CN102510851B - 亚甲基富勒烯衍生物及使用其的光电转换器件 - Google Patents
亚甲基富勒烯衍生物及使用其的光电转换器件 Download PDFInfo
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- CN102510851B CN102510851B CN201080042543.XA CN201080042543A CN102510851B CN 102510851 B CN102510851 B CN 102510851B CN 201080042543 A CN201080042543 A CN 201080042543A CN 102510851 B CN102510851 B CN 102510851B
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- Prior art keywords
- alkyl
- methanofullerene
- methanofullerene derivative
- derivative
- nmr
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- 239000000463 material Substances 0.000 claims abstract description 48
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 40
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 26
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000001721 carbon Chemical group 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 12
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006073 displacement reaction Methods 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims description 7
- WHLUQAYNVOGZST-UHFFFAOYSA-N tifenamil Chemical group C=1C=CC=CC=1C(C(=O)SCCN(CC)CC)C1=CC=CC=C1 WHLUQAYNVOGZST-UHFFFAOYSA-N 0.000 claims description 6
- 229920000547 conjugated polymer Polymers 0.000 claims description 3
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims description 3
- 239000004065 semiconductor Substances 0.000 abstract description 10
- -1 p-phenylene vinylene Chemical group 0.000 description 56
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 32
- 239000004215 Carbon black (E152) Substances 0.000 description 24
- 229930195733 hydrocarbon Natural products 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 22
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 20
- 238000000034 method Methods 0.000 description 19
- 238000005481 NMR spectroscopy Methods 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 15
- 125000003118 aryl group Chemical group 0.000 description 13
- 239000000758 substrate Substances 0.000 description 13
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 description 12
- 125000003545 alkoxy group Chemical group 0.000 description 12
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 12
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 11
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 10
- 239000012300 argon atmosphere Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 10
- 239000010408 film Substances 0.000 description 9
- 239000005864 Sulphur Substances 0.000 description 8
- 229930192474 thiophene Natural products 0.000 description 8
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 7
- 125000006350 alkyl thio alkyl group Chemical group 0.000 description 7
- 239000000203 mixture Substances 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
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910003472 fullerene Inorganic materials 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000002955 isolation Methods 0.000 description 5
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920000123 polythiophene Polymers 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229920000109 alkoxy-substituted poly(p-phenylene vinylene) Polymers 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 150000003573 thiols Chemical class 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-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
- 125000000066 S-methyl group Chemical group [H]C([H])([H])S* 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 2
- 125000001118 alkylidene group Chemical group 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 150000004292 cyclic ethers Chemical class 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000002933 cyclohexyloxy group Chemical group C1(CCCCC1)O* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 230000005669 field effect Effects 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 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 2
- 239000002674 ointment Substances 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 125000002958 pentadecyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 125000004035 thiopropyl group Chemical group [H]SC([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-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
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 1
- STTGYIUESPWXOW-UHFFFAOYSA-N 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline Chemical compound C=12C=CC3=C(C=4C=CC=CC=4)C=C(C)N=C3C2=NC(C)=CC=1C1=CC=CC=C1 STTGYIUESPWXOW-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 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
- QENGPZGAWFQWCZ-UHFFFAOYSA-N Methylthiophene Natural products CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 229920000280 Poly(3-octylthiophene) Polymers 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910003087 TiOx Inorganic materials 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001656 butanoic acid esters Chemical group 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000007248 cellular mechanism Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000001186 cumulative effect Effects 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
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 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 1
- 230000000694 effects Effects 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000006232 ethoxy propyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000005308 flint glass Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 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
- 150000002390 heteroarenes Chemical class 0.000 description 1
- 125000005842 heteroatom Chemical group 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
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 125000002960 margaryl 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])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
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 125000004372 methylthioethyl group Chemical group [H]C([H])([H])SC([H])([H])C([H])([H])* 0.000 description 1
- 238000004776 molecular orbital Methods 0.000 description 1
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Abstract
提供一种新型亚甲基富勒烯衍生物,其可作为有机半导体材料用于电子器件如有机FET和电致发光器件或者太阳能电池。具体地提供由通式(I)表示的亚甲基富勒烯衍生物,其特征在于13C-NMR中C2和C2′的化学位移值的平均值为80.10ppm以上,C2和C2′为存在于富勒烯(FL)上的并键合至C1的碳原子。在通式(1)中,FL为富勒烯;X1和X2各自为芳族烃基或烷基等;C2和C2′为存在于FL上并与C1键合的碳原子;和n为1至10的整数。
Description
技术领域
本发明涉及亚甲基富勒烯衍生物。本发明的亚甲基富勒烯衍生物为可在电子器件如有机场效应晶体管(有机FET)和电致发光器件以及太阳能电池中作为有机半导体材料而应用的材料,本发明还涉及使用这些亚甲基富勒烯衍生物的光电转换器件。
背景技术
由于并不伴随CO2的排放,将光能如日光转换成电能的太阳能发电是一种极清洁的发电方式,并已期望通过减少温室气体排放来解决全球变暖问题。有机薄膜太阳能电池可期望大面积并通过简便廉价的方式生产,因此由于其重量轻和极好的灵活性而被认为是有前景的下一代太阳能电池。然而,有机薄膜太阳能电池的转换效率的显著提高已成为电池实际使用的重要问题。
1992年,Sariciftci指出作为空穴输送材料(hole transportmaterial)的导电聚合物和富勒烯C60的异质结电池(heterojunction cell)可提供有效的电荷分离(参见非专利文献1、专利文献1)。
此外,为了增强富勒烯与空穴输送材料的相容性的目的,合成了亚甲基富勒烯,其中苯基和丁酸酯基经亚甲基而交联(苯基-C61-丁酸甲基酯:phenyl-C61-butyric acid methyl ester,PCBM)。当将聚[2-甲氧基,5-(2’-乙基-己氧基)-对苯乙炔]((MEH-PPV),其中将烷氧基引入于聚对苯乙炔中)与PCBM混合以形成活性层时,具有该活性层的所得MEH-PPV/PCBM***与C60相比显著改进了光转换效率(参见非专利文献2)。
Sariciftci等人用本体异质结结构已实现了3.5%的能量转换效率,所述本体异质结结构包括作为空穴输送材料的共轭聚合物如聚(3-己基噻吩)P3HT和亚甲基富勒烯衍生物PCBM的混合活性层(参见非专利文献3)。
Heeger和Carroll等人各自报道了通过加热该共混膜器件实现了大约5%的能量转换效率(参见非专利文献4和5)。
为了促进能量转换效率的显著改进,目前重要的是发展新型p型半导体材料和n型半导体材料。P3HT和PCBM分别为目前制造器件的p型半导体和n型导体用标准材料,因此,目前仅通过改进器件来增强转换效率。尽管已报道某些新型聚合物用于p型半导体,但在光电转换材料中使用的、n型半导体用富勒烯衍生物的研发实例仅几种,因此,毫不夸张地说,没有什么超过PCBM。
当目前考虑富勒烯衍生物的设计方针时,富勒烯衍生物与空穴输送材料的相容性是极其重要的,这可由以下事实明显看出来:为了增强富勒烯与空穴输送材料的相容性的目的而合成PCBM来生产供体/受体配混膜,并且MEH-PPV/PCBM***与C60相比在光电转换效率上显著改进。还报道了用给电子取代基取代PCBM苯环增加了LUMO(最低未占据分子轨道(lowestunoccupied molecular orbital),无电子占据的分子轨道中具有最低能量的轨道),并且当含取代基的PCBM组装入器件时,可增加开端电压(open end voltage),导致能量转换效率的增加(非专利文献6)。
在这些情况下,需要可溶性优异,与作为p型半导体的聚合物的相容性增强,并具有高开端电压的富勒烯衍生物的分子设计。
本发明的发明人提出了一种新型亚甲基富勒烯衍生物以满足这些需求(专利文献2),但开端电压不充分。需要具有更高开端电压的亚甲基富勒烯衍生物。
引用列表
专利文献
专利文献1:美国专利5331183号
专利文献2:日本特开公报2009-57356号
非专利文献
非专利文献1:N.S.Sariciftci,L.Smilowitz,A.J.Heeger,F.Wudl,“Science”vol.258,pp.1474-1476,1992
非专利文献2:C.J.Brabec,F.Padinger,N.S.Sariciftci,J.C.Hummelen,“Journal of Applied Physics”,vol.85,p.6866,1999
非专利文献3:F.Padinger,R.S.Rittberger,N.S.Sariciftci,“Advanced Functional Material”,vol.13-1,pp.85-88,2003
非专利文献4:M.R-Reyes,K.Kim,D.L.Carroll,“AppliedPhysics Letters”,vol.87,083506,2005
非专利文献5:W.Ma,C.Yang,X.Gong,K.Lee,A.J.Heeger“Advanced Functional Material”,vol.15,pp.1617-1622,2005
非专利文献6:F.B.Kooistra,J.Knol,F.Kastenberg,L.M.Popescu,W.J.H.Verhees,J.M.Kroon,J.C.Hummelen,“OrganicLetters”,vol.9,pp.551-554,2007
发明内容
发明要解决的问题
鉴于上述问题,作为本发明人进行的广泛研究的结果,他们通过进行从PCBM中除去吸电子基团如酯等的分子设计,已成功开发了可溶性和LUMO高的亚甲基富勒烯衍生物。
用于解决问题的方案
即,本发明涉及由式(I)表示的亚甲基富勒烯衍生物,其中键合至C1的FL上的碳C2和C2′,的13C-NMR化学位移值的平均值为80.10ppm以上,
其中FL表示富勒烯,X1和X2各自为(a)衍生自芳烃、多环芳烃、骨架中包含杂原子的芳香杂环烃或多环芳香杂环烃的一价基团,(b)衍生自具有取代至少一个氢原子的卤素或烷基、烷氧基、烷基硫代基(alkylthio)或芳基的芳烃、多环芳烃、骨架中包含杂原子的芳香杂环烃或多环芳香杂环烃的一价基团,(c)衍生自芳烃、多环芳烃、骨架中包含杂原子的芳香杂环烃或多环芳香杂环烃的至多30个链节的低聚物的一价基团,或(d)选自烷基、烷氧基、烷氧烷基、烷基硫代基和烷基硫代烷基的基团,FL经次甲基碳C1键合至X1和X2,C2和C2′键合至C1的FL上的碳原子,和n为1至10的整数。
本发明还涉及前述由式(I)表示的富勒烯衍生物,其中式(I)中的X1为衍生自由式(II)表示的芳环或噻吩环的一价基团,
本发明还涉及前述亚甲基富勒烯衍生物,其中式(I)中的X2为烷基、烷氧基、烷氧烷基、烷基硫代基或烷基硫代烷基。
本发明还涉及光电转换器件,其包括前述亚甲基富勒烯衍生物作为电子输送材料。
本发明还涉及前述光电转换器件,其包括包含噻吩环的共轭高分子化合物作为空穴输送材料。
发明的效果
本发明提供亚甲基富勒烯衍生物,其增强可溶性、与聚合物的相容性和开端电压,且电荷迁移率和电荷分离能力优异,此类亚甲基富勒烯衍生物的使用导致光电转换器件在电子性质和耐久性上优异。
本发明的新型亚甲基富勒烯衍生物是可应用于电子器件例如有机FETs或电致发光器件等的有机半导体材料。
具体实施方式
以下将详细描述本发明的亚甲基富勒烯衍生物。
本发明的亚甲基富勒烯衍生物为由下式(I)表示的化合物并具有其中富勒烯上的C2和C2′与键合至X1和X2的C1交联的结构。
在式(I)中,环状的FL表示富勒烯。术语“富勒烯”为具有三维封闭壳核结构的化合物的集合术语,其中Sp2型碳原子彼此球形键合。此类化合物的具体实例包括富勒烯、其衍生物以及在它们的骨架中包括金属原子或化合物的那些。具体实例包括由化学式如C60、C70、C76、C78、C82、C84、C90和C96表示的那些。其中,优选C60和C70。
在式(I)中,X1和X2各自为(a)衍生自芳烃、多环芳烃、骨架中包含杂原子的芳香杂环烃或多环芳香杂环烃的一价基团,(b)衍生自具有取代至少一个氢原子的卤素或烷基、烷氧基、烷基硫代基或芳基的芳烃、多环芳烃、骨架中包含杂原子的芳香杂环烃或多环芳香杂环烃的一价基团,(c)衍生自芳烃、多环芳烃、骨架中包含杂原子的芳香杂环烃或多环芳香杂环烃的至多30个链节的低聚物的一价基团,或(d)选自烷基、烷氧基、烷氧烷基、烷基硫代基和烷基硫代烷基的基团。
芳烃和多环芳烃优选具有6至30个碳原子的那些,如苯、萘和蒽。
芳香杂环烃和多环芳香杂环烃优选具有6至30个碳原子的那些。杂原子优选硫。实例包括噻吩类芳香杂环化合物如噻吩、苯并噻吩和噻吩并噻吩。
芳烃、多环芳烃、芳香杂环烃和多环芳香杂环烃的实例包括具有由式(II)表示的芳环或噻吩环的化合物
芳烃、多环芳烃、芳香杂环烃和多环芳香杂环烃可具有取代基如卤原子、烷基、烷氧基、烷基硫代基和芳基以便改进与溶剂的可溶性、与空穴输送材料的相容性和当用于光电转换器件时的耐久性。
卤原子的实例包括氟、氯、溴和碘。
烷基可为环烷基并包括具有1至30个、优选1至18个碳原子的烷基,如甲基、乙基、丙基、异丙基、2-乙基丙基和环己基。烷基的全部或部分氢可为包含不饱和键的基团或包含芳环如苯基的取代基。上述烷基可使用氨基彼此键合。上述烷基的末端可为羟基、硫羟基(thiol)或氨基。可选地,烷基可在烷基链的中间包含醚键(-O-)或重复单元数为1至15的环氧乙烷基团。此外,两个取代基可在末端彼此键合,以形成例如环醚。
烷氧基的实例包括具有1至30个、优选1至18个碳原子的那些,如甲氧基、乙氧基、丙氧基、异丙氧基、丁氧基、叔丁氧基、2-乙基丙氧基和环己氧基。
烷基硫代基的实例包括具有1至30、优选1至18个碳原子的那些,如甲硫基、乙硫基、丙硫基、异丙硫基、丁硫基、叔丁硫基、2-乙基丙硫基和环己硫基。
芳基的实例包括具有6至30个、优选6至18个碳原子的那些,如苯基和萘基。芳基的全部或部分氢可被具有1至12个、优选1至8个碳原子的烷基取代。
可选地,衍生自上述化合物的低聚物的一价基团可优选用作X1和X2。作为低聚物不对芳环的缩合数加以特别限定,其优选30个链节以下,更优选20个链节以下,特别优选2个链节至8个链节。
式(I)中用作X1和X2的烷基、烷氧基、烷氧烷基、烷基硫代基和烷基硫代烷基优选以下基团。
烷基可为环烷基并包括具有1至30个、优选1至18个碳原子的烷基,如甲基、乙基、丙基、异丙基、2-乙基丙基、己基、环己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、十五烷基、十六烷基、十五烷基和十八烷基。
烷基的全部或部分氢可为包含不饱和键的基团或包含芳环如苯基的取代基。上述烷基可使用氨基彼此键合。上述烷基的末端可为羟基、硫羟基或氨基。可选地,烷基可在烷基链的中间包含醚键(-O-)或重复单元数为1至15的环氧乙烷基团。此外,两个取代基可在末端彼此键合,以形成例如环醚。进一步可选地,芳环为稠环。
烷氧基的实例包括具有1至30个、优选1至18个碳原子的那些,如甲氧基、乙氧基、丙氧基、异丙氧基、丁氧基、叔丁氧基、2-乙基丙氧基和环己氧基。
烷氧烷基由R1-O-R2表示,其中R1为具有1至30个、优选1至18个碳原子的烷基和R2为具有1至30个、优选1至18个碳原子的亚烷基。烷氧烷基的实例包括甲氧甲基、乙氧甲基、甲氧乙基、乙氧乙基、甲氧丙基、乙氧丙基、甲氧丁基、乙氧丁基、甲氧戊基、乙氧戊基、甲氧己基和乙氧己基。
烷基硫代基的实例包括具有1至30个、优选1至18个碳原子的那些,如甲硫基、乙硫基、丙硫基、异丙硫基、丁硫基、叔丁硫基、2-乙基丙硫基和环己硫基。
烷基硫代烷基由R3-S-R4-表示,其中R3为具有1至30个、优选1至18个碳原子的烷基和R4为具有1至30个、优选1至18个碳原子的亚烷基。烷基硫代烷基的实例包括甲硫甲基、乙硫甲基、甲硫乙基、乙硫乙基、甲硫丙基、乙硫丙基、甲硫丁基、乙硫丁基、甲硫戊基、乙硫戊基、甲硫己基和乙硫己基。
在本发明的由式(I)表示的亚甲基富勒烯衍生物中,X1优选(a)衍生自芳烃、多环芳烃、骨架中包含杂原子的芳香杂环烃或多环芳香杂环烃的一价基团,(b)衍生自具有取代至少一个氢原子的卤素或烷基、烷氧基、烷基硫代基或芳基的芳烃、多环芳烃、骨架中包含杂原子的芳香杂环烃或多环芳香杂环烃的一价基团,(c)衍生自芳烃、多环芳烃、骨架中包含杂原子的芳香杂环烃或多环芳香杂环烃的至多30个链节的低聚物的一价基团,或(d)选自烷基、烷氧基、烷氧烷基、烷基硫代基和烷基硫代烷基的基团。
如果可实现本发明的目的,则不对亚甲基富勒烯衍生物有多少对键合X1和X2的次甲基碳加以特别限定。然而,式(I)中取代基的数量“n”优选1至10、更优选1至5的整数。
本发明的由式(I)表示的亚甲基富勒烯衍生物的特征在于,键合至C1的FL上的C2和C2′的13C-NMR化学位移值的平均值为80.10ppm以上,该C1与FL、X1和X2键合。
在本发明中,化学位移的平均值在下文中称作“CS值”。
CS值(ppm)=[CS(C2)+CS(C2′)]/2
CS(C2):碳C2的13C-NMR化学位移值(ppm)
CS(C2′):碳C2′的13C-NMR化学位移值(ppm)
在本发明中,13C-NMR谱的测量如下。
在用于NMR的具有直径5mm的样品管中将10至50mg样品在1ml氘氯仿中完全溶解并均质化之后,在室温下(27℃)使样品进行质子去耦法(proton decoupling method)以测定13C-NMR谱。
在90°回转角(flip angle)和5T1以上的脉冲间隔(T1表示甲基的自旋晶格弛豫时间的最大值)的条件下进行测量。优选使用可提供25MHz以上的13C核共振频率(core resonance frequency)的NMR设备在1000次以上的累积数下进行测量,以便增加测量精密度。
在本发明中,CS值必须为80.10ppm以上,优选80.20ppm以上、更优选80.30ppm以上。CS值的上限为100.00ppm。
小于80.10ppm的CS值是不优选的,这是因为其引起由来自次甲基的给电子性质的降低产生的所得太阳能电池的开端电压低。对于光电转换材料,大于100.00ppm的CS值是不优选的,这是因为其显著损害C60接受电子的性质。
将给出合成本发明的亚甲基富勒烯衍生物的方法的实例的描述。然而,本发明不限于该方法。在50至150℃的温度下,在溶剂如邻二氯苯和吡啶中加热回流甲苯磺酰腙(其为期望的亚甲基富勒烯的前体(下述实施例中的1a、3a、5a、6a和比较例中的2a和4a))和富勒烯1至12个小时,以生产期望的亚甲基富勒烯衍生物。
接下来将描述使用本发明的亚甲基富勒烯衍生物生产的光电转换器件。
本发明的光电转换器件可为具有光电转换层的异质结型器件,所述光电转换层在基板上通过将本发明的亚甲基富勒烯衍生物(作为用作光吸收材料的电子输送材料)与适当的空穴输送材料结合而形成。异质结型电子器件显示光电转换器件的特性,例如亚甲基富勒烯衍生物和空穴输送材料通过吸收光来产生电荷以便输出电荷,即,通过吸收光来改变电流值。
本发明的光电转换器件的具体结构可以是其中依次层压透明导电基板、本发明的亚甲基富勒烯和空穴输送材料的光电转换层以及对电极的结构。
空穴输送材料可为空穴输送聚合物,如聚噻吩、聚吡咯、聚苯胺、聚呋喃、聚吡啶或聚咔唑。这些聚合物中,聚噻吩类空穴输送材料优选用作本发明的亚甲基富勒烯衍生物的空穴输送材料。
对于聚噻吩,可适当使用其中作为单体单元的噻吩或取代的噻吩在2-和5-位聚合的那些。取代的噻吩的实例包括烷基取代的噻吩和芳基取代的噻吩。噻吩结构更具体的实例包括聚(3-甲基噻吩)、聚(3-丁基噻吩)、聚(3-己基噻吩)、聚(3-辛基噻吩)、聚(3-癸基噻吩)、聚(3-十二烷基噻吩)、聚(3-苯基噻吩)和聚(3-对烷基苯基噻吩)。这些聚噻吩中,优选具高移动性的那些,例如以空间规则方式(sterically regulated manner)聚合的那些。
光电转换层可通过以下来形成:在溶剂中溶解本发明的亚甲基富勒烯衍生物和空穴输送材料以产生溶液,并在透明导电基板上涂布该溶液,随后除去溶剂。
如果溶剂可溶解亚甲基富勒烯衍生物和空穴输送材料二者,则不对溶剂加以特别限定。溶剂的实例包括苯、甲苯、二甲苯、氯仿、二氯甲烷、四氢呋喃、二噁烷、四氯化碳、乙苯、氯苯、二氯苯、丙基苯、二氯乙烯和甲基氯。不对亚甲基富勒烯衍生物和空穴输送材料的浓度加以特别限定。然而,鉴于生产,浓度优选约为0.1至5质量%的程度。如果亚甲基富勒烯衍生物和空穴输送材料不易溶解,可将其搅拌并加热。
不对在透明导电基板上涂布溶解有亚甲基富勒烯衍生物和空穴输送材料的溶液的方法加以特别限定。所述方法的实例包括浇铸(casting)、旋涂、喷涂和棒涂。不对涂布量加以特别限定。然而,通常以0.002至0.1ml每cm2基板的量涂布溶液。然后除去溶剂从而形成光电转换层。可通过加热基板来除去溶剂。
透明导电板通常通过在透明基板上方层压透明电极层来生产。不对透明基板加以特别限定。基板的材料、厚度、大小和形状可取决于目的而适当地选择。例如,基板可为着色或无色玻璃、嵌丝玻璃(wire glass)、玻璃砖或可选地为着色或无色透明树脂。此类树脂的具体实例包括聚酯如聚对苯二甲酸乙二酯、聚酰胺、聚砜、聚醚砜、聚醚醚酮、聚苯硫醚、聚碳酸酯、聚酰亚胺、聚甲基丙烯酸甲酯、聚苯乙烯、三乙酸纤维素和聚甲基戊烯。此处所使用的术语“透明”表示透射率为10至100%。此处所使用的基板为常温下具有光滑表面的那些,其表面可以是平坦的或压力弯曲或变形的。
不对形成透明电极的导电层的透明导电膜加以特别限定。所述膜可为金、银、铬、铜或钨的金属膜或者金属氧化物的导电膜。金属氧化物的优选实例包括通过向氧化锡或氧化锌掺杂痕量不同金属元素来产生的那些,如铟锡氧化物(ITO(In2O3:Sn))、氟掺杂的锡氧化物(FTO(SnO2:F))和铝掺杂的锌氧化物(AZO(ZnO:Al))。膜厚度通常为1nm至50μm,优选10nm至10μm。表面电阻(电阻率)根据基板的用途来适当地选择,但通常为0.01至500Ω/sq,优选0.1至50Ω/sq。
在光电转换层上方层压对电极从而生产光电转换器件。对电机可为金属如金、铂、银、铜、铝、镁、锂和钾或者碳电极。对电极可通过以下布置:真空沉积、电子束真空沉积、溅射或在溶剂中分散的金属细颗粒被涂布的常规方法,然后通过蒸发除去溶剂。在形成对电极金属层之前,可形成各种有机和无机材料的层以便改进光电子转换层和对电极金属层之间的粘合性以及激子阻挡性质(exciton block properties)。如果此类材料符合本发明的目的,则不对此类材料加以特别限定。实例包括有机物膜如菲咯啉(phenanthroline)和浴铜灵以及无机物如LiF和TiOx的那些。
其中亚甲基富勒烯衍生物和空穴输送材料行使作为太阳能电池的功能的机制例如由S.S.Sun和N.S.Sariciftci在“OrganicPhotovoltaics”(Taylor和Francis)中所描述。通常,当形成亚甲基富勒烯和空穴输送材料的混合物的膜时,它们在纳米尺度上相分离并形成它们相互渗透的相分离结构。该结构称作本体异质结。在该结构中,通过光照亚甲基富勒烯和空穴输送材料各自产生激子(电子-空穴对),该激子在富勒烯衍生物和空穴输送材料的界面为电荷分离的,从而产生自由载流子(电子和空穴)。所得自由电子和空穴传送分别作为吸电子和给电子的亚甲基富勒烯相和空穴输送相并各自达到相应的电极,从而产生光伏电力(photovoltaic power)。该过程期间,激子必须扩散到亚甲基富勒烯衍生物和空穴输送材料层之间的界面从而为电荷分离的。然而,由于激子具有寿命(τ),激子的质量在吸收光后随时间流逝而降低。当将直至激子质量衰减至1/e所用的时间长度(τ)定义为激子的寿命时,其扩散长度定义为LD=(D×τ)1/2,其中D为扩散常数。由于激子需要电荷分离为自由载流子以便产生高效太阳能电池,因此有必要尽可能缩短通过吸收光产生的激子的扩散持续时间。如果由各亚甲基富勒烯相和空穴输送相的相分离所得的结构(相区(domain))太大,则激子成为电荷分离的所移动的平均距离长,导致光电转换性质的降低。为了通过允许激子有效地分离电荷来生产高效太阳能电池,需要增强亚甲基富勒烯与空穴输送材料的相容性以便使相分离结构不变得太大。
亚甲基富勒烯衍生物和空穴输送材料的相容性是指在涂布后出去溶剂所得的固体膜状态下,亚甲基富勒烯衍生物和空穴输送材料的混合性质。亚甲基富勒烯衍生物和空穴输送材料需要在纳米尺度充分地相分离来实现高光电转换性质,但如果它们的相容性差,则其相分离极大,因此,如上所述引起器件性质劣化。固体状态的相容性可通过使用扩散性质或X射线分析由原子力显微镜观察平均相区大小(domain size)来测定,从而可获得相分离结构的图像。
器件性质可通过以下来评价:将末端粘附至透明电极和对电极,并期望参阅例如JIS C 8911至8919和JIS C 8931至8940来测量光照与否时电流值的变化。
可选地,可进行各种密封处理以改进器件的耐久性。如果密封方法符合本方法的目的,则不对密封方法加以特别限定。例如,可用各种低透气性材料来密封器件。获得低透气性的密封方法可通过用具有低透气性的粘合剂来将气体阻挡层如上述基板材料粘结到器件来进行,从而增强器件的耐久性。
实施例
本发明将参考以下实施例更详细地描述,但本发明不受限于此。
(实施例1)
用以下方式合成由式(I)表示的亚甲基富勒烯衍生物1b(PCP),其中X1为苯基,X2为戊烷基,n=1。
向25ml梨形烧瓶中放入300.0mg C60,然后在氩气气氛下将其溶解在9ml干燥的邻二氯苯(ODCB)中并经受超声波60分钟。向50ml含有戴氏冷凝器和搅拌器的双颈烧瓶放入172mg甲苯磺酰腙1a和当量,即27mg甲氧基钠,然后在氩气气氛下将其溶解在6ml干燥的吡啶中并搅拌15分钟。其后,将C60的ODCB溶液添加到混合物中并在70℃的温度下加热1小时并进一步在100℃的温度下加热4小时。反应后,通过真空蒸馏除去ODCB和吡啶,并用循环制备(recycle preparative)GPC(展开剂:氯仿)分离和提纯残留物,从而生产58mg褐色固体。在3ml ODCB中溶解固体,然后在170℃的温度下加热4.5小时。其后,通过真空蒸馏除去溶剂。并用循环制备GPC(展开剂:氯仿)分离和提纯残留物,从而生产56.6mg亚甲基富勒烯衍生物1b(15.4%产率)。所得产物用高效液相色谱(展开剂:甲苯和甲醇2∶3)证实并用1H-NMR、13C-NMR和IR鉴定。亚甲基富勒烯衍生物1b的CS值为80.47ppm。
[分析数据]
IR(KBr)2961,2918,2856,2328,1599,1493,1426,1260,1185,1092,1019,866,799,694,585,573,548,526cm-1;
1H-NMR(300MHz;CDCl3)δ7.84(d,2H,6.9Hz),7.48-7.35(m、3H),2.80(t,2H,8.1Hz),1.82-1.72(m,2H),1.46-1.26(m,4H),0.84(t,3H,7.2Hz);
13C-NMR(75MHz,CDCl3)δ149.17,148.30,146.00,145.25,145.20,145.09,144.90,144.85,144.80,144.74,145.56,144.43,144.04,143.85,143.20,143.09,143.06,143.00,142.37,142.29,142.21,141.04,140.78,138.10,137.59,137.37,132.18,128.28,128.06,80.47,52.77,34.33,31.86,26.70,22.63,14.02
(比较例1)
参考以下合成由式(I)表示的亚甲基富勒烯衍生物2b(PCBM),其中X1为苯基,X2为3-(甲氧基羰基)丙基,n=1:J.C.Hummelen,B.W.Knight,F.LePeq,F.Wudl的题为“Journal ofAmerican Chemical Society”vol.6,pp.532-538,1995的文献。
所得产物用高效液相色谱证实并用1H-NMR、13C-NMR和IR鉴定。亚甲基富勒烯衍生物2b的CS值为79.88ppm。
(实施例2)
用以下方式合成由式(I)表示的亚甲基富勒烯衍生物3b(EThCP),其中X1为5-乙基噻吩-2-基,X2为戊烷基,n=1。
向25ml梨形烧瓶中放入100.0mg C60,然后在氩气气氛下将其溶解在3ml干燥的邻二氯苯(ODCB)中并经受超声波60分钟。向50ml含有戴氏冷凝器和搅拌器的双颈烧瓶放入78.8mg甲苯磺酰腙3a和当量,即12.2mg甲氧基钠,然后在氩气气氛下将其溶解在2ml干燥的吡啶中并搅拌15分钟。其后,将C60的ODCB溶液添加到混合物中并在70℃的温度下加热2小时并进一步在100℃的温度下加热4小时。反应后,通过真空蒸馏除去ODCB和吡啶,并用循环制备GPC(展开剂:氯仿)分离和提纯残留物,从而生产44.0mg亚甲基富勒烯衍生物3b(34.6%产率)。所得产物用高效液相色谱(展开剂:甲苯和甲醇2∶3)证实并用1H-NMR、13C-NMR和IR鉴定。亚甲基富勒烯衍生物3b的CS值为80.73ppm。
[分析数据]
IR(KBr)2952,2921,2852,2359,1427,1375,1186,805,740,574,555,526,451cm-1;
1H-NMR(300MHz;CDCl3)δ7.24(d、1H、3.6Hz),6.78(d,1H,3.6Hz),2.99-2.84(m,4H),1.95-1.85(m、2H),1.55-1.48(m,4H),1.41(t,3H,7.5Hz),0.94(t,3H,7.2Hz);
13C-NMR(75MHz、CDCl3)δ148.91,148.18,145.88,145.32,145.28,145.25,145.20,144.90,144.87,144.85,144.73,144.64,144.51,144.19,143.91,143.89,143.19,143.12,143.08,143.00,142.98,142.39,142.32,142.22,141.00,140.77,138.32,138.19,136.74,131.57,122.10,80.73,47.17,34.58,31.70,26.85,23.71,22.67,15.57,14.03
(比较例2)
用以下方式合成由式(I)表示的亚甲基富勒烯衍生物4b(EThCBM),其中X1为5-乙基噻吩-2-基,X2为3-(甲氧基羰基)丙基,n=1。
向25ml梨形烧瓶中放入50mg C60,然后在氩气气氛下将其溶解在1.5ml干燥的邻二氯苯(ODCB)中并经受超声波60分钟。向50ml含有戴氏冷凝器和搅拌器的双颈烧瓶放入56.7mg甲苯磺酰腙4a和8mg甲氧基钠,然后在氩气气氛下将其溶解在1ml干燥的吡啶中并搅拌15分钟。其后,将C60的ODCB溶液从梨形烧瓶添加到混合物中并在70℃的温度下加热4小时并进一步在100℃的温度下加热1.5小时。并用硅胶柱色谱(展开剂:甲苯)分离并提纯所得溶液,从而生产29.5mg亚甲基富勒烯衍生物4b(EThCBM)(52.2%产率)。所得产物用高效液相色谱证实并用1H-NMR、13C-NMR和IR鉴定。亚甲基富勒烯衍生物4b的CS值为80.08ppm。
[分析数据]
IR(KBr)2960,1737(C=O;s),1456,1428,1376,1263,1186,1170,983,885,806,741,572,562,525(s),445,432cm-1;1H-NMR(300MHz;CDCl3)δ7.27(d、1H、3.60Hz),6.78(d、1H、3.60Hz),3.69(s、3H),2.99-2.90(m,4H),2.58(t,2H,7.5Hz),2.29-2.19(m,2H),1.41(t,3H,7.5Hz);
13C-NMR(75MHz;CDCl3)δ173.50(C=O),148.50,148.40,147.65,145.74,145.23,145.20,145.18,145.13,144.81,144.72,144.64,144.57,144.47,144.14,143.82,143.78,143.10,143.04,143.00,142.92,142.90,142.26,142.17,142.13,142.11,140.92,140.70,138.26,138.10,135.97,131.77(CH),122.20(CH),80.08(桥头),51.66(OCH3),46.20(桥),33.86(CH2),33.71(CH2),23.68(CH2),22.52(CH2),15.53(CH3)
(实施例3)
用以下方式合成由式(I)表示的亚甲基富勒烯衍生物5b(EThCN),其中X1为5-乙基噻吩-2-基,X2为壬基,n=1。
向100ml梨形烧瓶中放入1,000mg C60,然后在氩气气氛下将其溶解在30ml干燥的邻二氯苯(ODCB)中并经受超声波60分钟。向100ml含有戴氏冷凝器和搅拌器的双颈烧瓶放入700mg甲苯磺酰腙5a和90mg甲氧基钠,然后在氩气气氛下将其溶解在20ml干燥的吡啶中并搅拌15分钟。其后,将C60的ODCB溶液添加到混合物中并在70℃的温度下加热2小时并进一步在100℃的温度下加热4小时。反应后,通过真空蒸馏除去ODCB和吡啶,并用循环制备GPC(展开剂:氯仿)分离和提纯残留物,从而生产473mg亚甲基富勒烯衍生物5b(35.1%产率)。所得产物用高效液相色谱(展开剂:甲苯和甲醇2∶3)证实并用1H-NMR、13C-NMR和IR鉴定。亚甲基富勒烯衍生物5b的CS值为80.54ppm。
[分析数据]
IR(KBr)2918,2848,1940,1457,1427,1185,803,740,669,554,526cm-1;
1H-NMR(300MHz;CDCl3)δ7.24(d、1H、3.6Hz),6.78(d,1H,3.6Hz),2.99-2.84(m,4H),1.94-1.84(m,2H),1.58-1.49(m,4H),1.41(t,3H,7.5Hz),1.35-1.20(m,8H),0.88(t,3H,7.2Hz);
13C-NMR(75MHz,CDCl3)δ148.82,148.10,145.81,145.23,145.20,145.17,145.12,144.81,144.77,144.66,144.56,144.43,144.11,143.84,143.82,143.12,143.04,143.00,142.93,142.91,142.31,142.25,142.14,140.92,140.69,138.22,138.12,136.61,131.56,122.03,80.54,47.05,34.49,31.92,29.58,29.47,29.33,27.10,23.70,22.70,15.55,14.14
(实施例4)
用以下方式合成由式(I)表示的亚甲基富勒烯衍生物6b(EThCHpd),其中X1为5-乙基噻吩-2-基,X2为十七烷基,n=1。
向50ml梨形烧瓶中放入500mg C60,然后在氩气气氛下将其溶解在15ml干燥的邻二氯苯(ODCB)中并经受超声波60分钟。向100ml含有戴氏冷凝器和搅拌器的双颈烧瓶放入440mg甲苯磺酰腙6a和45mg甲氧基钠,然后在氩气气氛下将其溶解在10ml干燥的吡啶中并搅拌15分钟。其后,将C60的ODCB溶液添加到混合物中并在70℃的温度下加热2小时并进一步在100℃的温度下加热4小时。反应后,通过真空蒸馏除去ODCB和吡啶,并用循环制备GPC(展开剂:氯仿)分离和提纯残留物,从而生产218mg亚甲基富勒烯衍生物6b(29.0%产率)。所得产物用高效液相色谱(展开剂:甲苯和甲醇2∶3)证实并用1H-NMR、13C-NMR和IR鉴定。亚甲基富勒烯衍生物6b的CS值为80.53ppm。
[分析数据]
IR(KBr)2918,2847,1716,1540,1461,1427,1374,1212,1185,803,718,525cm-1;
1H-NMR(300MHz;CDCl3)δ7.24(d,1H,3.6Hz),6.78(d,1H,3.6Hz),2.99-2.84(m,4H),1.94-1.84(m,2H),1.58-1.49(m,4H),1.41(t,3H,7.5Hz),1.32-1.19(m,24H),0.879(t,3H,7.2Hz);
13C-NMR(75MHz、CDCl3)δ148.81,148.09,145.79,145.22,145.19,144.80,144.64,144.55,144.42,144.10,143.82,142.99,142.92,142.30,142.23,142.13,140.91,140.68,138.10,136.60,131.54,122.02,80.53,47.04,34.45,31.93,29.72,29.60,29.55,29.42,29.37,27.06,23.69,22.70,15.54,14.13
(实施例5)
在已清洗的、通过溅射在其上面形成表面电阻15Ω/sq的ITO膜的玻璃基板上,在5000rpm(50s)下旋涂Baytron P(由H.C.Stark GmbH制造),然后在120℃的温度下干燥10分钟。以重量比0.8∶1.0将亚甲基富勒烯衍生物1b与具有分子量17,500的聚(3-己基噻吩)(由Sigma-Aldrich Co.LLC制造)混合,然后溶解于氯苯中以使亚甲基富勒烯衍生物1b的浓度为1重量%。结果,两种材料均完全溶解并形成均质混合溶液。在800rpm(50s)下将该混合溶液旋涂在玻璃基板上从而形成光电转换层。将含光电转换层的ITO-玻璃基板在氮气气氛下干燥过夜,然后在约10-5托的真空下沉积0.5nm厚度的LiF和100nm厚度的Al以形成对电极,从而生产光电转换器件。所得器件在氮气气氛下密封。对于密封,使用玻璃板和环氧密封剂。在100mW/cm2的人造日光照射密封的器件的同时,测量其电压-电流特性。由电压-电流特性计算最大效率。结果示于表1。
(比较例3)
以与实施例5相同的方式使用亚甲基富勒烯衍生物2b(PCBM)生产光电转换器件来测量电压-电流特性,由其计算最大效率。结果示于表1。
(实施例6)
以与实施例5相同的方式使用亚甲基富勒烯衍生物3b生产光电转换器件来测量电压-电流特性,由其计算最大效率。结果示于表1。
(比较例4)
以与实施例5相同的方式使用亚甲基富勒烯衍生物4b生产光电转换器件来测量电压-电流特性,由其计算最大效率。结果示于表1。
如表1所示,其中亚甲基富勒烯的CS值大于80.10ppm的实施例5和6的开端电压和光电转换效率比比较例3和4高。
[表1]
产业上的可利用性
本发明的亚甲基富勒烯衍生物为可在电子器件如有机场效应晶体管(有机FET)和电致发光器件以及太阳能电池中作为有机半导体材料而应用的材料,并因此具有显著的工业价值。
Claims (4)
1.一种由式(I)表示的亚甲基富勒烯衍生物,其中键合至C1的FL上的碳C2和C2′的13C-NMR化学位移值的平均值为80.10ppm以上且100.00ppm以下,
其中FL表示富勒烯,X1为衍生自由式(II)表示的噻吩环的一价基团,X2为具有1至30个碳原子的烷基,FL经次甲基碳C1键合至X1和X2,C2和C2′为键合至C1的FL上的碳原子,和n为1至10的整数,
其中,所述噻吩环具有烷基取代基R,所述R为具有1至30个碳原子的烷基。
2.根据权利要求1所述的亚甲基富勒烯衍生物,其由下述式(III)的任一种表示:
3.一种光电转换器件,其包括权利要求1或2所述的亚甲基富勒烯衍生物作为电子输送材料。
4.根据权利要求3所述的光电转换器件,其包括含有噻吩环的共轭高分子化合物作为空穴输送材料。
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US9196843B2 (en) | 2012-07-17 | 2015-11-24 | Ricoh Company, Ltd. | Fullerene derivative, and method of preparing the same |
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WO2014190070A1 (en) * | 2013-05-22 | 2014-11-27 | Robinson Alex Philip Graaham | Fullerenes |
JP6340782B2 (ja) | 2013-12-11 | 2018-06-13 | 株式会社リコー | フラーレン誘導体およびその製造方法 |
RU2554590C1 (ru) * | 2014-01-29 | 2015-06-27 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Башкирский государственный университет" | Метанофуллерены в качестве органических материалов для солнечных батарей |
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