KR20130048175A - Organic semiconductor compound, process for producing the organic semiconductor compound and organic solar cells using the same - Google Patents
Organic semiconductor compound, process for producing the organic semiconductor compound and organic solar cells using the same Download PDFInfo
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- KR20130048175A KR20130048175A KR1020120121881A KR20120121881A KR20130048175A KR 20130048175 A KR20130048175 A KR 20130048175A KR 1020120121881 A KR1020120121881 A KR 1020120121881A KR 20120121881 A KR20120121881 A KR 20120121881A KR 20130048175 A KR20130048175 A KR 20130048175A
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- South Korea
- Prior art keywords
- formula
- alkyl
- chemical formula
- heteroaryl
- aryl
- Prior art date
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 147
- 239000004065 semiconductor Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims description 24
- 230000008569 process Effects 0.000 title description 2
- 229920000642 polymer Polymers 0.000 claims abstract description 66
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 40
- 239000000126 substance Substances 0.000 claims abstract description 37
- -1 amino, hydroxy Chemical group 0.000 claims abstract description 34
- 125000003118 aryl group Chemical group 0.000 claims abstract description 30
- 125000001072 heteroaryl group Chemical group 0.000 claims abstract description 28
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 24
- 125000004419 alkynylene group Chemical group 0.000 claims abstract description 22
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 16
- 150000002367 halogens Chemical class 0.000 claims abstract description 16
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 14
- 125000001424 substituent group Chemical group 0.000 claims abstract description 12
- 125000000304 alkynyl group Chemical group 0.000 claims abstract description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 8
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 8
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 8
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims abstract description 8
- 125000000739 C2-C30 alkenyl group Chemical group 0.000 claims abstract description 7
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 claims abstract description 5
- 239000000178 monomer Substances 0.000 claims abstract description 3
- 239000000758 substrate Substances 0.000 claims description 11
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 230000005525 hole transport Effects 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 7
- 125000000732 arylene group Chemical group 0.000 claims description 6
- 125000005549 heteroarylene group Chemical group 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 125000001979 organolithium group Chemical group 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 31
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 230000015572 biosynthetic process Effects 0.000 description 20
- 238000003786 synthesis reaction Methods 0.000 description 20
- 239000000463 material Substances 0.000 description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 150000007523 nucleic acids Chemical class 0.000 description 12
- 102000039446 nucleic acids Human genes 0.000 description 12
- 108020004707 nucleic acids Proteins 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 0 **[Si-]1c2cc(N)ccc2-c2ccc(*)cc12 Chemical compound **[Si-]1c2cc(N)ccc2-c2ccc(*)cc12 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000000370 acceptor Substances 0.000 description 9
- 238000004770 highest occupied molecular orbital Methods 0.000 description 9
- 238000000354 decomposition reaction Methods 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 238000011049 filling Methods 0.000 description 6
- 150000003949 imides Chemical class 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 6
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- 125000005605 benzo group Chemical group 0.000 description 5
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- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 description 5
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
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- 229920000144 PEDOT:PSS Polymers 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
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- 238000000137 annealing Methods 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 4
- 230000000877 morphologic effect Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- CSABAZBYIWDIDE-UHFFFAOYSA-N sulfino hydrogen sulfite Chemical compound OS(=O)OS(O)=O CSABAZBYIWDIDE-UHFFFAOYSA-N 0.000 description 3
- 238000004809 thin layer chromatography Methods 0.000 description 3
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 3
- TUCRZHGAIRVWTI-UHFFFAOYSA-N 2-bromothiophene Chemical compound BrC1=CC=CS1 TUCRZHGAIRVWTI-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 238000006069 Suzuki reaction reaction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229920000109 alkoxy-substituted poly(p-phenylene vinylene) Polymers 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical compound CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 description 2
- TXOCYFXCASYKQH-UHFFFAOYSA-N ethyl 2-(4-bromothiophen-3-yl)-2-oxoacetate Chemical compound C(C)OC(C(=O)C1=CSC=C1Br)=O TXOCYFXCASYKQH-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 125000005462 imide group Chemical group 0.000 description 2
- 229960004592 isopropanol Drugs 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- QKDYDXJISKWZQE-UHFFFAOYSA-N selenopheno[3,2-b]selenophene Chemical compound [se]1C=CC2=C1C=C[se]2 QKDYDXJISKWZQE-UHFFFAOYSA-N 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- TTXREHJILPRMDI-UHFFFAOYSA-N thieno[3,4-b]thiophene-2,3-dicarboxylic acid Chemical compound S1C=2C(C(=C1C(=O)O)C(=O)O)=CSC2 TTXREHJILPRMDI-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 1
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 1
- PDQRQJVPEFGVRK-UHFFFAOYSA-N 2,1,3-benzothiadiazole Chemical compound C1=CC=CC2=NSN=C21 PDQRQJVPEFGVRK-UHFFFAOYSA-N 0.000 description 1
- OOCWTIOGJOIPGS-UHFFFAOYSA-N 2-butyloctan-1-amine Chemical compound CCCCCCC(CN)CCCC OOCWTIOGJOIPGS-UHFFFAOYSA-N 0.000 description 1
- ASAVFBNAUMXKHJ-UHFFFAOYSA-N 2-decyltetradecan-1-amine Chemical compound CCCCCCCCCCCCC(CN)CCCCCCCCCC ASAVFBNAUMXKHJ-UHFFFAOYSA-N 0.000 description 1
- VGKLVWTVCUDISO-UHFFFAOYSA-N 3,4-dibromothiophene Chemical compound BrC1=CSC=C1Br VGKLVWTVCUDISO-UHFFFAOYSA-N 0.000 description 1
- MZSAMHOCTRNOIZ-UHFFFAOYSA-N 3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxy-N-phenylaniline Chemical compound NCC1=CC(=NC(=C1)C(F)(F)F)OC=1C=C(NC2=CC=CC=C2)C=CC=1 MZSAMHOCTRNOIZ-UHFFFAOYSA-N 0.000 description 1
- OUCUHGDRVOLLGQ-UHFFFAOYSA-N C(C)OC(=O)C1SC=2C1=C(SC2)C(=O)OCC Chemical compound C(C)OC(=O)C1SC=2C1=C(SC2)C(=O)OCC OUCUHGDRVOLLGQ-UHFFFAOYSA-N 0.000 description 1
- LAJBDHMJTJGESC-UHFFFAOYSA-N C(CCCCCCCCCCC)C1=C(SC(=C1)[Sn](C)(C)C)CCC=1SC(=CC1CCCCCCCCCCCC)[Sn](C)(C)C Chemical compound C(CCCCCCCCCCC)C1=C(SC(=C1)[Sn](C)(C)C)CCC=1SC(=CC1CCCCCCCCCCCC)[Sn](C)(C)C LAJBDHMJTJGESC-UHFFFAOYSA-N 0.000 description 1
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 description 1
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 description 1
- QFNNTXRADJEWLJ-UHFFFAOYSA-N CCC1=C2C(=C(SC2=C(S1)CC)C(=O)O)C(=O)O Chemical compound CCC1=C2C(=C(SC2=C(S1)CC)C(=O)O)C(=O)O QFNNTXRADJEWLJ-UHFFFAOYSA-N 0.000 description 1
- CLODYMSCWRYGME-UHFFFAOYSA-N CCCCCCCCN(C(C(C1SC2C(S3)Br)C2=C3Br)=O)C1=O Chemical compound CCCCCCCCN(C(C(C1SC2C(S3)Br)C2=C3Br)=O)C1=O CLODYMSCWRYGME-UHFFFAOYSA-N 0.000 description 1
- UZYQPVUUZYBVMB-UHFFFAOYSA-N CCCCCCCCN(C(C1=C2SC3C(C(Cc4c(c5c6cc(C(C)(C)C)[s]5)OCCCCCCCC)Sc4c6OCCCCCCCC)SC(C(C)C)C13)=O)C2=O Chemical compound CCCCCCCCN(C(C1=C2SC3C(C(Cc4c(c5c6cc(C(C)(C)C)[s]5)OCCCCCCCC)Sc4c6OCCCCCCCC)SC(C(C)C)C13)=O)C2=O UZYQPVUUZYBVMB-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- 239000005751 Copper oxide Substances 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
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- ZEEBGORNQSEQBE-UHFFFAOYSA-N [2-(3-phenylphenoxy)-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound C1(=CC(=CC=C1)OC1=NC(=CC(=C1)CN)C(F)(F)F)C1=CC=CC=C1 ZEEBGORNQSEQBE-UHFFFAOYSA-N 0.000 description 1
- SAHIZENKTPRYSN-UHFFFAOYSA-N [2-[3-(phenoxymethyl)phenoxy]-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound O(C1=CC=CC=C1)CC=1C=C(OC2=NC(=CC(=C2)CN)C(F)(F)F)C=CC=1 SAHIZENKTPRYSN-UHFFFAOYSA-N 0.000 description 1
- ABRVLXLNVJHDRQ-UHFFFAOYSA-N [2-pyridin-3-yl-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound FC(C1=CC(=CC(=N1)C=1C=NC=CC=1)CN)(F)F ABRVLXLNVJHDRQ-UHFFFAOYSA-N 0.000 description 1
- WWFYMTROHDOCAS-UHFFFAOYSA-N [H][Sn-]([H])c1cc(c(OCCCCCCCC)c(c(C2)c3OCCCCCCCC)SC2[SnH](C)C)c3[s]1 Chemical compound [H][Sn-]([H])c1cc(c(OCCCCCCCC)c(c(C2)c3OCCCCCCCC)SC2[SnH](C)C)c3[s]1 WWFYMTROHDOCAS-UHFFFAOYSA-N 0.000 description 1
- DSCRNZFCNFDDOV-UHFFFAOYSA-N [Sn]CC1=CC=CS1 Chemical compound [Sn]CC1=CC=CS1 DSCRNZFCNFDDOV-UHFFFAOYSA-N 0.000 description 1
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- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
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- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
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- HIHKYDVSWLFRAY-UHFFFAOYSA-N thiophene-2,3-dicarboxylic acid Chemical compound OC(=O)C=1C=CSC=1C(O)=O HIHKYDVSWLFRAY-UHFFFAOYSA-N 0.000 description 1
- KKRPPVXJVZKJON-UHFFFAOYSA-N trimethyl-(5-trimethylstannylthiophen-2-yl)stannane Chemical compound C[Sn](C)(C)C1=CC=C([Sn](C)(C)C)S1 KKRPPVXJVZKJON-UHFFFAOYSA-N 0.000 description 1
- WCHYSNDRWAMSCS-UHFFFAOYSA-N trimethyl-[5-[2-(5-trimethylstannylthiophen-2-yl)ethyl]thiophen-2-yl]stannane Chemical compound S1C([Sn](C)(C)C)=CC=C1CCC1=CC=C([Sn](C)(C)C)S1 WCHYSNDRWAMSCS-UHFFFAOYSA-N 0.000 description 1
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 1
- 238000002061 vacuum sublimation Methods 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
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Abstract
Description
본 발명은 유기 반도체 화합물, 이의 제조방법 및 이를 채용한 유기 태양전지에 관한 것이다.The present invention relates to an organic semiconductor compound, a manufacturing method thereof and an organic solar cell employing the same.
보다 구체적으로 분자 내 전자 받게 영역에 알킬 이미드를 포함하는 방향족 화합물을 도입한 유기 반도체 화합물, 이의 제조방법, 이러한 유기 반도체 화합물을 함유하는 고분자 화합물 및 고분자 화합물을 함유하는 유기 태양전지에 관한 것이다.More specifically, the present invention relates to an organic semiconductor compound in which an aromatic compound containing an alkyl imide is introduced into an intramolecular electron accepting region, a method for preparing the same, a polymer compound containing such an organic semiconductor compound, and an organic solar cell containing the polymer compound.
최근 환경문제와 화석 에너지 자원의 고갈에 따라 대체 에너지 개발의 중요성이 대두되고 있다. 그 중에 가장 각광받는 분야가 바로 태양전지 분야이며 거의 무한대에 가까운 에너지 자원이면서도 친환경적이고 높은 효율을 가지는 것으로 알려져 있다. Recently, the importance of alternative energy development is increasing due to environmental problems and exhaustion of fossil energy resources. Among them, the most prominent field is the solar cell field, and it is known that it has almost infinity energy resources and is environmentally friendly and has high efficiency.
태양전지 분야는 오래 전부터 무기물을 기반으로 한 태양전지의 개발이 이루어져 오고 있으며 최근에 들어서는 상용화를 위해 높은 가격경쟁력을 가지는 태양전지의 개발이 이슈가 되고 있다. 이러한 추세로 인해 기존의 벌크(bulk)한 태양전지보다 보다 얇은 박막형 태양전지 위주로 개발이 진행되고 있다. 발전(Plant)용 태양전지의 개발은 대부분 무기물 타입의 태양전지가 주를 이루고 있으며 저가형 휴대기기의 발전용으로 유기 태양전지가 개발되고 있다. In the solar cell field, development of solar cells based on inorganic materials has been made for a long time, and recently, development of solar cells having high price competitiveness for commercialization has become an issue. Due to this trend, development is being focused on thinner thin film solar cells than conventional bulk solar cells. Most of the development of solar cells for power plants is mainly inorganic type solar cells, and organic solar cells are being developed for the development of low-cost portable devices.
반면 유기태양전지는 가볍고 플라스틱 기판위에 소자 구현이 가능하기 때문에 두루마리식 혹은 입고 다니는 태양전지로 응용될 가능성이 높다. 이미 단일 셀 효율로는 8%가 넘는 유기태양전지가 보고되고 있으며 7~9% 사이의 높은 유기태양전지가 보고되고 있다. Organic solar cells, on the other hand, are likely to be used as rollable or wearable solar cells because they are lightweight and can be implemented on plastic substrates. Already, more than 8% of organic solar cells have been reported with single cell efficiency, and high organic solar cells of 7-9% have been reported.
최초 유기태양전지 개발은 단분자 재료인 CuPc와 Perylene을 이용한 이종접합구조로부터 시작되었으며 당시 1%의 효율을 보고하였다. 그러나 2000년대 유기물 태양전지에 관한 연구가 단분자에서 고분자로 전환되면서 급격하게 효율이 향상되었다. 현재까지 개발된 대표적인 고분자계 유기태양전지 재료로는 P3HT[폴리(3-헥실티오펜)]과 MEH-PPV[폴리(2-메톡시-5-(2-에틸-헥소일)-1,4-페닐렌-바이닐렌)], PCPDTBT[폴리(2,6-(4,4-비스-(2-에틸헥실)-4H-싸이클로펜타 [2,1-b;3,4-b]-다이싸이오펜)-얼터-4,7-(2,1,3-벤조싸이아다이아졸)] 등이 있다. 기존에는 MEH-PPV 및 P3HT를 이용하여 n 타입 재료인 PCBM(페닐-C61-부틸릭엑시드메틸이서)와 혼합하여 활성층을 만들었다. The first development of organic solar cell started with heterojunction structure using CuPc and Perylene, which are monomolecular materials, and reported 1% efficiency at that time. However, as the research on organic solar cells in the 2000s changed from monomolecules to polymers, the efficiency improved dramatically. Representative polymer organic solar cell materials developed to date include P3HT [poly (3-hexylthiophene)] and MEH-PPV [poly (2-methoxy-5- (2-ethyl-hexyl) -1,4 -Phenylene-vinylene)], PCPDTBT [poly (2,6- (4,4-bis- (2-ethylhexyl) -4H-cyclopenta [2,1-b; 3,4-b] -di Thiophene) -alter-4,7- (2,1,3-benzothiadiazol)], etc. Previously, MEH-PPV and P3HT were used to form n-type PCBM (phenyl-C61-butylic). Acid methyl) to form an active layer.
또한 P3HT의 경우 높은 결정성을 가지므로 형태학적 개선을 위해 어닐링을 실시하여 5%가 넘는 효율을 보고하였다. 그러나 P3HT와 같은 한 가지 반복단위로 중합된 고분자 재료들은 장파장을 흡수하는데 한계가 있으며 더 높은 효율을 구현하기 위해서는 장파장을 흡수하는 신규 재료 개발이 필요하게 되었다. 빛의 장파장 영역을 흡수하는 여러 가지 방법이 연구되었고 그 중 분자 내 전자 주게와 전자 받게를 교대 중합하여 만든 고분자 재료가 에너지 벤드갭을 변환시킴으로써 장파장을 흡수할 수 있다는 것이 보고되면서 중점적으로 연구되기 시작하였다. In addition, P3HT has a high crystallinity, so annealing was performed for morphological improvement and reported an efficiency of more than 5%. However, polymer materials polymerized with one repeating unit, such as P3HT, are limited in absorbing long wavelengths, and in order to realize higher efficiency, new materials that absorb long wavelengths need to be developed. Several methods of absorbing the long wavelength region of light have been studied, and among them, polymer materials made by alternating polymerization of electron donors and electron acceptors in a molecule are reported to be able to absorb long wavelengths by converting energy bend gaps. It was.
이러한 일례로 한국등록특허 제 1042530호에 알콕시기를 곁사슬로 가지는 방향족 재료를 분자 내 전자주게로 사용한 유기태양전지를 개시하고 있다.For example, Korean Patent No. 1042530 discloses an organic solar cell using an aromatic material having an alkoxy group as a side chain as an intramolecular electron donor.
그러나 여전히 유기 태양전지의 활성층으로 장파장의 빛을 흡수해 높은 효율을 구현할 수 있는 재료의 개발이 요구되고 있다. However, there is still a need to develop a material capable of absorbing long wavelengths of light into an active layer of an organic solar cell and realizing high efficiency.
본 발명은 높은 용해도를 가져 n타입(전자 받게) 재료(일례로 PCBM)와 혼합 시 형태학적으로 우수하면서도 장파장의 흡수를 가능하게 하는 유기 반도체 화합물을 제공한다. The present invention provides an organic semiconductor compound that has high solubility and allows for absorption of long wavelengths while being morphologically excellent when mixed with n-type (electron acceptor) materials (eg, PCBM).
또한, 본 발명은 밴드갭 조절이 가능하며, 높은 전자밀도를 가지는 전자 받게구조를 도입하여 높은 단락전류를 가지면서 열적으로 안정하여 높은 충진율을 가지는 유기 반도체 화합물을 제공한다.In addition, the present invention provides an organic semiconductor compound that can control the band gap, and has an electron accepting structure having a high electron density and thermally stable while having a high short-circuit current to have a high filling rate.
또한 본 발명은 본 발명에 유기 반도체 화합물을 제조하는 방법을 제공한다.The present invention also provides a method for producing an organic semiconductor compound.
또한, 본 발명은 본 발명에 따른 유기 반도체 화합물을 단위체로 포함하며, 유기 태양전지의 활성층의 p타입재료인 고분자 화합물을 제공한다.The present invention also provides a polymer compound comprising the organic semiconductor compound according to the present invention as a unit and a p-type material of the active layer of the organic solar cell.
또한, 본 발명은 본 발명에 따른 고분자 화합물을 활성층으로 가지는 유기 태양전지를 제공한다.The present invention also provides an organic solar cell having the polymer compound according to the present invention as an active layer.
본 발명은 유기 반도체 화합물, 이의 제조방법, 이를 함유하는 고분자 화합물 및 이러한 고분자 화합물을 함유하는 유기 태양전지를 제공한다.The present invention provides an organic semiconductor compound, a method for producing the same, a polymer compound containing the same, and an organic solar cell containing the polymer compound.
본 발명의 유기 반도체 화합물은 하기 화학식 1로 표시된다.The organic semiconductor compound of the present invention is represented by the following formula (1).
[화학식 1][Formula 1]
[상기 화학식 1에서,[In
Z는 S 또는 Se이고;Z is S or Se;
R은 C1-C30알킬, C2~C30알킬렌, C2~C30알키닐렌, C6~C30아릴 또는 C3~C30헤테로아릴이며, 상기 알킬, 알킬렌, 알키닐렌, 아릴 및 헤테로아릴은 C1-C30알킬, C2-C30알케닐, C2-C30알키닐, C1-C30알콕시, 아미노기, 하이드록시기, 할로겐기, 사이아노기, 나이트로기, 트리플루오로메틸기 및 실릴기로 선택되는 하나 이상의 치환기로 더 치환될 수 있다.]R is C 1 -C 30 alkyl, C 2 -C 30 alkylene, C 2 -C 30 alkynylene, C 6 -C 30 aryl or C 3 -C 30 heteroaryl, the alkyl, alkylene, alkynylene, Aryl and heteroaryl are C 1 -C 30 alkyl, C 2 -C 30 alkenyl, C 2 -C 30 alkynyl, C 1 -C 30 alkoxy, amino, hydroxy, halogen, cyano, nitro And one or more substituents selected from a group, a trifluoromethyl group and a silyl group.]
본 발명의 유기 반도체 화합물은 높은 전자밀도를 가지는 이미드를 도입한 방향족 구조의 화합물로 티오페노티오펜 또는 셀레노페노셀레노펜 융합고리와 이미드를 통해 전자밀도를 향상시키고 이미드에 치환기를 도입하여 용해도를 향상시키게 되며, 작고 딱딱한 방향족 그룹은 분자간 상호작용을 높여주어 이를 전자주게로 도입하여 전자받게와 전자주게를 교대중합한 고분자 화합물은 유기 태양전지의 활성층 재로로 높은 효율과 우수한 열적 안정성을 나타낸다.The organic semiconductor compound of the present invention is an aromatic compound incorporating an imide having a high electron density to improve electron density through thiophenothiophene or selenophenoselenophene fused ring and imide and introduce a substituent into the imide. Solubility is improved, and small and hard aromatic groups enhance the intermolecular interactions and introduce them into electron donors, and polymer compounds that alternately polymerize electron acceptors and electron donors are used as active layer materials for organic solar cells, resulting in high efficiency and excellent thermal stability. Indicates.
구체적으로 상기 화학식 1에서 이미드의 N에 알킬치환기를 가져 유기용매에 대한 높은 용해도를 가져 모폴로지(morphology)의 향상시킬 수 있고, 높은 전자밀도를 가져 우수한 전기적 특성을 가지기위한 측면에서, 상기 R은 C1-C30알킬기일 수 있으며, 상기 Z는 S일 수 있다.Specifically, in Formula 1, N has an alkyl substituent on N-imide to have high solubility in an organic solvent, thereby improving morphology, and having a high electron density in terms of having excellent electrical properties. It may be a C 1 -C 30 alkyl group, Z may be S.
또한 본 발명은 상기 화학식 1로 표시되는 유기 반도체 화합물의 제조방법을 제공한다.In another aspect, the present invention provides a method for producing an organic semiconductor compound represented by the formula (1).
본 발명의 상기 화학식 1로 표시되는 유기 반도체 화합물의 제조방법은, Method for producing an organic semiconductor compound represented by Formula 1 of the present invention,
하기 화학식 2로 표시되는 화합물과 화학식 3으로 표시되는 화합물을 반응시켜 하기 화학식 4로 표시되는 화합물을 제조하는 단계;Preparing a compound represented by Chemical Formula 4 by reacting the compound represented by Chemical Formula 2 with the compound represented by Chemical Formula 3;
하기 화학식 4로 표시되는 화합물을 산화시켜 화학식 5로 표시되는 화합물을 제조하는 단계;Preparing a compound represented by Chemical Formula 5 by oxidizing the compound represented by Chemical Formula 4;
하기 화학식 5로 표시되는 화합물을 무수아세틱산과 반응시켜 화학식 6으로 표시되는 화합물을 제조하는 단계;및Reacting a compound represented by Formula 5 with acetic anhydride to prepare a compound represented by Formula 6; and
하기 화학식 6으로 표시되는 화합물을 하기 화학식 7로 표시되는 화합물과 반응시켜 화학식 1로 표시되는 화합물을 제조하는 단계;를 포함한다.To prepare a compound represented by the formula (1) by reacting the compound represented by the formula (6) with a compound represented by the formula (7).
[화학식 2][Formula 2]
[화학식 3](3)
[화학식 4][Formula 4]
[화학식 5][Chemical Formula 5]
[화학식 6][Formula 6]
[화학식 7][Formula 7]
RNH2 RNH 2
[상기 화학식 2 내지 7에서, [In
Z는 S 또는 Se이고;Z is S or Se;
R은 C1-C30알킬, C2~C30알킬렌, C2~C30알키닐렌, C6~C30아릴 또는 C3~C30헤테로아릴이며, 상기 알킬, 알킬렌, 알키닐렌, 아릴 및 헤테로아릴은 C1-C30알킬, C2-C30알케닐, C2-C30알키닐, C1-C30알콕시, 아미노기, 하이드록시기, 할로겐기, 사이아노기, 나이트로기, 트리플루오로메틸기 및 실릴기로 선택되는 하나 이상의 치환기로 더 치환될 수 있으며;R is C 1 -C 30 alkyl, C 2 -C 30 alkylene, C 2 -C 30 alkynylene, C 6 -C 30 aryl or C 3 -C 30 heteroaryl, the alkyl, alkylene, alkynylene, Aryl and heteroaryl are C 1 -C 30 alkyl, C 2 -C 30 alkenyl, C 2 -C 30 alkynyl, C 1 -C 30 alkoxy, amino, hydroxy, halogen, cyano, nitro May be further substituted with one or more substituents selected from groups, trifluoromethyl groups and silyl groups;
R1 또는 R2는 서로 독립적으로, C1-C30알킬이며;R 1 or R 2 are, independently from each other, C 1 -C 30 alkyl;
X는 할로겐이다.]X is halogen.]
본 발명의 일 실시예에 따른 상기 화학식 4의 제조 시 촉매가 사용될 수 있으며 보다 구체적으로 산화구리를 사용할 수 있다.In the preparation of Chemical Formula 4 according to an embodiment of the present invention, a catalyst may be used, and more specifically, copper oxide may be used.
본 발명의 일 실시예에 따른 상기 화학식 1은 상기 화학식 6, 1몰에 대하여 화학식 7, 0.5 ~ 2몰로 반응시켜 제조될 수 있다.
본 발명의 상기 화학식 1로 표시되는 유기 반도체 화합물의 제조방법의 일 실시예에 따른 상기 화학식 2의 화합물은 유기리튬 존재하에 하기 화학식 8의 화합물과 하기 화학식 9의 화합물을 반응시켜 제조되는 것일 수 있다.According to an embodiment of the method for preparing an organic semiconductor compound represented by Chemical Formula 1, the compound of Chemical Formula 2 may be prepared by reacting a compound of Chemical Formula 8 with a compound of Chemical Formula 9 in the presence of an organic lithium. .
[화학식 8][Formula 8]
[화학식 9][Chemical Formula 9]
(상기 화학식 8 또는 화학식 9에서,(In Formula 8 or Formula 9,
X 또는 X1은 할로겐이며;X or X 1 is halogen;
R1은 C1-C20알킬이다.)R 1 is C 1 -C 20 alkyl.)
본 발명의 일 실시예에 따른 유기리튬은 유기화합물과 리튬으로 구성된 물질이면, 모두 가능하나, 바람직하게 알킬리튬이며, 보다 바람직하게는 에틸리튬, n-부틸리튬, tert-부틸리튬일 수 있다.The organolithium according to an embodiment of the present invention may be any material as long as it is a material composed of an organic compound and lithium, but is preferably alkyllithium, more preferably ethyllithium, n-butyllithium, tert-butyllithium.
바람직하게 상기 화학식 1 내지 7에서 Z는 S이며, R은 C1-C20알킬기일 수 있다.Preferably, in
본 발명의 유기 반도체 화합물의 제조방법에서 사용되는 용매는 통상의 유기합성에서 사용되는 용매라도 모두 가능하나, 이에 한정이 있는 것은 아니며, 반응시간과 온도 또한 발명의 핵심을 벗어나지 않는 범위내에서 변경이 가능하다.The solvent used in the method of preparing the organic semiconductor compound of the present invention may be any solvent used in conventional organic synthesis, but is not limited thereto, and the reaction time and temperature may be changed within a range not departing from the core of the present invention. It is possible.
또한 본 발명은 상기 화학식 1로 표시되는 유기 반도체 화합물을 단위체로 포함하는 고분자 화합물을 제공한다.In another aspect, the present invention provides a polymer compound comprising an organic semiconductor compound represented by the formula (1) as a unit.
본 발명의 상기 화학식 1로 표시되는 유기 반도체 화합물을 단위체로 포함하는 고분자 화합물은 유기 반도체 화합물을 이미드기와 티오페노티오펜 또는 셀레노페노셀레노펜 융합고리를 가져 전자밀도가 높고, 이미드기의 N에 치환기를 가져 용해도가 향상되어 본 발명의 유기 반도체 화합물을 단위체로 포함하는 고분자 화합물을 활성층으로 함유하는 유기 태양전지는 높은 효율과 높은 안정성을 나타낸다.The polymer compound including the organic semiconductor compound represented by
즉, 본 발명의 유기 반도체 화합물을 전자주게로 도입하고 전자받게인 화합물과 교대중합하여 제조된 본 발명의 고분자 화합물은 높은 용해도, 전하이동도 및 안정성을 가진다.That is, the polymer compound of the present invention prepared by introducing the organic semiconductor compound of the present invention into an electron donor and alternating polymerization with an electron acceptor compound has high solubility, charge mobility and stability.
본 발명에 따른 고분자 화합물은 하기 화학식 11로 표시되는 것일 수 있다.The polymer compound according to the present invention may be represented by the following formula (11).
[화학식 11][Formula 11]
(상기 화학식 11에서,(11)
Z는 S 또는 Se이고;Z is S or Se;
Ar은 C6-C30아릴렌 또는 C3-C30헤테로아릴렌이며;Ar is C 6 -C 30 arylene or C 3 -C 30 heteroarylene;
R은 C1-C30알킬, C2~C30알킬렌, C2~C30알키닐렌, C6~C30아릴 및 C3~C30헤테로아릴로부터 선택되며, 상기 알킬, 알킬렌, 알키닐렌, 아릴 및 헤테로아릴은 C1-C20알킬, C2-C20알케닐, C2-C20알키닐, C1-C20알콕시, 아미노기, 하이드록시기, 할로겐기, 사이아노기, 나이트로기, 트리플루오로메틸기 및 실릴기로 선택되는 하나 이상의 치환기로 더 치환될 수 있으며;R is selected from C 1 -C 30 alkyl, C 2 -C 30 alkylene, C 2 -C 30 alkynylene, C 6 -C 30 aryl and C 3 -C 30 heteroaryl, said alkyl, alkylene, alkoxy Niylene, aryl and heteroaryl are C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 1 -C 20 alkoxy, amino, hydroxy, halogen, cyano, May be further substituted with one or more substituents selected from nitro, trifluoromethyl and silyl groups;
상기 n은 1 내지 1000의 정수이다.) N is an integer of 1 to 1000.)
본발명의 고분자 화합물은 본 발명의 유기 반도체 화합물을 전자주게로 전자받게인 화합물과 교대중합되도록 구성하여 이를 포함하는 유기 태양전지의 전기특성 및 안정성을 높인다.The polymer compound of the present invention is configured to alternately polymerize the organic semiconductor compound of the present invention with an electron acceptor compound as an electron donor to increase electrical characteristics and stability of an organic solar cell including the same.
바람직하게 상기 화학식 11에서 Ar은 하기 구조에서 선택되는 하나이상인 것일 수 있다.Preferably Ar in Formula 11 may be one or more selected from the following structures.
(상기 구조식에서,(In the above structural formula,
R11 및 R12는 서로 독립적으로 수소, C1-C30알킬, C2~C30알킬렌, C2~C30알키닐렌, C6~C30아릴 및 C3~C30헤테로아릴로부터 선택되며; 상기 알킬, 알킬렌, 알키닐렌, 아릴 및 헤테로아릴은 할로겐, C1-C30알킬, C1-C30알콕시, C6~C30아릴 및 C3~C30헤테로아릴로 더 치환될 수 있다.)R 11 and R 12 independently of one another are selected from hydrogen, C 1 -C 30 alkyl, C 2 -C 30 alkylene, C 2 -C 30 alkynylene, C 6 -C 30 aryl and C 3 -C 30 heteroaryl Become; The alkyl, alkylene, alkynylene, aryl and heteroaryl may be further substituted with halogen, C 1 -C 30 alkyl, C 1 -C 30 alkoxy, C 6 -C 30 aryl and C 3 -C 30 heteroaryl. .)
바람직하게 상기 화학식 11은 하기 화학식 12로 표시될 수 있다.Preferably, Formula 11 may be represented by the following
[화학식 12][Chemical Formula 12]
(상기 화학식 12에서,(In the above formula (12)
Ar은 C6-C30아릴렌 또는 C3-C30헤테로아릴렌이며;Ar is C 6 -C 30 arylene or C 3 -C 30 heteroarylene;
R21은 C1-C30알킬이며;R 21 is C 1 -C 30 alkyl;
상기 n은 1 내지 1000의 정수이다.)N is an integer of 1 to 1000.)
보다 바람직하게는 상기 Ar은 하기 구조에서 선택되는 아릴렌 또는 헤테로아릴렌일 수 있다.More preferably, Ar may be arylene or heteroarylene selected from the following structures.
(상기 구조식에서, (In the above structural formula,
R11 및 R12는 서로 독립적으로 수소, C1-C30알킬, C2~C30알킬렌, C2~C30알키닐렌, C6~C30아릴 및 C3~C30헤테로아릴로부터 선택되며; 상기 알킬, 알킬렌, 알키닐렌, 아릴 및 헤테로아릴은 할로겐, C1 -C30알킬, C1 -C30알콕시, C6~C30아릴 및 C3~C30헤테로아릴로 더 치환될 수 있다.)R 11 and R 12 independently of one another are selected from hydrogen, C 1 -C 30 alkyl, C 2 -C 30 alkylene, C 2 -C 30 alkynylene, C 6 -C 30 aryl and C 3 -C 30 heteroaryl Become; It said alkyl, alkylene, alkynylene, aryl and heteroaryl are halogen, C 1 - may be further substituted with a C 30 alkoxy, C 6 ~ C 30 aryl, and C 3 ~ C 30 heteroaryl, - C 30 alkyl, C 1 .)
본 발명의 일 실시예에 따른 고분자 화합물은 바람직하게 하기 구조식으로 예시될 수 있으나, 이에 한정이 있는 것은 아니다.The polymer compound according to an embodiment of the present invention may be preferably exemplified by the following structural formula, but is not limited thereto.
(상기 화학식 구조에서 n은 1 내지 1000의 정수이다.)(N is an integer of 1 to 1000 in the formula structure.)
본 발명에 따른 유기 반도체 화합물을 단위체로 하는 고분자 화합물을 합성하기 위한 방법으로, 알킬화반응, 브롬화반응, 고리화반응, 환원반응, 탈수반응, 스틸러커플링반응, 스즈키커플링반응 등의 방법을 통하여 제조할 수 있으나 상기의 합성방법으로 한정하는 것은 아니며, 상기의 합성방법 이외에도 통상적으로 사용되는 유기화학 반응에 의하여 합성될 수 있다.A method for synthesizing a polymer compound using the organic semiconductor compound as a unit according to the present invention, through alkylation reaction, bromination reaction, cyclization reaction, reduction reaction, dehydration reaction, stiller coupling reaction, Suzuki coupling reaction, etc. It may be prepared, but is not limited to the above synthesis method, and may be synthesized by an organic chemical reaction that is commonly used in addition to the above synthesis method.
또한 본 발명은 본 발명의 고분자 화합물을 함유하는 유기태양전지를 제공한다.The present invention also provides an organic solar cell containing the polymer compound of the present invention.
본 발명의 일 실시예에 따른 유기태양전지는 기판, 투명전극, 정공수송층, 활성층, 전자수송층, 금속전극이 순차적으로 적층된 것일 수 있으며, 본 발명에 따른 상기 화학식 11의 고분자 화합물을 활성층의 p타입으로 사용되는 유기 태양전지를 제공한다.An organic solar cell according to an embodiment of the present invention may be a substrate, a transparent electrode, a hole transport layer, an active layer, an electron transport layer, a metal electrode sequentially stacked, the polymer compound of Formula 11 according to the present invention p of the active layer Provided is an organic solar cell used as a type.
일반적으로 본 발명에 따른 유기 태양전지는 이하 상술하는 방법으로 제조될 수 있으나 이는 일례를 들어 설명하는 것으로 이에 한정이 있는 것은 아니다.In general, the organic solar cell according to the present invention may be manufactured by the above-described method, but this is described by way of example and is not limited thereto.
태양전지는 일반적으로 도 1과 같이 유리기판/투명전극(ITO)/정공수송층/활성층(전자주게/전자받게)/전자수송층/금속전극(Al)으로 이루어진다. 구동원리는 빛이 유기기판과 ITO, 정공수송층을 통과하여 활성층에 도달하게 되면 p타입(전자주게) 고분자와 n타입(전자받게) 사이에서 여기자(Exciton)가 발생하게 되고 n타입의 물질을 따라 전자가 뜀(호핑)을 통해 금속전극으로 이동하게 되고 남은 정공은 정공수송층을 통해 ITO층으로 이동하게 된다. 이렇게 분리된 전자와 정공은 전류와 전압을 발생시키게 되고 전력을 생성시키게 된다. 정공수송층은 PEDOT:PSS[폴리(3,4-에틸렌다이옥시티오펜)]:[폴리(스티렌설포네이트)]로 이루어져 있으며 전자가 양극인 ITO층으로 이동하는 것을 막아주면서 정공의 수송을 원활하게 도와준다. The solar cell is generally composed of a glass substrate / transparent electrode (ITO) / hole transport layer / active layer (electron donor / electron acceptor) / electron transport layer / metal electrode (Al) as shown in FIG. The driving principle is that when light reaches the active layer through the organic substrate, the ITO, and the hole transport layer, excitons are generated between the p-type (electron donor) polymer and the n-type (electron acceptor). The electrons move to the metal electrode through hopping, and the remaining holes move to the ITO layer through the hole transport layer. These separated electrons and holes generate currents and voltages and generate power. The hole transport layer is composed of PEDOT: PSS [poly (3,4-ethylenedioxythiophene)]: [poly (styrenesulfonate)] and helps to transport holes while preventing electrons from moving to the anode ITO layer. give.
또한 본 발명의 활성층은 보다 바람직하게 p타입과 n타입의 계면을 넓게 하는 괴상이종접합(bulk-heterojunction)으로 이루어져 있는 것이 좋으며 이를 통해 생성되는 여기자가 쉽게 전자와 정공으로 분리될 수 있다는 장점을 가지게 된다. In addition, the active layer of the present invention is more preferably composed of bulk-heterojunction (bulk-heterojunction) to widen the interface between the p-type and n-type and has the advantage that the excitons generated through this can be easily separated into electrons and holes do.
보다 상세하게 설명하면, 투명전극인 ITO가 코팅된 유리기판위에 PEDOT-PSS(Baytron P TP AI 4083, Bayer AG)를 스핀코팅하여 30-50nm 두께로 층을 코팅한다. 그 후 120 oC에서 60분간 어닐링을 하여 용매를 제거한다. 활성층은 본 발명에 따른 고분자 화합물과 PCBM 유도체 및 첨가제(DIO;다이아이오도옥탄, ODT;옥타다이싸이올)를 60 oC에서 12시간동안 교반시킨 후에 0.45 μm크기의 필터로 물질을 필터한 후에 PEDOT-PSS 층위에 스핀코팅을 이용하여 100 nm 두께로 코팅한다. 그 후에 고진공 (10-6 torr)에서 10 nm 두께로 TiO2(인듐 틴 옥사이드)를 코팅하고 금속 전극으로 알루미늄(Al)을 100 nm 두께로 증착한다. 증착 후 필요에 따라 글러브 박스 안에서 120-150 oC의 온도로 30분간 어닐링을 실시하여 형태학적 최적화를 실시한다. In more detail, PEDOT-PSS (Baytron P TP AI 4083, Bayer AG) is spin-coated on a glass substrate coated with a transparent electrode ITO to coat a layer with a thickness of 30-50 nm. Thereafter, the solvent is removed by annealing at 120 ° C. for 60 minutes. After the active layer was stirred at 60 ° C. for 12 hours, the polymer compound, the PCBM derivative, and the additive (DIO; diio-octane, ODT; octadithiol) according to the present invention were filtered through a 0.45 μm filter. 100 nm thick is coated on the PEDOT-PSS layer using spin coating. After that, TiO 2 (indium tin oxide) is coated to a thickness of 10 nm at high vacuum (10 −6 torr) and aluminum (Al) is deposited to a thickness of 100 nm with a metal electrode. After deposition, morphological optimization is performed by annealing at a temperature of 120-150 ° C. for 30 minutes in the glove box if necessary.
상기 기판은 유리기판 이외에도 플라스틱 기판으로 PET[폴리(에틸렌테레프탈레이트), PES[폴리(이서술폰) 등의 소재를 사용할 수 있다.In addition to the glass substrate, the substrate may use a material such as PET (poly (ethylene terephthalate), PES (poly (esulfone)), etc. as a plastic substrate.
본 발명에 따른 유기반도체 화합물을 사용하는 활성층은 스크린 인쇄법, 프린팅법, 스핀캐스팅법, 스핀코팅법, 딥핑법 또는 잉크분사법을 통하여 박막으로 형성될 수 있다.The active layer using the organic semiconductor compound according to the present invention may be formed into a thin film by screen printing, printing, spin casting, spin coating, dipping or ink spraying.
상기 금속 전극은 전도성 물질이면 가능하나, 금(Au), 은(Ag), 알루미늄(Al), 니켈(Ni), 크롬(Cr) 및 인듐틴산화물(ITO)로 이루어진 군으로부터 선택된 물질로 형성되는 것이 바람직하다.The metal electrode may be a conductive material, but may be formed of a material selected from the group consisting of gold (Au), silver (Ag), aluminum (Al), nickel (Ni), chromium (Cr), and indium tin oxide (ITO). It is preferable.
또한 투명전극은 제한이 있는 것은 아니나, ITO(인듐틴옥사이드), ZnO(아연옥사이드), MnO(망간옥사이드)등이 사용될 수 있다.In addition, the transparent electrode is not limited, but ITO (indium tin oxide), ZnO (zinc oxide), MnO (manganese oxide) and the like can be used.
본 발명에 따른 유기 반도체 화합물은 전자 주게 화합물이 이미드에 치환된 치환기를 가짐으로써 높은 용해도를 가질 뿐만 아니라 이미드와 티오페노티오펜 또는 세레노페노셀레노펜 융합고리가 가지는 높은 전자밀도로 인해 이를 단위체로 함유하는 고분자 화합물을 유기 태양전지에 적용하면 단락전류(Jsc)값을 향상시킬 수 있다. The organic semiconductor compound according to the present invention has not only high solubility because the electron donor compound has a substituent substituted in the imide, but also due to the high electron density of the imide and thiophenothiophene or serenophenoselenophene fused ring. By applying a polymer compound containing a unit to an organic solar cell, a short circuit current (Jsc) value can be improved.
또한 본 발명은 본 발명에 따른 유기 반도체 화합물을 함유하는 고분자 화합물은 유기 태양전지의 활성층의 p타입재료로 사용되며 에너지 밴드갭을 조절하여 높은 개방 전압을 가질 수 있어 이를 채용한 유기 태양전지는 높은 효율을 가질 수 있다.In addition, according to the present invention, the polymer compound containing the organic semiconductor compound according to the present invention is used as a p-type material of the active layer of the organic solar cell and may have a high open voltage by adjusting the energy band gap. Can have efficiency.
또한 본 발명은 전자 주게 화합물인 유기 반도체 화합물의 이미드에 치환되는 치환기의 구조에 따라 이를 채용한 유기 태양전지의 산화 안정성, 개방 전압값 및 전류 밀도를 향상 시킬 수 있다.In addition, the present invention can improve the oxidative stability, the open voltage value and the current density of the organic solar cell employing the same according to the structure of the substituent substituted in the imide of the organic semiconductor compound which is an electron donor compound.
또한 본 발명에 따른 유기 반도체 화합물뿐만 아니라 이를 단위체로 함유하는 고분자 화합물은 용매에 대한 용해도가 높아 스핀코팅이나 프린팅 같은 용액 공정으로도 제조할 수 있어 비용을 절감할 수 있을 뿐만 아니라 대면적화가 가능한 장점을 가진다.In addition, not only the organic semiconductor compound according to the present invention but also a polymer compound containing the monomer as a high solubility in a solvent can be prepared by a solution process such as spin coating or printing, which can reduce cost and large area. Has
도 1은 유리기판/투명전극(ITO)/정공수송층(PEDOT:PSS)/활성층(p/n)/전자수송층(TiO2)/금속전극(Al)으로 제조되는 일반적인 유기태양전지 구조를 보여주는 단면도이다.
도 2는 실시예 4, 5에 따른 유기반도체 화합물의 용액상 및 필름상의 UV-vis 흡수 스펙트라를 나타낸 도면이다.
도 3은 실시예 6에 따른 유기반도체 화합물의 용액상 및 필름상의 UV-vis 흡수 스펙트라를 나타낸 도면이다.
도 4는 실시예 7에 따른 유기반도체 화합물의 용액상 및 필름상의 UV-vis 흡수 스펙트라를 나타낸 도면이다.
도 5는 실시예 4, 5에 따른 유기반도체 화합물의 전기적 특성(cyclic voltammetry)을 나타낸 도면이다.
도 6은 실시예 6, 7에 따른 유기반도체 화합물의 전기적 특성(cyclic voltammetry)을 나타낸 도면이다.
도 7은 실시예 4를 DSC를 통해 분자의 분절운동을 관측한 도면이다.
도 8은 실시예 5를 DSC를 통해 분자의 분절운동을 관측한 도면이다.
도 9는 실시예 6를 DSC를 통해 분자의 분절운동을 관측한 도면이다.
도 10은 실시예 7를 DSC를 통해 분자의 분절운동을 관측한 도면이다.
도 11은 실시예 4를 TGA를 통해 분자의 분해온도를 관측한 도면이다.
도 12는 실시예 5를 TGA를 통해 분자의 분해온도를 관측한 도면이다.
도 13은 실시예 6을 TGA를 통해 분자의 분해온도를 관측한 도면이다.
도 14는 실시예 7를 TGA를 통해 분자의 분해온도를 관측한 도면이다.
도 15는 실시예 4,5를 유기태양전지소자로 제작하여 측정한 전류밀도-전압 곡선(J-V)의 도면이다.
도 16은 실시예 4, 5를 유기 태양전지소자로 제작하여 외부양자효율을 측정한 도면이다.
도 17은 실시예 6를 유기태양전지소자로 제작하여 측정한 전류밀도-전압 곡선(J-V)도면이다.
도 18은 실시예 7을 유기태양전지소자로 제작하여 측정한 전류밀도-전압 곡선(J-V)도면이다.
도 19은 실시예 6, 7을 유기 태양전지소자로 제작하여 외부양자효율을 측정한 도면이다.1 is a cross-sectional view showing a general organic solar cell structure made of a glass substrate / transparent electrode (ITO) / hole transport layer (PEDOT: PSS) / active layer (p / n) / electron transport layer (TiO 2 ) / metal electrode (Al). to be.
FIG. 2 is a view showing UV-vis absorption spectra of solution phase and film phase of organic semiconductor compounds according to Examples 4 and 5. FIG.
3 is a view showing the UV-vis absorption spectra of the solution phase and the film phase of the organic semiconductor compound according to Example 6.
4 is a view showing a solution phase and a film-like UV-vis absorption spectra of the organic semiconductor compound according to Example 7.
5 is a view showing the electrical properties (cyclic voltammetry) of the organic semiconductor compound according to Examples 4, 5.
6 is a view showing the electrical properties (cyclic voltammetry) of the organic semiconductor compound according to Examples 6, 7.
FIG. 7 is a view of observing segmental motion of molecules in Example 4 through DSC. FIG.
FIG. 8 is a diagram of Example 5 observing segmental motion of molecules through DSC. FIG.
FIG. 9 is a diagram of Example 6 observing segmental motion of molecules through DSC. FIG.
FIG. 10 is a diagram illustrating a segmental motion of a molecule of Example 7 through DSC. FIG.
FIG. 11 is a diagram illustrating a decomposition temperature of molecules through Example 4 in TGA. FIG.
12 is a view of the decomposition temperature of the molecule through a TGA Example 5.
FIG. 13 is a view illustrating a decomposition temperature of a molecule of Example 6 through TGA. FIG.
FIG. 14 is a view illustrating a decomposition temperature of molecules through TGA in Example 7.
FIG. 15 is a diagram of current density-voltage curves JV measured by fabricating Examples 4 and 5 with the organic solar cell device.
16 is a view illustrating the external quantum efficiency of Examples 4 and 5 by using an organic solar cell device.
FIG. 17 is a view showing a current density-voltage curve ( JV ) measured by fabricating Example 6 as an organic solar cell device. FIG.
FIG. 18 is a drawing showing a current density-voltage curve ( JV ) measured by fabricating an organic solar cell device of Example 7. FIG.
19 is a view illustrating an external quantum efficiency by fabricating Examples 6 and 7 as an organic solar cell device.
본 발명은 하기의 실시예에 의하여 보다 명확히 이해될 수 있으며, 하기의 실시예는 본 발명의 예시 목적에 불과하며 발명의 영역을 제한하고자 하는 것은 아니다. The present invention can be more clearly understood by the following examples, which are only intended to illustrate the present invention and are not intended to limit the scope of the invention.
또한 본 발명에서 언급되는 용어중 특별히 정의하지 않는다면 당업자들 사이에서 통상적으로 사용되어 의미로 이해되는 것을 의미한다.In addition, unless specifically defined among the terms mentioned in the present invention means that it is commonly used among those skilled in the art and understood by meaning.
ID(Drain current): Drain에 흐르는 전류I D (Drain current): Current flowing through the drain
VG(Gate voltage): Gate에 인가되는 VoltageV G (Gate voltage): Voltage applied to the gate
IPCE(Incident-Photon-to-electron Conversion Efficiency): 양자효율Incident-Photon-to-electron Conversion Efficiency (IPCE): Quantum Efficiency
Mn(Number of molecular weight): 수평균 분자량Number of molecular weight (Mn): number average molecular weight
PDI(Poly dispersity index): 다분산지수Poly dispersity index (PDI): polydispersity index
HOMO(highest occupied molecular orbital): 최고점유 분자궤도Highest occupied molecular orbital (HOMO)
LUMO(lowest unoccupied molecular orbital): 최저비점유 분자궤도Lowest unoccupied molecular orbital (LUMO)
Band gap: HOMO와 LUMO 사이의 공간Band gap: the space between HOMO and LUMO
Voc: 특정한 온도와 일조 강도에서 부하를 연결하지 않은(개방 상태의)태양광발전Voc: Photovoltaic power generation without open load at specific temperature and sunshine intensity
장치 양단에 걸리는 전압.The voltage across the device.
Jsc: 특정한 온도와 일조 강도에서 단락 조건에 있는 태양전지나 모듈 등 태양광발전장치의 출력 전류. 단위 면적당 단락 전류를 특별히 Jsc라고 하는 경우도 있다.Jsc: The output current of a photovoltaic device, such as a solar cell or module, in a short circuit condition at a specific temperature and sunshine intensity. The short circuit current per unit area is sometimes called Jsc.
[실시예 1] 1,3-다이브로모-6-옥틸-5H-싸이에노[3',4',4,5]싸이에노[2,3-c]피롤-5,7(6H)-다이온의 합성Example 1 1,3-Dibromo-6-octyl-5H-thieno [3 ', 4', 4,5] cyeno [2,3-c] pyrrole-5,7 (6H) Synthesis of Dion
화합물 1-1(에틸-2-(4-브로모싸이오펜-3-일)-2-옥쏘아세테이트)의 합성Synthesis of Compound 1-1 (Ethyl-2- (4-bromothiophen-3-yl) -2-oxoacetate)
플라스크에 3,4-다이브로모싸이오펜(120.0 g, 0.49601 mol)을 넣고 다이에틸이서 600 mL에 녹인 후 -78 oC 로 온도를 낮추고 t-BuLi (437.65 mL, 0.74401 mol, 1.7 M solution)을 10분에 걸쳐 천천히 첨가한다. 20분간 -78 oC로 유지하면서 교반시키고 다이에틸이서 100 mL 에 diethyl oxalate(76.11 g, 0.52081 mol)를 녹인 후 액체질소를 이용하여 -78 oC로 온도를 낮추고 투입시킨다. -78 oC에서 1시간 동안 교반시키고 저온용기를 제거하고 0 oC로 온도를 올린 후 4시간동안 교반시킨다. 다시 0 oC까지 냉각시키고 300 mL의 2N-HCl을 빠르게 주입한다. 그 후, Ether로 추출하고 수분제거 후, 100 oC 에서 진공승화시켜 다이에틸옥살레이트를 제거한다. 그리고 남은 용매를 다이에틸이서에 희석시키고 실리카겔로 도포한 후 핵산:에틸아세테이트(1:20)의 비율로 칼럼분리하여 진노랑색의 점성이 있는 액체인 표제화합물(91.35 g)을 얻었다. (수득률: 70%) Add 3,4-dibromothiophene (120.0 g, 0.49601 mol) to the flask, dissolve in 600 mL of diethyl, lower the temperature to -78 o C, and add t-BuLi (437.65 mL, 0.74401 mol, 1.7 M solution). Add slowly over 10 minutes. Stir for 20 minutes while maintaining at -78 o C. Dissolve diethyl oxalate (76.11 g, 0.52081 mol) in 100 mL of diethyl and lower the temperature to -78 o C using liquid nitrogen. Stir at -78 o C for 1 h, remove the cold container, raise temperature to 0 o C and stir for 4 h. Cool to 0 o C again and rapidly inject 300 mL of 2N-HCl. Thereafter, the mixture was extracted with Ether and removed with water, followed by vacuum sublimation at 100 ° C. to remove diethyl oxalate. The remaining solvent was diluted with diethyl ether and coated with silica gel, followed by column separation with a ratio of nucleic acid: ethyl acetate (1:20) to give the title compound (91.35 g) as a dark yellow viscous liquid. (Yield: 70%)
1H NMR(300MHz, CDCl3)[ppm] δ8.49-8.48(d,1H), 7.38-7.37(d,1H), 4.45-4.44(m,2H), 1.44-1.40(t, 3H). 1 H NMR (300 MHz, CDCl 3 ) [ppm] δ 8.49-8.48 (d, 1H), 7.38-7.37 (d, 1H), 4.45-4.44 (m, 2H), 1.44-1.40 (t, 3H).
13C NMR(300MHz, CDCl3)[ppm] δ 178.29, 162.26, 138.64, 133.87, 125.88, 110.76, 62.75, 14.02.
13 C NMR (300 MHz, CDCl 3 ) [ppm] δ 178.29, 162.26, 138.64, 133.87, 125.88, 110.76, 62.75, 14.02.
화합물 1-2(다이에틸싸이에토[3,2-c]싸이오펜-2,3-다이카르복실레이트)의 합성Synthesis of Compound 1-2 (Diethylthieto [3,2-c] thiophene-2,3-dicarboxylate)
에틸-2-(4-브로모싸이오펜-3-일)-2-옥소아세테이트 (75.00 g, 0.28505 mol)과 포타슘카보네이트 (55.15 g, 0.39908 mol), 산화구리(Ⅱ) (18.14 g, 0.28804 mol)를 DMF 220 mL에 녹인다. 그 후에 에틸 멀캅토아세테이트 (37.68 g, 0.31356 mol)를 넣고 80 oC로 온도를 올리고 24시간동안 교반시킨다. 필터를 통해 고체를 걸러내고 여액을 다이에틸이서와 물로 추출 후 수분을 제거한다. 그 후 핵산으로 칼럼분리하여 노란색 점성이 있는 액체인 표제화합물(32.42g)을 얻었다(수득률: 40%). Ethyl-2- (4-bromothiophen-3-yl) -2-oxoacetate (75.00 g, 0.28505 mol) with potassium carbonate (55.15 g, 0.39908 mol), copper (II) (18.14 g, 0.28804 mol ) Is dissolved in 220 mL of DMF. Then add ethyl mercaptoacetate (37.68 g, 0.31356 mol) and raise the temperature to 80 o C and stir for 24 hours. The solid is filtered through a filter, and the filtrate is extracted with diethyl ether and water and then water is removed. After column separation with nucleic acid to give the title compound (32.42g) as a yellow viscous liquid (yield: 40%).
1H NMR (300MHz, CDCl3)[ppm] δ7.73-7.72(d,1H), 7.31-7.30(d,1H), 4.43-4.36(m,4H), 1.41-1.34(t,6H). 1 H NMR (300 MHz, CDCl 3 ) [ppm] δ7.73-7.72 (d, 1H), 7.31-7.30 (d, 1H), 4.43-4.36 (m, 4H), 1.41-1.34 (t, 6H).
13C NMR (300MHz, CDCl3)[ppm] δ 162.88, 162.25, 143.67, 142.24, 136.51, 124.76, 117.02, 112.08, 62.31, 61.70, 14.16, 14.09.
13 C NMR (300 MHz, CDCl 3 ) [ppm] δ 162.88, 162.25, 143.67, 142.24, 136.51, 124.76, 117.02, 112.08, 62.31, 61.70, 14.16, 14.09.
화합물 1-3(싸이에노[3,4-b]싸이오펜-2,3-다이카르복실릭엑시드)의 합성Synthesis of Compound 1-3 (thioeno [3,4-b] thiophene-2,3-dicarboxylic acid)
다이에틸싸이에노[3,4-b]싸이오펜-2,3-다이카르복실레이트 (29.20 g, 0.10269 mol)를 메탄올 200 mL에 넣고 포타슘하이드록사이드 (23.05 g, 0.41076 mol, 45% 수용액)을 넣은 후 2시간 동안 가열 환류시킨다. 그 후에 에틸아세테이와 2N-HCl로 추출 후 수분을 제거한다. 다시 에틸아세테이트와 핵산으로 재결정을 잡아 노란색 고체인 표제화합물(16.4 g)을 얻었다(수득률: 70%). Diethylthieno [3,4-b] thiophene-2,3-dicarboxylate (29.20 g, 0.10269 mol) was added to 200 mL of methanol and potassium hydroxide (23.05 g, 0.41076 mol, 45% aqueous solution. ) And heat to reflux for 2 hours. After that, the mixture is extracted with ethyl acetate and 2N-HCl, and then water is removed. Recrystallized with ethyl acetate and nucleic acid again to give the title compound (16.4 g) as a yellow solid (yield: 70%).
1H NMR (300MHz, CDCl3)[ppm] δ8.09-8.08(d,1H), 7.75-7.74(d,1H), 5.38(s,2OH).
1 H NMR (300 MHz, CDCl 3 ) [ppm] δ 8.09-8.08 (d, 1H), 7.75-7.74 (d, 1H), 5.38 (s, 2OH).
화합물 1-4(싸이에노[3,4-b]싸이오펜퓨란-2,3-다이온)의 합성Synthesis of Compound 1-4 (thioeno [3,4-b] thiophenfuran-2,3-dione)
싸이에노[3,4-b]싸이오펜-2,3-다이카르복실릭엑시드 (5.00 g, 0.02191 mol)를 아세틱언하이드라이드(50 mL)에 넣고 4시간동안 140 oC에서 환류시킨다. 그 후에 액체질소를 이용하여 0 oC로 온도를 낮추고 석출된 고체를 걸러낸 후 물과 다이에틸이서로 추출 후 다이에틸이서와 핵산으로 재결정하여 표제화합물인 진노란색 고체( 4.15 g)을 얻었다(수득률: 90%). Thieno [3,4-b] thiophene-2,3-dicarboxylic acid (5.00 g, 0.02191 mol) is added to acetic anhydride (50 mL) and refluxed at 140 ° C. for 4 hours. Thereafter, the temperature was lowered to 0 o C using liquid nitrogen, and the precipitated solid was filtered, extracted with water and diethyl ether, and then recrystallized with diethyl ether and nucleic acid to obtain a title compound (4,15 g). Yield: 90%).
1H NMR (300MHz, CDCl3)[ppm] δ8.03-8.02(d,1H), 7.63-7.62(d,1H).
1 H NMR (300 MHz, CDCl 3 ) [ppm] δ 8.03-8.02 (d, 1H), 7.63-7.62 (d, 1H).
화합물 1-5(6-Compound 1-5 (6- 옥틸Octyl -5H--5H- 싸이에노[3',4',4,5]싸이에노Cyeno [3 ', 4', 4,5] Cyeno [2,3-c]피롤-5,7(6H)-[2,3-c] pyrrole-5,7 (6H)- 다이온Dion )의 합성) Synthesis of
싸이에노[3,4-b]싸이오펜퓨란-2,3-다이온 (2.00 g, 0.00951 mol)과 옥틸아민 (1.352 g, 0.01046 mol)을 무수DMF 20 mL에 녹인다. 140 oC로 온도를 올리고 4시간동안 가열 환류시킨다. 박막크로마토그래피로 반응 정도를 확인 한 후, 물로 천천히 반응을 종결시키고 클로로포름으로 추출 후 건조시킨다. 그 후 아황산다이클로라이드 용액(1.0 M 메틸렌클로라이드) 50mL에 넣고 3시간동안 60 oC에서 환류시킨다. 나온 물질을 이서로 추출하고 수분제거 후 핵산으로 칼럼분리하여 노란색 고체인 표제화합물(1.41 g)을 얻었다(수득률: 46%). Dissolve thieno [3,4-b] thiophenfuran-2,3-dione (2.00 g, 0.00951 mol) and octylamine (1.352 g, 0.01046 mol) in 20 mL of anhydrous DMF. The temperature is raised to 140 ° C. and heated to reflux for 4 hours. After checking the reaction degree by thin layer chromatography, the reaction was slowly terminated with water, extracted with chloroform and dried. Then add 50 mL of disulphite solution (1.0 M methylene chloride) and reflux at 60 ° C. for 3 hours. The resulting material was extracted with Ecer and water was removed, followed by column separation with nucleic acid to give the title compound (1.41 g) as a yellow solid (yield: 46%).
1H NMR (300MHz, CDCl3)[ppm] δ7.86-7.85(d,1H), 7.50-7.49(d,1H), 3.65-3.60(t,2H), 1.67-1.34(d,2H) 1.34-1.27(m,10H), 0.91-0.86(t, 3H). 1 H NMR (300 MHz, CDCl 3 ) [ppm] δ 7.86-7.85 (d, 1H), 7.50-7.49 (d, 1H), 3.65-3.60 (t, 2H), 1.67-1.34 (d, 2H) 1.34 -1.27 (m, 10H), 0.91-0.86 (t, 3H).
13C NMR (300MHz, CDCl3)[ppm] δ 164.38, 163.83, 149.60, 143.93, 135.90, 131.63, 116.02, 113.82, 38.53, 31.78, 29.16, 28.84, 26.80, 22.63, 14.08.
13 C NMR (300 MHz, CDCl 3 ) [ppm] δ 164.38, 163.83, 149.60, 143.93, 135.90, 131.63, 116.02, 113.82, 38.53, 31.78, 29.16, 28.84, 26.80, 22.63, 14.08.
1,3-다이브로모-6-옥틸-5H-싸이에노[3',4',4,5]싸이에노[2,3-c]피롤-5,7(6H)-다이온의 합성Synthesis of 1,3-dibromo-6-octyl-5H-thieno [3 ', 4', 4,5] cyeno [2,3-c] pyrrole-5,7 (6H) -dione
6-옥틸-5 H-싸이에노[3',4',4,5]싸이에노[2,3-c]피롤-5,7(6H)-다이온 (3.40 g, 0.01058 mol)을 클로로포름 50 mL에 녹이고 호일로 빛을 차단한다. 그 후 n-브로모쑥신이미드(NBS) (5.65 g, 0.03173 mol)을 0 oC에서 넣고 2시간동안 실온에서 교반시킨다. 물로 반응을 종결시키고 메틸렌다이클로라이드로 추출하고 수분을 제거한다. 유기층을 감압증류하고 핵산으로 칼럼분리하여 주황색 고체인 표제화합물(3.80 g)을 얻었다(수득률: 75%). 6-octyl-5H-thieno [3 ', 4', 4,5] thieno [2,3-c] pyrrole-5,7 (6H) -dione (3.40 g, 0.01058 mol) Dissolve in 50 mL of chloroform and block the light with foil. Then n-bromosuccinimide (NBS) (5.65 g, 0.03173 mol) is added at 0 ° C. and stirred at room temperature for 2 hours. Terminate the reaction with water, extract with methylenedichloride and remove moisture. The organic layer was distilled under reduced pressure and column separated with nucleic acid to give the title compound (3.80 g) as an orange solid (yield: 75%).
1H NMR (300MHz, CDCl3)[ppm] δ3.65-3.61(t,2H), 1.69-1.64(m,2H), 1.33-1.27(m,10H), 0.91-0.87(t, 3H). 1 H NMR (300 MHz, CDCl 3 ) [ppm] δ 3.65-3.61 (t, 2H), 1.69-1.64 (m, 2H), 1.33-1.27 (m, 10H), 0.91-0.87 (t, 3H).
13C NMR (300MHz, CDCl3)[ppm] δ 163.83, 162.68, 150.89, 145.11, 137.26, 132.27, 102.81, 100.33, 39.20, 32.17, 30.10, 29.53, 29.10, 27.19, 23.01, 14.46. 13 C NMR (300 MHz, CDCl 3 ) [ppm] δ 163.83, 162.68, 150.89, 145.11, 137.26, 132.27, 102.81, 100.33, 39.20, 32.17, 30.10, 29.53, 29.10, 27.19, 23.01, 14.46.
HRMS: calcd for C16H17Br2NO2S2,476.9067 ;found,476.9068.HRMS: calcd for C 16 H 17 Br 2 NO 2 S 2 , 476.9067; found, 476.9068.
[실시예 2] 1,3-다이브로모-5-(2-데실테트라데실)-2,7-다이싸이아-5-아자-싸이클로펜타[a]팬탈렌-4,6-다이온Example 2 1,3-Dibromo-5- (2-decyltetradecyl) -2,7-dicya-5-aza-cyclopenta [a] pentane-4,6-dione
화합물 2-1(5-(2-데실테트라데실)-2,7-다이싸이아-5-아자-싸이클로펜타[a]팬탈렌-4,6-다이온)의 제조Preparation of Compound 2-1 (5- (2-decyltetradecyl) -2,7-dithia-5-aza-cyclopenta [a] pentane-4,6-dione)
싸이에노[3,4-b]싸이오펜퓨란-2,3-다이온 (5.00 g, 0.02378 mol)과 2-데실테트라데칸-1-아민(9.253 g, 0.02616 mol)을 무수DMF 50 mL에 녹인다. 140 oC로 온도를 올리고 4시간동안 가열 환류시킨다. 박막크로마토그래피로 반응 정도를 확인 한 후, 물로 천천히 반응을 종결시키고 클로로포름으로 추출 후 건조시킨다. 그 후 아황산다이클로라이드 용액(1.0 M 메틸렌클로라이드) 50mL에 넣고 3시간동안 60 oC에서 환류시킨다. 나온 물질을 이서로 추출하고 수분제거 후 핵산으로 칼럼분리하여 노란색 고체인 표제화합물(4.7 g)을 얻었다(수득률: 36%). Thieno [3,4-b] thiophenfuran-2,3-dione (5.00 g, 0.02378 mol) and 2-decyltetradecane-1-amine (9.253 g, 0.02616 mol) were added to 50 mL of anhydrous DMF. Dissolve. The temperature is raised to 140 ° C. and heated to reflux for 4 hours. After checking the reaction degree by thin layer chromatography, the reaction was slowly terminated with water, extracted with chloroform and dried. Then add 50 mL of disulphite solution (1.0 M methylene chloride) and reflux at 60 ° C. for 3 hours. The resulting material was extracted with Ecer and water was removed, followed by column separation with nucleic acid to give the title compound (4.7 g) as a yellow solid (yield: 36%).
1H NMR (300MHz, CDCl3)[ppm] δ7.84-7.83(d,1H), 7.49-7.48(d,1H), 3.52-3.50(d,2H), 1.84 (s,1H) 1.25(s,40H), 0.90-0.86(t, 6H). 1 H NMR (300 MHz, CDCl 3 ) [ppm] δ 7.84-7.83 (d, 1H), 7.49-7.48 (d, 1H), 3.52-3.50 (d, 2H), 1.84 (s, 1H) 1.25 (s , 40H), 0.90-0.86 (t, 6H).
13C NMR (300MHz, CDCl3)[ppm] δ 164.51, 163.99, 149.53, 143.96, 135.94, 131.55, 115.98, 113.75, 42.71, 37.21, 31.92, 31.44, 29.96, 29.68, 29.65, 29.61, 29.35, 26.31, 22.69, 18.45, 14.11
13 C NMR (300 MHz, CDCl 3 ) [ppm] δ 164.51, 163.99, 149.53, 143.96, 135.94, 131.55, 115.98, 113.75, 42.71, 37.21, 31.92, 31.44, 29.96, 29.68, 29.65, 29.61, 29.35, 26.31, 22.69 , 18.45, 14.11
화합물 2(1,3-다이브로모-5-(2-데실테트라데실)-2,7-다이싸이아-5-아자-싸이클로펜타[a]팬탈렌-4,6-다이온)의 제조Preparation of Compound 2 (1,3-Dibromo-5- (2-decyltetradecyl) -2,7-dithia-5-aza-cyclopenta [a] panylene-4,6-dione)
5-(2-데실테트라데실)-2,7-다이싸이아-5-아자-싸이클로펜타[a]팬탈렌-4,6-dion (4.50 g, 0.00824 mol)을 클로로포름 50 mL에 녹이고 호일로 빛을 차단한다. 그 후 n-브로모쑥신이미드(NBS) (4.40 g, 0.02473 mol)을 0 oC에서 넣고 2시간동안 실온에서 교반시킨다. 물로 반응을 종결시키고 메틸렌다이클로라이드로 추출하고 수분을 제거한다. 유기층을 감압증류하고 핵산으로 칼럼분리하여 주황색 고체인 표제화합물(4.50 g)을 얻었다(수득률: 78%). Dissolve 5- (2-decyltetradecyl) -2,7-diisia-5-aza-cyclopenta [a] pentane-4,6-dion (4.50 g, 0.00824 mol) in 50 mL of chloroform and place it in foil. Block the light. Then n-bromosuccinimide (NBS) (4.40 g, 0.02473 mol) is added at 0 ° C. and stirred at room temperature for 2 hours. Terminate the reaction with water, extract with methylenedichloride and remove moisture. The organic layer was distilled under reduced pressure and column separated with nucleic acid to give the title compound (4.50 g) as an orange solid (yield: 78%).
1H NMR (300MHz, CDCl3)[ppm] δ3.53-3.50(d,2H), 1.85(s,1H), 1.26 (s,40H), 0.89-0.87(t, 6H). HRMS: calcd for C16H17Br2NO2S2, 703.1551 found: 703.1552
1 H NMR (300 MHz, CDCl 3 ) [ppm] δ 3.53-3.50 (d, 2H), 1.85 (s, 1H), 1.26 (s, 40H), 0.89-0.87 (t, 6H). HRMS: calcd for C16H17Br2NO2S2, 703.1551 found: 703.1552
[실시예 3] 1,3- 다이브로모 -5-(2- 부틸옥틸 )-2,7- 다이싸이아 -5- 아자 - 싸이클로펜타[a]팬탈렌 -4,6- 다이온 Example 3 1,3- Dibromo -5- (2- butyloctyl ) -2,7 - dithia - 5- aza - cyclopenta [a] pentane- 4,6 -dione
화합물 3-1(5-(2-Compound 3-1 (5- (2- 부틸옥틸Butyloctyl )-2,7-) -2,7- 다이싸이아Daisia -5--5- 아자Keep it up -- 싸이클로펜타[a]팬탈렌Cyclopenta [a] pentane -4,6--4,6- 다이온Dion )의 제조Manufacturing
싸이에노[3,4-b]싸이오펜퓨란-2,3-다이온 (3.33 g, 0.01584 mol)과 2-부틸옥탄-1-아민(3.229 g, 0.01742 mol)을 무수DMF 50 mL에 녹인다. 140 oC로 온도를 올리고 4시간동안 가열 환류시킨다. 박막크로마토그래피로 반응 정도를 확인 한 후, 물로 천천히 반응을 종결시키고 클로로포름으로 추출 후 건조시킨다. 그 후 아황산다이클로라이드 용액(1.0 M 메틸렌클로라이드) 50mL에 넣고 3시간동안 60 oC에서 환류시킨다. 나온 물질을 이서로 추출하고 수분제거 후 핵산으로 칼럼분리하여 노란색 고체인 표제화합물(2.5 g)을 얻었다(수득률: 47%). Dissolve thieno [3,4-b] thiophenfuran-2,3-dione (3.33 g, 0.01584 mol) and 2-butyloctan-1-amine (3.229 g, 0.01742 mol) in 50 mL of anhydrous DMF. . The temperature is raised to 140 ° C. and heated to reflux for 4 hours. After checking the reaction degree by thin layer chromatography, the reaction was slowly terminated with water, extracted with chloroform and dried. Then add 50 mL of disulphite solution (1.0 M methylene chloride) and reflux at 60 ° C. for 3 hours. The resulting material was extracted with Ecer and water was removed, followed by column separation with nucleic acid to give the title compound (2.5 g) as a yellow solid (yield: 47%).
1H NMR(300 MHz, CDCl3)[ppm] δ7.82-7.79 (t, 1H), 7.45-7.44 (d, 1H), 3.53-3.47 (d, 2H), 1.81 (s, 1H) 1.25-1.20 (m, 16H), 0.89-0.82 (m, 6H). 13C NMR (300MHz, CDCl3)[ppm] δ 164.49, 163.97, 149.46, 143.91, 135.86, 131.48, 115.99, 113.81, 42.62, 37.19, 31.80, 31.41, 31.08, 29.63, 28.47, 26.25, 23.00, 22.62, 18.40, 14.06. MS (EI) m/z: 377 (M+). 1 H NMR (300 MHz, CDCl 3 ) [ppm] δ 7.82-7.79 (t, 1H), 7.45-7.44 (d, 1H), 3.53-3.47 (d, 2H), 1.81 (s, 1H) 1.25- 1.20 (m, 16 H), 0.89-0.82 (m, 6 H). 13 C NMR (300 MHz, CDCl 3 ) [ppm] δ 164.49, 163.97, 149.46, 143.91, 135.86, 131.48, 115.99, 113.81, 42.62, 37.19, 31.80, 31.41, 31.08, 29.63, 28.47, 26.25, 23.00, 22.62, 18.40 , 14.06. MS (EI) m / z: 377 (M < + >).
화합물 3(1,3-다이브로모-5-(2-부틸옥틸)-2,7-다이싸이아-5-아자-싸이클로펜타[a]팬탈렌-4,6-다이온)의 제조Preparation of Compound 3 (1,3-Dibromo-5- (2-butyloctyl) -2,7-dithia-5-aza-cyclopenta [a] pentane-4,6-dione)
5-(2-부틸옥틸)-2,7-다이싸이아-5-아자-싸이클로펜타[a]팬탈렌-4,6-dion (2.60 g, 0.00689 mol)을 클로로포름 50 mL에 녹이고 호일로 빛을 차단한다. 그 후 n-브로모쑥신이미드(NBS) (3.06 g, 0.01722 mol)을 0 oC에서 넣고 2시간동안 실온에서 교반시킨다. 물로 반응을 종결시키고 메틸렌다이클로라이드로 추출하고 수분을 제거한다. 유기층을 감압증류하고 핵산으로 칼럼분리하여 주황색 고체인 표제화합물(4.50 g)을 얻었다(수득률: 78%). Dissolve 5- (2-butyloctyl) -2,7-dithia-5-aza-cyclopenta [a] pentane-4,6-dion (2.60 g, 0.00689 mol) in 50 mL of chloroform and light with foil. To block. Then n-bromosuccinimide (NBS) (3.06 g, 0.01722 mol) is added at 0 ° C. and stirred at room temperature for 2 hours. Terminate the reaction with water, extract with methylenedichloride and remove moisture. The organic layer was distilled under reduced pressure and column separated with nucleic acid to give the title compound (4.50 g) as an orange solid (yield: 78%).
1H NMR(300MHz, CDCl3)[ppm] δ3.53-3.51 (d, 2H), 1.85 (s, 1H), 1.31-1.28 (t, 16H), 0.92-0.87 (m, 6H). 13C NMR(300MHz, CDCl3)[ppm] δ42.62, 37.17, 31.75, 31.40, 31.07, 29.60, 28.41, 26.23, 23.00, 22.60, 18.40, 14.05. HRMS: calcd for C16H17Br2NO2S2, 532.9693 found: 532.9692
1 H NMR (300 MHz, CDCl 3 ) [ppm] δ 3.53-3.51 (d, 2H), 1.85 (s, 1H), 1.31-1.28 (t, 16H), 0.92-0.87 (m, 6H). 13 C NMR (300 MHz, CDCl 3 ) [ppm] δ 42.62, 37.17, 31.75, 31.40, 31.07, 29.60, 28.41, 26.23, 23.00, 22.60, 18.40, 14.05. HRMS: calcd for C 16 H 17 Br 2 NO 2 S 2 , 532.9693 found: 532.9692
[실시예 4] 고분자 1(PEBTTPD)의 합성Example 4 Synthesis of Polymer 1 (PEBTTPD)
상기 고분자는 스틸러 커플링을 통해 중합할 수 있다. 1,3-다이브로모-6-옥틸-5H-싸이에노[3',4',4,5]싸이에노[2,3-c]피롤-5,7(6H)-다이온(0.50 g 0.00104 mol)과 2,6-비스(트리메틸스타닐)-4,8-비스((2-에틸헥실)옥시)벤조 [1,2-b:4,5-b']다이싸이오펜 (0.806 g 0.00104 mmol)을 5 mL 클로로벤젠 용액(CB)에 녹이고 질소 치환을 실시한다. 그 후에 촉매로 Pd2(dba)3(Tris(dibenzylideneaceton)dipalladium(0))(0.019 mg, 2 mol%)와 p(o-tol)3(Tri(o-toly)phosphine)(0.025 g/ 8 mol%)을 넣고 110 oC에서 48시간 동안 환류시킨다. 그후 말단기 반응을 종결시키기 위해서 2-브로모싸이오펜 (0.1g)을 넣고 6시간 동안 환류시키고, 2-싸이오펜메틸틴(0.1 g)을 넣어 6시간동안 환류시킨다. 반응혼합물을 메탄올 (300 mL) 에 천천히 침전시키고 고체를 걸러낸다. 걸러낸 고체는 속실렛을 통해 메탄올, 핵산, 클로로포름 순으로 정제한다. 내려온 액체를 메탄올에 다시 침전시키고 여과한 후 건조시켜 침전을 시켜 검녹색 고체인 표제화합물(0.72 g)을 얻었다(수득률 90%). The polymer may polymerize through a stiller coupling. 1,3-Dibromo-6-octyl-5H-cyeno [3 ', 4', 4,5] cyeno [2,3-c] pyrrole-5,7 (6H) -dione (0.50 g 0.00104 mol) and 2,6-bis (trimethylstannyl) -4,8-bis ((2-ethylhexyl) oxy) benzo [1,2-b: 4,5-b '] diothiophene (0.806 g 0.00104 mmol) is dissolved in 5 mL chlorobenzene solution (CB) and subjected to nitrogen substitution. Pd 2 (dba) 3 (Tris (dibenzylideneaceton) dipalladium (0)) (0.019 mg, 2 mol%) and p (o-tol) 3 (Tri (o-toly) phosphine) (0.025 g / 8) mol%) and refluxed at 110 ° C. for 48 hours. Then, in order to terminate the end group reaction, 2-bromothiophene (0.1 g) was added and refluxed for 6 hours, and 2-thiophenmethyltin (0.1 g) was added and refluxed for 6 hours. The reaction mixture is slowly precipitated in methanol (300 mL) and the solid is filtered off. The filtered solid is purified through soxhlet in the order of methanol, nucleic acid and chloroform. Precipitated liquid was precipitated again in methanol, filtered and dried to give the title compound (0.72 g) as a dark green solid (yield 90%).
1H NMR (300 MHz, CDCl3)[ppm]: 7.21(s, 2H), 4.04-3.98(s, 6H), 1.46-1.35(m, 30H), 1.04-0.95(s, 15H)
1 H NMR (300 MHz, CDCl 3 ) [ppm]: 7.21 (s, 2H), 4.04-3.98 (s, 6H), 1.46-1.35 (m, 30H), 1.04-0.95 (s, 15H)
[실시예 5] 고분자 2(POBTTPD)의 합성Example 5 Synthesis of Polymer 2 (POBTTPD)
1,3-다이브로모-6-옥틸-5 H-싸이에노[3',4',4,5]싸이에노[2,3-c]피롤-5,7(6H)-다이온(0.50 g 0.00104 mol)과 2,6-비스(트리메틸스타닐)-4,8-비스((2-옥틸)옥시)벤조[1,2-b:4,5-b'']다이싸이오펜(0.806 g 0.00104 mmol), Pd2(dba)3 (0.019 mg, 2 mol%)와 p(o-tol)3(0.025 g/ 8 mol%)을 사용한 것을 제외하고 실시예 1과 동일한 방법으로 합성하여 표제화합물(0.72 g)을 얻었다(수득률: 90%).1,3-Dibromo-6-octyl-5H-cyeno [3 ', 4', 4,5] cyeno [2,3-c] pyrrole-5,7 (6H) -dione ( 0.50 g 0.00104 mol) and 2,6-bis (trimethylstannyl) -4,8-bis ((2-octyl) oxy) benzo [1,2-b: 4,5-b ''] diothiophene ( 0.806 g 0.00104 mmol), Pd 2 (dba) 3 (0.019 mg, 2 mol%) and p (o-tol) 3 (0.025 g / 8 mol%) was synthesized in the same manner as in Example 1 The title compound (0.72 g) was obtained (yield: 90%).
1H NMR (300 MHz, CDCl3)[ppm]: 7.20(s, 2H), 4.03-4.00(s, 6H), 1.47-1.35(m, 30H), 1.04-0.96(s, 15H)
1 H NMR (300 MHz, CDCl 3 ) [ppm]: 7.20 (s, 2H), 4.03-4.00 (s, 6H), 1.47-1.35 (m, 30H), 1.04-0.96 (s, 15H)
[실시예 6] 고분자 3(POBOBDTPD)의 합성Example 6 Synthesis of Polymer 3 (POBOBDTPD)
1,3-다이브로모-6-(부틸옥틸)-5 H-싸이에노[3',4',4,5]싸이에노[2,3-c]피롤-5,7(6H)-다이온(0.40 g 0.00075 mol)과 2,6-비스(트리메틸스타닐)-4,8-비스((2-옥틸)옥시)벤조[1,2-b:4,5-b'']다이싸이오펜(0.577 g 0.00075 mmol), Pd2(dba)3 (0.014 mg, 2 mol%)와 p(o-tol)3(0.018 g/ 8 mol%)을 사용한 것을 제외하고 실시예 1과 동일한 방법으로 합성하여 표제화합물(0.45 g)을 얻었다(수득률: 73%).1,3-Dibromo-6- (butyloctyl) -5H-thieno [3 ', 4', 4,5] cyeno [2,3-c] pyrrole-5,7 (6H)- Dione (0.40 g 0.00075 mol) and 2,6-bis (trimethylstannyl) -4,8-bis ((2-octyl) oxy) benzo [1,2-b: 4,5-b ''] di Same method as in Example 1 except using thiophene (0.577 g 0.00075 mmol), Pd 2 (dba) 3 (0.014 mg, 2 mol%) and p (o-tol) 3 (0.018 g / 8 mol%) To give the title compound (0.45 g) (yield: 73%).
1H NMR (300 MHz, CDCl3)[ppm]: 7.20(s, 2H), 4.03-4.00(d, 6H), 1.55(s, 1H) 1.47-1.35 (m, 40H), 1.04-0.96(s, 12H).
1 H NMR (300 MHz, CDCl 3 ) [ppm]: 7.20 (s, 2H), 4.03-4.00 (d, 6H), 1.55 (s, 1H) 1.47-1.35 (m, 40H), 1.04-0.96 (s , 12H).
[실시예 7] 고분자 4(PEBOBDTPD)의 합성Example 7 Synthesis of Polymer 4 (PEBOBDTPD)
1,3-다이브로모-6-(부틸옥틸)-5 H-싸이에노[3',4',4,5]싸이에노[2,3-c]피롤-5,7(6H)-다이온(0.500 g 0.00093 mol)과 2,6-비스(트리메틸스타닐)-4,8-비스((2-에틸옥틸)옥시)벤조[1,2-b:4,5-b'']다이싸이오펜(0.721 g 0.00093 mmol), Pd2(dba)3 (0.017 mg, 2 mol%)와 p(o-tol)3(0.023 g/ 8 mol%)을 사용한 것을 제외하고 실시예 1과 동일한 방법으로 합성하여 표제화합물(0.60 g)을 얻었다(수득률: 79%).1,3-Dibromo-6- (butyloctyl) -5H-thieno [3 ', 4', 4,5] cyeno [2,3-c] pyrrole-5,7 (6H)- Dione (0.500 g 0.00093 mol) and 2,6-bis (trimethylstannyl) -4,8-bis ((2-ethyloctyl) oxy) benzo [1,2-b: 4,5-b ''] Same as Example 1 except using dithiophene (0.721 g 0.00093 mmol), Pd 2 (dba) 3 (0.017 mg, 2 mol%) and p (o-tol) 3 (0.023 g / 8 mol%) Synthesis was carried out by the method to obtain the title compound (0.60 g) (a yield: 79%).
1H NMR (300 MHz, CDCl3)[ppm]: 7.20(s, 2H), 4.03-4.00(s, 6H), 1.55(m, 3H), 1.47-1.35(m, 32H), 1.04-0.96(s, 18H)
1 H NMR (300 MHz, CDCl 3 ) [ppm]: 7.20 (s, 2H), 4.03-4.00 (s, 6H), 1.55 (m, 3H), 1.47-1.35 (m, 32H), 1.04-0.96 ( s, 18 H)
[실시예 8] 고분자 5(PPBTTPD)의 합성Example 8 Synthesis of Polymer 5 (PPBTTPD)
상기 고분자는 스즈키 커플링을 통해 중합할 수 있다. 1,3-다이브로모-6-옥틸-5 H-싸이에노[3',4',4,5]싸이에노[2,3-c]피롤-5,7(6H)-다이온(0.50 g 0.00104 mol)과 1,4-비스(4,4,5,5-테트라메틸-1,3,2-다이옥사보란-2-일)벤젠(0.344 g 0.0010 mmol)을 5 mL 톨루엔 용액에 녹이고 2M K2CO3와 알리카트 336을 넣은 후 질소 치환을 실시한다. 여기에 촉매로 Pd(PPh3)4 (0.06 g, 5 mol%)을 넣고 100 oC에서 48시간 동안 환류시킨다. 그 후 말단기 반응을 종결시키기 위해서 2-브로모싸이오펜 (0.1g)을 넣고 6시간 동안 환류시키고, 2-싸이오펜보로닉엑시드(0.1 g)을 넣어 6시간동안 환류시킨다. 반응혼합물을 메탄올 (300 mL) 에 천천히 침전시키고 고체를 여과한다. 여과한 고체를 속실렛을 통해 메탄올, 핵산, 클로로포름 순으로 정제한다. 내려온 액체를 메탄올에 다시 침전시키고 필터를 통해 걸러낸 후 건조시켜 침전을 시켜 검녹색 고체인 표제화합물 (0.37 g)을 얻었다(수득률 90%). The polymer may be polymerized through Suzuki coupling. 1,3-Dibromo-6-octyl-5H-cyeno [3 ', 4', 4,5] cyeno [2,3-c] pyrrole-5,7 (6H) -dione ( 0.50 g 0.00104 mol) and 1,4-bis (4,4,5,5-tetramethyl-1,3,2-dioxaboran-2-yl) benzene (0.344 g 0.0010 mmol) were added to a 5 mL toluene solution. Dissolve and add 2M K 2 CO 3 and Alicart 336 and perform nitrogen substitution. Pd (PPh 3 ) 4 (0.06 g, 5 mol%) was added as a catalyst and refluxed at 100 ° C. for 48 hours. Then, in order to terminate the end group reaction, 2-bromothiophene (0.1 g) was added and refluxed for 6 hours, and 2-thiophenoboronic acid (0.1 g) was added and refluxed for 6 hours. The reaction mixture is slowly precipitated in methanol (300 mL) and the solid is filtered off. The filtered solid is purified through soxhlet in the order of methanol, nucleic acid and chloroform. The down liquid was precipitated again in methanol, filtered through a filter, dried, and precipitated to obtain the title compound (0.37 g) as a dark green solid (yield 90%).
1H NMR (300 MHz, CDCl3)[ppm]: 7.79(d, 2H), 7.51(d, 2H), 3.42(s, 2H), 1.46-1.20(m, 12H), 0.88(m, 3H).
1 H NMR (300 MHz, CDCl 3 ) [ppm]: 7.79 (d, 2H), 7.51 (d, 2H), 3.42 (s, 2H), 1.46-1.20 (m, 12H), 0.88 (m, 3H) .
[실시예 9] 고분자 6(PTBTTPD)의 합성Example 9 Synthesis of Polymer 6 (PTBTTPD)
2,5-비스(트리메틸스타닐)싸이오펜(0.427 g 0.00104 mmol)을 사용한 것을 제외하고 실시예 1과 동일한 방법으로 합성하여 표제화합물(0.38 g)을 얻었다(수득률: 90%).Synthesis was carried out in the same manner as in Example 1 except for using 2,5-bis (trimethylstannyl) thiophene (0.427 g 0.00104 mmol) to obtain the title compound (0.38 g) (yield: 90%).
1H NMR (300 MHz, CDCl3)[ppm]: 7.73-7.69(d, 1H), 7.17(d, 1H), 3.42(m, 2H), 1.47-1.35(m, 12H), 0.88(m, 3H).
1 H NMR (300 MHz, CDCl 3 ) [ppm]: 7.73-7.69 (d, 1H), 7.17 (d, 1H), 3.42 (m, 2H), 1.47-1.35 (m, 12H), 0.88 (m, 3H).
[실시예 10] 고분자 7(PTBTTPD)의 합성Example 10 Synthesis of Polymer 7 (PTBTTPD)
2,6-비스(4,4,5,5-테트라메틸-1,3,2-다이옥사보란-2-일)-4,4-다이옥틸-4H-싸이클로펜타[2,1-b:3,4-b']다이싸이오펜(0.624 g 0.00104 mmol)을 사용한 것을 제외하고 실시예 8과 동일한 방법으로 합성하여 표제화합물(0.68 g)을 얻었다(수득률: 90%).2,6-bis (4,4,5,5-tetramethyl-1,3,2-dioxaboran-2-yl) -4,4-dioctyl-4H-cyclopenta [2,1-b: 3,4-b '] dithiophene (0.624 g 0.00104 mmol) was obtained in the same manner as in Example 8 to obtain the title compound (0.68 g) (yield: 90%).
1H NMR (300 MHz, CDCl3)[ppm]: 6.98(s, 2H), 3.42(m, 2H), 1.87(m. 4H), 1.47-1.35(m, 36H), 0.88(m, 9H).
1 H NMR (300 MHz, CDCl 3 ) [ppm]: 6.98 (s, 2H), 3.42 (m, 2H), 1.87 (m. 4H), 1.47-1.35 (m, 36H), 0.88 (m, 9H) .
[실시예 11] 고분자 8(PDETTPD)의 합Example 11 Sum of Polymer 8 (PDETTPD)
1,2-비스(3-도데실-5(트리메틸스타닐)싸이오펜-2-일)에탄(0.535 g 0.00063 mmol)을 사용한 것을 제외하고 실시예 1과 동일한 방법으로 합성하여 표제화합물(0.43 g)을 얻었다(수득률: 80%).The title compound (0.43 g) was synthesized in the same manner as in Example 1 except for using 1,2-bis (3-dodecyl-5 (trimethylstannyl) thiophen-2-yl) ethane (0.535 g 0.00063 mmol). ) Was obtained (yield: 80%).
1H NMR (300 MHz, CDCl3)[ppm]: 7.05-6.99(d, 2H), 6.80-6.68(d, 2H), 3.42(m, 2H), 2.65-2.62(m, 4H), 1.61-1.54(m, 6H), 1.35-1.29(m, 46H), 0.88(m, 9H).
1 H NMR (300 MHz, CDCl 3 ) [ppm]: 7.05-6.99 (d, 2H), 6.80-6.68 (d, 2H), 3.42 (m, 2H), 2.65-2.62 (m, 4H), 1.61- 1.54 (m, 6H), 1.35-1.29 (m, 46H), 0.88 (m, 9H).
[실시예 12] 고분자 9(PETTTTPD)의 합성Example 12 Synthesis of Polymer 9 (PETTTTPD)
1,2-비스(5-(트리메틸스타닐)싸이오펜-2-일)에탄(0.365 g 0.00071 mmol)을 사용한 것을 제외하고 실시예 1과 동일한 방법으로 합성하여 표제화합물(0.48 g)을 얻었다(수득률: 92%).The title compound (0.48 g) was obtained by the same method as Example 1 except for using 1,2-bis (5- (trimethylstannyl) thiophen-2-yl) ethane (0.365 g 0.00071 mmol) ( Yield: 92%).
1H NMR (300 MHz, CDCl3)[ppm]: 7.73-7.70(d, 2H), 7.35-7.32(m, 2H), 6.80-6.68(d, 2H), 3.32-3.31(m, 2H), 2.12-2.10(m, 1H), 1.30-1.21(m, 40H), 0.88(m, 6H).
1 H NMR (300 MHz, CDCl 3 ) [ppm]: 7.73-7.70 (d, 2H), 7.35-7.32 (m, 2H), 6.80-6.68 (d, 2H), 3.32-3.31 (m, 2H), 2.12-2.10 (m, 1 H), 1.30-1.21 (m, 40 H), 0.88 (m, 6H).
[실시예 13] 고분자 10(PPDDTBTTPD)의 합성Example 13 Synthesis of Polymer 10 (PPDDTBTTPD)
2,6-비스(트리메틸스타닐)-4,8-비스((2-도데실)싸이오페닐)벤조[1,2-b:4,5-b']다이싸이오펜(0.25 g 0.00051 mmol)을 사용한 것을 제외하고 실시예 1과 동일한 방법으로 합성하여 표제화합물(0.43 g)을 얻었다(수득률:83%). 2,6-bis (trimethylstannyl) -4,8-bis ((2-dodecyl) thiophenyl) benzo [1,2-b: 4,5-b '] diothiophene (0.25 g 0.00051 mmol ) The title compound (0.43 g) was obtained in the same manner as in Example 1 except for using) (yield: 83%).
1H NMR (300 MHz, CDCl3)[ppm]: 7.76-7.73(d, 2H), 7.35-7.32(m, 2H), 6.92-6.89(d, 2H), 3.32-3.31(m, 2H), 2.82-2.78(m, 6H), 1.30-1.21(m, 46H), 0.88(m, 9H).
1 H NMR (300 MHz, CDCl 3 ) [ppm]: 7.76-7.73 (d, 2H), 7.35-7.32 (m, 2H), 6.92-6.89 (d, 2H), 3.32-3.31 (m, 2H), 2.82-2.78 (m, 6H), 1.30-1.21 (m, 46H), 0.88 (m, 9H).
[실시예 14] 고분자 11(PDBTTPD)의 합성Example 14 Synthesis of Polymer 11 (PDBTTPD)
(4,4'-다이도데실-2,2'-바이싸이오펜-5,5'-다이일)비스(트리메틸스타닐)(0.781 g 0.00094 mmol)을 사용한 것을 제외하고 실시예 1과 동일한 방법으로 합성하여 표제화합물(0.53 g)을 얻었다(수득률:69%).Same method as in Example 1, except using (4,4'-didodecyl-2,2'-bithiophen-5,5'-diyl) bis (trimethylstannyl) (0.781 g 0.00094 mmol) To give the title compound (0.53 g) (yield: 69%).
1H NMR (300 MHz, CDCl3)[ppm]: 6.85-6.79(d, 2H), 3.32-3.31(m, 2H), 2.60-2.58(m, 2H), 1.60-1.58(m, 4H), 1.30-1.21(m, 46H), 0.88(m, 9H).
1 H NMR (300 MHz, CDCl 3 ) [ppm]: 6.85-6.79 (d, 2H), 3.32-3.31 (m, 2H), 2.60-2.58 (m, 2H), 1.60-1.58 (m, 4H), 1.30-1.21 (m, 46H), 0.88 (m, 9H).
[실시예 15] 유기반도체 소자제작Example 15 Fabrication of Organic Semiconductor Device
ITO가 코팅된 유리기판을 아세톤과 IPA(Isopropylalcohol)로 세척한 후에, PEDOT-PSS (Baytron P TP AI 4083, Bayer AG)를 ITO층 위에 코팅한다. 이때 두께는 30-50 nm 정도가 되도록 하며 120℃에서 60분간 어닐링을 실시한다. 활성층으로 상기 실시예 4, 5, 6 및 7에서 제조한 고분자 화합물과 PCBM 유도체 및 첨가제(DIO;다이아이오도옥탄, ODT;옥타다이싸이올)를 60 oC에서 12시간동안 교반시킨 후에 0.45 μm 크기의 필터로 물질을 필터한 후에 PEDOT-PSS 층위에 스핀코팅을 이용하여 100 nm 두께로 코팅한다. 그 후에 고진공 (10-6 torr)에서 10 nm 두께로 TiO2(인듐틴 옥사이드)를 코팅하고 알루미늄(Al)을 100 nm 두께로 증착하여 유기 태양전지 소자를 제작하였다. 필요에 따라 형태학적 특성의 개선을 목표로 어닐링을 실시하기도 한다.
After the ITO-coated glass substrate is washed with acetone and IPA (Isopropylalcohol), PEDOT-PSS (Baytron P TP AI 4083, Bayer AG) is coated on the ITO layer. At this time, the thickness is about 30-50 nm and annealed at 120 ℃ 60 minutes. 0.45 μm after stirring the polymer compound prepared in Examples 4, 5, 6 and 7 and PCBM derivatives and additives (DIO; diiooctane, ODT; octadithiol) at 60 o C for 12 hours as an active layer The material is filtered with a filter of size and then coated onto the PEDOT-PSS layer by spin coating to a thickness of 100 nm. Subsequently, TiO 2 (indium tin oxide) was coated at 10 nm in high vacuum (10 −6 torr) and aluminum (Al) was deposited at a thickness of 100 nm to fabricate an organic solar cell device. If necessary, annealing may be carried out with the aim of improving the morphological properties.
또한 전류밀도-전압 곡선(J-V) 측정에는 Keithley사의 4200 소스를 이용하였으며 AM 1.5 G 조건 하에 표준 PVM132(NREL, 100mW/cm2의 세기로 측정함) 범위 하에서 유기 태양전지 소자 특성을 측정하여 도 15, 17, 18에 나타내었다.(Oriel 1kW solarsimulator 사용).In addition, Keithley's 4200 source was used to measure the current density-voltage curve ( JV ), and organic solar cell device characteristics were measured under the standard PVM132 (NREL, measured at 100 mW / cm 2 ) under AM 1.5 G. , 17, 18 (using Oriel 1kW solarsimulator).
상기 실시예 4, 5에서 합성된 고분자 화합물(PEBTTPD, POBTTPD)과 상기 실시에 6, 7에서 합성된 고분자 화합물의 광 흡수영역을 용액상태와 필름상태에서 측정하여 결과를 도 2, 3, 4에 도시하였다. 하기에 도 2, 3, 4 그래프에 대한 결과값을 표 1로 정리하였다.The light absorption regions of the polymer compounds (PEBTTPD, POBTTPD) synthesized in Examples 4 and 5 and the polymer compounds synthesized in Examples 6 and 7 were measured in the solution state and the film state. Shown. 2, 3 and 4 summarized the results in Table 1 below.
(nm)UV-S (max)
(nm)
(nm)UV-F (max)
(nm)
(nm)UV-ann (max)
(nm)
(nm)UV-edge
(nm)
(optical)
(eV)Band gap
(optical)
(eV)
(optical)
(eV)LUMO
(optical)
(eV)
(electronic)
(eV)HOMO
(electronic)
(eV)
(실시예 4)PEBTTPD
(Example 4)
(939-ann)919
(939-ann)
(1.32)1.35
(1.32)
(실시예 5)POBTTPD
(Example 5)
(947-ann)934
(947-ann)
(1.31)1.33
(1.31)
(실시예 6)POBOBDTPD
(Example 6)
(실시예 7)PEBOBDTPD
(Example 7)
여기서 실시예 4, 5, 6, 7의 HOMO값은 하기에 도 2, 3, 4에서 측정한 결과값을 이용하여 계산한 값이다. 또한 밴드갭은 필름상태에서 UV흡수파장에서 구하였다. 표 1의 결과에서 보이는 바와 같이 본 발명에 따른 유기 반도체 화합물은 밴드갭이 넓어 장파장의 빛까지 흡수할 수 있으며 즉, 태양광과 유사한 파장영역의 빛까지 흡수가 가능하기 때문에 보다 많은 전류를 생산하게 되어 높은 단락전류가 발생할 수 있다.Here, the HOMO values of Examples 4, 5, 6, and 7 are values calculated by using the result values measured in FIGS. 2, 3, and 4 below. The bandgap was also obtained at the UV absorption wavelength in the film state. As shown in the results of Table 1, the organic semiconductor compound according to the present invention has a wide bandgap, which can absorb light having a long wavelength, that is, it can absorb even light in a wavelength region similar to sunlight, thereby producing more current. High short-circuit current can occur.
도 5와 도 6은 각각 실시예 4, 5에서 합성된 고분자 화합물(PEBTTPD, POBTTPD)과 실시예 6, 7에서 합성된 고분자 화합물의 전기화학적 특성을 분석하기 위해서 싸이클로 볼타메트리를 이용하여 측정한 것으로 Bu4NClO4(0.1 몰농도)의 용매 하에서 50 mV/s의 조건으로 측정하였다. 측정 시 카본 전극을 사용하여 코팅을 통해 전압을 인가하였다. 도 5와 도 6의 그래프에 대한 결과값을 하기 표 2에 정리하여 나타내었다.5 and 6 are measured using a cyclo voltametry to analyze the electrochemical properties of the polymer compounds (PEBTTPD, POBTTPD) synthesized in Examples 4 and 5 and the polymer compounds synthesized in Examples 6 and 7, respectively. It was measured under the conditions of 50 mV / s under a solvent of Bu 4 NClO 4 (0.1 molarity). In the measurement, a voltage was applied through the coating using a carbon electrode. Results of the graphs of FIGS. 5 and 6 are summarized in Table 2 below.
(eV)HOMO
(eV)
(eV)LUMO
(eV)
(Electronic)
(eV)Band gap
(Electronic)
(eV)
(실시예 4)
PEBTTPD
(Example 4)
(실시예 5)
POBTTPD
(Example 5)
(실시예 6)POBOBDTPD
(Example 6)
(실시예 7)PEBOBDTPD
(Example 7)
표 2에 나타낸 바와 같이 낮은 HOMO값을 가지는 것을 알 수 있는데 이는 기존의 Acceptor보다 상대적으로 전자를 잘 잡아당기기 때문에 낮은 값을 가지는 것으로 설명할 수 있다. 낮은 HOMO값을 가지게 되면 높은 개방전압의 형성이 가능할 뿐만 아니라 산화안정성도 높아지게 되어 상용화에 큰 이득이 된다.As shown in Table 2, it can be seen that it has a low HOMO value, which can be described as having a low value because it attracts electrons better than the conventional acceptor. Having a low HOMO value not only enables the formation of a high open voltage but also increases the oxidation stability, which is a great advantage for commercialization.
도 7, 8, 9, 10에서는 실시예 4, 5, 6, 7에서 합성된 고분자 화합물에 대한 열적 특성(DSC)을 측정한 것으로 실시예 4, 5, 6, 7의 고분자 화합물은 유리전이온도값이 측정되지 않았으며 이것으로 본 발명에 따라 제조된 유기 반도체 화합물이 비정질의 특성을 가지는 것을 알 수 있다. 7, 8, 9, and 10 measured the thermal properties (DSC) for the polymer compounds synthesized in Examples 4, 5, 6, and 7, wherein the polymer compounds of Examples 4, 5, 6, and 7 have a glass transition temperature. No value was measured, indicating that the organic semiconductor compound prepared according to the present invention has amorphous properties.
도 11, 12, 13, 14에서는 각각 실시예 4, 5, 6, 7에서 합성된 고분자 화합물의 분해온도를 TGA를 이용하여 측정한 결과를 도시한 것이다. 11, 12, 13 and 14 show the results obtained by measuring the decomposition temperature of the polymer compounds synthesized in Examples 4, 5, 6 and 7 using TGA, respectively.
실시예 4의 고분자 화합물(PEBTTPD)의 5% 분해가 일어나는 온도는 337℃로 측정되으며 실시예 5의 고분자 화합물(POBTTPD)의 5% 분해가 일어나는 온도는 339℃로 측정되었다. 실시예 6의 고분자 화합물(POBOBDTPD)의 5% 분해가 일어나는 온도는 355℃였으며 실시예 7의 고분자 화합물(PEBOBDTPD)의 5% 분해가 일어나는 온도는 345℃로 측정되었다. 따라서 본 발명에 따른 고분자 화합물은 높은 온도에서도 분해가 일어나지 않아 열적으로 안정한 화합물인 것을 알 수 있다.The temperature at which 5% degradation of the polymer compound (PEBTTPD) of Example 4 occurred was measured at 337 ° C., and the temperature at which 5% decomposition of the polymer compound (POBTTPD) of Example 5 occurred was measured at 339 ° C. The temperature at which 5% degradation of the polymer compound of Example 6 (POBOBDTPD) was 355 ° C and the temperature at which 5% degradation of the polymer compound of Example 7 (PEBOBDTPD) was measured at 345 ° C. Therefore, it can be seen that the polymer compound according to the present invention is a thermally stable compound because decomposition does not occur even at a high temperature.
한편 유기태양전지의 특성은 크게 4가지 특성으로 나타낼 수 있는데, 단락전류(Short circuit current; Jsc), 개방전압(Open circuit voltage; Voc), 충진율(Fill factor; FF), 전력 변환 효율(Power conversion efficiency: PCE)이다. 이들 간의 상관관계는 아래의 식 1로 표현할 수 있다.On the other hand, the characteristics of the organic solar cell can be classified into four characteristics: short circuit current (Jsc), open circuit voltage (Voc), fill factor (FF), and power conversion efficiency (Power conversion). efficiency: PCE). The correlation between them can be expressed by
식1에 의하면 고효율을 구현하기 위해서는 소자에 높은 단락전류와 개방전압이 필요하다. 또한 높은 충진율을 가져야만 고효율의 소자구현이 가능하다. 높은 단락전류를 구현하기 위해서는 재료적으로 높은 전하이동도를 가져야 하며 높은 개방전압은 분자 내 전자주게의 HOMO 값과 LUMO 값에 연관이 있다. 또한 높은 충진율을 가지기 위해서는 일반적으로 전자 받게로 사용되는 PCBM과 혼합하였을 때 형태학적 특성이 우수해야만 한다. 따라서 위와 같은 여러 가지 조건이 충족되었을 때 비로소 고효율의 유기태양전지가 가능해 진다.According to
도 15, 17, 18은 각각 실시예 4와 5에서 합성된 고분자 화합물(PEBTTPD, POBTTPD)과 실시예 6 내지 7에서 합성 고분자 화합물의 유기태양전지 특성을 측정한 결과값을 도시하였으며, 이에 해당하는 결과값을 하기 표 3에 나타내었다. 15, 17 and 18 show the results of measuring the organic solar cell characteristics of the polymer compounds (PEBTTPD, POBTTPD) synthesized in Examples 4 and 5 and the synthetic polymer compounds in Examples 6 to 7, respectively. The results are shown in Table 3 below.
실시예 4의 고분자 화합물(PEBTTPD)의 경우 13.5 mA/cm2의 높은 단락전류(Jsc)값을 보여주며 0.72 V의 높은 개방전압(Voc) 값을 나타내고 있으며, 충진률(FF)이 54%로 5.3%의 효율을 보여준다. 또한 실시예 5의 고분자 화합물(POBTTPD)의 경우 실시예 4의 고분자 화합물에 비해 낮은 개방전압(0.7 eV) 및 단락전류(11.1 mA/cm2)를 보여주고 있으나 높은 충진률(64%)로 인해 효율이 5.0%로 나타난다.The polymer compound (PEBTTPD) of Example 4 exhibits a high short circuit current (Jsc) of 13.5 mA / cm 2 , a high open voltage (Voc) of 0.72 V, and a filling rate (FF) of 54%. 5.3% efficiency. In addition, the polymer compound of Example 5 (POBTTPD) shows a lower open voltage (0.7 eV) and a short circuit current (11.1 mA / cm 2 ) than the polymer compound of Example 4, but due to the high filling rate (64%) The efficiency is 5.0%.
또한 실시예 6에서 합성된 고분자 화합물(POBOBDTPD)의 경우 9.39 mA/cm2의 높은 단락전류(Jsc)값을 보여주며 0.68 V의 높은 개방전압(Voc) 값을 나타내고 있다. 그 결과 4.02%의 효율을 보여준다. 또한 실시예 7에서 합성된 고분자 화합물(PEBOBDTPD)의 경우 실시예 3의 고분자 화합물에 비해 낮은 개방전압(0.64 eV) 및 단락전류(4.81 mA/cm2)및 낮 충진률(46%)로 인해 효율이 1.41%로 나타난다.In addition, the polymer compound (POBOBDTPD) synthesized in Example 6 shows a high short circuit current (Jsc) value of 9.39 mA / cm 2 and a high open voltage (Voc) value of 0.68 V. The result shows an efficiency of 4.02%. In addition, the polymer compound (PEBOBDTPD) synthesized in Example 7 has a low open voltage (0.64 eV), short circuit current (4.81 mA / cm 2 ) and low filling rate (46%) compared to the polymer compound of Example 3 This is 1.41%.
도 16 및 도 19은 각각 상기 실시예 4 내지 5에서 합성된 고분자 화합물(PEBTTPD, POBTTPD)과 실시예 6 내지 7에서 합성된 고분자 화합물(PEBOBDTPD)을 PCBM([6,6]-phenyl C71 butyric acid methyl ester)과 혼합하여 소자를 제작하였을 경우 나타나는 에너지 광자효율을 나타낸 그림이다. 도 16, 도 19에서 보이는 바와 같이 실시예 5(POBTTPD)의 에너지 양자효율은 약 58%이며 실시예 4 (PEBTTPD)의 경우 약 55%정도를 나타내고 있어 높은 효율을 가지는 것을 알 수 있다. 또한 실시예 6(POBOBDTPD)의 에너지 양자효율은 약 50%이며 실시예 7 (PEBOBDTPD)의 경우 약 35%정도를 나타내고 있어 낮은 효율을 가지는 것을 알 수 있다.16 and 19 illustrate the polymer compounds (PEBTTPD and POBTTPD) synthesized in Examples 4 to 5 and the polymer compounds (PEBOBDTPD) synthesized in Examples 6 to 7, respectively, to PCBM ([6,6] -phenyl C71 butyric acid. This figure shows the energy photon efficiency when the device is manufactured by mixing with methyl ester). As shown in FIGS. 16 and 19, the energy quantum efficiency of Example 5 (POBTTPD) is about 58% and about 55% of Example 4 (PEBTTPD). In addition, the energy quantum efficiency of Example 6 (POBOBDTPD) is about 50% and about 35% of Example 7 (PEBOBDTPD), and thus it can be seen that it has low efficiency.
Claims (15)
[화학식 1]
[상기 화학식 1에서,
Z는 S 또는 Se이고;
R은 C1-C30알킬, C2~C30알킬렌, C2~C30알키닐렌, C6~C30아릴 또는 C3~C30헤테로아릴이며, 상기 알킬, 알킬렌, 알키닐렌, 아릴 및 헤테로아릴은 C1-C30알킬, C2-C30알케닐, C2-C30알키닐, C1-C30알콕시, 아미노기, 하이드록시기, 할로겐기, 사이아노기, 나이트로기, 트리플루오로메틸기 및 실릴기로 선택되는 하나 이상의 치환기로 더 치환될 수 있다.]A polymer compound prepared by using the organic semiconductor compound monomer represented by Formula 1 below.
[Formula 1]
[In the above formula (1)
Z is S or Se;
R is C 1 -C 30 alkyl, C 2 -C 30 alkylene, C 2 -C 30 alkynylene, C 6 -C 30 aryl or C 3 -C 30 heteroaryl, the alkyl, alkylene, alkynylene, Aryl and heteroaryl are C 1 -C 30 alkyl, C 2 -C 30 alkenyl, C 2 -C 30 alkynyl, C 1 -C 30 alkoxy, amino, hydroxy, halogen, cyano, nitro And one or more substituents selected from a group, a trifluoromethyl group and a silyl group.]
상기 고분자 화합물은 하기 화학식 11로 표시되는 것인 고분자 화합물.
[화학식 11]
(상기 화학식 11에서,
Z는 S 또는 Se이고;
Ar은 C6-C30아릴렌 또는 C3-C30헤테로아릴렌이며;
R은 C1-C30알킬, C2~C30알킬렌, C2~C30알키닐렌, C6~C30아릴 및 C3~C30헤테로아릴로부터 선택되며, 상기 알킬, 알킬렌, 알키닐렌, 아릴 및 헤테로아릴은 C1-C20알킬, C2-C30알케닐, C2-C30알키닐, C1-C30알콕시, 아미노기, 하이드록시기, 할로겐기, 사이아노기, 나이트로기, 트리플루오로메틸기 및 실릴기로 선택되는 하나 이상의 치환기로 더 치환될 수 있으며;
상기 n은 1 내지 1000의 정수이다.)The method of claim 1,
The polymer compound is represented by the following formula (11).
(11)
(11)
Z is S or Se;
Ar is C 6 -C 30 arylene or C 3 -C 30 heteroarylene;
R is selected from C 1 -C 30 alkyl, C 2 -C 30 alkylene, C 2 -C 30 alkynylene, C 6 -C 30 aryl and C 3 -C 30 heteroaryl, said alkyl, alkylene, alkoxy Niylene, aryl and heteroaryl are C 1 -C 20 alkyl, C 2 -C 30 alkenyl, C 2 -C 30 alkynyl, C 1 -C 30 alkoxy, amino, hydroxy, halogen, cyano, May be further substituted with one or more substituents selected from nitro, trifluoromethyl and silyl groups;
N is an integer of 1 to 1000.)
Ar은 하기 구조에서 선택되는 하나이상인 것인 고분자 화합물.
(상기 구조식에서,
R11 및 R12는 서로 독립적으로 수소, C1-C30알킬, C2~C30알킬렌, C2~C30알키닐렌, C6~C30아릴 및 C3~C30헤테로아릴로부터 선택되며; 상기 알킬, 알킬렌, 알키닐렌, 아릴 및 헤테로아릴은 할로겐, C1-C30알킬, C1-C30알콕시, C6~C30아릴 및 C3~C30헤테로아릴로 더 치환될 수 있다.)The method of claim 2,
Ar is one or more polymer compounds selected from the following structures.
(In the above structural formula,
R 11 and R 12 independently of one another are selected from hydrogen, C 1 -C 30 alkyl, C 2 -C 30 alkylene, C 2 -C 30 alkynylene, C 6 -C 30 aryl and C 3 -C 30 heteroaryl Become; The alkyl, alkylene, alkynylene, aryl and heteroaryl may be further substituted with halogen, C 1 -C 30 alkyl, C 1 -C 30 alkoxy, C 6 -C 30 aryl and C 3 -C 30 heteroaryl. .)
상기 화학식 11은 하기 화학식 12로 표시되는 고분자 반도체 화합물.
[화학식 12]
(상기 화학식 12에서,
Ar은 C6-C30아릴렌 또는 C3-C30헤테로아릴렌이며;
R은 C1-C30알킬이며;
상기 n은 1 내지 1000의 정수이다.)The method of claim 2,
Formula 11 is a polymer semiconductor compound represented by the following formula (12).
[Chemical Formula 12]
(In the above formula (12)
Ar is C 6 -C 30 arylene or C 3 -C 30 heteroarylene;
R is C 1 -C 30 alkyl;
N is an integer of 1 to 1000.)
Ar은 하기 구조에서 선택되는 아릴렌 또는 헤테로아릴렌인 유기 반도체 화합물.
(상기 구조식에서,
R11 및 R12는 서로 독립적으로 수소, C1-C30알킬, C2~C30알킬렌, C2~C30알키닐렌, C6~C30아릴 및 C3~C30헤테로아릴로부터 선택되며; 상기 알킬, 알킬렌, 알키닐렌, 아릴 및 헤테로아릴은 할로겐, C1-C30알킬, C1-C30알콕시, C6~C30아릴 및 C3~C30헤테로아릴로 더 치환될 수 있다.)5. The method of claim 4,
Ar is an arylene or hetero arylene selected from the following structures.
(In the above structural formula,
R 11 and R 12 independently of one another are selected from hydrogen, C 1 -C 30 alkyl, C 2 -C 30 alkylene, C 2 -C 30 alkynylene, C 6 -C 30 aryl and C 3 -C 30 heteroaryl Become; The alkyl, alkylene, alkynylene, aryl and heteroaryl may be further substituted with halogen, C 1 -C 30 alkyl, C 1 -C 30 alkoxy, C 6 -C 30 aryl and C 3 -C 30 heteroaryl. .)
상기 화학식 11은 하기 구조에서 선택되는 것인 고분자 반도체 화합물.
(상기 화학식 구조에서 n은 1 내지 1000의 정수이다.)6. The method of claim 5,
Formula 11 is a polymer semiconductor compound that is selected from the following structure.
(N is an integer of 1 to 1000 in the formula structure.)
[화학식 1]
[상기 화학식 1에서,
Z는 S 또는 Se이고;
R은 C1-C30알킬, C2~C30알킬렌, C2~C30알키닐렌, C6~C30아릴 또는 C3~C30헤테로아릴이며, 상기 알킬, 알킬렌, 알키닐렌, 아릴 및 헤테로아릴은 C1-C30알킬, C2-C30알케닐, C2-C30알키닐, C1-C30알콕시, 아미노기, 하이드록시기, 할로겐기, 사이아노기, 나이트로기, 트리플루오로메틸기 및 실릴기로 선택되는 하나 이상의 치환기로 더 치환될 수 있다.]An organic semiconductor compound represented by the following formula (1).
[Formula 1]
[In the above formula (1)
Z is S or Se;
R is C 1 -C 30 alkyl, C 2 -C 30 alkylene, C 2 -C 30 alkynylene, C 6 -C 30 aryl or C 3 -C 30 heteroaryl, the alkyl, alkylene, alkynylene, Aryl and heteroaryl are C 1 -C 30 alkyl, C 2 -C 30 alkenyl, C 2 -C 30 alkynyl, C 1 -C 30 alkoxy, amino, hydroxy, halogen, cyano, nitro And one or more substituents selected from a group, a trifluoromethyl group and a silyl group.]
상기 R은 C1-C30알킬기인 유기 반도체 화합물.8. The method of claim 7,
Wherein R is a C 1 -C 30 alkyl group.
상기 Z는 S인 유기 반도체 화합물.8. The method of claim 7,
Z is S, an organic semiconductor compound.
화학식 4로 표시되는 화합물을 산화시켜 화학식 5로 표시되는 화합물을 제조하는 단계;
화학식 5로 표시되는 화합물을 무수아세틱산과 반응시켜 화학식 6으로 표시되는 화합물을 제조하는 단계;및
화학식 6으로 표시되는 화합물을 하기 화학식 7로 표시되는 화합물과 반응시켜 화학식 1로 표시되는 화합물을 제조하는 단계;를 포함하는 화학식 1로 표시되는 유기 반도체 화합물의 제조방법.
[화학식 1]
[화학식 2]
[화학식 3]
[화학식 4]
[화학식 5]
[화학식 6]
[화학식 7]
RNH2
[상기 화학식 1 내지 7에서,
Z는 S 또는 Se이고;
R은 C1-C30알킬, C2~C30알킬렌, C2~C30알키닐렌, C6~C30아릴 또는 C3~C30헤테로아릴이며, 상기 알킬, 알킬렌, 알키닐렌, 아릴 및 헤테로아릴은 C1-C30알킬, C2-C30알케닐, C2-C30알키닐, C1-C30알콕시, 아미노기, 하이드록시기, 할로겐기, 사이아노기, 나이트로기, 트리플루오로메틸기 및 실릴기로 선택되는 하나 이상의 치환기로 더 치환될 수 있으며;
R1 또는 R2는 서로 독립적으로, C1-C30알킬이며;
X는 할로겐이다.]Preparing a compound represented by Chemical Formula 4 by reacting the compound represented by Chemical Formula 2 with the compound represented by Chemical Formula 3;
Preparing a compound represented by Chemical Formula 5 by oxidizing the compound represented by Chemical Formula 4;
Preparing a compound represented by Chemical Formula 6 by reacting the compound represented by Chemical Formula 5 with acetic anhydride; and
A method for preparing an organic semiconductor compound represented by Chemical Formula 1, comprising: reacting a compound represented by Chemical Formula 6 with a compound represented by Chemical Formula 7 to prepare a compound represented by Chemical Formula 1.
[Formula 1]
(2)
(3)
[Chemical Formula 4]
[Chemical Formula 5]
[Chemical Formula 6]
(7)
RNH 2
[In Formulas 1 to 7,
Z is S or Se;
R is C 1 -C 30 alkyl, C 2 -C 30 alkylene, C 2 -C 30 alkynylene, C 6 -C 30 aryl or C 3 -C 30 heteroaryl, the alkyl, alkylene, alkynylene, Aryl and heteroaryl are C 1 -C 30 alkyl, C 2 -C 30 alkenyl, C 2 -C 30 alkynyl, C 1 -C 30 alkoxy, amino, hydroxy, halogen, cyano, nitro May be further substituted with one or more substituents selected from groups, trifluoromethyl groups and silyl groups;
R 1 or R 2 are, independently from each other, C 1 -C 30 alkyl;
X is halogen.]
상기 화학식 2의 화합물은 유기리튬 존재하에 하기 화학식 8의 화합물과 하기 화학식 9의 화합물을 반응시켜 제조되는 것인 화학식 1로 표시되는 유기 반도체 화합물의 제조방법.
[화학식 8]
[화학식 9]
(상기 화학식 8 또는 화학식 9에서,
X 또는 X1은 할로겐이며;
R1은 C1-C30알킬이다.)The method of claim 10,
The compound of Formula 2 is prepared by reacting a compound of Formula 8 and a compound of Formula 9 in the presence of an organolithium.
[Chemical Formula 8]
[Chemical Formula 9]
(In Formula 8 or Formula 9,
X or X 1 is halogen;
R 1 is C 1 -C 30 alkyl.)
상기 화학식 1은 상기 화학식 6, 1몰에 대하여 상기 화학식 7, 0.5 ~ 2.0몰로 반응시키는 것인 화학식 1로 표시되는 유기 반도체 화합물의 제조방법.The method of claim 10,
The Chemical Formula 1 is a method for producing an organic semiconductor compound represented by Chemical Formula 1 will be reacted with Chemical Formula 7, 0.5 to 2.0 moles with respect to Formula 6, 1 mole.
Z는 S이며, R은 C1-C30알킬기인 화학식 1로 표시되는 유기 반도체 화합물의 제조방법.The method of claim 10,
Z is S, and R is a C 1 -C 30 alkyl group.
상기 유기 태양전지는 구조가 기판, 투명전극, 정공수송층, 활성층, 전자수송층, 금속전극이 순차적으로 적층된 구조인 유기 태양전지. The method of claim 14,
The organic solar cell has a structure in which a substrate, a transparent electrode, a hole transport layer, an active layer, an electron transport layer, and a metal electrode are sequentially stacked.
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| CN103435783A (en) * | 2013-07-15 | 2013-12-11 | 中国科学院化学研究所 | Conjugated polymer, and preparation method and application thereof |
| WO2014204082A1 (en) * | 2013-06-20 | 2014-12-24 | 경상대학교산학협력단 | Organic semiconductor compound, method for preparing same, and organic solar cell employing same |
| WO2015122722A1 (en) * | 2014-02-14 | 2015-08-20 | 주식회사 엘지화학 | Copolymer and organic solar cell comprising same |
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| KR101563120B1 (en) | 2013-06-20 | 2015-11-06 | 경상대학교산학협력단 | organic semiconductor compound, process for producing the organic semiconductor compound and organic solar cells using the Same |
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| WO2014204082A1 (en) * | 2013-06-20 | 2014-12-24 | 경상대학교산학협력단 | Organic semiconductor compound, method for preparing same, and organic solar cell employing same |
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| CN103435783A (en) * | 2013-07-15 | 2013-12-11 | 中国科学院化学研究所 | Conjugated polymer, and preparation method and application thereof |
| WO2015122722A1 (en) * | 2014-02-14 | 2015-08-20 | 주식회사 엘지화학 | Copolymer and organic solar cell comprising same |
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