%; H, 4.43%; O, 8.64%.
IR (ATR): νmax/cm−1 2951, 2927, 2855, 1722, 1616, 1573, 1456, 1414, 1379, 1330, 1279, 1218, 1167, 1122, 1040, 896, 789, 766, 725, 696,670, 575, 526. IR (ATR): νmax / cm -1 2951, 2927, 2855, 1722, 1616, 1573, 1456, 1414, 1379, 1330, 1279, 1218, 1167, 1122, 1040, 896, 789, 766, 725, 696,670, 575, 526.
HRMS (ESI): calcd for C104H65O8[M+H] 1441.4674, found 1441.4664. HRMS (ESI): calcd for C104H65O8 [M + H] 1441.4674, found 1441.4664.
製造例3
(NC60BAの異性体の分離)
分取カラムとしてNacalaiTesque cosmosil buckyprepを備えたリサイクル分取ゲル浸透クロマトグラフィーにより、50℃でNC60BAの異性体を分離し、NC60BA(trans−2)、NC60BA(trans−4)、及びNC60BA(e)を分取した。リサイクル分取ゲル浸透クロマトグラフィーによる測定で得られたチャートの面積比から、分取したNC60BA(trans−2)の純度、NC60BA(trans−4)の純度、及びNC60BA(e)の純度が、いずれも99%以上であることを確認した。
Production Example 3
(Separation of NC60BA isomers)
Separation of NC60BA isomers at 50 ° C. by recycle preparative gel permeation chromatography equipped with a Nacalai Tesque cosmosil buckyprep as a preparative column to obtain NC60BA (trans-2), NC60BA (trans-4), and NC60BA (e). Sorted. From the area ratio of the chart obtained by the measurement by recycle preparative gel permeation chromatography, the purity of NC60BA (trans-2), NC60BA (trans-4), and NC60BA (e), Was also confirmed to be 99% or more.
NC60BA(trans−2)
1H NMR (C2D2Cl4、393K、400MHz): δ 8.13(s, 2H), 8.07(s, 2H), 4.92(d, 2H, J= 14.15 Hz), 4.74(d, 4H, J= 14.15 Hz), 4.63(d, 2H, J= 14.16 Hz), 4.45(m, 8H), 1.90(m, 8H), 1.59-1.39(m, 24H), 0.99(m, 12H).
IR (ATR): νmax/cm−1 2952, 2928, 2856, 1723, 1616, 1574, 1558, 1538, 1495, 1464, 1456, 1431, 1415, 1378, 1331, 1280, 1221, 1203, 1168, 1122, 1086, 1040, 900, 790, 767, 737, 696, 671, 577, 561, 542, 528.
HRMS (ESI): calcd for C104H65O8[M+H] 1441.4674, found 1441.4640.
NC60BA (trans-2)
1 H NMR (C 2 D 2 Cl 4 , 393 K, 400 MHz): δ 8.13 (s, 2H), 8.07 (s, 2H), 4.92 (d, 2H, J = 14.15 Hz), 4.74 (d, 4H, J = 14.15 Hz), 4.63 (d, 2H, J = 14.16 Hz), 4.45 (m, 8H), 1.90 (m, 8H), 1.59-1.39 (m, 24H), 0.99 (m, 12H).
IR (ATR): νmax / cm -1 2952, 2928, 2856, 1723, 1616, 1574, 1558, 1538, 1495, 1464, 1456, 1431, 1415, 1378, 1331, 1280, 1221, 1203, 1168, 1122, 1086, 1040, 900, 790, 767, 737, 696, 671, 577, 561, 542, 528.
HRMS (ESI): calcd for C104H65O8 [M + H] 1441.4674, found 1441.4640.
NC60BA(trans−4)
1H NMR (C2D2Cl4、393K、400MHz): δ 7.98(s, 2H), 7.86(s, 2H), 4.58(d, 2H, J= 14.15 Hz), 4.50(d, 2H, J= 14.15 Hz), 4.45-4.35(m, 12H), 1.87(m, 8H), 1.55-1.37(m, 24H), 0.99(m, 12H).
IR (ATR): νmax/cm−1 2952, 2927, 2855, 1717, 1616, 1573, 1453, 1377, 1330, 1278, 1217, 1165, 1121, 697, 538, 524, 506, 491, 469, 457, 418.
HRMS (ESI): calcd for C104H65O8[M+H] 1441.4674, found 1441.4641.
NC60BA (trans-4)
1 H NMR (C 2 D 2 Cl 4 , 393K, 400 MHz): δ 7.98 (s, 2H), 7.86 (s, 2H), 4.58 (d, 2H, J = 14.15 Hz), 4.50 (d, 2H, J = 14.15 Hz), 4.45-4.35 (m, 12H), 1.87 (m, 8H), 1.55-1.37 (m, 24H), 0.99 (m, 12H).
IR (ATR): νmax / cm -1 2952, 2927, 2855, 1717, 1616, 1573, 1453, 1377, 1330, 1278, 1217, 1165, 1121, 697, 538, 524, 506, 491, 469, 457, 418.
HRMS (ESI): calcd for C104H65O8 [M + H] 1441.4674, found 1441.4641.
NC60BA(e)
1H NMR(C2D2Cl4、393K、400MHz): δ 7.92(s, 1H), 7.90(s, 2H), 7.84(s, 1H), 4.44-4.31(m, 14H), 4.09(b, 2H), 1.85(m, 8H), 1.56-1.42(m, 24H), 0.97(m, 12H).
IR (ATR): νmax/cm−1 2952, 2926, 2855, 1723, 1570, 1458, 1412, 1373, 1330, 1279, 1219, 1198, 1170, 1122, 1026, 889, 552, 526.
HRMS (ESI): calcd for C104H65O8[M+H] 1441.4674, found 1441.4638.
NC60BA (e)
1 H NMR (C 2 D 2 Cl 4 , 393K, 400 MHz): δ 7.92 (s, 1H), 7.90 (s, 2H), 7.84 (s, 1H), 4.44-4.31 (m, 14H), 4.09 (b , 2H), 1.85 (m, 8H), 1.56-1.42 (m, 24H), 0.97 (m, 12H).
IR (ATR): νmax / cm -1 2952, 2926, 2855, 1723, 1570, 1458, 1412, 1373, 1330, 1279, 1219, 1198, 1170, 1122, 1026, 889, 552, 526.
HRMS (ESI): calcd for C104H65O8 [M + H] 1441.4674, found 1441.4638.
実施例1
(有機薄膜太陽電池の作製及び評価)
シート抵抗が5Ω/sqのITO(ジオマテック株式会社製)薄膜が設けられたガラス基板をアセトンに浸して10分間超音波洗浄を行い、次いで、エタノールに浸して10分間超音波洗浄を行った。ガラス基板を乾燥させた後、UV−オゾン処理を行った。次いで、ガラス基板のITO薄膜上に、ポリスチレンスルホン酸でドープされたポリ(エチレンジオキシチオフェン)を含む液(PEDOT:PSS、Clevios P製)を1000rpmの条件でスピンコートし、ホットプレートを用いて、200℃で10分間乾燥させて、PEDOT:PSS層を形成した。次いで、ポリ(3−ヘキシルチオフェン)とNC60BA(trans−2)とを含むo−ジクロロベンゼン溶液を、1500rpm、1分間の条件でPEDOT:PSS層上にスピンコートし、バルクヘテロ接合構造の活性層を形成した。o−ジクロロベンゼン溶液中のポリ(3−ヘキシルチオフェン)の濃度は15mg/mLであり、o−ジクロロベンゼン溶液中のNC60BA(trans−2)の濃度は13.5mg/mLであった。その後、活性層を150℃で15分間アニールした。活性層の厚さは90nmであった。次いで、活性層上にAlを蒸着し、有機薄膜太陽電池を作製した。有機薄膜太陽電池の光電変換効率は、PECK2400−Nを用いて測定した。結果を表1に示す。
Example 1
(Production and evaluation of organic thin-film solar cells)
A glass substrate provided with an ITO (manufactured by Geomat Co., Ltd.) thin film having a sheet resistance of 5Ω / sq was immersed in acetone and subjected to ultrasonic cleaning for 10 minutes, and then immersed in ethanol and subjected to ultrasonic cleaning for 10 minutes. After the glass substrate was dried, UV-ozone treatment was performed. Next, a liquid (PEDOT: PSS, manufactured by Clevios P) containing poly (ethylenedioxythiophene) doped with polystyrene sulfonic acid is spin-coated on the ITO thin film of the glass substrate under the condition of 1000 rpm, and a hot plate is used. And dried at 200 ° C. for 10 minutes to form a PEDOT: PSS layer. Next, an o-dichlorobenzene solution containing poly (3-hexylthiophene) and NC60BA (trans-2) is spin-coated on the PEDOT: PSS layer at 1500 rpm for 1 minute, and an active layer having a bulk heterojunction structure is formed. Formed. The concentration of poly (3-hexylthiophene) in the o-dichlorobenzene solution was 15 mg / mL, and the concentration of NC60BA (trans-2) in the o-dichlorobenzene solution was 13.5 mg / mL. Thereafter, the active layer was annealed at 150 ° C. for 15 minutes. The thickness of the active layer was 90 nm. Subsequently, Al was vapor-deposited on the active layer, and the organic thin film solar cell was produced. The photoelectric conversion efficiency of the organic thin film solar cell was measured using PECK2400-N. The results are shown in Table 1.
実施例2
(有機薄膜太陽電池の作製及び評価)
NC60BA(trans−2)に代えてNC60BA(trans−4)を用いた以外は実施例1と同様に有機薄膜太陽電池を作製し、光電変換効率を測定した。結果を表1に示す。
Example 2
(Production and evaluation of organic thin-film solar cells)
An organic thin film solar cell was produced in the same manner as in Example 1 except that NC60BA (trans-4) was used instead of NC60BA (trans-2), and the photoelectric conversion efficiency was measured. The results are shown in Table 1.
実施例3
(有機薄膜太陽電池の作製及び評価)
NC60BA(trans−2)に代えてNC60BA(e)を用いた以外は実施例1と同様に有機薄膜太陽電池を作製し、光電変換効率を測定した。結果を表1に示す。
Example 3
(Production and evaluation of organic thin-film solar cells)
An organic thin-film solar cell was produced in the same manner as in Example 1 except that NC60BA (e) was used instead of NC60BA (trans-2), and the photoelectric conversion efficiency was measured. The results are shown in Table 1.
比較例1
(有機薄膜太陽電池の作製及び評価)
NC60BA(trans−2)に代えて、製造例2で製造した複数の異性体を含む混合物であるNC60BAを用いた以外は実施例1と同様に有機薄膜太陽電池を作製し、光電変換効率を測定した。結果を表1に示す。
Comparative Example 1
(Production and evaluation of organic thin-film solar cells)
An organic thin film solar cell was prepared in the same manner as in Example 1 except that NC60BA, which was a mixture containing a plurality of isomers produced in Production Example 2, was used instead of NC60BA (trans-2), and the photoelectric conversion efficiency was measured. did. The results are shown in Table 1.
Claims (13)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012126978A JP6101007B2 (en) | 2012-06-04 | 2012-06-04 | Photoelectric conversion element |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012126978A JP6101007B2 (en) | 2012-06-04 | 2012-06-04 | Photoelectric conversion element |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2013251485A true JP2013251485A (en) | 2013-12-12 |
JP6101007B2 JP6101007B2 (en) | 2017-03-22 |
Family
ID=49849866
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2012126978A Active JP6101007B2 (en) | 2012-06-04 | 2012-06-04 | Photoelectric conversion element |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP6101007B2 (en) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000344764A (en) * | 1999-05-28 | 2000-12-12 | Univ Tokyo | C60 fullerene molecular derivative and synthesis of c60 fullerene molecular derivative |
US6162926A (en) * | 1995-07-31 | 2000-12-19 | Sphere Biosystems, Inc. | Multi-substituted fullerenes and methods for their preparation and characterization |
JP2009076683A (en) * | 2007-09-20 | 2009-04-09 | Dainippon Printing Co Ltd | Organic thin-film solar cell |
JP2011504168A (en) * | 2007-09-21 | 2011-02-03 | ソレンネ ベーヴェー | Fullerene multi-adduct composition |
JP2011238847A (en) * | 2010-05-12 | 2011-11-24 | Mitsubishi Chemicals Corp | Photoelectric conversion element |
-
2012
- 2012-06-04 JP JP2012126978A patent/JP6101007B2/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6162926A (en) * | 1995-07-31 | 2000-12-19 | Sphere Biosystems, Inc. | Multi-substituted fullerenes and methods for their preparation and characterization |
JP2000344764A (en) * | 1999-05-28 | 2000-12-12 | Univ Tokyo | C60 fullerene molecular derivative and synthesis of c60 fullerene molecular derivative |
JP2009076683A (en) * | 2007-09-20 | 2009-04-09 | Dainippon Printing Co Ltd | Organic thin-film solar cell |
JP2011504168A (en) * | 2007-09-21 | 2011-02-03 | ソレンネ ベーヴェー | Fullerene multi-adduct composition |
JP2011238847A (en) * | 2010-05-12 | 2011-11-24 | Mitsubishi Chemicals Corp | Photoelectric conversion element |
Also Published As
Publication number | Publication date |
---|---|
JP6101007B2 (en) | 2017-03-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5639753B2 (en) | Fullerene derivatives | |
JP5369384B2 (en) | Organic photoelectric conversion device and polymer useful for production thereof | |
TW201130883A (en) | High-polymer compound, film containing the same and ink composition | |
EP2457898A1 (en) | Fullerene derivative | |
JP5906803B2 (en) | Organic photoelectric conversion element material and method for producing organic photoelectric conversion element | |
JP2010092964A (en) | Fullerene derivative | |
JP6687025B2 (en) | Photoelectric conversion element | |
JP2011181719A (en) | Fullerene derivative and method of manufacturing the same | |
JP2010034494A (en) | Organic photoelectric conversion element | |
JP5213392B2 (en) | Fullerene derivatives | |
US8673958B2 (en) | Fullerene derivatives | |
JP2013237828A (en) | Method for producing nitrogen-containing compound | |
WO2012111784A1 (en) | Manufacturing method for organic photoelectric conversion element | |
JP5740823B2 (en) | Compound and device using the same | |
JP2015013844A (en) | Fullerene derivative | |
JP6101007B2 (en) | Photoelectric conversion element | |
JP5927965B2 (en) | Manufacturing method of organic photoelectric conversion element | |
JP5503184B2 (en) | Fullerene derivative, composition and organic photoelectric conversion device | |
JP5515261B2 (en) | Composition and organic photoelectric conversion device using the same | |
WO2013047293A1 (en) | Photoelectric conversion element | |
JP6697820B2 (en) | Photoelectric conversion element and fullerene derivative | |
JP2015105233A (en) | Fullerene derivative | |
JP5481911B2 (en) | Fullerene derivatives | |
JP5855391B2 (en) | Method for producing compound | |
WO2011132573A1 (en) | Fullerene derivative and method for producing same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
RD04 | Notification of resignation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7424 Effective date: 20140509 |
|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20150309 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20150309 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20160202 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20160331 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20160823 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20161005 |
|
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: 20170214 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20170224 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 6101007 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |