KR101484007B1 - new organic semiconductor compound and a method for manufacturing the same - Google Patents
new organic semiconductor compound and a method for manufacturing the same Download PDFInfo
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- KR101484007B1 KR101484007B1 KR20120113974A KR20120113974A KR101484007B1 KR 101484007 B1 KR101484007 B1 KR 101484007B1 KR 20120113974 A KR20120113974 A KR 20120113974A KR 20120113974 A KR20120113974 A KR 20120113974A KR 101484007 B1 KR101484007 B1 KR 101484007B1
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- KR
- South Korea
- Prior art keywords
- compound
- organic semiconductor
- formula
- alkyl
- organic
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 97
- 239000004065 semiconductor Substances 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims description 21
- 238000004519 manufacturing process Methods 0.000 title abstract description 13
- 239000010409 thin film Substances 0.000 claims abstract description 21
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 32
- 239000000126 substance Substances 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 18
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 13
- 150000002431 hydrogen Chemical class 0.000 claims description 12
- -1 R 29 Chemical compound 0.000 claims description 11
- 229910052736 halogen Inorganic materials 0.000 claims description 11
- 150000002367 halogens Chemical class 0.000 claims description 11
- 125000003545 alkoxy group Chemical group 0.000 claims description 10
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012776 electronic material Substances 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 45
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 23
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 21
- 239000007787 solid Substances 0.000 description 21
- 239000010410 layer Substances 0.000 description 20
- 239000000203 mixture Substances 0.000 description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 125000001072 heteroaryl group Chemical group 0.000 description 17
- 239000002904 solvent Substances 0.000 description 17
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 125000001424 substituent group Chemical group 0.000 description 13
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 12
- 239000003153 chemical reaction reagent Substances 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 11
- 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 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 125000006736 (C6-C20) aryl group Chemical group 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 125000004414 alkyl thio group Chemical group 0.000 description 7
- 125000005843 halogen group Chemical group 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- 229910052711 selenium Inorganic materials 0.000 description 7
- 125000006649 (C2-C20) alkynyl group Chemical group 0.000 description 6
- 125000006651 (C3-C20) cycloalkyl group Chemical group 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 125000003342 alkenyl group Chemical group 0.000 description 6
- 229940125904 compound 1 Drugs 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 229930192474 thiophene Natural products 0.000 description 6
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 6
- TUCRZHGAIRVWTI-UHFFFAOYSA-N 2-bromothiophene Chemical compound BrC1=CC=CS1 TUCRZHGAIRVWTI-UHFFFAOYSA-N 0.000 description 5
- 238000006619 Stille reaction Methods 0.000 description 5
- 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 5
- 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 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 229940125782 compound 2 Drugs 0.000 description 5
- 229940126214 compound 3 Drugs 0.000 description 5
- 229940125898 compound 5 Drugs 0.000 description 5
- 125000000753 cycloalkyl group Chemical group 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 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 5
- 238000002211 ultraviolet spectrum Methods 0.000 description 5
- 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 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- ZTYYDUBWJTUMHW-UHFFFAOYSA-N furo[3,2-b]furan Chemical group O1C=CC2=C1C=CO2 ZTYYDUBWJTUMHW-UHFFFAOYSA-N 0.000 description 4
- 150000002642 lithium compounds Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000002900 organolithium compounds Chemical class 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- VJYJJHQEVLEOFL-UHFFFAOYSA-N thieno[3,2-b]thiophene Chemical group S1C=CC2=C1C=CS2 VJYJJHQEVLEOFL-UHFFFAOYSA-N 0.000 description 4
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229920000144 PEDOT:PSS Polymers 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- NSLJAYQJTGJPBW-UHFFFAOYSA-N S1C=CC2=C1C=CS2.C2=CC=CC=C2 Chemical compound S1C=CC2=C1C=CS2.C2=CC=CC=C2 NSLJAYQJTGJPBW-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 235000019439 ethyl acetate Nutrition 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 125000006835 (C6-C20) arylene group Chemical group 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- YFWCQBIKGWTZQQ-UHFFFAOYSA-N 6-bromothieno[3,2-b]thiophene Chemical compound C1=CSC2=C1SC=C2Br YFWCQBIKGWTZQQ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-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
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 125000005549 heteroarylene group Chemical group 0.000 description 2
- 125000000592 heterocycloalkyl group Chemical group 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 2
- 229910052609 olivine Inorganic materials 0.000 description 2
- 239000010450 olivine Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- DKLWRIQKXIBVIS-UHFFFAOYSA-N 1,1-diiodooctane Chemical compound CCCCCCCC(I)I DKLWRIQKXIBVIS-UHFFFAOYSA-N 0.000 description 1
- GSGMEQUXTCYOAU-UHFFFAOYSA-N 1,3-dibromo-5-octylthieno[3,4-c]pyrrole-4,6-dione Chemical compound S1C(Br)=C2C(=O)N(CCCCCCCC)C(=O)C2=C1Br GSGMEQUXTCYOAU-UHFFFAOYSA-N 0.000 description 1
- UHHOTOYDCIDUJQ-UHFFFAOYSA-N 1-(4,6-dibromothieno[2,3-c]thiophen-2-yl)-2-ethylhexan-1-one Chemical compound S1C(Br)=C2SC(C(=O)C(CC)CCCC)=CC2=C1Br UHHOTOYDCIDUJQ-UHFFFAOYSA-N 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-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
- MNCFWGMXRWYWMN-UHFFFAOYSA-N 2-ethylhexyl 4,6-dibromothieno[2,3-c]thiophene-2-carboxylate Chemical compound S1C(Br)=C2SC(C(=O)OCC(CC)CCCC)=CC2=C1Br MNCFWGMXRWYWMN-UHFFFAOYSA-N 0.000 description 1
- SLDBNSTUPSSFMW-UHFFFAOYSA-N 4,7-bis(5-bromo-4-octan-3-ylthiophen-2-yl)-2,1,3-benzothiadiazole Chemical compound S1C(Br)=C(C(CC)CCCCC)C=C1C(C1=NSN=C11)=CC=C1C1=CC(C(CC)CCCCC)=C(Br)S1 SLDBNSTUPSSFMW-UHFFFAOYSA-N 0.000 description 1
- FEOWHLLJXAECMU-UHFFFAOYSA-N 4,7-dibromo-2,1,3-benzothiadiazole Chemical compound BrC1=CC=C(Br)C2=NSN=C12 FEOWHLLJXAECMU-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- YIIMEMSDCNDGTB-UHFFFAOYSA-N Dimethylcarbamoyl chloride Chemical compound CN(C)C(Cl)=O YIIMEMSDCNDGTB-UHFFFAOYSA-N 0.000 description 1
- PHXQIAWFIIMOKG-UHFFFAOYSA-N NClO Chemical compound NClO PHXQIAWFIIMOKG-UHFFFAOYSA-N 0.000 description 1
- PEXNSYNUJUGNRB-UHFFFAOYSA-N O1C=CC2=C1C=CO2.C2=CC=CC=C2 Chemical compound O1C=CC2=C1C=CO2.C2=CC=CC=C2 PEXNSYNUJUGNRB-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- LRFNBIOKAMMZCS-UHFFFAOYSA-N S1C=CC2=C1C1=C(S2)SC=C1.C1=CC=CC=C1 Chemical compound S1C=CC2=C1C1=C(S2)SC=C1.C1=CC=CC=C1 LRFNBIOKAMMZCS-UHFFFAOYSA-N 0.000 description 1
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000008859 change Effects 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
- NWSBNVVOFKKFNV-UHFFFAOYSA-N chloroform;oxolane Chemical compound ClC(Cl)Cl.C1CCOC1 NWSBNVVOFKKFNV-UHFFFAOYSA-N 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- YRUMDWGUXBZEPE-UHFFFAOYSA-N cyclohexane Chemical compound C1CCCCC1.C1CCCCC1 YRUMDWGUXBZEPE-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Natural products CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
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- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000006413 ring segment Chemical group 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- DAUYIKBTMNZABP-UHFFFAOYSA-N thiophene-3-carboxamide Chemical compound NC(=O)C=1C=CSC=1 DAUYIKBTMNZABP-UHFFFAOYSA-N 0.000 description 1
- ZAPAMMDQEWCVAM-UHFFFAOYSA-N tin;hydrate Chemical class O.[Sn] ZAPAMMDQEWCVAM-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Images
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
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- H—ELECTRICITY
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Abstract
본 발명은 유기 전자재료로 사용가능한 유기 반도체 화합물, 이의 제조방법 및 이를 함유하는 광활성층과 이러한 광활성층을 함유하는 유기박막 태양전지를 제공하는 것으로, 본 발명에 따른 유기 반도체 화합물을 함유하는 광활성층은 용액공정이 가능하며, 이러한 광활성층을 함유하는 유기박막 태양전지는 높은 효율을 가진다.The present invention provides an organic semiconductor compound that can be used as an organic electronic material, a method for producing the same, and a photoactive layer containing the photoactive layer and an organic thin film solar cell containing the photoactive layer. The organic thin film solar cell containing such a photoactive layer has high efficiency.
Description
본 발명은 신규한 유기 반도체 화합물, 이의 제조방법 및 이를 함유하는 광활성층과 유기박막 태양전지에 관한 것이다.The present invention relates to a novel organic semiconductor compound, a method for producing the same, and a photoactive layer and an organic thin film solar cell containing the same.
석유자원 고갈의 위기감, 국제적인 기후변화 협약 발효, 신흥개발도상국들의 경제성장에 따른 폭발적인 에너지 수요 등으로 인해 기존 화석 에너지와는 다른 청정 무제한의 에너지가 요구되고 있으며, 이에 따라 국가적인 차원에서 신재생에너지의 기술개발이 활발하게 진행되고 있다. Due to the crisis of depletion of petroleum resources, the enactment of the international climate change agreement, and the explosive energy demand due to the economic growth of emerging developing countries, clean and unlimited energy is required which is different from the existing fossil energy. Technology is being actively developed.
이러한 신재생에너지 중에서 태양광을 전기에너지로 변환하는 광전변환소자인 태양전지는 다른 에너지원과는 달리 무한하고 환경 친화적이므로 시간이 갈수록 그 중요성이 더해가고 있다.Among these renewable energies, solar cells, which are photoelectric conversion devices that convert sunlight into electrical energy, are infinite and environmentally friendly, unlike other energy sources, and their importance is increasing with time.
기존의 태양전지는 광흡수층이 단결정 또는 다결정 실리콘으로 형성된 이른바 단결정 또는 다결정 실리콘 태양전지가 많이 사용되어 왔으나, 상기 실리콘 태양전지는 실리콘의 높은 생산단가와 가공의 어려움으로 제조비용이 높고 플렉서블 기판에는 적용할 수 없는 등의 문제점이 있다.Conventionally, monocrystalline or polycrystalline silicon solar cells, in which a light absorbing layer is formed of a single crystal or polycrystalline silicon, have been widely used. However, the silicon solar cell has high manufacturing cost due to high production cost of silicon and difficult processing, There is a problem that it can not be performed.
따라서 상기와 같은 실리콘 태양전지의 문제점을 보완하기 위해 간단한 공정으로 저비용화와 대면적화를 동시에 만족할 수 있는 유기 태양전지에 관한 연구가 활발하게 진행되고 있다.Therefore, in order to overcome the problems of the silicon solar cell as described above, studies on an organic solar cell that can satisfy both a low cost and a large size at the same time by a simple process have been actively conducted.
유기태양전지는 유리기판을 비롯하여 플라스틱 등 거의 모든 종류의 기판을 사용할 수 있을 뿐만아니라, 기판형태에 제한없이 곡면, 구면 등 다양한 형태로 구부리거나 접을 수 있어 휴대가 용이하여 최근 요구되는 박막화, 소형화, 플렉시블화에 적합하다. Organic solar cells can be used for almost all kinds of substrates such as glass substrates and plastics and can be folded or folded into various shapes such as curved surfaces and spherical shapes without limitation in the substrate type, It is suitable for flexible.
즉, 유기태양전지는 사람의 옷뿐만 아니라 가방 등에 부착하거나 휴대용 전지전자 제품에 부착하여 사용할 수 있으며, 고분자를 광활성층으로 채용한 유기태양전지박막은 빛에 대한 투명도가 높아서 건물의 유리 창 또는 자동차의 유리창 등에 부착하여 건물 내 외관 디자인용으로도 동시에 활용할 수 있어 응용범위가 매우 넓을 것으로 예상되고 있다. That is, the organic solar cell can be attached not only to human clothes, but also to a bag or the like, or attached to a portable battery electronic product. An organic solar cell thin film adopting a polymer as a photoactive layer has high transparency to light, It is expected that the application range will be very wide because it can be used simultaneously for the exterior design of the building.
그러나 유기태양전지의 상용화를 위해서는 유기태양전지의 가장 중요한 요소인 광활성층의 유기 화합물이 인쇄, 코팅등의 간단한 공정이 가능하도록한 용액공정에 적합하도록 용매에 대한 용해도가 높아야하며, 전하이동도가 높아 태양전지의 고효율화가 뒤따라야한다.However, in order to commercialize organic solar cells, the organic compound of the photoactive layer, which is the most important factor of the organic solar cell, should be solved to a solvent suitable for a solution process that enables simple processes such as printing and coating, High efficiency of solar cells should follow.
따라서, 높은 용해도와 우수한 전기특성을 가지는 유기태양전지의 광활성층용 재료에 대한 연구가 지속적으로 요구되고 있는 실정이다. Therefore, there is a continuing need for research on a material for a photoactive layer of an organic solar cell having high solubility and excellent electric characteristics.
본 발명은 유기 전자재료 특히, 유기태양전지의 박막에 사용될 수 있는 유기 반도체 화합물을 제공한다.The present invention provides an organic semiconductor material which can be used for a thin film of an organic electronic material, in particular, an organic solar cell.
또한 본 발명은 본 발명의 유기 반도체 화합물의 신규한 제조방법을 제공한다.The present invention also provides a novel process for preparing an organic semiconductor compound of the present invention.
또한 본 발명은 본 발명의 유기 반도체 화합물을 함유하는 광활성층과 유기박막 태양전지를 제공한다.The present invention also provides a photoactive layer containing an organic semiconductor compound of the present invention and an organic thin film solar cell.
본 발명은 용매에 대한 용해도가 높아 용액공정에 적용가능하며, 전자밀도가 높아 고효율을 가질 수 있는 유기 전자재료인 유기 반도체 화합물을 제공한다.The present invention provides an organic semiconductor compound which can be applied to a solution process because of its high solubility in a solvent, and which has high electron density and can have high efficiency.
본 발명의 유기 반도체 화합물은 하기 화학식 1로 표시된다.The organic semiconductor compound of the present invention is represented by the following general formula (1).
[화학식 1][Chemical Formula 1]
(상기 화학식 1에서,(In the
A는 (C6-C20)아릴렌 또는 (C3-C20)헤테로아릴렌이며,A is (C6-C20) arylene or (C3-C20) heteroarylene,
Z는 S, O 또는 Se이고; Z is S, O or Se;
R1 및 R2는 서로 독립적으로 (C1-C20)알킬기, (C1-C20)알킬티오기, C6-C20아르(C1-C20)알킬기 또는 (C3-C20)헤테로아릴이며, 상기 알킬, 알킬티오, 아르알킬 및 헤테로아릴은 (C1-C20)알킬, (C2-C20)알케닐, (C2-C20)알키닐, (C1-C20)알콕시, 아미노기, 하이드록시기, 할로겐기, 사이아노기, 나이트로기, 트리플루오로메틸기 및 실릴기로 선택되는 하나 이상의 치환기로 더 치환될 수 있으며;R 1 and R 2 are independently selected from (C1-C20) alkyl, (C1-C20) alkylthio, C 6 -C 20 ahreu (C1-C20) alkyl or (C3-C20) heteroaryl, and each other, said alkyl, Alkylthio, aralkyl and heteroaryl are optionally substituted with one or more substituents selected from the group consisting of (C1-C20) alkyl, (C2-C20) alkenyl, (C2- C20) alkynyl, A nitro group, a trifluoromethyl group, and a silyl group;
R11 또는 R12는 서로 독립적으로 수소, 할로겐, (C1-C20)알킬, (C6-C20)아릴, (C3-C20)헤테로아릴, (C3-C20)시클로알킬, 5원 내지 7원의 헤테로시클로알킬, 시아노, 나이트로 또는 하이드록시이며;R 11 or R 12 independently from each other are hydrogen, halogen, (C 1 -C 20) alkyl, (C 6 -C 20) aryl, (C 3 -C 20) heteroaryl, (C 3 -C 20) cycloalkyl, Cycloalkyl, cyano, nitro or hydroxy;
n는 1 내지 500의 정수이다.)and n is an integer of 1 to 500.)
본 발명의 상기 화학식 1로 표시되는 유기 반도체 화합물은 벤젠고리를 중심으로 양쪽에 티에노티오펜고리, 퓨로퓨란고리 또는 셀레노페노셀레노펜고리가 융합되어 있는 구조, 즉, 벤젠-티에노티오펜 융합고리, 벤젠-퓨로퓨란 융합고리 또는 벤젠-셀레노페노셀레노펜 융합고리를 가져 높은 전자밀도를 가지며, 중심 벤젠고리의 1, 4번위치에 치환기를 가지므로 용매에 대한 높은 용해도를 가진다.The organic semiconductor compound represented by
따라서 본 발명의 유기 반도체 화합물은 벤젠고리의 1, 4번위치에 치환기를 가지고 2, 3번위치와 5,6번위치에 티에노티오펜고리, 퓨로퓨란고리 또는 셀레노페노셀레노펜고리가 융합되어 있는 구조를 포함하고 있어, 이러한 벤젠-티에노티오펜 융합고리, 벤젠-퓨로퓨란 융합고리 또는 벤젠-셀레노페노셀레노펜 융합고리를 가지는 고분자를 포함하여 제조되는 광전자 소자 특히, 유기박막 태양전지의 용액화 공정을 가능하게 하는 동시에 고효율화를 이룰 수 있다. Therefore, the organic semiconductor compound of the present invention has a substituent at
본 발명에 기재된 「알킬」, 「알콕시」 및 그 외 「알킬」부분을 포함하는 치환체는 직쇄 또는 분쇄 형태를 모두 포함한다. 또한 본 발명에 기재된 「아릴」은 하나의 수소 제거에 의해서 방향족 탄화수소로부터 유도된 유기 라디칼로, 각 고리에 적절하게는 4 내지 7개, 바람직하게는 5 또는 6개의 고리원자를 포함하는 단일 또는 융합고리계를 포함하며, 다수개의 아릴이 단일결합으로 연결되어 있는 형태까지 포함한다. 구체적인 예로 페닐, 나프틸, 비페닐, 안트릴, 인데닐(indenyl), 플루오레닐 등을 포함하지만, 이에 한정되지 않는다. 본 발명에 기재된 「헤테로아릴」은 방향족 고리 골격 원자로서 B, N, O, S, P(=O), Si 및 P로부터 선택되는 1 내지 4개의 헤테로원자를 포함하고, 나머지 방향족 고리 골격 원자가 탄소인 아릴 그룹을 의미하는 것으로, 5 내지 6원 단환 헤테로아릴, 및 하나 이상의 벤젠환과 축합된 다환식 헤테로아릴이며, 부분적으로 포화될 수도 있다. 또한, 본 발명에서의 헤테로아릴은 하나 이상의 헤테로아릴이 단일결합으로 연결된 형태도 포함한다.The substituents comprising " alkyl ", " alkoxy " and other " alkyl " moieties described in this invention encompass both linear and branched forms. The term " aryl " in the present invention means an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen, and may be a single or fused ring containing 4 to 7, preferably 5 or 6 ring atoms, A ring system, and a form in which a plurality of aryls are connected by a single bond. Specific examples include, but are not limited to, phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, and the like. "Heteroaryl" in the present invention includes 1 to 4 heteroatoms selected from B, N, O, S, P (= O), Si and P as aromatic ring skeletal atoms and the remaining aromatic ring skeletal atoms are carbon Means a 5 to 6 membered monocyclic heteroaryl and a polycyclic heteroaryl condensed with at least one benzene ring and may be partially saturated. The heteroaryl in the present invention also includes a form in which one or more heteroaryl is connected to a single bond.
본 발명의 상기 화학식 1에서 A는 이 분야에서 통상적으로 사용되는 전자 받게 화합물이라면 모두 가능하나, 바람직하게는 하기 구조에서 선택되는 것일 수 있다. In formula (1) of the present invention, A may be any electron accepting compound commonly used in the art, but may be selected from the following structures.
(상기 식에서,(Wherein,
Z는 S, O 또는 Se이며,Z is S, O or Se,
R21 내지 R37은 서로 독립적으로, 수소, 할로겐, (C1-C20)알킬기, (C1-C20)알콕시, (C1-C20)알콕시카보닐, (C6-C20)아르(C1-C20)알킬이며;R 21 to R 37 are independently of each other, hydrogen, halogen, (C1-C20) alkyl, (C1-C20) alkoxy, (C1-C20) alkoxycarbonyl, (C6-C20) aralkyl (C1-C20) alkyl ;
R21 내지 R37의 알킬기, 알콕시, 알콕시카보닐 및 아르알킬은 (C1-C20)알킬, (C2-C20)알케닐, (C2-C20)알키닐, (C1-C20)알콕시, 아미노기, 하이드록시기, 할로겐기, 사이아노기, 나이트로기, 트리플루오로메틸기 및 실릴기로 선택되는 하나 이상의 치환기로 더 치환될 수 있으며;The alkyl group, alkoxy, alkoxycarbonyl and aralkyl of R 21 to R 37 are selected from the group consisting of (C 1 -C 20) alkyl, (C 2 -C 20) alkenyl, (C 2 -C 20) alkynyl, A halogen atom, a cyano group, a nitro group, a trifluoromethyl group, and a silyl group;
R41 내지 R44는 수소 또는 (C1-C20)알킬기이며;R 41 to R 44 are hydrogen or a (C 1 -C 20) alkyl group;
o는 1 내지 2의 정수이다.)and o is an integer of 1 to 2.)
본 발명의 유기 반도체 화합물을 나타내는 상기 화학식 1은 하기 화학식 2 내지 하기 화학식 5에서 선택되는 어느 하나로 표시될 수 있다. The organic semiconductor compound represented by
[화학식 2](2)
[화학식 3](3)
[화학식 4][Chemical Formula 4]
[화학식 5][Chemical Formula 5]
(상기 화학식 2 내지 5에서,(In the above formulas 2 to 5,
Z는 S, O 또는 Se이고;Z is S, O or Se;
R3 및 R4는 서로 독립적으로 (C3-C20)헤테로아릴이며, 상기 헤테로아릴은 (C1-C20)알킬, (C2-C20)알케닐, (C2-C20)알키닐, (C1-C20)알콕시, 아미노기, 하이드록시기, 할로겐기, 사이아노기, 나이트로기, 트리플루오로메틸기 및 실릴기로 선택되는 하나 이상의 치환기로 더 치환될 수 있으며;R 3 and R 4 are independently (C3-C20), and heteroaryl each other, wherein the heteroaryl is (C1-C20) alkyl, (C2-C20) alkenyl, (C2-C20) alkynyl, (C1-C20) Which may further be substituted with at least one substituent selected from the group consisting of a halogen atom, an alkoxy group, an amino group, a hydroxyl group, a halogen group, a cyano group, a nitro group, a trifluoromethyl group and a silyl group;
R11 또는 R12는 서로 독립적으로 수소, 할로겐, (C1-C20)알킬, (C6-C20)아릴, (C3-C20)헤테로아릴, (C3-C20)시클로알킬, 5원 내지 7원의 헤테로시클로알킬, 시아노, 나이트로 또는 하이드록시이며;R 11 or R 12 independently from each other are hydrogen, halogen, (C 1 -C 20) alkyl, (C 6 -C 20) aryl, (C 3 -C 20) heteroaryl, (C 3 -C 20) cycloalkyl, Cycloalkyl, cyano, nitro or hydroxy;
R21, R22, R29, R30, R33 및 R34은 서로 독립적으로, 수소, 할로겐, (C1-C20)알킬기, (C1-C20)알콕시,(C6-C20)아르(C1-C20)알킬이며; R 21, R 22, R 29 ,
R41은 수소 또는 (C1-C20)알킬기이며;R 41 is hydrogen or a (C 1 -C 20) alkyl group;
n는 1 내지 500의 정수이다.)and n is an integer of 1 to 500.)
바람직하게 높은 용해도와 높은 전하이동도를 얻기위한 측면에서 상기 화학식 2는 하기 화학식 6으로, 상기 화학식 3은 하기 화학식 7로, 상기 화학식 5는 하기 화학식 8로, 상기 화학식 6은 하기화학식 9로 표시될 수 있다.In order to obtain high solubility and high charge mobility, the compound of Formula 2 is represented by Formula 6, Formula 3 is represented by Formula 7, Formula 5 is represented by Formula 8, and Formula 6 is represented by Formula 9 .
[화학식 6][Chemical Formula 6]
[화학식 7](7)
[화학식 8][Chemical Formula 8]
[화학식 9][Chemical Formula 9]
(상기 화학식 6 내지 9에서,(In the
R5, R6, R11, R12는 서로 독립적으로 수소, 할로겐, (C1-C20)알킬, (C1-C20)알콕시, 하이드록시, 사아노기 또는 나이트로이며;R 5 , R 6 , R 11 and R 12 are (C1-C20) alkyl, (C1-C20) alkoxy, hydroxy, cyano or nitro;
R21, R22, R29, R30, R33 및 R34은 서로 독립적으로, 수소, 할로겐, (C1-C20)알킬기, (C1-C20)알콕시 또는 (C6-C20)아르(C1-C20)알킬이며; R 21, R 22, R 29 ,
R41은 수소 또는 (C1-C20)알킬기이며;R 41 is hydrogen or a (C 1 -C 20) alkyl group;
p 또는 q는 1 내지 3의 정수이며;p or q is an integer of 1 to 3;
n는 1 내지 500의 정수이다.)and n is an integer of 1 to 500.)
또한 본 발명은 상기 화학식 1로 표시되는 유기 반도체 화합물의 신규한 제조방법을 제공하는 것으로, 상기 화학식 1은 하기 화학식 10의 화합물과 하기 화학식 11의 화합물을 반응시켜 제조된다.The present invention also provides a novel process for preparing an organic semiconductor compound represented by Chemical Formula 1, wherein the
[화학식 10][Chemical formula 10]
[화학식 11](11)
X1-A-X2 X 1 -AX 2
(상기 화학식 1, 10 및 11에서,(In the formulas (1), (10) and (11)
A는 (C6-C20)아릴렌 또는 (C3-C20)헤테로아릴렌이며;A is (C6-C20) arylene or (C3-C20) heteroarylene;
X1 또는 X2는 할라이드이며;X 1 or X 2 is halide;
T는 Sn(R51)(R52)(R53)이며, R51 내지 R53는 (C1-C10)알킬이며;T is Sn ( R51 ) ( R52 ) ( R53 ), R51 To R 53 is (C1-C10) alkyl;
Z는 S, O 또는 Se이고; Z is S, O or Se;
R1 및 R2는 서로 독립적으로 (C1-C20)알킬기, (C1-C20)알킬티오기, (C6-C20)아르(C1-C20)알킬기 또는 (C3-C20)헤테로아릴이며, 상기 알킬, 알킬티오, 아르알킬 및 헤테로아릴은 (C1-C20)알킬, (C2-C20)알케닐, (C2-C20)알키닐, (C1-C20)알콕시, 아미노기, 하이드록시기, 할로겐기, 사이아노기, 나이트로기, 트리플루오로메틸기 및 실릴기로 선택되는 하나 이상의 치환기로 더 치환될 수 있으며;R 1 and R 2 are independently of each other a (C 1 -C 20) alkyl group, a (C 1 -C 20) alkylthio group, a (C 6 -C 20) aryl (C 1 -C 20) alkyl group or (C 3 -C 20) Alkylthio, aralkyl and heteroaryl are optionally substituted with one or more substituents selected from the group consisting of (C1-C20) alkyl, (C2-C20) alkenyl, (C2- C20) alkynyl, A nitro group, a trifluoromethyl group, and a silyl group;
R11 또는 R12는 서로 독립적으로 수소, 할로겐, (C1-C20)알킬, (C6-C20)아릴, (C3-C20)헤테로아릴, (C3-C20)시클로알킬, 5원 내지 7원의 헤테로시클로알킬, 시아노, 나이트로 또는 하이드록시이며;R 11 or R 12 independently from each other are hydrogen, halogen, (C 1 -C 20) alkyl, (C 6 -C 20) aryl, (C 3 -C 20) heteroaryl, (C 3 -C 20) cycloalkyl, Cycloalkyl, cyano, nitro or hydroxy;
n는 1 내지 500의 정수이다.)and n is an integer of 1 to 500.)
본 발명의 일 실시예에 따른 상기 화학식 10은 하기 화학식 12의 화합물과 하기 화학식 13의 화합물을 반응시켜 제조될 수 있다.The formula (10) according to an embodiment of the present invention may be prepared by reacting a compound of the following formula (12) with a compound of the following formula (13).
[화학식 12][Chemical Formula 12]
[화학식 13][Chemical Formula 13]
Sn(R51)(R52)(R53)(X3)Sn (R 51 ) (R 52 ) (R 53 ) (X 3 )
(상기 화학식 12 또는 13에서,(In the above formula (12) or (13)
R51 내지 R53는 (C1-C10)알킬이며;R 51 To R 53 is (C1-C10) alkyl;
X3은 할라이드이며;X 3 is halide;
Z는 S, O 또는 Se이고;Z is S, O or Se;
R1 및 R2는 서로 독립적으로 (C1-C20)알킬기, (C1-C20)알킬티오기, (C6-C20)아르(C1-C20)알킬기 또는 (C3-C20)헤테로아릴이며, 상기 알킬, 알킬티오, 아르알킬 및 헤테로아릴은 (C1-C20)알킬, (C2-C20)알케닐, (C2-C20)알키닐, (C1-C20)알콕시, 아미노기, 하이드록시기, 할로겐기, 사이아노기, 나이트로기, 트리플루오로메틸기 및 실릴기로 선택되는 하나 이상의 치환기로 더 치환될 수 있으며;R 1 and R 2 are independently of each other a (C 1 -C 20) alkyl group, a (C 1 -C 20) alkylthio group, a (C 6 -C 20) aryl (C 1 -C 20) alkyl group or (C 3 -C 20) Alkylthio, aralkyl and heteroaryl are optionally substituted with one or more substituents selected from the group consisting of (C1-C20) alkyl, (C2-C20) alkenyl, (C2- C20) alkynyl, A nitro group, a trifluoromethyl group, and a silyl group;
R11 또는 R12는 서로 독립적으로 수소, 할로겐, (C1-C20)알킬, (C6-C20)아릴, (C3-C20)헤테로아릴, (C3-C20)시클로알킬, 5원 내지 7원의 헤테로시클로알킬, 시아노, 나이트로 또는 하이드록시이다.)R 11 or R 12 independently from each other are hydrogen, halogen, (C 1 -C 20) alkyl, (C 6 -C 20) aryl, (C 3 -C 20) heteroaryl, (C 3 -C 20) cycloalkyl, Cycloalkyl, cyano, nitro or hydroxy.
본 발명의 일 실시예에 따른 상기 화학식 12는 하기 화학식 14의 화합물에 하기 화학식 15의 화합물을 첨가하고, 할로겐화주석 화합물 또는 이의 수화물을 첨가하여 제조될 수 있다.The compound of formula (12) may be prepared by adding a compound of formula (15) to a compound of formula (14) and adding a tin halide compound or a hydrate thereof to the compound of formula (14).
[화학식 14][Chemical Formula 14]
[화학식 15][Chemical Formula 15]
R1-HR 1 -H
(상기 화학식 14 또는 15에서,(In the above formula (14) or (15)
Z는 S, O 또는 Se이고; Z is S, O or Se;
R1는 (C1-C20)알킬기, (C1-C20)알킬티오기, (C6-C20)아르(C1-C20)알킬기 또는 (C3-C20)헤테로아릴이며, 상기 알킬, 알킬티오, 아르알킬 및 헤테로아릴은 (C1-C20)알킬, (C2-C20)알케닐, (C2-C20)알키닐, (C1-C20)알콕시, 아미노기, 하이드록시기, 할로겐기, 사이아노기, 나이트로기, 트리플루오로메틸기 및 실릴기로 선택되는 하나 이상의 치환기로 더 치환될 수 있으며;R 1 is a (C1-C20) alkyl group, a (C1-C20) alkylthio group, a (C6-C20) The heteroaryl is optionally substituted with one or more substituents selected from the group consisting of (C1-C20) alkyl, (C2-C20) alkenyl, (C2- C20) alkynyl, Which may be further substituted with one or more substituents selected from a trifluoromethyl group and a silyl group;
R11 또는 R12는 서로 독립적으로 수소, 할로겐, (C1-C20)알킬, (C6-C20)아릴, (C3-C20)헤테로아릴, (C3-C20)시클로알킬, 5원 내지 7원의 헤테로시클로알킬, 시아노, 나이트로 또는 하이드록시이다.)R 11 or R 12 independently from each other are hydrogen, halogen, (C 1 -C 20) alkyl, (C 6 -C 20) aryl, (C 3 -C 20) heteroaryl, (C 3 -C 20) cycloalkyl, Cycloalkyl, cyano, nitro or hydroxy.
상기 화학식 14와 화학식 15를 반응시켜 상기 화학식 12를 제조할 시에 R2는 상기 R1과 동일하거나 상이한 치환기일 수 있다. 즉, 상기 화학식 15의 화합물과 상기 화학식 14를 반응시킬 시 생성된 화학식 12의 치환기인 R1과 R2는 동일한 치환기 일 수 있다.In preparing Formula 12 by reacting Formula 14 and Formula 15, R 2 may be the same or different substituent as R 1 . That is, R 1 and R 2, which are substituents of the formula (12), may be the same substituent when the compound of formula (15) is reacted with the compound of formula (14).
본 발명의 일 실시예에 따른 할로겐화주석 화합물 또는 이의 수화물은 구입과 취급이 용이한 할로겐화주석 수화물의 사용이 바람직하며 이러한 일례로, SnCl2ㅇㆍH2O일 수 있다.The tin halide compound or the hydrate thereof according to an embodiment of the present invention is preferably a tin halide hydrate which is easy to purchase and handle. For example, SnCl 2 .H 2 O can be used.
보다 상세하게, 상기 화학식 12는 상기 화학식 14의 화합물에 유기리튬화합물을 첨가하고 상기 화학식 15의 화합물을 첨가하여 교반한 후 할로겐화주석 수화물을 첨가하여 제조될 수 있다.More specifically, Formula 12 may be prepared by adding an organolithium compound to the compound of Formula 14, adding the compound of Formula 15, stirring, and then adding halogenated tin hydrate.
본 발명의 유기리튬화합물은 유기물과 리튬이 결합된 형태의 화합물로 일례로 n-뷰틸리튬, tert-뷰틸리튬, n-메틸리튬등을 들 수 있다.The organolithium compound of the present invention is a compound in which an organic material is combined with lithium, and examples thereof include n-butyllithium, tert-butyllithium, and n-methyllithium.
본 발명의 일 실시예에 따른 상기 화학식 14는 통상의 알려진 방법으로 제조가 가능하나, 본 발명의 일 실시예 1과 실시예 2에서 보이는 방법에 따라 제조될 수 있으며, 반응효율과 경제적인 면에서 실시예 2의 방법에 따라 제조하는 것이 바람직하다.The formula (14) according to an embodiment of the present invention can be prepared by a known method, but it can be prepared according to the method shown in Example 1 and Example 2 of the present invention, It is preferable to prepare it according to the method of Example 2.
즉, 본 발명의 일 실시예에 따른 상기 화학식 14는 하기 화학식 16의 화합물에 유기리튬화합물 및 할로겐화구리와 반응시켜 하기 화학식 17의 길만시약을 제조하는 단계; That is, the formula (14) according to an embodiment of the present invention may be prepared by reacting a compound of formula (16) with an organic lithium compound and copper halide to prepare a Gilman reagent of formula (17);
하기 화학식 17의 길만시약과 하기 화학식 18의 화합물을 탄소-탄소 짝지움 반응시켜 하기 화학식 19의 화합물을 제조하는 단계; 및Reacting a Gilman reagent of Formula 17 with a compound of Formula 18 to form a compound of Formula 19; And
하기 화학식 19의 화합물을 유기리튬화합물과 반응시켜 상기 화학식 14을 제조하는 단계;를 포함하여 제조될 수 있다.Reacting a compound represented by the following formula (19) with an organic lithium compound to prepare the compound represented by the formula (14).
[화학식 16][Chemical Formula 16]
[화학식 17][Chemical Formula 17]
[화학식 18][Chemical Formula 18]
[화학식 19][Chemical Formula 19]
(상기 화학식 16 내지 19에서,(In the above formulas 16 to 19,
R11은 수소, 할로겐, (C1-C20)알킬, (C6-C20)아릴, (C3-C20)헤테로아릴, (C3-C20)시클로알킬, 5원 내지 7원의 헤테로시클로알킬, 시아노, 나이트로 또는 하이드록시이며;R 11 is selected from hydrogen, halogen, (C 1 -C 20) alkyl, (C 6 -C 20) aryl, (C 3 -C 20) heteroaryl, (C 3 -C 20) cycloalkyl, 5-7 membered heterocycloalkyl, Nitro or hydroxy;
X4 내지 X5는 할라이드이며;X 4 to X 5 are halides;
Z는 S, O 또는 Se이며; Z is S, O or Se;
Y는 NR61R62, SiR63R64R65, SR66 또는 OR67이고;Y is NR 61 R 62 , SiR 63 R 64 R 65 , SR 66 or OR 67 ;
R61 내지 R67은 각각 독립적으로 수소, 할로겐, (C1-C10)알킬, (C6-C20)아릴, (C3-C20)헤테로아릴, 5원 내지 7원의 헤테로시클로알킬 또는 (C3-C20)시클로알킬이다.)R 61 to R 67 are each independently selected from the group consisting of hydrogen, halogen, (C 1 -C 10) alkyl, (C 6 -C 20) aryl, (C 3 -C 20) heteroaryl, 5-7 membered heterocycloalkyl, Lt; / RTI >
본 발명의 일 실시예에 따른 상기 화학식 14의 화합물은 할로겐기를 가지는 티오펜, 할로겐기를 가지는 퓨란 또는 할로겐기를 가지는 셀레노펜을 유기리튬화합물 및 할로겐화구리와 먼저 반응시켜 길만시약을 제조하고, 제조된 길만시약을 이용하여 탄소-탄소 짝지음 반응을 유발해 벤젠고리의 양쪽에 티에노티오펜, 퓨로퓨란 또는 셀레노페노셀레노펜이 융합된 헤테로고리를 제조할 수 있어, 기존의 방법에 비해 공정단계가 줄었고 수율도 향상되었다.The compound of Formula 14 according to an embodiment of the present invention may be prepared by first reacting thiophene having a halogen group, furan having a halogen group or selenophen having a halogen group with an organolithium compound and copper halide to prepare a Gilman reagent, It is possible to produce a heterocycle fused with thienothiophene, furofuran or selenophenocelenophene on both sides of the benzene ring by causing a carbon-carbon pairing reaction using a reagent, so that the process steps are reduced compared with the conventional method The yield was also improved.
본 발명의 일 실시예에 따른 상기 화학식 17의 길만시약은 -80 내지 -60℃에서 수행될 수 있으며, 보다 상세하게 -80 내지 -60℃의 유기용매 존재 하에 상기 화학식 16의 화합물과 유기리튬화합물을 먼저 반응시킨 후, 할로겐화구리를 첨가하여 제조될 수 있다.The Gilman reagent of Formula 17 according to an embodiment of the present invention can be performed at -80 to -60 캜, more specifically, in the presence of an organic solvent at -80 to -60 캜, , Followed by addition of copper halide.
본 발명의 일 실시예에 따른 할로겐화구리는 할로겐기를 가지는 구리화합물로, CuI, CuBr, CuCl등을 들 수 있으며, 반응성측면에서 CuI가 보다 바람직하다.The copper halide according to an embodiment of the present invention is a copper compound having a halogen group, and examples thereof include CuI, CuBr, and CuCl, and CuI is more preferable in terms of reactivity.
본 발명의 일 실시예에 따른 상기 화학식 19의 화합물은 상기 화학식 17의 길만시약과 상기 화학식 18의 화합물의 탄소-탄소 짝지음 반응시켜 제조될 수 있으며, 이때의 반응은 -80 내지 30℃에서 12 내지 20시간동안 수행될 수 있으며, 보다 상세하게는 -80 내지 30℃에서 13 내지 18시간동안 수행되는 것이 반응의 수율을 높이고 과반응되어 생기는 부생성물을 줄일 수 있다.The compound of Formula 19 according to an embodiment of the present invention may be prepared by a carbon-carbon coupling reaction between the Gilman reagent of Formula 17 and the compound of Formula 18. The reaction may be carried out at -80 to 30 ° C To 20 hours. More specifically, performing the reaction at -80 to 30 占 폚 for 13 to 18 hours can increase the yield of the reaction and reduce the byproducts which are generated by over-reaction.
본 발명의 일 실시예에 따른 상기 화학식 19의 화합물은 상기 화학식 16의 화합물과 상기 화학식 18의 화합물을 1: 2 내지 10의 몰(mol)비로 반응시켜 제조될 수 있으며, The compound of Formula 19 may be prepared by reacting the compound of Formula 16 with the compound of Formula 18 in a molar ratio of 1: 2 to 10,
상기 화학식 18의 화합물이 길만시약 1몰에 대하여 2몰 미만으로 투입이 되는 경우 상기 길만시약의 리튬(Li)이온이 본 발명에서 원하는 위치에 반응하여 결합하지 않아 본 발명의 범주에 벗어나는 부산물이 생성될 수 있으며, 그에 따라 반응 수율이 낮아지는 점이 발생할 수 있다. When the compound of Formula 18 is added in an amount of less than 2 mol per 1 mol of the Gilman reagent, lithium (Li) ions of the above-described Gilman reagent do not react at desired positions in the present invention and are not bound to form a by- And accordingly, the reaction yield may be lowered.
상기 화학식 14의 제조 시 사용되는 유기리튬화합물은 상기 화학식 19의 화합물 1몰에 대하여 0.5 내지 2몰 투입하여 반응에 참여될 수 있다. 유기리튬화합물이 과량 첨가될 경우 과반응에 의해 부산물이 생성되어 반응 수율이 감소할 수 있고, 유기리튬화합물이 소량 첨가되는 경우 반응공정시간이 길어지게 되는 점이 발생할 수 있다. The organolithium compound used in the preparation of the compound of formula (14) may be added to the reaction by adding 0.5 to 2 moles per 1 mole of the compound of formula (19). When the organic lithium compound is added in an excessive amount, by-products may be formed due to over-reaction, and the reaction yield may be decreased. When a small amount of the organic lithium compound is added, the reaction process time may be prolonged.
본 발명에 있어서 사용되는 용매는 반응조건과 반응물질의 종류등에 따라 적절한 용매를 선택하여 사용할 수 있으며, 일례로 테트라하이드로퓨란(THF), 디에틸에테르(ether), 헥산(Hexane), 사이클로헥산(Cyclohexane), 톨루엔(Toluene) 또는 이들의 혼합용매 하에서 수행될 수 있다.The solvent used in the present invention may be selected from a suitable solvent depending on the reaction conditions and the kind of the reactant. For example, tetrahydrofuran (THF), diethyl ether, hexane (hexane), cyclohexane Cyclohexane, toluene or a mixed solvent thereof.
또한 본 발명은 본 발명의 유기 반도체 화합물을 함유하는 광활성층과 이러한 광활성층을 포함하는 유기박막 태양전지를 제공한다.The present invention also provides a photoactive layer containing an organic semiconductor compound of the present invention and an organic thin film solar cell comprising such a photoactive layer.
본 발명의 일 실시예에 따른 광활성층은 본 발명의 유기 반도체 화합물을 함유하는 유기 반도체 화합물용액을 제조하여 스크린 프린팅 및 잉크젯 스프레이등의 방법으로 제조가 가능하며, 본 발명에 따른 광활성층을 함유하는 유기박막 태양전지는 통상적인 방법으로 제조될 수 있다.The photoactive layer according to one embodiment of the present invention can be prepared by a method such as screen printing and ink jet spray by preparing an organic semiconductor compound solution containing the organic semiconductor compound of the present invention, The organic thin film solar cell can be manufactured by a conventional method.
본 발명의 유기 반도체 화합물은 중심의 벤젠고리의 2,3위치와 5,6위치에 각각 티에노티오펜, 퓨로퓨란 또는 셀레노페노셀레노펜 고리와 융합된 구조를 가져 높은 전자밀도를 가지는, 전자주게 화합물과 전자받게 화합물이 교대중합하는 고분자로, 본 발명의 유기 반도체 화합물을 광활성층으로 함유하는 유기박막 태양전지는 높은 효율을 나타낸다.The organic semiconductor compound of the present invention has an electron donating structure having a structure fused with a thienothiophene, a furofuran or a selenophenocelenophene ring at the 2,3 position of the central benzene ring and the 5,6 position respectively, The organic thin film solar cell containing the organic semiconductor compound of the present invention as a photoactive layer shows high efficiency.
또한 본 발명의 유기 반도체 화합물은 전자주게 화합물인 벤젠-티에노티오펜 융합고리, 벤젠-퓨로퓨란 융합고리 또는 벤젠-셀레노페노셀레노펜 융합고리의 중심인 벤젠고리의 1, 4위치에 다양한 치환기를 가져 용매에 대한 용해도가 높아 용액공정의 적용이 가능하다.In addition, the organic semiconductor compound of the present invention may contain various substituents at the 1 and 4 positions of benzene-thienothiophene fused ring, benzene-furoofuran fused ring or benzene-selenophenocosenophene fused ring which is the electron donor compound The solubility in the solvent is high, so that the solution process can be applied.
또한 본 발명의 유기 반도체 화합물의 제조방법은 길만시약을 먼저 제조하고, 제조된 길만시약을 직접 반응에 참여시킴으로써 반응단계를 대폭 축소하고 높은 수율을 가지므로 매우 경제적이며 효과적이다.In addition, the method of preparing the organic semiconductor compound of the present invention is very economical and effective because it greatly reduces the reaction step and has a high yield by first preparing the Gilman reagent and directly participating in the Gilman reagent.
또한 본 발명의 유기 반도체 화합물을 함유하는 광활성층은 용액공정으로 제조가 가능하여 다양한 소재에 단순한 공정으로 제조가 가능하며, 본 발명의 광활성층을 함유하는 유기박막 태양전지는 높은 효율을 가진다. In addition, the photoactive layer containing the organic semiconductor compound of the present invention can be prepared by a solution process, and can be manufactured by a simple process on various materials. The organic thin film solar cell containing the photoactive layer of the present invention has high efficiency.
도 1은 일반적인 유기박막 태양전지 소자의 구조를 일례로 나타낸 도면이며,
도 2는 본 발명의 실시예 2에서 제조된 유기 반도체 화합물의 UV 스펙트럼을 나타낸 도면이며,
도 3은 본 발명의 실시예 3에서 제조된 유기 반도체 화합물의 UV 스펙트럼을 나타낸 도면이며,
도 4는 본 발명의 실시예 5에서 제조된 유기 반도체 화합물의 UV 스펙트럼을 나타낸 도면이며,
도 5는 본 발명의 실시예 2에서 제조된 유기 반도체 화합물의 TGA값을 측정한 도면이며,
도 6은 본 발명의 실시예 3에서 제조된 유기 반도체 화합물의 TGA값을 측정한 도면이며,
도 7은 본 발명의 실시예 5에서 제조된 유기 반도체 화합물의 TGA값을 측정한 도면이며,
도 8은 본 발명의 실시예 2에서 제조된 유기 반도체 화합물을 함유하는 유기박막 태양전지 소자의 전환효율 특성을 나타낸 도면이며,
도 9는 본 발명의 실시예 2에서 제조된 유기 반도체 화합물을 함유하는 유기박막 태양전지 소자의 효율 특성을 나타낸 도면이다.FIG. 1 is a view showing an example of the structure of a general organic thin film solar cell element,
2 is a diagram showing a UV spectrum of the organic semiconductor compound prepared in Example 2 of the present invention,
3 is a diagram showing a UV spectrum of the organic semiconductor compound prepared in Example 3 of the present invention,
4 is a diagram showing a UV spectrum of the organic semiconductor compound prepared in Example 5 of the present invention,
5 is a graph showing the TGA value of the organic semiconductor compound prepared in Example 2 of the present invention,
6 is a graph showing the TGA value of the organic semiconductor compound prepared in Example 3 of the present invention,
7 is a graph showing the TGA value of the organic semiconductor compound prepared in Example 5 of the present invention,
8 is a graph showing the conversion efficiency characteristics of the organic thin film solar cell element containing the organic semiconductor compound prepared in Example 2 of the present invention,
9 is a graph showing efficiency characteristics of an organic thin film solar cell element containing an organic semiconductor compound prepared in Example 2 of the present invention.
이하에서 본 발명의 구체적인 실시예를 제시하는 바, 하기의 실시예는 본 발명의 예시 목적에 불과한 것으로 본 발명을 한정하고자 하는 것은 아니다.
The following examples illustrate the present invention and are not intended to limit the scope of the present invention.
[실시예 1] 화합물 1-2의 제조[Example 1] Preparation of Compound 1-2
화합물 a-1의 제조Preparation of compound a-1
잘 건조시킨 250 mL 이구 둥근 바닥 플라스크에 3-bromothieno[3,2-b]thiophene (10.0 g, 45.64 mmol)과 copper (Ⅰ) cyanide (10.20 g, 0.114 mol)을 넣고 quinoline (100 mL) 에 녹였다. 질소 기류 하에서 2시간 동안 환류시킨 다음 실온으로 온도를 낮추고 CH2Cl2로 추출하였다. 유기층을 2 M HCl과 물로 씻어준 다음 MgSO4로 건조시킨 후 회전식 증발기를 사용하여 용매를 제거하였다. n-Hexane/EtOAc(5/1)용매를 사용하여 컬럼 크로마토그래피로 분리하여 노란색 고체 화합물 a-1을 4.6 g (61%)의 수득율로 얻었다. 3-bromothieno [3,2-b] thiophene (10.0 g, 45.64 mmol) and copper (Ⅰ) cyanide (10.20 g, 0.114 mol) were placed in a well-dried 250 mL round bottom flask and dissolved in quinoline . The mixture was refluxed under a nitrogen stream for 2 hours, cooled to room temperature and extracted with CH 2 Cl 2 . The organic layer was washed with 2 M HCl and water, dried over MgSO 4, and then the solvent was removed using a rotary evaporator. n- Hexane / EtOAc (5/1) as the eluent to give yellow solid compound a-1 in a yield of 4.6 g (61%).
IR (KBr): 3109 (sp2C-H),2969(sp3C-H),2227 (C≡N); IR (KBr): 3109 (sp 2 CH), 2969 (sp 3 CH), 2227 (C = N);
1H-NMR (300 MHz, CDCl3):δ7.99(d, 1H, J=1.42Hz), 7.53(dd, 1H, J=5.28, 1.42Hz), 7.29(d, 1H, J=5.27Hz); 1 H-NMR (300 MHz, CDCl 3 ):? 7.99 (d, 1H, J = 1.42 Hz), 7.53 (dd, 1H, J = 5.28, 1.42 Hz) );
13C-NMR(75MHz,CDCl3):δ139.8, 139.1, 137.8, 129.7, 119.7, 114.1, 103.7; 13 C-NMR (75 MHz, CDCl 3 ):? 139.8, 139.1, 137.8, 129.7, 119.7, 114.1, 103.7;
EI,MSm/z(%):165(100,M+)EI, MS m / z (%): 165 (100, M < + &
화합물 a-2의 제조Preparation of compound a-2
잘 건조시킨 100 mL 이구 둥근 바닥 플라스크에 화합물 a-1 (7.00 g, 42.36 mmol)과 potassium hydroxide (10.70 g, 0.191 mol)을 넣고 ethylene glycol (150 mL)에 녹였다. 질소 기류 하에서 12시간 동안 환류시킨 다음 실온으로 온도를 낮추고 conc-HCl과 물을 첨가하여 반응을 종결시켰다. ether로 추출한 후 유기층을 물로 씻어준 다음 MgSO4로 건조시킨 후 회전식 증발기를 사용하여 용매를 제거하였다. 물을 사용해서 재결정하여 살구색 고체 화합물 a-2, 6.92 g 을 얻었다(89%).Compound a-1 (7.00 g, 42.36 mmol) and potassium hydroxide (10.70 g, 0.191 mol) were placed in a well-dried 100 mL two-necked round bottom flask and dissolved in ethylene glycol (150 mL). The mixture was refluxed under a nitrogen stream for 12 hours, then cooled to room temperature, conc. HCl and water were added to terminate the reaction. ether. The organic layer was washed with water, dried over MgSO 4, and then the solvent was removed using a rotary evaporator. Recrystallization using water gave 6.92 g (89%) of a pale green solid compound a-2.
EI,MSm/z(%):184(100,M+)EI, MS m / z (%): 184 (100, M < + &
화합물 a-3의 제조Preparation of compound a-3
잘 건조시킨 250 mL 이구 둥근 바닥 플라스크에 화합물 a-2 (6.92 g, 37.56 mmol)을 넣고 thionyl chloride (70 mL)에 녹였다. 질소 기류 하에서 6시간 동안 환류시킨 다음 실온으로 온도를 낮추고 회전식 증발기를 사용하여 용매를 제거한 뒤 정제 없이 어두운 갈색 고체 화합물 a-3을 얻었다. 정제없이 다음 반응에 사용하였다.Compound a-2 (6.92 g, 37.56 mmol) was added to a well-dried 250 mL two-neck round bottom flask and dissolved in thionyl chloride (70 mL). The mixture was refluxed under a nitrogen stream for 6 hours, then cooled to room temperature, and the solvent was removed using a rotary evaporator to obtain a dark brown solid compound a-3 without purification. The following reaction was used without purification.
화합물 1-1의 제조Preparation of Compound 1-1
잘 건조시킨 500 mL 이구 둥근 바닥 플라스크에 화합물 a-3 (10.00 g, 49.34 mmol)을 넣고 benzene (180 mL)에 녹였다. 실온에서 dimethylamine 과량을 천천히 적가하였다. 질소 기류 하에서 12시간 동안 교반하였다. Ether로 추출하고 유기층을 물로 씻어준 다음 MgSO4로 건조시킨 후 회전식 증발기를 사용하여 용매를 제거하였다. n-Hexane/EtOAc(1/1)용매를 사용하여 컬럼 크로마토그래피로 분리해서 갈색 액체 화합물 1-1을 4.3 g을 얻었다(41%). Compound a-3 (10.00 g, 49.34 mmol) was added to a well-dried 500 mL two-neck round bottom flask and dissolved in benzene (180 mL). The dimethylamine excess was slowly added dropwise at room temperature. The mixture was stirred for 12 hours under a stream of nitrogen. Ether. The organic layer was washed with water, dried over MgSO 4, and then evaporated using a rotary evaporator. The residue was subjected to column chromatography using n- hexane / EtOAc (1/1) solvent to obtain 4.3 g of brown liquid compound 1-1 (41%).
mp 124 ℃; mp 124 [deg.] C;
IR (KBr): 3098-3025 (sp2C-H), 1624(C=O), 1501-1460(C=C);IR (KBr): 3098-3025 (sp 2 CH), 1624 (C = O), 1501-1460 (C = C);
1H-NMR(300MHz,CDCl3):δ7.61 (d, 1 H, J=1.51,1.24㎐), 7.48 (dd, 1 H, J=5.28,1.55㎐), 7.26 (d, 1 H, J=5.28,1.23㎐), 3.21 (s, 6H); 1 H-NMR (300 MHz, CDCl 3 ):? 7.61 (d, 1H, J = 1.51,1.24 Hz), 7.48 (dd, 1H, J = 5.28, 1.55 Hz) J = 5.28, 1.23 Hz), 3.21 (s, 6H);
13C-NMR(75MHz,CDCl3):δ165.0, 140.0, 138.1, 129.2, 128.6, 128.3, 118.8; EI, MS m/z (%): 211 (100, M+) 13 C-NMR (75 MHz, CDCl 3 ):? 165.0, 140.0, 138.1, 129.2, 128.6, 128.3, 118.8; EI, MS m / z (%): 211 (100, M < + &
화합물 1-2의 제조Preparation of Compound 1-2
잘 건조시킨 100 mL 이구 둥근 바닥 플라스크에 화합물 1-1 (3.90 g, 18.46 mmol)을 넣고 THF (40 mL)에 녹였다. 실온에서 n-BuLi (1.6 M in hexane, 12.69 mL, 20.31 mmol)을 천천히 적가하였다. 질소 기류 하에서 10 분 동안 교반한 다음 물을 사용하여 반응을 종결시킨 후 올리브색 침전이 가라앉으면 유리거르개로 거른 다음 과량의 물과 THF로 씻은 후 건조시켜 갈색 고체 화합물 1-2,1.4 g을 얻었다(46%). Compound 1-1 (3.90 g, 18.46 mmol) was added to a well-dried 100 mL two-neck round bottom flask and dissolved in THF (40 mL). N-BuLi (1.6 M in hexane, 12.69 mL, 20.31 mmol) was slowly added dropwise at room temperature. After stirring for 10 minutes under a nitrogen stream, the reaction was terminated with water. After the olivine precipitate had settled down, it was filtered through a glass column, washed with excess water and THF, and dried to obtain brown solid compound 1-2, 1.4 g 46%).
EI,MSm/z(%):332(100,M+)
EI, MS m / z (%): 332 (100, M < + &
[실시예 2] 유기 반도체 화합물 1의 제조[Example 2] Production of
화합물 1-1의 제조Preparation of Compound 1-1
잘 건조시킨 250 mL 삼구 둥근 바닥 플라스크에 3-bromothieno[3,2-b]thiophene (10.0 g, 45.63 mmol)를 넣고 ether(150 ml) 에 녹였다. 온도를 -8oC로 낮추고 n-BuLi (2.5 M in hexane, 19.17 mL, 47.92 mmol)을 천천히 적가하였다. 질소 기류 하에서 40 분 동안 교반한 다음 copper(I) iodide (4.35 g, 22.81 mmol) 을 여러 번 나눠서 첨가하였다. 질소 기류 하에서 온도를 -8oC를 유지하면서 1시간동안 교반하여 길만시약을 제조하였다. 3-bromothieno [3,2-b] thiophene (10.0 g, 45.63 mmol) was added to a well-dried 250 mL three-neck round bottom flask and dissolved in ether (150 mL). The temperature was reduced to -8 ° C and n- BuLi (2.5 M in hexane, 19.17 mL, 47.92 mmol) was slowly added dropwise. After stirring for 40 minutes under a stream of nitrogen, copper (I) iodide (4.35 g, 22.81 mmol) was added several times in portions. And the mixture was stirred for 1 hour while maintaining the temperature at -8 ° C under a nitrogen stream to prepare a Gilman reagent.
다른 잘 건조시킨 500 mL 삼구 둥근 바닥 플라스크에 dimethylcarbamyl chloride (5.64 g, 52.48 mmol)을 첨가하여 ehter (200 mL) 에 녹이고 온도를 -8oC로 유지하였다. 여기에 상기에서 제조한 길만시약을 케뉼러나, 주사기를 이용하여 첨가하였다. 그 후에 혼합물의 온도를 -8oC로 10분에서 15분 유지하고 천천히 실온으로 올려서 14 시간 교반하였다. 반응혼합물을 Ether로 추출하고 유기층을 물로 씻어준 다음 MgSO4로 건조시킨 후 용매를 제거하여 n-Hexane/EtOAc (1/1)로 컬럼 크로마토그래피 분리해서 표제화합물인 갈색 액체를 6.6 g (68.44%)의 수득율로 얻었다. To another well-dried 500 mL three-neck round bottom flask, dimethylcarbamyl chloride (5.64 g, 52.48 mmol) was added and dissolved in ehter (200 mL) and the temperature was maintained at -8 ° C. Here, the above-prepared Gilman reagent was added using a syringe or a catenary. After that, the temperature of the mixture was kept at -8 ° C for 10 minutes to 15 minutes, slowly raised to room temperature and stirred for 14 hours. The reaction mixture was extracted with ether, and the organic layer was washed with water, dried over MgSO 4, and then the solvent was removed. The residue was subjected to column chromatography with n- hexane / EtOAc (1/1) to obtain 6.6 g (68.44% ). ≪ / RTI >
mp 124 ℃ mp 124 ° C
IR (KBr): 3098-3025 (sp2 C-H), 1624 (C=O), 1501-1460 (C=C) IR (KBr): 3098-3025 (sp 2 CH), 1624 (C = O), 1501-1460 (C = C)
1H-NMR (300 MHz, CDCl3): δ 7.61 (d, 1 H, J = 1.51, 1.24 ㎐), 7.48 (dd, 1 H, J = 5.28, 1.55 ㎐), 7.26 (d, 1 H, J = 5.28, 1.23 ㎐), 3.21 (s, 6H) 1 H-NMR (300 MHz, CDCl 3 ):? 7.61 (d, 1H, J = 1.51, 1.24 Hz), 7.48 (dd, 1H, J = 5.28, 1.55 Hz) J = 5.28, 1.23 D), 3.21 (s, 6H)
13C NMR (75 MHz, CDCl3): δ 165.0, 140.0, 138.1, 129.2, 128.6, 128.3, 118.8 13 C NMR (75 MHz, CDCl 3 ): 隆 165.0, 140.0, 138.1, 129.2, 128.6, 128.3, 118.8
EI, MS m/z (%): 211 (100, M+)
EI, MS m / z (%): 211 (100, M < + &
화합물 1-2의 제조Preparation of Compound 1-2
잘 건조시킨 100 mL 이구 둥근바닥플라스크에, 화합물 1-1(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 여과하고 과량의 물과 THF로 세척한 후 건조시켜 갈색 고체인 화합물 1-2, 1.4 g (91.9%)을 얻었다.Compound 1-1 (N-dimethylthieno [3,2-b] thiophene-3-carboxamid) (3.90 g, 18.46 mmol) was added to a well-dried 100 mL two-neck 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. After the olivine precipitate had settled, it was filtered, washed with excess water and THF, and dried to obtain 1.4 g (91.9% ≪ / RTI >
EI, MS m/z (%): 332 (100, M+)
EI, MS m / z (%): 332 (100, M < + &
화합물 1-3의 제조Preparation of compounds 1-3
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 0oC로 낮추고 n-BuLi (2.5 M in hexane, 16.5 mL, 42.2 mmol)을 천천히 적가하고, 온도를 50oC로 올려 질소 기류 하에서 2 시간 동안 교반한 다음 화합물 1-2 (4.155 g, 12.5 mmol)을 재빠르게 첨가하고 질소 기류 하에서 1 시간 동안 더 교반한 후 실온으로 온도를 내려 SnCl2``H2O in 10% HCl(30ml)을 넣고 1 시간동안 교반하였다. 반응혼합물에 얼음물을 첨가하고, Ether로 추출하고 유기층을 물로 씻어준 다음 MgSO4로 건조시킨 후 용매를 제거하였다. n-Hexane 용매를 사용하여 컬럼 크로마토그래피로 분리해서 노란 고체인 화합물 1-3, 4.0 g (31.2%)을 얻었다.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. , 12.5 mmol) was rapidly added thereto. The mixture was further stirred for 1 hour in a nitrogen stream, the temperature was lowered to room temperature, and SnCl 2 ' ' H 2 O in 10% HCl (30 ml) was added thereto and stirred for 1 hour. Ice water was added to the reaction mixture and extracted with ether. The organic layer was washed with water, dried over MgSO 4, and then the solvent was removed. n- Hexane as an eluent to obtain Compound (1-3) (4.0 g, 31.2%) as a yellow solid.
1H-NMR (300 MHz, CDCl3): δ 7.47-7.45 (d, 1 H), 7.31-7.29 (d, 1 H), 7.12 (s, 1 H), 2.93-2.70 (m, 4H), 2.17-2.15 (m, 4H), 1.60-1.41 (m, 28H), 0.92-0.89 (m, 6H) 1 H-NMR (300 MHz, CDCl 3 ):? 7.47-7.45 (d, 1H), 7.31-7.29 (d, 1H), 7.12 2.17-2.15 (m, 4H), 1.60-1.41 (m, 28H), 0.92-0.89 (m, 6H)
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, 30.17, 30.07, 29.08, 28.78, 23.48, 14.65
EI, MS m/z (%): 1027 (100, M+)
EI, MS m / z (%): 1027 (100, M < + &
화합물 1-4의 제조Preparation of compounds 1-4
잘 건조시킨 100 mL 삼구 둥근 바닥 플라스크에 화합물 1-3 (1.0 g, 0.9729 mmol)를 넣고 THF (30 ml) 에 녹였다. 온도를 0oC로 낮추고 n-BuLi (2.5 M in hexane, 0.856 mL, 0.2141 mmol)을 천천히 적가하고, 50oC로 올리고 질소 기류 하에서 2 시간 동안 교반한 다음 실온으로 온도를 내려준다. 그리고 trimethyltin chloride (1 M in THF, 2.14 mL, 2.14 mmol)을 천천히 적가해주고 실온에서 3시간동안 교반한다. 반응혼합물을 얼음물에 붓고, Ether로 추출하고 유기층을 물로 씻어준 다음 MgSO4로 건조시킨 후 저온에서 용매를 제거하였다. n-Hexane과 IPA (isopropyl alcohol)을 이용하여 재결정 하고 여과하여 고체인 화합물 1-4, 1.0 g (75%)을 얻었다.Compound 1-3 (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, stirred at 50 ° C under a nitrogen stream for 2 hours and then allowed to cool to room temperature. Then trimethyltin chloride (1 M in THF, 2.14 mL, 2.14 mmol) was slowly added dropwise and stirred at room temperature for 3 hours. The reaction mixture was poured into ice water, and extracted with Ether and the solvent was removed at a low temperature and the organic layer was washed with water and then dried over MgSO 4. Recrystallization using n- hexane and IPA (isopropyl alcohol) and filtration gave solid compounds 1-4 and 1.0 g (75%).
1H-NMR (300 MHz, CDCl3): δ 7.32 (s, 1 H), 7.13 (s, 1 H), 2.96-2.67 (m, 4H), 1.83-1.73 (m, 4 H), 1.49-1.31 (m, 28 H), 0.92-0.88 (m, 6 H), 0.50-0.31 (m, 9 H) 1 H-NMR (300 MHz, CDCl 3 ):? 7.32 (s, 1H), 7.13 (s, 1H), 2.96-2.67 (m, 4H), 1.83-1.73 1.31 (m, 28 H), 0.92-0.88 (m, 6 H), 0.50-0.31 (m, 9 H)
EI, MS m/z (%): 1353 (100, M+)
EI, MS m / z (%): 1353 (100, M < + &
화합물 1의 제조Preparation of Compound (1)
상기 화합물 1은 스틸레(Stille) 커플링 반응을 통해 중합할 수 있다. 화합물 1-4 (0.50 g, 0.000369 mol)와 4,7-dibromobenzo[c][1,2,5]thiadiazole (0.1086 g, 0.000369 mmol)을 chlorobenzene(CB)(7.5 mL)에 녹이고 플라스크를 질소로 치환한다. 여기에 촉매로 Pd2(dba)3 (Tris(dibenzylideneacetone)dipalladium(0)) (0.01014 g, 2 mol%)와 P(o-tol)3(Tri(o-tolyl)phosphine)(0.0089 g, 8 mol%)을 넣고 110℃에서 48시간 동안 가열환류시켰다. 2-bromothiophene (0.1g)을 넣고 6시간 교반시키고, 2-tributyltin thiophene (0.1g)을 넣고 6시간 교반시키며 end-capping 을 해주었다. 이 반응혼합물을 메탄올 (300 mL)에 천천히 첨가하여 침전을 형성시키고 생성된 고체를 여과한다. 여과한 고체는 속실렛(sohxlet)을 통해 메탄올, 헥산, 톨루엔, 클로로포름 순으로 정제한다. 얻어진 액체를 메탄올에 다시 침전시키고 필터로 여과한 후 건조시켜 검정색 고체인 화합물 1을 얻었다(수득률 85%). The
1H-NMR (300 MHz, CDCl3): δ7.97(broad, 2H), 6.91-6.52(broad, 4H), 2.95-2.78(broad, 8H), 1.55-1.25(m, 64H), 1.04-0.79(m, 12H). 1 H-NMR (300 MHz, CDCl 3 ):? 7.97 (broad, 2H), 6.91-6.52 (broad, 4H), 2.95-2.78 0.79 (m, 12 H).
Mn = 87000, Mw = 188870 PDI = 2.147
Mn = 87000, Mw = 188870 PDI = 2.147
[실시예 3] 유기 반도체 화합물 2의 제조[Example 3] Production of organic semiconductor compound 2
상기 화합물 2은 스틸레(Stille) 커플링 반응을 통해 중합할 수 있다. 화합물 1-4 (0.50 g, 0.000369 mol)와 4,7-bis(5-bromo-4-(octan-3-yl)thiophen-2-yl)benzo[c][1,2,5]thiadiazole (0.2522 g, 0.000369 mmol)을 chlorobenzene(CB)(7.5 mL)에 녹이고 플라스크를 질소로 치환한다. 여기에 촉매로 Pd2(dba)3 (Tris(dibenzylideneacetone)dipalladium(0)) (0.01014 g, 2 mol%)와 P(o-tol)3(Tri(o-tolyl)phosphine)(0.0089 g, 8 mol%)을 넣고 110℃에서 12시간 동안 가열환류시켰다. 2-bromothiophene (0.1g)을 넣고 6시간 교반시키고, 2-tributyltin thiophene (0.1g)을 첨가하고 6시간 교반시키며 end-capping 을 해주었다. 이 반응혼합물을 메탄올 (300 mL)에 천천히 첨가하여 침전을 형성시키고 생성된 고체를 여과하였다. 여과한 고체는 속실렛(sohxlet)을 통해 메탄올, 헥산, 톨루엔, 클로로포름 순으로 정제하였다. 얻어진 액체를 메탄올에 다시 침전시키고 필터로 여과한 후 건조시켜 암녹색 고체인 유기 반도체 화합물 2을 얻었다(수득률 84%). The compound 2 can be polymerized through a Stille coupling reaction. Compound 1-4 (0.50 g, 0.000369 mol) and 4,7-bis (5-bromo-4- (octan-3-yl) thiophen-2-yl) benzo [c] [1,2,5] thiadiazole 0.2522 g, 0.000369 mmol) is dissolved in chlorobenzene (CB) (7.5 mL) and the flask is replaced with nitrogen. This catalyst Pd 2 (dba) to 3 (Tris (dibenzylideneacetone) dipalladium ( 0)) (0.01014 g, 2 mol%) and P (o-tol) 3 ( Tri (o-tolyl) phosphine) (0.0089 g, 8 mol%) was added and the mixture was refluxed at 110 ° C for 12 hours. 2-bromothiophene (0.1 g) was added and stirred for 6 hours. 2-tributyltin thiophene (0.1 g) was added and the mixture was stirred for 6 hours and end-capped. The reaction mixture was slowly added to methanol (300 mL) to form a precipitate and the resulting solid was filtered. The filtered solid was purified through a soxlet in the order of methanol, hexane, toluene and chloroform. The obtained liquid was precipitated again in methanol, filtered through a filter, and dried to obtain an organic semiconductor compound 2 as a dark green solid (yield: 84%).
1H-NMR (300 MHz, CDCl3): δ7.98(broad, 2H), 6.91-6.52(broad, 6H), 2.85-2.67(broad, 10H), 1.60-1.25(m, 84H), 1.02-0.78(m, 24H). 1 H-NMR (300 MHz, CDCl 3 ):? 7.98 (broad, 2H), 6.91-6.52 (broad, 0.78 (m, 24H).
Mn: 78800 Mw: 164750 PDI: 2.09
Mn: 78800 Mw: 164750 PDI: 2.09
[실시예 4] 유기 반도체 화합물 3의 제조[Example 4] Production of
상기 유기 반도체 화합물 3은 스틸레(Stille) 커플링 반응을 통해 중합할 수 있다. 화합물 1-4 (0.50 g, 0.000369 mol)와 1,3-dibromo-5-octyl-4H-thieno[3,4-c]pyrrole-4,6(5H)-dione(0.1563 g, 0.000369 mmol)을 chlorobenzene(CB)(7.5 mL)에 녹이고 플라스크를 질소로 치환한다. 여기에 촉매로 Pd2(dba)3 (Tris(dibenzylideneacetone)dipalladium(0)) (0.01014 g, 2 mol%)와 P(o-tol)3(Tri(o-tolyl)phosphine)(0.0089 g, 8 mol%)을 넣고 110℃에서 24시간 동안 가열환류시켰다. 2-bromothiophene (0.1g)을 넣고 6시간 교반시키고, 2-tributyltin thiophene (0.1g)을 넣고 6시간 교반시키며 end-capping 을 해주었다. 이 반응혼합물을 메탄올 (300 mL)에 천천히 첨가하여 침전을 형성시키고 생성된 고체를 여과하였다. 여과한 고체는 속실렛(sohxlet)을 통해 메탄올, 헥산, 톨루엔, 클로로포름 순으로 정제하였다. 얻어진 액체를 메탄올에 다시 침전시키고 필터로 여과한 후 건조시켜 암청색 고체인 유기 반도체 화합물 3을 얻었다(수득률 80%). The
1H-NMR (300 MHz, CDCl3): δ 7.1-6.59(broad, 4H), 3.25-3.2(broad, 2H), 2.88(broad, 8H), 1.30-1.25(m, 76H), 1.04-0.88(m, 15H). 1 H-NMR (300 MHz, CDCl 3 ):? 7.1-6.59 (broad, 4H), 3.25-3.2 (broad, 2H), 2.88 (m, 15 H).
Mn: 52620 Mw: 112080 PDI: 2.13
Mn: 52620 Mw: 112080 PDI: 2.13
[[ 실시예Example 5] 유기 반도체 화합물 4의 제조 5] Production of organic semiconductor compound 4
상기 화합물 4은 스틸레(Stille) 커플링 반응을 통해 중합할 수 있다. 화합물 1-4 (0.50 g, 0.000369 mol)와 2-ethylhexyl 4,6-dibromothieno[3,4-b]thiophene-2-carboxylate (0.1703 g, 0.000369 mmol)을 chlorobenzene(CB)(7.5 mL)에 녹이고 플라스크를 질소로 치환하였다. 여기에 촉매로 Pd2(dba)3 (Tris(dibenzylideneacetone)dipalladium(0)) (0.01014 g, 2 mol%)와 P(o-tol)3(Tri(o-tolyl)phosphine)(0.0089 g, 8 mol%)을 넣고 110℃에서 24시간 동안 가열환류시켰다. 2-bromothiophene (0.1g)을 넣고 6시간 교반시키고, 2-tributyltin thiophene (0.1g)을 넣고 6시간 교반시키며 end-capping 을 해주었다. 이 반응혼합물을 메탄올 (300 mL)에 천천히 첨가하여 침전을 형성시키고 생성된 고체를 여과하였다. 여과한 고체는 속실렛(sohxlet)을 통해 메탄올, 헥산, 톨루엔, 클로로포름 순으로 정제하였다. 얻어진 액체를 메탄올에 다시 침전시키고 필터로 여과한 후 건조시켜 암청색 고체인 화합물 4을 얻었다(수득률 75%). The compound 4 can be polymerized through a Stille coupling reaction. The compound 1-4 (0.50 g, 0.000369 mol) and 2-ethylhexyl 4,6-dibromothieno [3,4-b] thiophene-2-carboxylate (0.1703 g, 0.000369 mmol) were dissolved in chlorobenzene (CB) The flask was replaced with nitrogen. This catalyst Pd 2 (dba) to 3 (Tris (dibenzylideneacetone) dipalladium ( 0)) (0.01014 g, 2 mol%) and P (o-tol) 3 ( Tri (o-tolyl) phosphine) (0.0089 g, 8 mol%) was added, and the mixture was heated to reflux at 110 占 폚 for 24 hours. 2-bromothiophene (0.1 g) was added and stirred for 6 hours. 2-tributyltin thiophene (0.1 g) was added and the mixture was stirred for 6 hours and end-capped. The reaction mixture was slowly added to methanol (300 mL) to form a precipitate and the resulting solid was filtered. The filtered solid was purified through a soxlet in the order of methanol, hexane, toluene and chloroform. The resulting liquid was precipitated again in methanol, filtered off with a filter and dried to give compound 4 as a dark blue solid (yield: 75%).
1H-NMR (300 MHz, CDCl3): δ8.23(broad, 1H), 7.1-6.59(broad, 4H), 4.65-4.44(broad, 2H), 2.88(broad, 8H), 2.21(m 1H), 1.30-1.25(m, 72H), 1.04-0.88(m, 18H). 1 H-NMR (300 MHz, CDCl 3): δ8.23 (broad, 1H), 7.1-6.59 (broad, 4H), 4.65-4.44 (broad, 2H), 2.88 (broad, 8H), 2.21 (m 1H ), 1.30-1.25 (m, 72H), 1.04-0.88 (m, 18H).
Mn: 25000 Mw: 64100 PDI: 2.56
Mn: 25000 Mw: 64100 PDI: 2.56
[실시예 6] 유기 반도체 화합물 5의 제조[Example 6] Production of
상기 유기 반도체 화합물 5는 스틸레(Stille) 커플링 반응을 통해 중합할 수 있다. 화합물 1-4 (0.50 g, 0.000369 mol)와 1-(4,6-dibromothieno[2,3-c]thiophen-2-yl)-2-ethylhexan-1-one (0.1590 g, 0.000369 mmol)을 chlorobenzene(CB)(7.5 mL)에 녹이고 플라스크를 질소로 치환하였다. 여기에 촉매로 Pd2(dba)3 (Tris(dibenzylideneacetone)dipalladium(0)) (0.01014 g, 2 mol%)와 P(o-tol)3(Tri(o-tolyl)phosphine)(0.0089 g, 8 mol%)을 넣고 110℃에서 24시간 동안 가열환류시켰다. 2-bromothiophene (0.1g)을 넣고 6시간 교반시키고, 2-tributyltin thiophene (0.1g)을 넣고 6시간 교반시키며 end-capping 을 해주었다. 이 반응혼합물을 메탄올 (300 mL)에 천천히 첨가하여 침전을 형성시키고 생성된 고체를 여과하였다. 여과한 고체는 속실렛(sohxlet)을 통해 메탄올, 헥산, 톨루엔, 클로로포름 순으로 정제하였다. 얻어진 액체를 메탄올에 다시 침전시키고 필터로 여과한 후 건조시켜 암적색 고체인 유기 반도체 화합물 5를 얻었다(수득률 70%). The
1H-NMR (300 MHz, CDCl3): δ8.23(broad, 1H), 7.1-6.59(broad, 4H), 2.88(broad, 8H), 2.21(m 1H), 1.30-1.25(m, 72H), 1.04-0.88(m, 18H). 1 H-NMR (300 MHz, CDCl 3 ):? 8.23 (broad, 1H), 7.1-6.59 (broad, 4H), 2.88 ), 1.04-0.88 (m, 18H).
Mn: 34160 Mw: 56710 PDI: 1.66
Mn: 34160 Mw: 56710 PDI: 1.66
[실시예 7][Example 7]
본 발명의 실시예 2 내지 6에서 제조한 유기 반도체 화합물 1 내지 5 각각 0.0025g을 하기 표 1의 각각의 용매, 1.2475g을 첨가하여 용해도를 측정하였으며, 그 결과를 하기 표 1에 나타내었다. The solubilities of 0.0025 g of each of the
(O:매우 잘녹음, △:녹음) (O: very well recorded, △: recorded)
표 1에서 보이는 바와 같이 본 발명의 유기 반도체 화합물은 유기 용매에 대한 높은 용해도를 나타내었으며, 따라서 본 발명의 유기 반도체 화합물은 용액공정적용에 매우 유리한 것을 알 수 있다.As shown in Table 1, the organic semiconductor compound of the present invention exhibited a high solubility in an organic solvent, and thus the organic semiconductor compound of the present invention is very advantageous for the solution process application.
또한 본 발명의 실시예 2 내지 3 및 5에서 제조한 유기 반도체 화합물 1 내지 2 및 4를 용액상과 필름상에서의 UV 스펙트럼을 측정하였다.The UV spectra of the
도 2는 실시예 2의 유기 반도체 화합물의 용액상과 필름상에서의 UV스펙트럼을 나타낸 도면이며, 도 3과 도 4는 각각 실시예 3와 실시예 5의 유기 반도체 화합물의 용액상과 필름상에서의 UV스펙트럼을 나타낸 도면으로, 도 2 내지 도 4에서 보이는 바와 같이 용액상에서 보다 필름상에서 장파장영역으로 이동하는 것으로 보아, 분자간 파이결합이 증가하는 특성이 있음을 알 수 있으며, 이것으로 본 발명의 유기 반도체 화합물의 전자밀도가 높다는 것을 알 수 있다.FIG. 2 is a diagram showing the solution phase of the organic semiconductor compound of Example 2 and the UV spectrum on the film. FIG. 3 and FIG. 4 are graphs showing the solution phase of the organic semiconductor compound of Examples 3 and 5 and the UV As shown in FIG. 2 to FIG. 4, the transition from the solution phase to the long wavelength region on the film shows that the intermolecular pi bonding is increased. As a result, the organic semiconductor compound Is high.
또한 도 5 내지 7에 각각 실시예 2, 실시예 3 및 실시예 5의 유기 반도체 고분자 화합물의 TGA값을 나타낸 도면으로, 도 5 내지 7에서 보이는 바와 같이 본 발명의 유기 반도체 화합물의 열안정성이 높은 것을 알 수 있으며, 높은 열안정성으로 인해 본 발명의 유기 반도체 화합물을 채용한 유기박막 소자는 우수한 전기특성을 가질 수 있다.
5 to 7 show the TGA values of the organic semiconductor polymer compounds of Examples 2, 3 and 5, respectively. As shown in FIGS. 5 to 7, the organic semiconductor compound of the present invention has a high thermal stability And the organic thin film device employing the organic semiconductor compound of the present invention due to its high thermal stability can have excellent electrical characteristics.
[실시예 8][Example 8]
본 발명의 실시예 2 내지 6에서 제조한 유기 반도체 화합물을 전기화학적 특성을 분석하기 위해서 싸이클로 볼타메트리(CV)를 이용하여 측정하였다. Bu4NClO4(0.1 몰농도)의 용매 하에서 50 mV/s의 조건으로 측정하였으며, 측정 시 카본 전극을 사용하여 코팅을 통해 전압을 인가하였고 그 결과를 하기 도 2에 나타내었다.The electrochemical characteristics of the organic semiconductor compounds prepared in Examples 2 to 6 of the present invention were measured using cyclotolyte (CV). This was measured under the condition of 50 mV / s in a solvent of 4 NClO 4 (0.1 molar concentration). Voltage was applied through a coating using a carbon electrode during measurement, and the result is shown in FIG.
(Electrochemical)
(eV)Band gap
(Electrochemical)
(eV)
표 2에서 보이는 바와 같이 본 발명의 유기 반도체 화합물은 낮은 밴드값을 가지고 있어 전하의 이동도가 높아 본 발명의 유기 반도체 화합물을 채용한 유기박막 소자는 우수한 전기 특성을 가진다.
As shown in Table 2, the organic semiconductor compound of the present invention has a low band value and high charge mobility. Thus, the organic thin film device employing the organic semiconductor compound of the present invention has excellent electrical characteristics.
[실시예 9] 유기 반도체 화합물을 함유하는 유기박막 태양전지 소자제작[Example 9] Fabrication of an organic thin film solar cell element containing an organic semiconductor compound
양극 투명전극인 ITO (Indium Tin Oxide)가 코팅된 유리 기판을 세척용액이 포함된 탈이온수에 담궈, 초음파 세척기에 15분간 세척하고, 다시 탈이온수, 아세톤, IPA로 각각 3번씩 세정한 뒤, 130 ℃ 오븐에서 5시간 건조 시켰다. 상기와 같이 세척된 ITO 유리 기판은 15분 자외선/오존 처리를 한 뒤, 스핀코팅 공정을 통하여 정공 전달층인 PEDOT:PSS (Baytron P TP AI 4083, Bayer AG) 층이 40 nm 두께로 ITO 유리 기판 위에 코팅하였다. 그리고 120 ℃ 60분 열처리 공정을 진행하고, 유기 활성층을 도포하기 위하여 아르곤으로 충진 된 글로브 박스로 소자를 옮겼다. 유기 활성층은 실시예 2에서 제조한 유기 반도체 화합물과 PC71BM유도체 및 첨가제 (DIO;다이아이오도옥탄)을 하기 표 1에 나타낸 바와 같은 혼합비율로 1,2-디클로로벤젠 혹은 클로로벤젠을 용매에 녹여 75oC 에서 12시간동안 교반시킨 후 제조하여 0.45 μm (PTFE) syringe filter를 통해 필터링한 유기 반도체 용액으로 스핀코팅 방법(2000 ~ 3000rpm)을 통하여 80 nm 두께로 PEDOT:PSS 층 위에 도포하여 제조하였다. 그 후 전자전달층인 LiF와 음극 전극 알루미늄 증착을 위하여 진공 챔버로 소자를 옮겼다. LiF는 8 nm, 알루미늄은 진공도 1×10-6torr에서 100 nm 두께로 증착 되었다. 필요에 따라 형태학적 특성의 개선을 목표로 어닐링을 실시하기도 한다. 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 소자 특성을 측정하였다.(Oriel 1kW solarsimulator 사용)The glass substrate coated with ITO (Indium Tin Oxide), which is a positive electrode, was immersed in deionized water containing washing solution, washed with an ultrasonic washing machine for 15 minutes, washed again with deionized water, acetone and IPA three times, Lt; 0 > C for 5 hours. The ITO glass substrate thus cleaned was subjected to ultraviolet / ozone treatment for 15 minutes, and then a layer of PEDOT: PSS (Baytron P TP AI 4083, Bayer AG) as a hole transport layer was formed on the ITO glass substrate Lt; / RTI > Then, a heat treatment process was performed at 120 ° C for 60 minutes, and the device was transferred to a glove box filled with argon to apply the organic active layer. The organic active layer was prepared by dissolving 1,2-dichlorobenzene or chlorobenzene in a solvent in the mixing ratio shown in Table 1 below with the organic semiconductor compound prepared in Example 2, PC 71 BM derivative, and additive (DIO; diiodooctane) The solution was prepared by stirring for 12 hours at 75 ° C. The organic semiconductor solution was filtered through a 0.45 μm (PTFE) syringe filter and applied on a PEDOT: PSS layer with a thickness of 80 nm through a spin coating method (2000-3000 rpm) Respectively. After that, the electron transport layer, LiF, and the cathode electrode were moved to a vacuum chamber for aluminum deposition. LiF was deposited to a thickness of 8 nm, and aluminum was deposited to a thickness of 100 nm at a vacuum degree of 1 × 10 -6 torr. If necessary, annealing may be performed to improve morphological characteristics. The current density-voltage curve ( JV ) measurement was carried out using a Keithley 4200 source and the device characteristics were measured under a standard PVM132 (NREL, measured at an intensity of 100 mW / cm 2 ) under AM 1.5 G (using an
하기 표 1에 실시예 2에서 제조된 유기 반도체 화합물용액의 조성비율과 이를 활성층으로 함유하는 유기박막 태양전지 소자의 전기특성을 나타내었다.Table 1 shows the composition ratio of the organic semiconductor compound solution prepared in Example 2 and the electrical characteristics of the organic thin film solar cell device containing the same as the active layer.
(with DIO 2%)Blend ratio
(with DIO 2%)
본 발명에 따른 벤젠-디티에노티오펜 융합고리를 가지는 유기 반도체 화합물은 용매에 대한 용해도가 높고 도 8과 표 3에서 보이는 바와 같이 이를 광활성층으로 함유하는 유기박막 태양전지의 효율이 매우 높은 것을 알 수 있다.The organic semiconductor compound having a benzene-dithienothiophene fused ring according to the present invention has a high solubility in a solvent and shows an extremely high efficiency of an organic thin film solar cell containing the photoactive layer as shown in FIG. 8 and Table 3 .
또한 도 9는 상기 실시예 2에서 합성된 유기반도체 화합물 1을 PC71BM과 혼합하여 소자를 제작하였을 경우 나타나는 유기박막 태양전지 소자의 전기특성 의 에너지 광자효율을 나타낸 도면으로, 유기 반도체 화합물의 에너지 양자효율은 약 53%정도를 나타내고 있으며, 이는 기존의 유기태양전지 기본 물질인 P3HT 소자와 대비하여 더욱 더 넓은 흡수영역대를 가지며, 양자효율 또한 뛰어난 것을 확인 할 수 있다. 9 is a graph showing the energy photon efficiency of the organic thin film solar cell device when the device is manufactured by mixing the
Claims (12)
[화학식 6]
[화학식 7]
[화학식 8]
[화학식 9]
(상기 화학식 6 내지 9에서,
R5 및 R6는 서로 독립적으로 (C1-C20)알킬이며;
R11 및 R12는 서로 독립적으로 수소, 할로겐, (C1-C20)알킬, (C1-C20)알콕시, 하이드록시, 사아노기 또는 나이트로이며;
R21, R22, R29, R30, R33 및 R34은 서로 독립적으로, 수소, 할로겐, (C1-C20)알킬기, (C1-C20)알콕시 또는 (C6-C20)아르(C1-C20)알킬이며;
R41은 수소 또는 (C1-C20)알킬기이며;
n는 1 내지 500의 정수이다.)A photoactive layer containing an organic semiconductor compound represented by the following Chemical Formulas (6) to (9).
[Chemical Formula 6]
(7)
[Chemical Formula 8]
[Chemical Formula 9]
(In the above formulas 6 to 9,
R 5 and R 6 is Independently of one another are (C1-C20) alkyl;
R 11 and R 12 is (C1-C20) alkyl, (C1-C20) alkoxy, hydroxy, cyano or nitro;
R 21, R 22, R 29 , R 30, R 33 and R 34 are independently, hydrogen, halogen, (C1-C20) alkyl, (C1-C20) alkoxy or (C6-C20) aralkyl (C1-C20 each other ) Alkyl;
R 41 is hydrogen or a (C 1 -C 20) alkyl group;
and n is an integer of 1 to 500.)
상기 화학식 6 내지 화학식 9에서 R11 및 R12는 수소인 유기 반도체 화합물을 함유하는 광활성층.5. The method of claim 4,
In Formula 6) to (9 R 11, and R 12 is A photoactive layer containing an organic semiconductor compound which is hydrogen.
상기 화학식 6 내지 화학식 9에서 R5 및 R6은 서로 동일하게 (C1-C20)알킬인 유기 반도체 화합물을 함유하는 광활성층.5. The method of claim 4,
Formula 6 to R 5 and R 6 in the formula (9) is A photoactive layer containing an organic semiconductor compound that is the same as (C1-C20) alkyl.
상기 화학식 6 내지 화학식 9에서 R21, R22, R29, R30, R33 및 R34은 서로 독립적으로 수소, (C1-C20)알킬 또는 (C1-C20)알콕시인 유기 반도체 화합물을 함유하는 광활성층.5. The method of claim 4,
Wherein R 21 , R 22, R 29 , R 30 , R 33 and R 34 are independently of each other hydrogen, (C 1 -C 20) alkyl or (C 1 -C 20) alkoxy, Photoactive layer.
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