KR20150145532A - Benzodithienothiophene derivatives and organic photovoltaic cell using the same - Google Patents
Benzodithienothiophene derivatives and organic photovoltaic cell using the same Download PDFInfo
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- KR20150145532A KR20150145532A KR1020140075538A KR20140075538A KR20150145532A KR 20150145532 A KR20150145532 A KR 20150145532A KR 1020140075538 A KR1020140075538 A KR 1020140075538A KR 20140075538 A KR20140075538 A KR 20140075538A KR 20150145532 A KR20150145532 A KR 20150145532A
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- alkyl
- formula
- compound represented
- following formula
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- HALHMGTVOORMIF-UHFFFAOYSA-N 9,11,19-trithiapentacyclo[10.7.0.02,10.03,8.013,18]nonadeca-1(12),2(10),3,5,7,13,15,17-octaene Chemical class S1C2=CC=CC=C2C2=C1SC1=C2SC2=CC=CC=C12 HALHMGTVOORMIF-UHFFFAOYSA-N 0.000 title abstract 4
- 238000013086 organic photovoltaic Methods 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims abstract description 61
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 24
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 claims description 22
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 16
- -1 amino, hydroxy Chemical group 0.000 claims description 13
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 150000002367 halogens Chemical class 0.000 claims description 10
- 125000001072 heteroaryl group Chemical group 0.000 claims description 8
- 125000006649 (C2-C20) alkynyl group Chemical group 0.000 claims description 7
- 125000003342 alkenyl group Chemical group 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 229920003986 novolac Polymers 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229910052711 selenium Inorganic materials 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 claims description 3
- BAXOFTOLAUCFNW-UHFFFAOYSA-N 1H-indazole Chemical compound C1=CC=C2C=NNC2=C1 BAXOFTOLAUCFNW-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 8
- 230000003647 oxidation Effects 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 19
- 239000010410 layer Substances 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 14
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 14
- 229910052782 aluminium Inorganic materials 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000004770 highest occupied molecular orbital Methods 0.000 description 9
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 229930192474 thiophene Natural products 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- WCZVZNOTHYJIEI-UHFFFAOYSA-N cinnoline Chemical class N1=NC=CC2=CC=CC=C21 WCZVZNOTHYJIEI-UHFFFAOYSA-N 0.000 description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 230000032258 transport Effects 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 239000000370 acceptor Substances 0.000 description 4
- 229910052788 barium Inorganic materials 0.000 description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 3
- RFECNLMBVTZYCH-UHFFFAOYSA-N 1,4-benzodioxine-2,3-dione Chemical class C1=CC=CC2=C1OC(=O)C(=O)O2 RFECNLMBVTZYCH-UHFFFAOYSA-N 0.000 description 3
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 229920003169 water-soluble polymer Polymers 0.000 description 3
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- HQALDKFFRYFTKP-UHFFFAOYSA-N 2-[4-[4-(2-benzyl-1-benzothiophen-3-yl)phenyl]-2-bromo-6-(3-methoxyphenyl)phenoxy]acetic acid Chemical compound COC1=CC=CC(C=2C(=C(Br)C=C(C=2)C=2C=CC(=CC=2)C=2C3=CC=CC=C3SC=2CC=2C=CC=CC=2)OCC(O)=O)=C1 HQALDKFFRYFTKP-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229920002284 Cellulose triacetate Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920000144 PEDOT:PSS Polymers 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 2
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical class C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 2
- 229910001632 barium fluoride Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000007646 gravure printing Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 150000003949 imides Chemical group 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 238000007641 inkjet printing Methods 0.000 description 2
- 150000002496 iodine Chemical class 0.000 description 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- SKRWFPLZQAAQSU-UHFFFAOYSA-N stibanylidynetin;hydrate Chemical compound O.[Sn].[Sb] SKRWFPLZQAAQSU-UHFFFAOYSA-N 0.000 description 2
- DKLWRIQKXIBVIS-UHFFFAOYSA-N 1,1-diiodooctane Chemical compound CCCCCCCC(I)I DKLWRIQKXIBVIS-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- POFKUHBNZIBLDM-UHFFFAOYSA-N 2,3-didecylthiophene Chemical compound CCCCCCCCCCC=1C=CSC=1CCCCCCCCCC POFKUHBNZIBLDM-UHFFFAOYSA-N 0.000 description 1
- LXOFYPKXCSULTL-UHFFFAOYSA-N 2,4,7,9-tetramethyldec-5-yne-4,7-diol Chemical group CC(C)CC(C)(O)C#CC(C)(O)CC(C)C LXOFYPKXCSULTL-UHFFFAOYSA-N 0.000 description 1
- MAGFQRLKWCCTQJ-UHFFFAOYSA-M 4-ethenylbenzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=C(C=C)C=C1 MAGFQRLKWCCTQJ-UHFFFAOYSA-M 0.000 description 1
- QMNVUZQWXKLEFP-UHFFFAOYSA-N 5-octylthieno[3,4-c]pyrrole-4,6-dione Chemical compound S1C=C2C(=O)N(CCCCCCCC)C(=O)C2=C1 QMNVUZQWXKLEFP-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- VDWHITZIFRMENS-UHFFFAOYSA-N N,N-dimethylthieno[3,2-b]thiophene-6-carboxamide Chemical compound CN(C(=O)C=1C2=C(SC=1)C=CS2)C VDWHITZIFRMENS-UHFFFAOYSA-N 0.000 description 1
- PHXQIAWFIIMOKG-UHFFFAOYSA-N NClO Chemical compound NClO PHXQIAWFIIMOKG-UHFFFAOYSA-N 0.000 description 1
- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- BNBQRQQYDMDJAH-UHFFFAOYSA-N benzodioxan Chemical class C1=CC=C2OCCOC2=C1 BNBQRQQYDMDJAH-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- KWTSZCJMWHGPOS-UHFFFAOYSA-M chloro(trimethyl)stannane Chemical compound C[Sn](C)(C)Cl KWTSZCJMWHGPOS-UHFFFAOYSA-M 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
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- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- KXCAEQNNTZANTK-UHFFFAOYSA-N stannane Chemical compound [SnH4] KXCAEQNNTZANTK-UHFFFAOYSA-N 0.000 description 1
- 229910000080 stannane Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- GKTQKQTXHNUFSP-UHFFFAOYSA-N thieno[3,4-c]pyrrole-4,6-dione Chemical compound S1C=C2C(=O)NC(=O)C2=C1 GKTQKQTXHNUFSP-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
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- 238000012546 transfer Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D495/04—Ortho-condensed systems
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/22—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains four or more hetero rings
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/50—Photovoltaic [PV] devices
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
Description
본 발명은 벤조다이사이에노사이오펜 유도체 및 이를 채용하고 있는 유기태양전지에 관한 것이다. 보다 구체적으로 본 발명은 분자 내 전자 주게인 벤조다이사이에노사이오펜과 전자 받게인 알킬기를 동시에 가지는 벤조다이사이에노사이오펜 유도체 및 이를 활성층 재료로 도입한 유기태양전지에 관한 것이다.[0001] The present invention relates to a benzodioxanedione derivative and an organic solar cell employing the same. More specifically, the present invention relates to benzodiisocyanate-free benzodiazene compounds having both nano-iodine and an electron-accepting alkyl group in an intramolecular electron donor, and an organic solar cell into which the nano-iodine is introduced as an active layer material.
최근 대표적 에너지원인 화석원료의 유한성과 화석원료 연소에 따른 이산화탄소 배출은 온실효과와 같은 환경 문제를 야기시키며, 환경 친화적 대체에너지 개발의 필요성 부각시켰다. 이러한 문제점을 극복하기 위한 노력의 일환으로 수력과 풍력 등 다양한 에너지원들이 연구되고 있으며, 무한한 사용이 가능한 태양광 역시 신 재생에너지의 에너지원으로서 연구되고 있다. 태양광을 이용한 태양전지는 크게 실리콘과 같은 무기물을 이용한 태양 전지와 유기물을 사용한 태양전지로 나눌 수 있는데 유기 박막 태양전지는 실리콘을 사용하는 무기 태양전지에 비해 낮은 생산단가와 자유자재로 구부릴 수 있는 플렉서블한 소자를 대면적화 할 수 있다는 장점으로 인하여 많은 연구가 진행되고 있다. 현재 유기 박막 태양전지의 대부분은 고분자 소재를 중심으로 연구되어 왔으나, 분자량 조절과 촉매제거가 힘들고 배치별 효율이 달라 태양전지 소자의 성능의 재현성이 떨어진다. 이러한 단점을 극복하고 고효율 유기태양전지를 만들기 위해서는 광흡수영역이 넓은 낮은 밴드갭을 가지고 있으며, 정공이동도가 우수하고, 적절한 분자 준위를 가지는 새로운 단분자를 개발할 필요성이 대두되고 있다.Recently, the finite nature of fossil raw materials and carbon dioxide emissions from fossil raw material combustion have caused environmental problems such as greenhouse effect and highlighted the need for environmentally friendly alternative energy development. As part of efforts to overcome these problems, various energy sources such as hydroelectric power and wind power have been studied, and solar energy that can be used infinitely is being studied as an energy source of renewable energy. Solar cells using solar light can be divided into solar cells using inorganic materials such as silicon and solar cells using organic materials. Organic thin film solar cells can be bent at low production cost and freely compared to inorganic solar cells using silicon Many researches have been carried out because of the merit that it is possible to make the flexible devices more compact. Most of the organic thin film solar cells have been studied mainly in polymer materials, but they are difficult to control the molecular weight and remove the catalyst, and the performance of the solar cell device is deteriorated due to the different efficiency in each batch. In order to overcome these disadvantages and to make a high efficiency organic solar cell, there is a need to develop a new single molecule having a wide absorption band, a low band gap, an excellent hole mobility and a suitable molecular level.
이에 본 발명자들은 낮은 에너지 밴드갭, 낮은 HOMO 값을 통한 큰 개방전압(Voc) 및 높은 전하이동도에 의한 높은 단락 전류(Jsc)를 가져 고효율 특성을 가질 것으로 예상되는 새로운 유기태양전지용 단분자 화합물로써, 벤조다이사이에노사이오펜 유도체를 설계하여 합성하고, 그 물성을 평가하여 본 발명을 완성하였다.Accordingly, the present inventors have found that a novel monomolecular compound for organic solar cells having a high energy bandgap, a high open-circuit voltage (Voc) through a low HOMO value and a high short-circuit current (Jsc) , And benzodiisocyanate were designed and synthesized, and their physical properties were evaluated to complete the present invention.
본 발명은 벤조다이사이에노사이오펜 유도체 및 이를 채용하고 있는 유기태양전지에 관한 것이다. 보다 구체적으로 본 발명은 분자 내 전자 주게인 벤조다이사이에노사이오펜과 전자 받게인 알킬기를 동시에 가지는 벤조다이사이에노사이오펜 유도체 및 이를 활성층 재료로 도입한 유기태양전지에 관한 것이다.[0001] The present invention relates to a benzodioxanedione derivative and an organic solar cell employing the same. More specifically, the present invention relates to benzodiisocyanate-free benzodiazene compounds having both nano-iodine and an electron-accepting alkyl group in an intramolecular electron donor, and an organic solar cell into which the nano-iodine is introduced as an active layer material.
본 발명은 하기 화학식 1로 표시되는 벤조다이사이에노사이오펜 유도체를 제공한다.The present invention provides benzodithiocyanato derivatives represented by the following general formula (1).
[화학식 1] [Chemical Formula 1]
[상기 화학식 1에서,[In the above formula (1)
Z1 내지 Z3는 S, O 또는 Se이고;Z 1 to Z 3 are S, O or Se;
R1 및 R2는 각각 독립적으로 수소 또는 (C1-C30)알킬이며;R 1 and R 2 are each independently hydrogen or (C 1 -C 30) alkyl;
R3 및 R4는 각각 독립적으로 수소 또는 (C1-C30)알킬, 
상기 R1 내지 R4, R11 및 R12 에서의 상기 알킬은 각각 독립적으로 (C1-C20)알킬, (C2-C20)알케닐, (C2-C20)알키닐, (C1-C30)알콕시, (C6~C30)아릴, (C3~C30)헤테로아릴, 아미노, 하이드록시 및 할로겐으로부터 선택되는 하나 이상의 치환기로 더 치환될 수 있다.]Wherein R 1 to R 4, R 11 and the alkyl in R 12 are each independently (C1-C20) alkyl, (C2-C20) alkenyl, (C2-C20) alkynyl, (C1-C30) alkoxy, (C6-C30) aryl, (C3-C30) heteroaryl, amino, hydroxy and halogen.
본 발명의 일실시예에 따른, 상기 벤조다이사이에노사이오펜 유도체는 하기 화학식 2로 표시되는 것일 수 있다.According to an embodiment of the present invention, the niscoiophene derivative between the benzodiazines may be represented by the following formula (2).
[화학식 2](2)
[상기 화학식 2에서,[In the formula (2)
R1 및 R2는 각각 독립적으로 수소 또는 (C1-C30)알킬이며;R 1 and R 2 are each independently hydrogen or (C 1 -C 30) alkyl;
R3 및 R4는 각각 독립적으로 수소 또는 (C1-C30)알킬, 
상기 R1 내지 R4, R11 및 R12 에서의 상기 알킬은 각각 독립적으로 (C1-C20)알킬, (C2-C20)알케닐, (C2-C20)알키닐, (C1-C30)알콕시, (C6~C30)아릴, (C3~C30)헤테로아릴, 아미노, 하이드록시 및 할로겐으로부터 선택되는 하나 이상의 치환기로 더 치환될 수 있다.]Wherein R 1 to R 4, R 11 and the alkyl in R 12 are each independently (C1-C20) alkyl, (C2-C20) alkenyl, (C2-C20) alkynyl, (C1-C30) alkoxy, (C6-C30) aryl, (C3-C30) heteroaryl, amino, hydroxy and halogen.
본 발명의 일실시예에 따른, 상기 벤조다이사이에노사이오펜 유도체는 상기 R1 및 R2는 각각 독립적으로 (C1-C20)알킬이며;According to an embodiment of the present invention, the benzodiene-nonaoiophene derivative is a compound wherein each of R 1 and R 2 is independently (C 1 -C 20) alkyl;
R3 및 R4는 각각 독립적으로 수소 또는 (C1-C30)알킬, 
R11 및 R12 는 각각 독립적으로 수소 또는 (C1-C30)알킬; 일 수 있다.R 11 and R 12 are each independently hydrogen or (C 1 -C 30) alkyl; Lt; / RTI >
본 발명의 일실시예에 따른, 상기 벤조다이사이에노사이오펜 유도체는 하기 화학식 3으로 표시되는 것일 수 있다.According to an embodiment of the present invention, the novathiophene derivative between the benzodiazines may be represented by the following formula (3).
[화학식 3](3)
[상기 화학식 3에서,[Formula 3]
상기 R1, R2 및 R21 내지 R24는 각각 독립적으로 (C5-C10)알킬이다.]Wherein R 1, R 2, and R < 21 & Each R < 24 > is independently (C5-C10) alkyl]
본 발명의 일실시예에 따른, 상기 벤조다이사이에노사이오펜 유도체는 하기 화합물에서 선택되는 것 일 수 있다.According to one embodiment of the present invention, the benzodiene-internaiophene derivative may be selected from the following compounds.
본 발명은 하기 화학식 4으로 표시되는 화합물과 n-부틸 리튬 (n-BuLi)을 반응시켜 하기 화학식 5로 표시되는 화합물을 제조하는 단계; 하기 화학식 5로 표시되는 화합물과 화학식 6로 표시되는 화합물을 반응시켜 하기 화학식 7으로 표시되는 화합물을 제조하는 단계; 하기 화학식 7으로 표시되는 화합물과 하기 화학식 8로 표시되는 화합물을 반응시켜 화합물 9로 표시되는 화합물을 제조하는 단계; 및 하기 화학식 9로 표시되는 화합물과 하기 화학식 10로 표시되는 화합물을 반응시켜 화합물 3으로 표시되는 화합물을 제조하는 단계;를 포함하는 벤조다이사이에노사이오펜 유도체의 제조방법을 제공한다. The present invention relates to a process for preparing a compound represented by the following formula (5) by reacting a compound represented by the following formula (4) with n-butyl lithium (n-BuLi) Reacting a compound represented by the following formula (5) with a compound represented by the following formula (6) to prepare a compound represented by the following formula (7); Reacting a compound represented by the formula (7) and a compound represented by the following formula (8) to prepare a compound represented by the formula (9); And a step of reacting a compound represented by the following formula (9) with a compound represented by the following formula (10) to prepare a compound represented by the formula (3).
[화학식 4][Chemical Formula 4]
[화학식 5][Chemical Formula 5]
[화학식 6][Chemical Formula 6]
[화학식 7](7)
[화학식 8][Chemical Formula 8]
[화학식 9][Chemical Formula 9]
[화학식 10][Chemical formula 10]
[화학식 3](3)
[상기 화학식 3 내지 화학식 10에서,[In the above Chemical Formulas 3 to 10,
T는 -Sn(R41)(R42)(R43)이고;T is -Sn (R 41) (R 42 ) (R 43) a;
R1, R2, R21 내지 R24, R31, R32 및 R41 내지 R43은 각각 독립적으로 (C5-C10)알킬이며;R 1, R 2, R 21 to R 24 , R 31, R 32 and R 41 to R 43 are each independently (C 5 -C 10) alkyl;
X1 및 X2는 할로겐이다.]X 1 and X 2 are halogen.]
본 발명은 상기 벤조다이사이에노사이오펜 유도체를 포함하는 유기전자소자를 제공한다.The present invention provides an organic electronic device comprising a non-iodine derivative between benzodia.
본 발명의 일실시예에 따른, 상기 유기전자소자는 유기태양전지일 수 있다.According to an embodiment of the present invention, the organic electronic device may be an organic solar cell.
본 발명에 따른 벤조다이사이에노사이오펜 유도체는 사이오펜에 치환된 긴 사슬의알킬기를 가짐으로써 높은 용해도를 가질 뿐만 아니라 벤조다이사이에노사이오펜이 가지는 높은 전자 밀도로 인해 높은 단락 전류(Jsc)를 가진다. The benzo-diene-internaiophene derivative according to the present invention has a long-chain alkyl group substituted in the thiophene, thereby not only has a high solubility but also a high short-circuit current (Jsc) due to the high electron density of the benzo- I have.
본 발명에 따른 벤조다이사이에노사이오펜 유도체는 분자 내에 전자 주게와 전자 받게를 동시에 가짐으로써, 낮은 에너지 밴드갭과 낮은 HOMO 값을 가질 수 있어 이를 채용한 유기태양전지는 우수한 효율을 가질 수 있다. The benzodiazene intermediate between benzodiazines according to the present invention may have both a low energy band gap and a low HOMO value by having an electron donor and an electron acceptor in the molecule at the same time so that the organic solar cell employing the same can have excellent efficiency.
또한, 본 발명에 따른 벤조다이사이에노사이오펜 유도체에 있어서, 사이오펜에 치환된 알킬기의 구조에 따라 이를 채용한 유기태양전지는 우수한 산화안정성, 개방 전압값 및 전류밀도를 가진다.In addition, the organic solar cell employing the benzodiisocyanine-based benzodioxane derivative according to the present invention has an excellent oxidation stability, an open-circuit voltage value and a current density depending on the structure of an alkyl group substituted with a thiophene.
도 1은 실시예 1 에서 합성된 벤조다이사이에노사이오펜 유도체(DTBD-TTPD)의 용액상 및 필름상의 UV-vis 흡수 스펙트라이며,
도 2는 실시예 1 에서 합성된 벤조다이사이에노사이오펜 유도체(DTBD-TTPD)의 전기적 특성(cyclic voltammetry) 도면이며,
도 3은 실시예 1 에서 합성된 벤조다이사이에노사이오펜 유도체(DTBD-TTPD)의 시차열량분석(DSC) 곡선이며,
도 4는 실시예 1 에서 합성된 벤조다이사이에노사이오펜 유도체(DTBD-TTPD)의 열중량분석(TGA) 곡선이며,
도 5는 실시예 1 에서 합성된 벤조다이사이에노사이오펜 유도체(DTBD-TTPD)를 도 3의 방법으로 측정하여 소자구현 시 나타나는 에너지 준위를 나타낸 도면이며,
도 6은 실시예 1 에서 합성된 벤조다이사이에노사이오펜 유도체(DTBD-TTPD)를 유기태양전지로 제작하고, 이의 특성을 측정한 결과값을 어닐링 온도별로 나타낸 도면(a)이고, 내부양자효율에 관한 그래프(b) 이다.1 is a UV-vis absorption spectrum of a solution phase of a benzodiisocyanate compound (DTBD-TTPD) synthesized in Example 1 and a film,
2 is a cyclic voltammetry diagram of the benzodiisocyanate derivative (DTBD-TTPD) synthesized in Example 1,
3 is a differential calorimetric analysis (DSC) curve of the benzodiisocyanate derivative (DTBD-TTPD) synthesized in Example 1,
4 is a thermogravimetric analysis (TGA) curve of the benzodiisocyanate derivative (DTBD-TTPD) synthesized in Example 1,
FIG. 5 is a graph showing energy levels of the benzodiisocyanate (DTBD-TTPD) synthesized in Example 1 measured by the method of FIG. 3,
6 is a view (a) showing the results of measurement of the properties of a benzodiisocyanate (DTBD-TTPD) derivative (DTBD-TTPD) synthesized in Example 1 by using an organic solar cell, (B) of FIG.
본 발명은 벤조다이사이에노사이오펜 유도체 및 이를 채용하고 있는 유기태양전지에 관한 것이다. 보다 구체적으로, 유기태양전지의 활성층 재료로 사용되는 본 발명에 따른 상기 벤조다이사이에노사이오펜 유도체는 분자 내 전자 주게인 벤조다이사이에노사이오펜과 전자 받게인 알킬기를 포함하는 것을 특징으로 한다.[0001] The present invention relates to a benzodioxanedione derivative and an organic solar cell employing the same. More specifically, the benzodiene-internaiophene derivative according to the present invention, which is used as an active layer material of an organic solar cell, is characterized by containing an internuclear electron donor benzothiophene and an electron acceptor alkyl group.
본 발명에 따른 상기 벤조다이사이에노사이오펜 유도체는 전자 주게와 전자 받게를 동시에 가지므로 낮은 에너지 밴드갭과 낮은 HOMO값을 가지게 된다. 따라서, 본 발명에 따른 화합물을 채용한 유기태양전지는 높은 전자 이동도에 의한 높은 단락 전류(Jsc)를 가져 고효율 특성을 가질 수 있으며, 산화안정성이 우수하고, 개방전압(Voc)을 향상시킬 수 있는 특징이 있다. Since the benzodiene-based novolak derivatives according to the present invention have both electron donors and electron acceptors, they have a low energy band gap and a low HOMO value. Therefore, the organic solar cell employing the compound according to the present invention has a high short-circuit current (Jsc) due to high electron mobility and can have high efficiency characteristics, and is excellent in oxidation stability and can improve the open-circuit voltage (Voc) There are features.
또한, 본 발명에 따른 상기 벤조다이사이에노사이오펜 유도체는 단분자 화합물로써, 고분자에 비해 불순물의 제거 할 수 있는 정제 공정이 용이하며, 화합물의 고순도화로 인해 전하이동특성 또한 우수하다. In addition, the benzodiisocyanide compound according to the present invention is a monomolecular compound, which is easier to purify than impurities due to the removal of impurities, and has excellent charge transfer properties due to high purity of the compound.
본 발명은 하기 화학식 1로 표시되는 벤조다이사이에노사이오펜 유도체를 포함한다.The present invention includes a benzodiacynoniophene derivative represented by the following formula (1).
[화학식 1][Chemical Formula 1]
[상기 화학식 1에서,[In the above formula (1)
Z1 내지 Z3는 S, O 또는 Se이고;Z 1 to Z 3 are S, O or Se;
R1 및 R2는 각각 독립적으로 수소 또는 (C1-C30)알킬이며;R 1 and R 2 are each independently hydrogen or (C 1 -C 30) alkyl;
R3 및 R4는 각각 독립적으로 수소 또는 (C1-C30)알킬, 
상기 R1 내지 R4, R11 및 R12 에서의 상기 알킬은 각각 독립적으로 (C1-C20)알킬, (C2-C20)알케닐, (C2-C20)알키닐, (C1-C30)알콕시, (C6~C30)아릴, (C3~C30)헤테로아릴, 아미노, 하이드록시 및 할로겐으로부터 선택되는 하나 이상의 치환기로 더 치환될 수 있다.]Wherein R 1 to R 4, R 11 and the alkyl in R 12 are each independently (C1-C20) alkyl, (C2-C20) alkenyl, (C2-C20) alkynyl, (C1-C30) alkoxy, (C6-C30) aryl, (C3-C30) heteroaryl, amino, hydroxy and halogen.
또한 상기 화학식 1로 표시되는 벤조다이사이에노사이오펜 유도체에 있어서, 유기태양전지의 높은 광전변환효율을 획득하게 위하여, 상기 Z1 내지 Z3 은 S인 하기 화학식 2로 표시되는 벤조다이사이에노사이오펜 유도체일 수 있다. 이는 우수한 정공이동도와 높은 광흡수율을 보이는 물질인 사이오펜을 도입하여, 분자간 상호작용을 높여줌으로써, 이를 함유한 유기태양전지는 높은 전자 이동도를 나타낼 수 있다. Further, in order to obtain a high photoelectric conversion efficiency of the organic solar cell in the benzodiacyanophene derivative represented by Formula 1, the Z 1 to Z 3 are S, which is S, Lt; / RTI > derivatives. By introducing thiophene, which is a material exhibiting excellent hole mobility and high light absorptivity, by enhancing the intermolecular interaction, the organic solar cell containing the thiophene can exhibit high electron mobility.
[화학식 2] (2)
[상기 화학식 2에서,[In the formula (2)
R1 및 R2는 각각 독립적으로 수소 또는 (C1-C30)알킬이며;R 1 and R 2 are each independently hydrogen or (C 1 -C 30) alkyl;
R3 및 R4는 각각 독립적으로 수소 또는 (C1-C30)알킬, 
상기 R1 내지 R4, R11 및 R12 에서의 상기 알킬은 각각 독립적으로 (C1-C20)알킬, (C2-C20)알케닐, (C2-C20)알키닐, (C1-C30)알콕시, (C6~C30)아릴, (C3~C30)헤테로아릴, 아미노, 하이드록시 및 할로겐으로부터 선택되는 하나 이상의 치환기로 더 치환될 수 있다.]Wherein R 1 to R 4, R 11 and the alkyl in R 12 are each independently (C1-C20) alkyl, (C2-C20) alkenyl, (C2-C20) alkynyl, (C1-C30) alkoxy, (C6-C30) aryl, (C3-C30) heteroaryl, amino, hydroxy and halogen.
상기 벤조다이사이에노사이오펜 유도체는 용해도를 높이기 위해, 이미드에 치환된 알킬 또는 사이오펜에 치환된 알킬의 길이 또는 알킬에 치환되는 치환기를 조절할 수 있다. In order to increase the solubility of the benzodiene-containing benzodiamide derivative, it is possible to control the length of alkyl substituted with imide or the alkyl substituted with thiophene or a substituent substituted with alkyl.
이때, 상기 이미드에 치환된 알킬 또는 사이오펜에 치환된 알킬은 전자를 공여할 수 있으면서 용해성을 높일 수 있도록 긴 사슬을 가지는 것이 유리하며, 바람직하게는 상기 화학식 1의 R1 및 R2는 각각 독립적으로 (C5-C30)알킬 일 수 있으며, 상기 알킬은 (C1-C20)알킬, (C2-C20)알케닐, (C2-C20)알키닐, (C1-C30)알콕시, (C6~C30)아릴, (C3~C30)헤테로아릴, 아미노, 하이드록시 및 할로겐으로부터 선택되는 하나 이상의 치환기로 더 치환될 수 있고, 상기 헤테로아릴은 NH, O, S 및 Se로부터 선택되는 하나 이상의 헤테로원자를 포함할 수 있으나 이에 한정되는 것은 아니다.At this time, it is advantageous that the alkyl substituted at the imide or the alkyl substituted at the thiophene has a long chain so as to be able to donate electrons and increase the solubility, and preferably R 1 and R 2 in the formula (C2-C20) alkenyl, (C2-C20) alkynyl, (C1-C30) alkoxy, (C6-C30) (C3-C30) heteroaryl, amino, hydroxy and halogen, said heteroaryl comprising one or more heteroatoms selected from NH, O, S and Se But is not limited thereto.
상기 화학식 2로 표시되는 벤조다이사이에노사이오펜 유도체에 있어서, 높은 용해성을 보이는 측면에서, 상기 R1 및 R2는 각각 독립적으로 (C1-C20)알킬이며;In the benzodiacyanophene derivative represented by
R3 및 R4는 각각 독립적으로 수소 또는 (C1-C30)알킬, 
R11 및 R12 는 각각 독립적으로 수소 또는 (C1-C20) 알킬; 인 벤조다이사이에노사이오펜 유도체일 수 있다.R 11 and R 12 are each independently hydrogen or (C 1 -C 20) alkyl; / RTI > can be a benzothiophene derivative.
바람직하게는, 하기 화학식 3으로 표시되는 벤조다이사이에노사이오펜 유도체일 수 있다.The benzodiisocyanate derivative represented by the following general formula (3) can be preferably used.
[화학식 3](3)
[상기 화학식 3에서,[Formula 3]
상기 R1, R2 및 R21 내지 R24는 각각 독립적으로 (C5-C10)알킬이다.]Wherein R 1, R 2, and R < 21 & Each R < 24 > is independently (C5-C10) alkyl]
또한, 낮은 에너지 밴드갭과 낮은 HOMO 값을 가지기 위한 측면에서, 하기 화합물에서 선택되는 것이 보다 바람직하다.Further, in view of having a low energy band gap and a low HOMO value, it is more preferable to select from the following compounds.
본 발명에 따른 벤조다이사이에노사이오펜 유도체는 하기 제조방법으로 제조 될 수 있다. 이는 하기 제조방법으로 한정되는 것은 아니며, 통상의 유기화학 반응에 의하여 제조될 수 있다. The benzodi sene novalophene derivative according to the present invention can be produced by the following production process. This is not limited to the following production method and can be produced by a conventional organic chemical reaction.
본 발명에 따른 벤조다이사이에노사이오펜 유도체는 하기 화학식 4으로 표시되는 화합물과 n-부틸 리튬 (n-BuLi)을 반응시켜 하기 화학식 5로 표시되는 화합물을 제조하는 단계; 하기 화학식 5로 표시되는 화합물과 화학식 6로 표시되는 화합물을 반응시켜 하기 화학식 7으로 표시되는 화합물을 제조하는 단계; 하기 화학식 7으로 표시되는 화합물과 하기 화학식 8로 표시되는 화합물을 반응시켜 화합물 9로 표시되는 화합물을 제조하는 단계; 및 하기 화학식 9로 표시되는 화합물과 하기 화학식 10로 표시되는 화합물을 반응시켜 화합물 3으로 표시되는 화합물을 제조하는 단계;를 포함하는 벤조다이사이에노사이오펜 유도체의 제조방법으로 제조될 수 있다.The benzodiisocyanate compound according to the present invention may be prepared by reacting a compound represented by the following formula (4) with n-butyl lithium (n-BuLi) to prepare a compound represented by the following formula (5) Reacting a compound represented by the following formula (5) with a compound represented by the following formula (6) to prepare a compound represented by the following formula (7); Reacting a compound represented by the formula (7) and a compound represented by the following formula (8) to prepare a compound represented by the formula (9); And reacting the compound represented by the following general formula (9) with a compound represented by the following general formula (10) to produce a compound represented by the general formula (3).
[화학식 4][Chemical Formula 4]
[화학식 5][Chemical Formula 5]
[화학식 6][Chemical Formula 6]
[화학식 7](7)
[화학식 8][Chemical Formula 8]
[화학식 9][Chemical Formula 9]
[화학식 10][Chemical formula 10]
[화학식 3](3)
[상기 화학식 3 내지 화학식 10에서,[In the above Chemical Formulas 3 to 10,
T는 -Sn(R41)(R42)(R43)이고;T is -Sn (R 41) (R 42 ) (R 43) a;
R1, R2, R21 내지 R24, R31, R32 및 R41 내지 R43은 각각 독립적으로 (C5-C10)알킬이며;R 1, R 2, R 21 to R 24 , R 31, R 32 and R 41 to R 43 are each independently (C 5 -C 10) alkyl;
X1 및 X2는 할로겐이다.]X 1 and X 2 are halogen.]
상기 화학식 1 에 있어서, 상기 R3와 R4는 서로 동일하거나 상이할 수 있으나, 서로 동일할 경우, 반응 효율 및 공정의 단순화로 인해 더욱 바람직하다. In the above formula (1), R 3 and R 4 may be the same or different from each other. However, when R 3 and R 4 are the same, they are more preferable because of the reaction efficiency and process simplification.
또한 본 발명은 상기 벤조다이사이에노사이오펜 유도체를 포함하는 유기전자소자를 포함한다.The present invention also includes an organic electronic device comprising a benzothiophene derivative between benzodiamides.
본 발명에 따른 상기 유기전자소자는 유기발광소자, 유기태양전지, 유기감광체 및 유기트랜지스터로 이루어진 군으로부터 선택될 수 있으며, 보다 바람직하게는 유기태양전지 일 수 있다. The organic electronic device according to the present invention may be selected from the group consisting of an organic light emitting device, an organic solar cell, an organophotoreceptor, and an organic transistor, and more preferably an organic solar cell.
일반적으로 본 발명에 따른 유기태양전지는 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 can be manufactured by the method described below, but the present invention is not limited thereto.
본 발명의 바람직한 실시예에 따라 제조된 유기태양전지는 기판, 제1전극, 정공수송층, 활성층, 전자수송층 및 제2전극으로 이루어진다. An organic solar cell manufactured according to a preferred embodiment of the present invention comprises a substrate, a first electrode, a hole transporting layer, an active layer, an electron transporting layer, and a second electrode.
상기 기판은 유리 및 석영판 이외에도 PET(polyethylene terephthalate), PEN(polyethylene naphthelate), PP(polyperopylene), PI(polyimide), PC(polycarbornate), PS(polystylene), POM(polyoxyethlene), AS 수지(acrylonitrile styrene copolymer), ABS 수지(acrylonitrile butadiene styrene copolymer) 및 TAC(Triacetyl cellulose) 등을 포함하는 플라스틱과 같은 유연하고 투명한 물질로 제조될 수 있다. In addition to glass and quartz, the substrate may be made of a material selected from the group consisting of polyethylene terephthalate (PEN), polyperopylene (PEN), polyimide, polyimide, polycarbonate, polystyrene, polyoxyethylenes, such as plastics, including acrylonitrile butadiene styrene copolymer, ABS resin, and TAC (triacetyl cellulose).
또한 상기 제1 전극은 스퍼터링, E-Beam, 열증착, 스핀코팅, 스크린 프린팅, 잉크젯 프린팅, 닥터 블레이드 또는 그라비아 프린팅법을 사용하여 투명전극 물질을 상기 기판의 일면에 도포되거나 필름형태로 코팅됨으로써 형성된다. 제1 전극(120)은 애노드의 기능을 하는 부분으로써, 후술하는 제2 전극(160)에 비해 일함수가 큰 물질로 투명성 및 도전성을 갖는 임의의 물질이 사용될 수 있다. 예를 들면, ITO(indium tin oxide), 금, 은, 플로린이 도핑된 틴 옥사이드(fluorine doped tin oxide; FTO), 알루미늄이 도핑된 징크 옥사이드(aluminium doped zink oxide, AZO), IZO(indium zink oxide), ZnO-Ga2O3, ZnO-Al2O3 및 ATO(antimony tin oxide) 등이 있으며, 바람직하게는 ITO를 사용하는 것이 좋다.The first electrode may be formed by coating a transparent electrode material on one side of the substrate or by coating it with a film using sputtering, E-beam, thermal evaporation, spin coating, screen printing, inkjet printing, doctor blade or gravure printing do. The first electrode 120 functions as an anode and may be made of any material having a higher work function than the second electrode 160 and having transparency and conductivity. For example, there are known indium tin oxide (ITO), gold, silver, fluorine doped tin oxide (FTO), aluminum doped zink oxide (AZO), indium zinc oxide ), ZnO-Ga 2 O 3 , ZnO-Al 2 O 3 and ATO (antimony tin oxide), and it is preferable to use ITO.
상기 제1 전극의 상부에는 정공 수송층이 스핀코팅 또는 딥코팅 등의 방법을 통해 도입되는데, 본 발명에서는 전도성 고분자 용액으로서 폴리리(3,4-에틸렌디옥시티오펜):폴리(4-스티렌설포네이트)[PEDOT:PSS]를 사용하는 것이 바람직하다. 이는 전자가 양극인 ITO(indium tin oxide)층으로 이동하는 것을 막아주면서 정공의 수송을 원활하게 도와준다.A hole transport layer is introduced onto the first electrode through spin coating or dip coating. In the present invention, a poly (3,4-ethylenedioxythiophene): poly (4-styrenesulfonate ) [PEDOT: PSS] is preferably used. This prevents the electrons from migrating to the ITO (indium tin oxide) layer as the anode and smoothly transports the holes.
또한 상기 활성층에는 본 발명에 따른 벤조다이사이에노사이오펜 유도체를 포함할 수 있으며, 이의 배합량은 용도에 따라 적절하게 조절될 수 있다. 또한 상기 벤조다이사이에노사이오펜 유도체는 PCBM 유도체 및 첨가제(DIO;다이아이오도옥탄, ODT;옥타다이싸이올)와 함께 포함될 수 있으며, 용도에 따라 적절하게 배합되어 사용될 수 있다. 상기 벤조다이사이에노사이오펜 유도체는 유기용매에 용해시키는데, 바람직하게는 아세톤, 메탄올, THF, 톨루엔, 자일렌, 테트랄린, 클로로포름, 클로로벤젠, 디클로로벤젠 또는 이들의 혼합용매 를 사용할 수 있으나 이에 한정되는 것은 아니다. 상기 벤조다이사이에노사이오펜 유도체는 60 내지 120nm 두께로 활성층에 도입되는 것이 바람직하다. 또한 본 발명에 따른 벤조다이사이에노사이오펜 유도체를 포함하는 상기 활성층은 높은 전자 밀도로 인하여, 단락전류밀도(short circuit current density) 및 개방전압(open circuit voltage)이 증가하여 에너지변환효율에 좋다. In addition, the active layer may contain a novolak type compound in the benzodiamide according to the present invention, and the compounding amount thereof may be suitably adjusted according to the use. Also, among these benzodiazines, the niscoiophene derivatives may be included together with PCBM derivatives and additives (DIO; diiodoctane, ODT; octadisthiol), and may be appropriately used according to the use. The novolak derivatives are dissolved in an organic solvent. The solvent is preferably selected from the group consisting of acetone, methanol, THF, toluene, xylene, tetralin, chloroform, chlorobenzene, dichlorobenzene, But is not limited thereto. The nonsiophene derivative between the benzodia is preferably introduced into the active layer to a thickness of 60 to 120 nm. In addition, the active layer containing a non-iodine derivative between the benzodiazines according to the present invention has a high electron density, which results in an increase in short circuit current density and open circuit voltage, which is good for energy conversion efficiency.
상기 전자수송층은 전자수송층의 모폴로지를 향상시키기 위해 계면활성제(surfactant)를 첨가하여 제조 할 수 있다. 이때, 상기 전자수송층은 친전자성 기능을 가지는 수용성 고분자를 물, 에탄올 또는 이들의 혼합용매에 용해하고, 상기 고분자 용액에 계면활성제를 첨가한 후 여과하여 박막을 형성하는 단계를 포함하여 제조할 수 있다. 이때, 상기 친전자성 기능기를 가지는 수용성 고분자로는 폴리[9,9-비스(6'-디에탄올아미노)헥실)-플루오렌]이 바람직하며, 상기 계면활성제는 2,4,7,9-테트라메틸-5-데킨-4,7-디올인 것이 바람직하지만, 이에 한정되는 것은 아니다. 또한 상기 수용성 고분자 및 계면활성제가 혼합된 용액을 스핀 코팅 등의 방법으로 2 내지 20nm 코팅하여 열처리하는 것이 좋다. 이때, 상기 전자수송층은 스핀코팅의 방법 외에도 딥코팅, 스크린 프린팅, 잉크젯 프린팅, 그라비아 프린팅, 스프레이 코팅, 닥터블레이드 또는 브러쉬 페인팅 등의 방법을 응용할 수 있으며, 본 발명이 이에 제한되는 것은 아니다.The electron transport layer may be prepared by adding a surfactant to improve the morphology of the electron transport layer. At this time, the electron transport layer may be prepared by dissolving a water-soluble polymer having an electrophilic function in water, ethanol or a mixed solvent thereof, adding a surfactant to the polymer solution, and then filtering to form a thin film have. As the water-soluble polymer having the electrophilic functional group, poly [9,9-bis (6'-diethanolamino) hexyl) -fluorene] is preferable, and the surfactant is 2,4,7,9- Tetramethyl-5-decyne-4,7-diol, but is not limited thereto. The solution mixed with the water-soluble polymer and the surfactant may be coated by 2 to 20 nm by a spin coating method and then heat-treated. At this time, the electron transport layer may be applied by dip coating, screen printing, inkjet printing, gravure printing, spray coating, doctor blade, brush painting or the like in addition to the spin coating method, but the present invention is not limited thereto.
또한 상기 제2 전극은 전자수송층이 도입된 상태에서 열증착기를 이용하여 증착될 수 있다. 이때 사용가능한 전극재료로는 불화리튬/알루미늄, 불화리튬/칼슘/알루미늄, 칼슘/알루미늄, 불화바륨/알루미늄, 불화바륨/바륨/알루미늄, 바륨/알루미늄, 알루미늄, 금, 은, 마스네슘:은 및 리튬:알루미늄 중에서 선택될 수 있으며, 바람직하게는 불화바륨/바륨/알루미늄 구조로 제작된 전극을 사용하는 것이 좋다.
Also, the second electrode may be deposited using a thermal evaporator in a state in which an electron transport layer is introduced. The electrode material that can be used in this case includes lithium fluoride / aluminum, lithium fluoride / calcium / aluminum, calcium / aluminum, barium fluoride / aluminum, barium fluoride / barium / aluminum, barium / aluminum, aluminum, gold, silver, Lithium, and aluminum. Preferably, an electrode made of a barium / barium / aluminum structure is used.
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, and the following examples are merely illustrative of the present invention and are not intended to limit the scope of the invention.
(실시예 1) 화합물 1의 제조(Example 1) Preparation of Compound 1
[a단계] 5-octyl-1,3-di(thiophen-2-yl)-4H-thieno[3,4-c]pyrrole-4,6(5H)-dione의 제조[Step a] Preparation of 5-octyl-1,3-di (thiophen-2-yl) -4H-thieno [3,4-c] pyrrole-4,6
잘 건조시킨 500 mL 삼구 둥근 바닥 플라스크에 1,3-dibromo-5-octyl-4H-thieno[3,4-c]pyrrole-4,6(5H)-dione (10.0 g, 23.63 mmol)과 tributyl(thiophen-2-yl)stannane (21.16 g, 56.71 mmol)을 넣고 toluene 300 mL에 녹였다. 질소가 담긴 풍선을 이용하여, 10 분 동안 질소기류 하를 유지시킨 후 pd(PPh3)2Cl2 (1.65 g, 2.36 mmol)을 넣고, 온도를 100 ℃로 올린 후, 질소기류 하에서 12 시간동안 교반하시켰다. 상기 혼합물을 클로로포름으로 추출하고 유기층을 물로 씻어준 다음 MgSO4로 건조시킨 후, 회전식 증발기를 이용하여 용매를 제거시켰다. 이를 n-Hexane/dichloromethane (4/1)의 혼합 용매를 사용하여 컬럼 크로마토그래피로 분리시켜 노란색 고체화합물을 6.1 g (60%) 을 수득하였다. 5-octyl-4H-thieno [3,4-c] pyrrole-4,6 (5H) -dione (10.0 g, 23.63 mmol) and tributyl thiophen-2-yl) stannane (21.16 g, 56.71 mmol) was dissolved in 300 mL of toluene. Pd (PPh 3 ) 2 Cl 2 (1.65 g, 2.36 mmol) was added to the flask, the temperature was raised to 100 ° C., and the flask was kept under a nitrogen stream for 12 hours Lt; / RTI > The mixture was extracted with chloroform. The organic layer was washed with water, dried over MgSO 4, and then the solvent was removed using a rotary evaporator. This was separated by column chromatography using a mixed solvent of n-hexane / dichloromethane (4/1) to obtain 6.1 g (60%) of yellow solid compound.
1H NMR (300 MHz, CDCl3): δ = 8.00 (s, 2H), 7.45 (s, 2H), 7.15 (t, 2H), 3.68(t, 2H), 1.72 (m, 2H), 1.32 (m, 10H), 0.88 (t, 3H).
1 H NMR (300 MHz, CDCl3 ): δ = 8.00 (s, 2H), 7.45 (s, 2H), 7.15 (t, 2H), 3.68 (t, 2H), 1.72 (m, 2H), 1.32 (m , 10H), 0.88 (t, 3H).
[b단계] 1-(5-bromothiophen-2-yl)-5-octyl-3-(thiophen-2-yl)-4H-thieno[3,4-c]pyrrole-4,6(5H)-dione의 제조[Step b] 1- (5-bromothiophen-2-yl) -5-octyl-3- (thiophen-2-yl) -4H-thieno [3,4- c] pyrrole- Manufacturing
잘 건조시킨 250 mL 삼구 둥근 바닥 플라스크에 5-octyl-1,3-di(thiophen-2-yl)-4H-thieno[3,4-c]pyrrole-4,6(5H)-dione (5.50 g, 12.79 mmol)과 Chloroform 100mL 및 DMF 100 mL 에 녹였다. NBS (2.27 g, 12.79 mmol) 를 Chloroform 50mL 및 DMF 50mL와 같이 녹인 후, -5 ℃로 내린 플라스크 용기에 천천히 적가시켰다. 10 시간 후, 혼합물을 클로로포름으로 추출하고 유기층을 물로 씻어준 다음 MgSO4로 건조시킨 후, 회전식 증발기를 이용하여 용매를 제거시켰다. 이를 n-Hexane/dichloromethane (5/1)의 혼합 용매를 사용하여 컬럼 크로마토그래피로 분리하고, n-Hexane 으로 재결정 후 노란색 고체화합물을 3.44 g (53%)을 수득하였다. A well-dried 250 mL three-neck round bottom flask was charged with 5-octyl-1,3-di (thiophen-2-yl) -4H-thieno [3,4-c] pyrrole-4,6 , 12.79 mmol), 100 mL of chloroform and 100 mL of DMF. NBS (2.27 g, 12.79 mmol) was dissolved in 50 mL of Chloroform and 50 mL of DMF, and then slowly dropped into a flask lowered to -5 ° C. 10 hours later, the mixture was extracted with chloroform and the organic layer was then washed with water, dried over MgSO 4, solvent was removed using a rotary evaporator. This was separated by column chromatography using a mixed solvent of n-hexane / dichloromethane (5/1), and 3.44 g (53%) of yellow solid compound after recrystallization with n-hexane was obtained.
1H NMR (300 MHz, CDCl3): δ = 8.00 (s, 2H), 7.45 (s, 2H), 7.15 (t, 2H), 3.68(t, 2H), 1.72 (m, 2H), 1.32 (m, 10H), 0.88 (t, 3H).
1 H NMR (300 MHz, CDCl3 ): δ = 8.00 (s, 2H), 7.45 (s, 2H), 7.15 (t, 2H), 3.68 (t, 2H), 1.72 (m, 2H), 1.32 (m , 10H), 0.88 (t, 3H).
[A단계] 5,10-Dione-Benzodithieno[3,2-b]thiophene(DTBD)의 제조[Step A] Preparation of 5,10-Dione-Benzodithieno [3,2-b] thiophene (DTBD)
잘 건조시킨 100 mL 이구 둥근 바닥 플라스크에 N,N-dimethylthieno[3,2-b]thiophene-3-carboxamid (3.90 g, 18.46 mmol)을 넣고 THF (40 mL)에 녹였다. 실온에서 n-BuLi (2.5 M in hexane, 8.125 mL, 20.31 mmol)을 천천히 적가하였다. 질소 기류 하에서 30 분 동안 교반한 다음 물을 사용하여 반응을 종결시킨 후 올리브색 침전이 가라앉으면 유리거르개로 거른 다음 과량의 물과 THF로 씻은 후 건조시켜 갈색 고체 화합물 1.4 g (91.9%)을 수득하였다. N, N-dimethylthieno [3,2-b] thiophene-3-carboxamid (3.90 g, 18.46 mmol) was added to a well-dried 100 mL round bottom flask and dissolved in THF (40 mL). N-BuLi (2.5 M in hexane, 8.125 mL, 20.31 mmol) was slowly added dropwise at room temperature. After stirring for 30 minutes under a stream of nitrogen, the reaction was terminated using water. When the olive-colored precipitate had settled down, it was filtered through a glass column, washed with excess water and THF and dried to obtain 1.4 g (91.9%) of a brown solid compound .
EI, MS m/z (%): 332 (100, M+)
EI, MS m / z (%): 332 (100, M < + &
[B단계] DTBDAT 의 제조[Step B] Production of DTBDAT
잘 건조시킨 100 mL 삼구 둥근 바닥 플라스크에 2,3-didecylthiophene (13.6 g, 37.4 mmol)를 넣고 THF (50 ml) 에 녹였다. 온도를 0 ℃로 낮추고 n-BuLi (2.5 M in hexane, 16.5 mL, 42.2 mmol)을 천천히 적가하고, 50 ℃로 올리고 질소 기류 하에서 2 시간 동안 교반한 다음 DTBD (4.155 g, 12.5 mmol) 을 재빠르게 넣어주고 50 ℃로 올리고 질소 기류 하에서 1 시간 동안 교반하고 RT로 온도를 내려주고 SnCl2 H2O in 10% HCl(30ml)을 넣고 1 시간 교반시켰다. 이를 얼음물에 붇고, Ether로 추출하고 유기층을 물로 씻어준 다음 MgSO4로 건조시킨 후 회전식 증발기를 사용하여 용매를 제거시켰다. 이를 n-Hexane 용매를 사용하여 컬럼 크로마토그래피로 분리해서 노란 고체 화합물 4.0 g (31.2%)을 수득하였다.2,3-didecylthiophene (13.6 g, 37.4 mmol) was added to a well-dried 100 mL three-neck round bottom flask and dissolved in THF (50 mL). The temperature was lowered to 0 ° C and n-BuLi (2.5 M in hexane, 16.5 mL, 42.2 mmol) was slowly added dropwise and the temperature was raised to 50 ° C. and stirred for 2 hours under a stream of nitrogen. The DTBD (4.155 g, 12.5 mmol) The mixture was heated to 50 ° C, stirred for 1 hour under a nitrogen stream, cooled to RT and added with SnCl 2 H 2 O in 10% HCl (30 ml) and stirred for 1 hour. The reaction mixture was poured into ice water and extracted with ether. The organic layer was washed with water, dried over MgSO 4, and then evaporated using a rotary evaporator. This was separated by column chromatography using n-hexane solvent to obtain 4.0 g (31.2%) of a yellow solid compound.
1H-NMR (300 MHz, CDCl3): δ 7.47-7.45 (d, 2H), 7.31-7.29 (d, 2H), 7.12 (s, 2H), 2.93-2.70 (m, 8H), 2.17-2.15 (m, 8H), 1.60-1.41 (m, 56H), 0.92-0.89 (m, 12H); 1 H-NMR (300 MHz, CDCl3): δ 7.47-7.45 (d, 2H), 7.31-7.29 (d, 2H), 7.12 (s, 2H), 2.93-2.70 (m, 8H), 2.17-2.15 ( m, 8H), 1.60-1.41 (m, 56H), 0.92-0.89 (m, 12H);
13C NMR (75 MHz, CDCl3): δ 143.8, 142.3, 139.7, 139.6, 134.4, 132.8, 131.4, 130.7, 130.2, 124.7, 120.5, 32.78, 32.72, 31.62, 31.35, 30.50, 30.44, 30.38, 30.24, 30.17, 30.07, 29.08, 28.78, 23.48, 14.65; 13 C NMR (75 MHz, CDCl 3):? 143.8, 142.3, 139.7, 139.6, 134.4, 132.8, 131.4, 130.7, 130.2, 124.7, 120.5, 32.78, 32.72, 31.62, 31.35, 30.50, 30.44, 30.38, 30.24, , 30.07, 29.08, 28.78, 23.48, 14.65;
EI, MS m/z (%): 1027 (100, M+)
EI, MS m / z (%): 1027 (100, M < + &
[C단계] DTBDATTin 의 제조[Step C] Preparation of DTBDATTin
잘 건조시킨 100 mL 삼구 둥근 바닥 플라스크에 DTBDAT (1.0 g, 0.9729 mmol)를 넣고 THF (30 ml) 에 녹였다. 온도를 0 ℃로 낮추고 n-BuLi (2.5 M in hexane, 0.856 mL, 0.2141 mmol)을 천천히 적가하고, 50 ℃로 올리고 질소 기류 하에서 2 시간 동안 교반한 다음 RT로 온도를 내려준다. 그리고 trimethyltin chloride (1 M in THF, 2.14 mL, 2.14 mmol) 을 천천히 적가해주고, RT에서 3 시간동안 교반시켰다. 이를 얼음물에 붓고, Ether로 추출하고 유기층을 물로 씻어준 다음 MgSO4로 건조시킨 후 회전식 증발기를 사용하여 저온에서 용매를 제거하였다. n-Hexane과 IPA (isopropyl alcohol)의 혼합용매를 이용하여 재결정하고, 필터로 걸러서 고체화합물인 DTBDATTin 1.0 g (75%)을 수득하였다.DTBDAT (1.0 g, 0.9729 mmol) was added to a well-dried 100 mL three-neck round bottom flask and dissolved in THF (30 mL). The temperature is lowered to 0 ° C and n-BuLi (2.5 M in hexane, 0.856 mL, 0.2141 mmol) is slowly added dropwise, heated to 50 ° C and stirred for 2 hours under a stream of nitrogen and then cooled to RT. Trimethyltin chloride (1 M in THF, 2.14 mL, 2.14 mmol) was slowly added dropwise and stirred at RT for 3 h. The mixture was poured into ice water and extracted with ether. The organic layer was washed with water, dried over MgSO 4, and then removed at low temperature using a rotary evaporator. Recrystallization was performed using a mixed solvent of n-hexane and IPA (isopropyl alcohol), and the solution was filtered to obtain 1.0 g (75%) of DTBDATTin as a solid compound.
1H-NMR (300 MHz, CDCl3): δ 7.32 (s, 2H), 7.13 (s, 2H), 2.96-2.67 (m, 8H), 1.83-1.73 (m, 8H), 1.49-1.31 (m, 56H), 0.92-0.88 (m, 12H), 0.50-0.31 (m, 18H); 1 H-NMR (300 MHz, CDCl3): δ 7.32 (s, 2H), 7.13 (s, 2H), 2.96-2.67 (m, 8H), 1.83-1.73 (m, 8H), 1.49-1.31 (m, 56H), 0.92-0.88 (m, 12H), 0.50-0.31 (m, 18H);
EI, MS m/z (%): 1353 (100, M+)
EI, MS m / z (%): 1353 (100, M < + &
[D단계] DTBD-TTPD 의 제조[Step D] Preparation of DTBD-TTPD
잘 건조시킨 100 mL 삼구 둥근 바닥 플라스크에 DTBDATTin (0.6 g, 0.44 mmol)과 1-(5-bromothiophen-2-yl)-5-octyl-3-(thiophen-2-yl)-4H-thieno[3,4-c]pyrrole-4,6(5H)-dione (0.49 g, 0.97 mmol)을 넣고 Toluene 18 mL에 녹였다. 질소가 담긴 풍선을 이용하여, 10 분동안 질소기류 하를 유지시켜준다. Pd(PPh3)4 (0.03 g, 0.026 mmol)을 넣고, 온도를 100 ℃로 올린 후, 질소기류 하에서 12 시간동안 교반시켰다. 상기 혼합물을 클로로포름으로 추출하고 유기층을 물로 씻어준 다음 MgSO4로 건조시킨 후, 회전식 증발기를 이용하여 용매를 제거시켰다. 이를 Ethyl acetate, chloroform 순서로 Soxhlet extractor를 이용하여 정제하여 검붉은 고체화합물 0.43 g (51%)을 수득하였다. A well-dried 100 mL three-neck round bottom flask was charged with DTBDATTin (0.6 g, 0.44 mmol) and 4H-thieno [3,4-c] pyrrole-4,6 (5H) -dione (0.49 g, 0.97 mmol) and dissolved in 18 mL of toluene. Using a balloon containing nitrogen, keep it under a stream of nitrogen for 10 minutes. Put Pd (PPh 3) 4 (0.03 g, 0.026 mmol), and then raising the temperature to 100 ℃, and stirred for 12 hours under a nitrogen stream. The mixture was extracted with chloroform. The organic layer was washed with water, dried over MgSO 4, and then the solvent was removed using a rotary evaporator. This was purified by using a Soxhlet extractor in the order of ethyl acetate and chloroform to obtain 0.43 g (51%) of a dark red solid compound.
1H NMR (300 MHz, CDCl3), δ = 7.96 (d, 2H), 7.80 (d, 2H), 7.40 (d, 2H), 7.28 (s, 2H), 7.06(m, 4H), 6.94 (d, 2H), 3.66 (t, 4H), 2.95 (t, 4H), 2.72 (t, 4H), 1.80-1.70 (br, 12H), 1.57-1.29 (br, 76H), 1.07-1.87 (m, 18H).
1 H NMR (300 MHz, CDCl 3), δ = 7.96 (d, 2H), 7.80 (d, 2H), 7.40 (d, 2H), 7.28 (s, 2H), 7.06 (m, 4H), 6.94 ( 2H), 3.66 (t, 4H), 2.95 (t, 4H), 2.72 (t, 4H), 1.80-1.70 (br, 12H), 1.57-1.29 (br, 18H).
[실시예 2] 유기태양전지제작[Example 2] Production of organic solar cell
세척된 투명전극인 ITO가 코팅된 유리기판 위에 PEDOT-PSS(Baytron P TP AI 4083, Bayer AG)를 스핀 코팅하여, 40 nm 두께로 코팅한 후 120 ℃에서 10 분간 어닐링을 하여 용매를 제거하였다. 활성층에 실시예1로부터 얻어진 벤조다이사이에노사이오펜 유도체 (DTBDT-TTPD) 5 mg 을 사용하여 PCBM 유도체(PC71BM) 와 1:2 중량비로 1,2-디클로로벤젠에 20 mg/ml 농도로 혼합한 후 60 ℃에서 12 시간동안 교반시킨 후 0.2 ㎛크기의 폴리테트라플루오로에틸렌 필터로 물질을 필터한 후 PEDOT-PSS 층위에 1000 rpm의 속도로 60초간 스핀 코팅하였다. 그 후에 고진공 (2 X 10-6 torr)에서 0.8 nm 두께로 LiF를 코팅하고 금속 전극으로 알루미늄(Al)을 80 nm 두께로 증착하여 유기태양전지를 제조하였다.PEDOT-PSS (Baytron P TP AI 4083, Bayer AG) was spin-coated on the cleaned transparent ITO-coated glass substrate to a thickness of 40 nm and annealed at 120 ° C for 10 minutes to remove the solvent. 5 mg of the benzodiamine derivative (DTBDT-TTPD) obtained from Example 1 was mixed with the PCBM derivative (PC 71 BM) in a ratio of 1: 2 by weight to the active layer at a concentration of 20 mg / ml in 1,2-dichlorobenzene The mixture was stirred at 60 ° C for 12 hours, filtered through a 0.2 μm polytetrafluoroethylene filter, and spin-coated on the PEDOT-PSS layer at a rate of 1000 rpm for 60 seconds. Thereafter, LiF was coated to a thickness of 0.8 nm at a high vacuum (2 × 10 -6 torr), and aluminum (Al) was deposited to a thickness of 80 nm as a metal electrode to produce an organic solar cell.
상기 방법으로 제조된 유기태양전지의 전류밀도-전압 (J-V) 특성을 Oriel 1000W solar simulator에 의해 100 mW/cm2(AM 1.5G)로써 태양광을 모사한 조명하에서 측정하고, Voc(open circuit voltage), JSC(short-circuit current density), FF(fill factor), 및 에너지 변환 효율(η, overall conversion efficiency)의 광전 파라미터(photovoltaic parameter)를 표 2에 정리 도시하였다.The current density-voltage (JV) characteristics of the organic solar cell fabricated by the above method were measured under the illumination simulating sunlight with 100 mW / cm 2 (AM 1.5G) by Oriel 1000W solar simulator, and Voc Table 2 summarizes the photovoltaic parameters of short-circuit current density (JSC), fill factor (FF), and overall conversion efficiency (η).
상기 실시예1로부터 얻어진 벤조다이사이에노사이오펜 유도체 (DTBDT-TTPD)의 광 흡수영역은 용액상태와 필름상태에서 측정하여 결과를 도 1에 도시하였다. 또한 실시예1로부터 얻어진 벤조다이사이에노사이오펜 유도체 (DTBDT-TTPD)의 전기화학적 특성을 분석하기 위해서 Bu4NClO4(0.1 몰농도)의 용매 하에서 50 mV/s의 조건에서 싸이클로 볼타메트리(cyclic voltammetry)를 이용하여 측정한 결과를 도 2에 도시하였으며, 측정 시 카본 전극을 사용하여 코팅을 통해 전압을 인가하였다. The light absorbing region of the benzodiisocyanate (DTBDT-TTPD) obtained from Example 1 was measured in a solution state and a film state, and the results are shown in Fig. In order to analyze the electrochemical characteristics of the benzodiisocyanate (DTBDT-TTPD) obtained from Example 1, the electrochemical characteristics of cyclodiophene derivative (DTBDT-TTPD) were measured under the condition of Bu 4 NClO 4 (0.1 molar concentration) and 50 mV / cyclic voltammetry) is shown in FIG. 2. The voltage is applied through a coating using a carbon electrode during the measurement.
하기 표 1에 실시예1로부터 얻어진 벤조다이사이에노사이오펜 유도체 (DTBDT-TTPD)의 광학적 및 전기화학적 성질을 기재하였다. 여기서 HOMO값은 도 5에서 측정한 결과값을 이용하여 계산한 값이다. 또한 밴드갭은 필름상태에서 UV흡수파장에서 구하였다.The optical and electrochemical properties of the benzodiascenotriene derivative (DTBDT-TTPD) obtained from Example 1 are shown in Table 1 below. Here, the HOMO value is a value calculated using the result measured in FIG. The bandgap was also obtained at the UV absorption wavelength in the film state.
표 1의 결과에서 보이는 바와 같이, 본 발명에 따른 벤조다이사이에노사이오펜 유도체는 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. 또한, 상기 표 1에 나타낸 바와 같이 상기 유기 반도체 화합물은 낮은 HOMO값을 가지는 것을 알 수 있는데, 이는 기존의 Acceptor보다 상대적으로 전자를 잘 잡아당기기 때문에 낮은 값을 가지는 것으로 설명할 수 있으며, 낮은 HOMO값으로 인해, 높은 개방전압의 형성이 가능할 뿐만 아니라 산화안정성도 높아지게 되어 상용화에 큰 이득이 된다. As shown in the results of Table 1, the benzao dyes among the benzodiazines according to the present invention have broad band gaps and can absorb light of long wavelengths, that is, they can absorb light in a wavelength region similar to sunlight High currents can be produced, resulting in high short circuit currents. In addition, as shown in Table 1, the organic semiconductor compound has a low HOMO value, which can be explained as having a lower value because it attracts electrons relatively more than the conventional acceptor, It is possible not only to form a high open-circuit voltage but also to increase oxidation stability, which is a great advantage in commercialization.
또한 도 5에서는 실시예1로부터 얻어진 벤조다이사이에노사이오펜 유도체 (DTBDT-TTPD)의 에너지 레벨을 도시한 것이다. 이때, 실시예1로부터 얻어진 벤조다이사이에노사이오펜 유도체 (DTBDT-TTPD)의 에너지 레벨은 2.15 eV 의 에너지 밴드갭을 가지며, 낮은 HOMO값을 가지기 때문에 높은 개방전압(Voc) 및 산화안정성을 가질 것으로 예상된다. 또한 LUMO값이 -3.62 eV로 쉽게 전자가 전극으로 이동할 수 있을 것이라 예상할 수 있다.5 also shows the energy level of the benzodiisocyanate derivative (DTBDT-TTPD) obtained from Example 1. FIG. At this time, since the energy level of the benzodiisocyanate (DTBDT-TTPD) obtained from Example 1 has an energy band gap of 2.15 eV and has a low HOMO value, it has high open-circuit voltage (Voc) and oxidation stability It is expected. Also, it can be expected that the LUMO value is -3.62 eV so that electrons can easily move to the electrode.
도 3 에서는 실시예1로부터 얻어진 벤조다이사이에노사이오펜 유도체 (DTBDT-TTPD)에 대한 열적 안정성을 측정하기 위해 DSC를 이용하여 측정한 결과를 도시한 것으로 유리전이온도값이 측정되지 않았으며, 이것으로 본 발명에 따른 유기 반도체 화합물을 비정질의 특성을 가지는 것을 알 수 있었다. FIG. 3 shows the results of measurement using DSC to measure the thermal stability of the benzodiisocyanate derivative (DTBDT-TTPD) obtained from Example 1, in which the glass transition temperature value was not measured. It was found that the organic semiconductor compound according to the present invention had amorphous characteristics.
도 4 에서는 실시예1로부터 얻어진 벤조다이사이에노사이오펜 유도체 (DTBDT-TTPD)의 분해온도를 TGA를 이용하여 측정한 결과를 도시한 것으로, 실시예1(DTBDT-TTPD)의 5 % 분해가 일어나는 온도는 463 ℃ 으로 측정되었다. 이와 같이 높은 온도에서도 분해가 일어나지 않아 본 발명에 따른 유기 반도체 화합물은 열적으로 안정한 화합물인 것을 알 수 있었다.4 shows the results of measurement of the decomposition temperature of the benzodiisocyanate derivative (DTBDT-TTPD) obtained from Example 1 using TGA, which shows that 5% decomposition of Example 1 (DTBDT-TTPD) The temperature was measured at 463 ° C. Since decomposition does not occur even at such a high temperature, it is found that the organic semiconductor compound according to the present invention is a thermally stable compound.
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.The characteristics of organic solar cells can be represented by four characteristics. Short circuit current (Jsc), open circuit voltage (Voc), fill factor (FF), power conversion efficiency : PCE). The correlation between them can be expressed by the following equation (1).
(식1)(Equation 1)
상기 식1에서, 상기 P in 은 유기태양전지에 입사되는 광세기이고, P out 은 광조사하에서 낼 수 있는 최대 전력이고, J sc 는 단락전류이며, V oc 는 개방전압값이며, FF 는 충진율이다. In the formula 1, wherein P in is the maximum power that a light intensity that is incident on the organic solar cell, P out can be under the light irradiation, J sc is the short circuit current, V oc is the open-circuit voltage value, FF is a fill factor to be.
식 1에 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 전자 공여체의 HOMO 값과 LUMO 값에 연관이 있다. 따라서 위와 같은 여러 가지 조건이 충족되었을 때 비로소 고효율의 유기태양전지가 가능해 진다.Equation 1 requires a high short-circuit current and open-circuit voltage to achieve high efficiency. In addition, high-efficiency devices can be realized by having a high packing rate. In order to realize a high short-circuit current, the material should have a high charge mobility. The high open-circuit voltage is related to the HOMO value and the LUMO value of the intramolecular electron donor. Therefore, when the above-mentioned various conditions are satisfied, high-efficiency organic solar cells become possible.
도 6에서는 실시예 2에서 합성된 유기 반도체 화합물을 이용한 유기태양전지 특성을 측정한 결과값을 도시하였다. 또한 해당하는 결과값을 하기 표 2 및 도6에 나타내었다. FIG. 6 shows the results of measuring the characteristics of the organic solar cell using the organic semiconductor compound synthesized in Example 2. FIG. The corresponding results are shown in Table 2 and FIG.
그 결과, 본 발명에 따른 유기 반도체 화합물은 밴드갭이 넓어 장파장의 빛까지 흡수할 수 있어, 보다 많은 전류를 생산함으로써, 높은 단락전류 값을 가지며, 낮은 HOMO값으로 인해, 높은 개방전압의 형성이 가능하므로, 효율이 우수한 유기태양전지로 제작될 수 있음을 확인할 수 있었다. As a result, the organic semiconductor compound according to the present invention has a wide band gap and can absorb light of a long wavelength, thereby producing more current, thereby having a high short-circuit current value, and a low HOMO value, Therefore, it can be confirmed that an organic solar cell having excellent efficiency can be manufactured.
Claims (8)
[화학식 1]
[상기 화학식 1에서,
Z1 내지 Z3는 S, O 또는 Se이고;
R1 및 R2는 각각 독립적으로 수소 또는 (C1-C30)알킬이며;
R3 및 R4는 각각 독립적으로 수소 또는 (C1-C30)알킬,
상기 R1 내지 R4, R11 및 R12 에서의 상기 알킬은 각각 독립적으로 (C1-C20)알킬, (C2-C20)알케닐, (C2-C20)알키닐, (C1-C30)알콕시, (C6~C30)아릴, (C3~C30)헤테로아릴, 아미노, 하이드록시 및 할로겐으로부터 선택되는 하나 이상의 치환기로 더 치환될 수 있다.]A benzodiacyanisophene derivative represented by the following formula (1).
[Chemical Formula 1]
[In the above formula (1)
Z 1 to Z 3 are S, O or Se;
R 1 and R 2 are each independently hydrogen or (C 1 -C 30) alkyl;
R 3 and R 4 are each independently hydrogen or (C 1 -C 30) alkyl,
Wherein R 1 to R 4, R 11 and the alkyl in R 12 are each independently (C1-C20) alkyl, (C2-C20) alkenyl, (C2-C20) alkynyl, (C1-C30) alkoxy, (C6-C30) aryl, (C3-C30) heteroaryl, amino, hydroxy and halogen.
하기 화학식 2로 표시되는 벤조다이사이에노사이오펜 유도체.
[화학식 2]
[상기 화학식 2에서,
R1 및 R2는 각각 독립적으로 수소 또는 (C1-C30)알킬이며;
R3 및 R4는 각각 독립적으로 수소 또는 (C1-C30)알킬,
상기 R1 내지 R4, R11 및 R12 에서의 상기 알킬은 각각 독립적으로 (C1-C20)알킬, (C2-C20)알케닐, (C2-C20)알키닐, (C1-C30)알콕시, (C6~C30)아릴, (C3~C30)헤테로아릴, 아미노, 하이드록시 및 할로겐으로부터 선택되는 하나 이상의 치환기로 더 치환될 수 있다.]The method according to claim 1,
A benzodiascene novolak derivative represented by the following formula (2).
(2)
[In the formula (2)
R 1 and R 2 are each independently hydrogen or (C 1 -C 30) alkyl;
R 3 and R 4 are each independently hydrogen or (C 1 -C 30) alkyl,
Wherein R 1 to R 4, R 11 and the alkyl in R 12 are each independently (C1-C20) alkyl, (C2-C20) alkenyl, (C2-C20) alkynyl, (C1-C30) alkoxy, (C6-C30) aryl, (C3-C30) heteroaryl, amino, hydroxy and halogen.
상기 R1 및 R2는 각각 독립적으로 (C1-C20)알킬이며;
R3 및 R4는 각각 독립적으로 수소 또는 (C1-C30)알킬,
R11 및 R12 는 각각 독립적으로 수소 또는 (C1-C20) 알킬; 인 벤조다이사이에노사이오펜 유도체.
3. The method of claim 2,
Wherein R 1 and R 2 are each independently (C 1 -C 20) alkyl;
R 3 and R 4 are each independently hydrogen or (C 1 -C 30) alkyl,
R 11 and R 12 are each independently hydrogen or (C 1 -C 20) alkyl; Benzodiisocyanate derivatives.
하기 화학식 3으로 표시되는 벤조다이사이에노사이오펜 유도체.
[화학식 3]
[상기 화학식 3에서,
상기 R1, R2 및 R21 내지 R24는 각각 독립적으로 (C5-C10)알킬이다.]The method of claim 3,
A benzodiascene novolak derivative represented by the following formula (3).
(3)
[Formula 3]
Wherein R 1, R 2, and R < 21 & Each R < 24 > is independently (C5-C10) alkyl]
하기 화합물에서 선택되는 것을 특징으로 하는 벤조다이사이에노사이오펜 유도체.
/ RTI > is selected from the following compounds.
하기 화학식 5로 표시되는 화합물과 화학식 6로 표시되는 화합물을 반응시켜 하기 화학식 7으로 표시되는 화합물을 제조하는 단계;
하기 화학식 7으로 표시되는 화합물과 하기 화학식 8로 표시되는 화합물을 반응시켜 화합물 9로 표시되는 화합물을 제조하는 단계; 및
하기 화학식 9로 표시되는 화합물과 하기 화학식 10로 표시되는 화합물을 반응시켜 화합물 3으로 표시되는 화합물을 제조하는 단계;를 포함하는 벤조다이사이에노사이오펜 유도체의 제조방법.
[화학식 4]
[화학식 5]
[화학식 6]
[화학식 7]
[화학식 8]
[화학식 9]
[화학식 10]
[화학식 3]
[상기 화학식 3 내지 화학식 10에서,
T는 -Sn(R41)(R42)(R43)이고;
R1, R2, R21 내지 R24, R31, R32 및 R41 내지 R43은 각각 독립적으로 (C5-C10)알킬이며;
X1 및 X2는 할로겐이다.]Reacting a compound represented by the following formula (4) with n-butyl lithium (n-BuLi) to prepare a compound represented by the following formula (5);
Reacting a compound represented by the following formula (5) with a compound represented by the following formula (6) to prepare a compound represented by the following formula (7);
Reacting a compound represented by the formula (7) and a compound represented by the following formula (8) to prepare a compound represented by the formula (9); And
Reacting a compound represented by the following formula (9) with a compound represented by the following formula (10) to produce a compound represented by the formula (3).
[Chemical Formula 4]
[Chemical Formula 5]
[Chemical Formula 6]
(7)
[Chemical Formula 8]
[Chemical Formula 9]
[Chemical formula 10]
(3)
[In the above Chemical Formulas 3 to 10,
T is -Sn (R 41) (R 42 ) (R 43) a;
R 1, R 2, R 21 to R 24 , R 31, R 32 and R 41 to R 43 are each independently (C 5 -C 10) alkyl;
X 1 and X 2 are halogen.]
상기 유기전자소자는 유기태양전지인 유기전자소자.8. The method of claim 7,
Wherein the organic electronic device is an organic solar cell.
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| KR20140047812A (en) * | 2012-10-15 | 2014-04-23 | 경상대학교산학협력단 | New organic semiconductor compound and a method for manufacturing the same |
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| KR20140047812A (en) * | 2012-10-15 | 2014-04-23 | 경상대학교산학협력단 | New organic semiconductor compound and a method for manufacturing the same |
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