KR101311584B1 - Compounds with hole conducting property, their use as co-adsorbent materials, and dye-sensitized solar cell comprising the same - Google Patents
Compounds with hole conducting property, their use as co-adsorbent materials, and dye-sensitized solar cell comprising the same Download PDFInfo
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- KR101311584B1 KR101311584B1 KR1020100126540A KR20100126540A KR101311584B1 KR 101311584 B1 KR101311584 B1 KR 101311584B1 KR 1020100126540 A KR1020100126540 A KR 1020100126540A KR 20100126540 A KR20100126540 A KR 20100126540A KR 101311584 B1 KR101311584 B1 KR 101311584B1
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- South Korea
- Prior art keywords
- dye
- mmol
- bis
- solar cell
- sensitized solar
- Prior art date
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 44
- 239000003463 adsorbent Substances 0.000 title claims description 15
- 239000000463 material Substances 0.000 title description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 62
- 239000000126 substance Substances 0.000 claims description 19
- 239000003792 electrolyte Substances 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 230000031700 light absorption Effects 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 6
- IUYGRHUSDXNIPR-UHFFFAOYSA-N 4-[3,6-bis[4-(2-ethylhexoxy)phenyl]carbazol-9-yl]benzoic acid Chemical compound C1=CC(OCC(CC)CCCC)=CC=C1C1=CC=C(N(C=2C=CC(=CC=2)C(O)=O)C=2C3=CC(=CC=2)C=2C=CC(OCC(CC)CCCC)=CC=2)C3=C1 IUYGRHUSDXNIPR-UHFFFAOYSA-N 0.000 claims description 5
- UZCYGTFOAXIOHT-UHFFFAOYSA-N 4-[bis(9,9-dimethylfluoren-2-yl)amino]benzoic acid Chemical compound C1=C2C(C)(C)C3=CC=CC=C3C2=CC=C1N(C=1C=C2C(C)(C)C3=CC=CC=C3C2=CC=1)C1=CC=C(C(O)=O)C=C1 UZCYGTFOAXIOHT-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 3
- DLIZBISBBKKROV-UHFFFAOYSA-N 4-[4-(2-ethylhexoxy)-n-[4-(2-ethylhexoxy)phenyl]anilino]benzoic acid Chemical compound C1=CC(OCC(CC)CCCC)=CC=C1N(C=1C=CC(=CC=1)C(O)=O)C1=CC=C(OCC(CC)CCCC)C=C1 DLIZBISBBKKROV-UHFFFAOYSA-N 0.000 claims description 2
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 91
- 239000000975 dye Substances 0.000 description 69
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 44
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 41
- 235000019439 ethyl acetate Nutrition 0.000 description 35
- 230000000052 comparative effect Effects 0.000 description 33
- 230000015572 biosynthetic process Effects 0.000 description 32
- 238000006243 chemical reaction Methods 0.000 description 32
- 238000003786 synthesis reaction Methods 0.000 description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 31
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 28
- 239000000243 solution Substances 0.000 description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 238000004440 column chromatography Methods 0.000 description 17
- 125000001072 heteroaryl group Chemical group 0.000 description 16
- 239000010410 layer Substances 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- 239000002904 solvent Substances 0.000 description 15
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 229910010413 TiO 2 Inorganic materials 0.000 description 14
- 239000011521 glass Substances 0.000 description 14
- -1 hectyl Chemical group 0.000 description 14
- 125000006732 (C1-C15) alkyl group Chemical group 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 13
- KXGVEGMKQFWNSR-LLQZFEROSA-N deoxycholic acid Chemical compound C([C@H]1CC2)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)[C@@H](O)C1 KXGVEGMKQFWNSR-LLQZFEROSA-N 0.000 description 13
- 229960003964 deoxycholic acid Drugs 0.000 description 13
- KXGVEGMKQFWNSR-UHFFFAOYSA-N deoxycholic acid Natural products C1CC2CC(O)CCC2(C)C2C1C1CCC(C(CCC(O)=O)C)C1(C)C(O)C2 KXGVEGMKQFWNSR-UHFFFAOYSA-N 0.000 description 13
- 239000003960 organic solvent Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 238000005481 NMR spectroscopy Methods 0.000 description 11
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 10
- 229910044991 metal oxide Inorganic materials 0.000 description 10
- 150000004706 metal oxides Chemical class 0.000 description 10
- 239000004065 semiconductor Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 125000001424 substituent group Chemical group 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 8
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 230000005525 hole transport Effects 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- 125000002524 organometallic group Chemical group 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 5
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 5
- 238000004587 chromatography analysis Methods 0.000 description 5
- 125000004446 heteroarylalkyl group Chemical group 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 5
- VOAAEKKFGLPLLU-UHFFFAOYSA-N (4-methoxyphenyl)boronic acid Chemical compound COC1=CC=C(B(O)O)C=C1 VOAAEKKFGLPLLU-UHFFFAOYSA-N 0.000 description 4
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 4
- FIHILUSWISKVSR-UHFFFAOYSA-N 3,6-dibromo-9h-carbazole Chemical compound C1=C(Br)C=C2C3=CC(Br)=CC=C3NC2=C1 FIHILUSWISKVSR-UHFFFAOYSA-N 0.000 description 4
- 239000005711 Benzoic acid Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- 235000010233 benzoic acid Nutrition 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
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- 238000000605 extraction Methods 0.000 description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 238000005215 recombination Methods 0.000 description 4
- 230000006798 recombination Effects 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 3
- BPMXOBNFOWJWKL-UHFFFAOYSA-N 2,3,4-triphenylphosphinine Chemical compound C1=CC=CC=C1C1=CC=PC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 BPMXOBNFOWJWKL-UHFFFAOYSA-N 0.000 description 3
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 3
- QUJGDNCWTBTBQD-UHFFFAOYSA-N 3,5-dibromobenzonitrile Chemical compound BrC1=CC(Br)=CC(C#N)=C1 QUJGDNCWTBTBQD-UHFFFAOYSA-N 0.000 description 3
- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 3
- 229960002218 sodium chlorite Drugs 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 3
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 3
- FLTAFGBYWZLPJL-UHFFFAOYSA-N (3-borono-5-cyanophenyl)boronic acid Chemical compound OB(O)C1=CC(C#N)=CC(B(O)O)=C1 FLTAFGBYWZLPJL-UHFFFAOYSA-N 0.000 description 2
- PLKHKVHXKXGJAO-UHFFFAOYSA-N 1-bromo-4-(2-ethylhexoxy)benzene Chemical compound CCCCC(CC)COC1=CC=C(Br)C=C1 PLKHKVHXKXGJAO-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- ZFBGPHMLWLSONG-UHFFFAOYSA-N 2-[4-(2-ethylhexoxy)phenyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound C1=CC(OCC(CC)CCCC)=CC=C1B1OC(C)(C)C(C)(C)O1 ZFBGPHMLWLSONG-UHFFFAOYSA-N 0.000 description 2
- XLNULEGMGFVHBN-UHFFFAOYSA-N 2-[4-[4-(2-ethylhexoxy)-n-[4-(2-ethylhexoxy)phenyl]anilino]phenyl]acetic acid Chemical compound C1=CC(OCC(CC)CCCC)=CC=C1N(C=1C=CC(OCC(CC)CCCC)=CC=1)C1=CC=C(CC(O)=O)C=C1 XLNULEGMGFVHBN-UHFFFAOYSA-N 0.000 description 2
- DVLSJPCXPNKPRJ-UHFFFAOYSA-N 2-iodo-9,9-dimethylfluorene Chemical compound C1=C(I)C=C2C(C)(C)C3=CC=CC=C3C2=C1 DVLSJPCXPNKPRJ-UHFFFAOYSA-N 0.000 description 2
- VNYQUOAQPXGXQO-UHFFFAOYSA-N 2-iodo-9h-fluorene Chemical compound C1=CC=C2C3=CC=C(I)C=C3CC2=C1 VNYQUOAQPXGXQO-UHFFFAOYSA-N 0.000 description 2
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- SBXJPNKMWHONQH-UHFFFAOYSA-N 3,5-bis[4-[3,6-bis(4-methoxyphenyl)carbazol-9-yl]phenyl]benzonitrile Chemical compound C1=CC(OC)=CC=C1C1=CC=C(N(C=2C=CC(=CC=2)C=2C=C(C=C(C=2)C#N)C=2C=CC(=CC=2)N2C3=CC=C(C=C3C3=CC(=CC=C32)C=2C=CC(OC)=CC=2)C=2C=CC(OC)=CC=2)C=2C3=CC(=CC=2)C=2C=CC(OC)=CC=2)C3=C1 SBXJPNKMWHONQH-UHFFFAOYSA-N 0.000 description 2
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- MWLPIUMDWBZQMK-UHFFFAOYSA-N 9-(4-bromophenyl)-3,6-bis(4-methoxyphenyl)carbazole Chemical compound C1=CC(OC)=CC=C1C1=CC=C(N(C=2C=CC(Br)=CC=2)C=2C3=CC(=CC=2)C=2C=CC(OC)=CC=2)C3=C1 MWLPIUMDWBZQMK-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- MENPBKCQWFJFTO-UHFFFAOYSA-N CCCCC(CC)COC1=CC=C(C=C1)C2=C(C(=CC=C2)C(=O)O)N Chemical compound CCCCC(CC)COC1=CC=C(C=C1)C2=C(C(=CC=C2)C(=O)O)N MENPBKCQWFJFTO-UHFFFAOYSA-N 0.000 description 2
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
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- UOMCJERKHZESES-UHFFFAOYSA-N 1-(2-ethylhexoxy)-4-iodobenzene Chemical compound CCCCC(CC)COC1=CC=C(I)C=C1 UOMCJERKHZESES-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- VLHWNGXLXZPNOO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-(2-morpholin-4-ylethyl)pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)CCN1CCOCC1 VLHWNGXLXZPNOO-UHFFFAOYSA-N 0.000 description 1
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- 229910000906 Bronze Inorganic materials 0.000 description 1
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- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
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- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical class [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
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- 238000001914 filtration Methods 0.000 description 1
- 238000003818 flash chromatography Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
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- 208000037797 influenza A Diseases 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
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- 239000002184 metal Substances 0.000 description 1
- LZXXNPOYQCLXRS-UHFFFAOYSA-N methyl 4-aminobenzoate Chemical compound COC(=O)C1=CC=C(N)C=C1 LZXXNPOYQCLXRS-UHFFFAOYSA-N 0.000 description 1
- CZNGTXVOZOWWKM-UHFFFAOYSA-N methyl 4-bromobenzoate Chemical compound COC(=O)C1=CC=C(Br)C=C1 CZNGTXVOZOWWKM-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
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- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C229/52—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
- C07C229/54—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring
- C07C229/60—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring with amino and carboxyl groups bound in meta- or para- positions
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Hybrid Cells (AREA)
- Indole Compounds (AREA)
Abstract
본 발명은, 하기 화학식1 또는 화학식2로 표시되는 정공전도특성을 갖는 화합물, 그의 공흡착체로서의 용도, 및 그를 포함하는 태양전지에 관한 것이다.The present invention relates to a compound having a hole conducting property represented by the following formula (1) or (2), its use as a coadsorbent, and a solar cell comprising the same.
Description
본 발명은 정공전도특성을 갖는 화합물, 그의 공흡착체로서의 용도, 및 그를 포함하는 염료감응 태양전지에 관한 것이다.The present invention relates to a compound having hole conducting properties, its use as a co-adsorbent, and a dye-sensitized solar cell comprising the same.
염료감응 태양전지의 작동원리는, 표면에 염료분자가 화학적으로 흡착된 n-형 나노입자 반도체 산화물 전극에 태양 빛(가시광선)이 흡수되면 염료분자가 전자-홀 쌍을 생성하고, 상기 전자는 반도체 산화물의 전도띠로 주입되어 나노입자간 계면을 통하여 투명 전도성 막으로 전달되어 전류를 발생시키며, 상기 홀은 산화-환원 전해질에 의해 전자를 받아 다시 환원되는 메카니즘으로 설명될 수 있다. The principle of operation of dye-sensitized solar cells is that dye molecules generate electron-hole pairs when solar light (visible light) is absorbed by n-type nanoparticle semiconductor oxide electrodes with dye molecules chemically adsorbed on the surface. It is injected into the conduction band of the semiconductor oxide and transferred to the transparent conductive film through the inter-nanoparticle interface to generate a current, and the hole may be described as a mechanism for receiving electrons by the redox electrolyte and reducing them again.
특히, 염료감응 태양전지의 광전환 효율은 다른 종류의 태양전지와는 달리 셀 제작 공정보다도 재료의 특성에 크게 의존한다. 재료측면에서 염료감응 태양전지의 광전환 효율에 가장 많은 영향을 미치는 인자로는 염료(dye), 전해질(electrolyte), 및 투명 금속 산화물 나노 구조(metal oxide)를 들 수 있는데, 이 요소들을 얼마나 잘 조합시키느냐에 따라서 광전환 효율이 크게 좌우된다.In particular, the light conversion efficiency of dye-sensitized solar cells, unlike other types of solar cells, depends more on the properties of the material than the cell fabrication process. In terms of materials, the most influential factors in the light conversion efficiency of dye-sensitized solar cells include dyes, electrolytes, and transparent metal oxide nanostructures. The light conversion efficiency greatly depends on the combination.
유기염료는 1) 높은 흡광 효율(분자내 π→π* 전이)을 나타내어 빛을 잘 흡수할 수 있고, 2) 다양한 구조의 분자설계가 용이하여 흡수 파장대를 자유롭게 조절할 수 있으며, 3) 금속을 사용하지 않음으로써 자원적인 제약이 없으며, 4) 유기금속 염료보다 훨씬 저가로 합성될 수 있다는 장점이 있다. 그에 반해 1) 유기금속 염료에 비해 아직은 효율이 낮고, 2) π-컨쥬게이션 유기 분자의 특성상 분자간 인력에 의한 π-π 스택킹(stacking)이 발생하기 쉬우며, 3) 유기물의 특성상 광흡수 후 여기 상태(π*)의 수명이 짧으며, 4) 가시광선 영역에서 흡수 스펙트럼의 파장대 폭이 넓지 않아 가시광선 전파장대의 빛을 흡수하기 힘들다는 단점을 가지고 있다. Organic dyes can absorb light well by 1) high absorption efficiency (molecular π → π * transition), 2) molecular structure of various structure is easy, and absorption wavelength band can be freely controlled, and 3) metal is used. By not doing so, there is no resource limitation and 4) it can be synthesized at a much lower cost than organometallic dyes. In contrast, 1) its efficiency is still lower than that of organometallic dyes, and 2) π-π stacking is prone to occur due to intermolecular attraction due to the nature of π-conjugated organic molecules. The lifetime of the excited state (π * ) is short, and 4) it is difficult to absorb light in the visible light field because the wavelength band of the absorption spectrum is not wide in the visible light region.
현재까지 유기금속 염료를 사용하는 염료감응 태양전지의 효율은 11.2% 정도가 최고이며, 최근 유기염료가 빠른 속도로 발전하여 유기금속 염료의 최대효율에 접근하고 있지만, 아직까지 유기금속 염료보다 더 높은 효율이 보고된 적은 없으며, 유기금속 염료 또한 최고 효율이 지난 몇 년간 정체되어 있는 상태이다. 따라서 염료감응 태양전지의 효율을 증가시키려면 새로운 염료의 개발도 필요하지만, n형 반도체의 전도띠를 높일 수 있는 물질을 개발하여 개방전압(Voc)의 증가를 통하여 효율을 높일 수 있는 산화물 전극의 최적화가 필요하다. To date, the efficiency of dye-sensitized solar cells using organometallic dyes is about 11.2%, and recently, organic dyes have developed rapidly, approaching the maximum efficiency of organometallic dyes, but still higher than organometallic dyes. No efficiency has been reported, and organometallic dyes have also been stagnant for several years. Therefore, in order to increase the efficiency of dye-sensitized solar cells, it is necessary to develop new dyes. However, by developing a material that can increase the conduction band of n-type semiconductors, an oxide electrode can be improved by increasing the open voltage (V oc ). Optimization is required.
DSSC(dye sensitized solar cell)에서 염료의 분자구조는 중요한 역할을 하게 된다. DSSC는 빛을 흡수한 후 염료와 금속 산화물의 계면에서 전하분리를 시작하는데, 이때 염료의 에너지 준위와 금속산화물 계면에서의 전자이동과정에 의해 태양전지의 성능이 결정된다. The molecular structure of the dye plays an important role in the dye sensitized solar cell (DSSC). After absorbing light, DSSC starts charge separation at the interface between the dye and the metal oxide. The performance of the solar cell is determined by the energy level of the dye and the electron transfer process at the metal oxide interface.
염료의 분자설계 이외에 부가물을 첨가함으로서 DSSC의 효율을 증가시킬 수 있는데, 그 예로 TBP(4-tert-butylpyridine)의 첨가나 공흡착체(co-adsorbent)로서 데옥시콜린산(deoxycholic acid, DCA)의 이용을 들 수 있다. 구체적으로, DCA는 금속 산화물 표면에서 염료의 응집을 방지하여 염료에서 금속 산화물로의 전자주입 효율을 향상시킨다. 그리고 DCA의 사용으로 금속 산화물 표면에 흡착되는 염료양이 감소되는 것도 광전류와 광전압을 개선시키는 효과를 제공한다. 개방회로 전압(VOC)의 최고 값은 태양광 시뮬레이터(AM 1.5G, 100mWcm-2)로 조명하였을 때 금속 산화물의 페르미(Fermi) 준위와 산화환원 쌍의 산화환원 퍼텐셜의 차이이다. 전해질에 TBP를 첨가하는 것은 금속 산화물의 전도띠 준위를 크게 올리고, DSSC의 VOC와 fill factor(FF)를 향상시키기 때문에 전지의 전체적인 효율을 향상시킨다. VOC의 향상은 암전류의 감소 즉, 주입된 전자와 전해질에 포함된 트리요오드(I3 -) 사이의 재결합의 감소를 의미한다. In addition to the molecular design of the dye, addition of additives can increase the efficiency of DSSC. For example, the addition of TBP (4- tert- butylpyridine) or deoxycholic acid (DCA) as a co-adsorbent. ) Can be used. Specifically, DCA prevents agglomeration of the dye on the metal oxide surface to improve the electron injection efficiency from the dye to the metal oxide. And metal oxides with the use of DCA Reducing the amount of dye adsorbed on the surface also provides the effect of improving the photocurrent and photovoltage. The highest value of the open circuit voltage (V OC ) is the difference between the Fermi level of the metal oxide and the redox potential of the redox pair when illuminated by the solar simulator (AM 1.5G, 100 mWcm −2 ). The addition of TBP to the electrolyte increases the conduction band level of the metal oxide and improves the overall efficiency of the cell because it improves the V OC and fill factor (FF) of the DSSC. An improvement in V OC means a reduction in dark current, ie a reduction in recombination between the injected electrons and the triiode (I 3 − ) contained in the electrolyte.
그러나 상기와 같은 종래의 방법은 주입된 전자와 산화된 염료 및 전해질의 I3 - 이온간의 재결합을 충분히 억제하지 못하기 때문에, DSSC가 이론적인 값보다 낮은 VOC를 나타내는 실질적인 원인으로 작용하는 것으로 보인다. However, such a conventional method does not sufficiently suppress the recombination between the injected electrons, the oxidized dye and the I 3 − ions of the electrolyte, and therefore appears to be a substantial cause of DSSC showing lower V OC than the theoretical value. .
본 발명은 기존에 사용해오던 데옥시콜린산(DCA)의 대용으로 사용할 수 있는 새로운 개념의 공흡착체로서, The present invention is a new concept co-adsorber that can be used as a substitute for deoxycholic acid (DCA),
기존의 I3 -/I-시스템의 산화-환원 전위 보다 낮은 새로운 산화-환원 전위를 형성하여 염료와의 개방전압손실을 줄이며, 또한 기본 전위 보다 낮아진 산화-환원 전위로 인하여 n형 반도체 전도띠의 페르미 레벨과의 전위차를 더욱 크게 형성하여 개방전압(Voc)을 높이며, 염료들의 응집을 방지하여 염료에서 금속 산화물로의 전자주입 효율을 높여 Jsc값을 상승시키며, 높은 정공(홀) 수송 능력으로 전기전도도 및 이온 전도도를 향상시켜서 TiO2/염료/전해질 계면에서 저항을 낮추고 더 높은 Jsc값을 제공하며, 분자량이 작아서 기공 채움(Pore filling)에 대한 문제 없이 TiO2 계면에 흡착이 가능하여 염료분자에 생긴 홀이 공흡착체 물질로 더욱더 빠르게 이동되게 하며, TiO2로 구성되는 반도체층과 요오드를 포함하는 전해질의 계면에서 일어나는 전자의 재결합을 감소시키는 정공전도특성을 갖는 화합물을 제공하는 것을 목적으로 한다.Existing I 3 - / I - oxidation of the system low new oxidation than the reduction potential of - forming a reduction potential to reduce the open-circuit voltage losses of the dye, also lower oxidation than the base potential - of the n-type semiconductor conduction band due to the reduction potential By increasing the potential difference with Fermi level to increase the open voltage (V oc ), prevent the aggregation of the dyes to increase the electron injection efficiency from the dye to the metal oxide to increase the Jsc value, high hole (hole) transport capacity Improved electrical and ionic conductivity reduces the resistance at the TiO 2 / dye / electrolyte interface, provides higher Jsc values, and the small molecular weight allows adsorption at the TiO 2 interface without problems of pore filling. Holes formed in TiO 2 are made to move faster and faster to the adsorbent material. It is an object of the present invention to provide a compound having a hole conduction property that reduces recombination of electrons occurring at an interface of an electrolyte including a semiconductor layer and iodine.
또한, 본 발명은 상기 정공전도특성을 갖는 공흡착체를 광흡수층에 포함함으로써 광전류와 광전압이 개선되는 염료감응 태양전지를 제공하는 것을 목적으로 한다.In addition, an object of the present invention is to provide a dye-sensitized solar cell in which the photocurrent and the photovoltage are improved by including the co-adsorbent having the hole conduction characteristics in the light absorption layer.
본 발명은, According to the present invention,
하기 화학식1 또는 화학식2로 표시되는 화합물을 제공한다:It provides a compound represented by the following formula (1) or formula (2):
상기 식에서In the above formula
R1, R2, R3, R4, R5 및 R6는 각각 독립적으로 수소; C1~C15의 알콕시로 치환 또는 비치환된 C1~C15의 알킬; C1~C15의 알킬로 치환 또는 비치환된 C1~C15의 알콕시; C1~C15의 알콕시로 치환된 C1~C15의 알콕시; C1~C15의 알콕시로 치환 또는 비치환된 C1~C15의 알킬, C1~C15의 알킬로 치환 또는 비치환된 C1~C15의 알콕시, 및 C1~C15의 알콕시로 치환된 C1~C15의 알콕시로 이루어진 군으로부터 선택되는 치환기로 치환 또는 비치환된 C5~C20의 아릴 또는 헤테로 아릴; 또는 C1~C15의 알콕시로 치환 또는 비치환된 C1~C15의 알킬, C1~C15의 알킬로 치환 또는 비치환된 C1~C15의 알콕시, 및 C1~C15의 알콕시로 치환된 C1~C15의 알콕시로 이루어진 군으로부터 선택되는 치환기로 치환 또는 비치환된 C6~C22의 아릴알킬 또는 헤테로 아릴알킬기이며;R1, R2, R3, R4, R5 and R6 are each independently hydrogen; C1 to C15 alkyl substituted or unsubstituted with C1 to C15 alkoxy; C1-C15 alkoxy optionally substituted with C1-C15 alkyl; C1 to C15 alkoxy substituted with C1 to C15 alkoxy; C1-C15 alkyl substituted or unsubstituted with C1-C15 alkoxy, C1-C15 alkoxy substituted or unsubstituted with C1-C15 alkyl, and C1-C15 alkoxy substituted with alkoxy of C1-C15 C5 ~ C20 aryl or hetero aryl unsubstituted or substituted with a substituent selected from the group; Or C1-C15 alkoxy substituted or unsubstituted with C1-C15 alkoxy, C1-C15 alkoxy substituted or unsubstituted with C1-C15 alkoxy, and C1-C15 alkoxy substituted with alkoxy of C1-C15 A C 6 -C 22 arylalkyl or hetero arylalkyl group unsubstituted or substituted with a substituent selected from the group consisting of;
R7은 결합 또는 부존재이며,R7 is a bond or absent,
R8 및 R9은 하나 또는 두개의 C1~C5의 알킬기로 치환 또는 비치환된 메틸렌기이거나 부존재이며; R8 and R9 are methylene groups unsubstituted or substituted with one or two C1 to C5 alkyl groups;
Ar은 C5~C20의 아릴 또는 헤테로 아릴이며, 상기 헤테로 아릴은 O, S 및 N으로 이루어진 군으로부터 선택되는 1~3개의 헤테로 원소를 포함하며;Ar is C5-C20 aryl or hetero aryl, wherein the hetero aryl comprises 1 to 3 hetero elements selected from the group consisting of O, S and N;
m은 0~5의 정수이고;m is an integer from 0 to 5;
n, o 및 p는 각각 독립적으로 0 또는 1이며;n, o and p are each independently 0 or 1;
단, 상기 Ar이 헤테로 아릴인 경우, R3, R4, R5 및 R6 중 하나 이상은 부존재하는 것일 수 있다. However, when Ar is hetero aryl, one or more of
상기 식에서In the above formula
R1, R2, R10 및 R11은 각각 독립적으로 수소; C1~C15의 알콕시로 치환 또는 비치환된 C1~C15의 알킬; C1~C15의 알킬로 치환 또는 비치환된 C1~C15의 알콕시; C1~C15의 알콕시로 치환된 C1~C15의 알콕시; C1~C15의 알콕시로 치환 또는 비치환된 C1~C15의 알킬, C1~C15의 알킬로 치환 또는 비치환된 C1~C15의 알콕시, 및 C1~C15의 알콕시로 치환된 C1~C15의 알콕시로 이루어진 군으로부터 선택되는 치환기로 치환 또는 비치환된 C5~C20의 아릴 또는 헤테로 아릴; 또는 C1~C15의 알콕시로 치환 또는 비치환된 C1~C15의 알킬, C1~C15의 알킬로 치환 또는 비치환된 C1~C15의 알콕시, 및 C1~C15의 알콕시로 치환된 C1~C15의 알콕시로 이루어진 군으로부터 선택되는 치환기로 치환 또는 비치환된 C6~C22의 아릴알킬 또는 헤테로 아릴알킬기이며;R 1,
Ar은 C5~C20의 아릴 또는 헤테로 아릴이며, 상기 헤테로 아릴은 O, S 및 N으로 이루어진 군으로부터 선택되는 1~3개의 헤테로 원소를 포함하며;Ar is C5-C20 aryl or hetero aryl, wherein the hetero aryl comprises 1 to 3 hetero elements selected from the group consisting of O, S and N;
n은 0 내지 3의 정수이다.
n is an integer of 0 to 3;
또한, 본 발명은,Further, according to the present invention,
상기 화학식1 또는 화학식2로 표시되는 화합물을 포함하는 정공전도특성을 갖는 공흡착체를 제공한다.
It provides a coadsorption body having a hole conduction property comprising a compound represented by the formula (1) or (2).
또한, 본 발명은,Further, according to the present invention,
상기 정공전도특성을 갖는 공흡착체를 광흡수층에 포함하는 것을 특징으로 하는 염료감응 태양전지를 제공한다.It provides a dye-sensitized solar cell, characterized in that it comprises a co-adsorbent having the hole conductivity in the light absorption layer.
본 발명의 정공전도특성을 갖는 화합물은 기존의 I3 -/I-시스템의 산화-환원 전위 보다 새로운 산화-환원 전위를 형성하여 염료와의 개방전압손실을 줄여주며, 또한 낮아진 산화-환원 전위로 인하여 n형 반도체의 전도띠의 페르미 레벨과의 전위차를 더욱 크게 형성하여 개방전압(Voc)을 더욱 증가시키는 효과를 제공한다.A compound having a hole-conductive properties of the present invention is conventional I 3 - a reduction potential of - reduces the open circuit voltage losses and to form a reduction potential of the dye, also lower oxidation - / I-system oxide-new oxidation than the reduction potential Therefore, the potential difference with the Fermi level of the conduction band of the n-type semiconductor is further increased to provide an effect of further increasing the open voltage V oc .
또한, 염료들의 응집을 방지하여 염료에서 금속 산화물로의 전자주입 효율을 높여 Jsc값을 상승시키며, 높은 정공(홀) 수송 능력으로 전기전도도 및 이온 전도도를 향상시켜서 TiO2/염료/전해질 계면 사이의 저항을 낮춰 더 높은 Jsc값을 제공하며, 분자량이 작아서 기공 채움에 대한 문제 없이 TiO2 계면에 흡착 가능하여 염료분자에 생긴 홀이 공흡착체 물질로 더욱더 빠르게 이동되게 하며, TiO2로 구성되는 반도체층과 요오드를 포함하는 전해질의 계면에서 일어나는 전자의 재결합을 감소시켜서 궁극적으로 염료감응 태양전지의 광전류와 광전압을 향상시키는 효과를 제공한다.In addition, it prevents agglomeration of dyes to increase the electron injection efficiency from dyes to metal oxides, thereby increasing the Jsc value, and improving the electrical conductivity and ion conductivity by the high hole (hole) transport ability, thereby improving the TiO 2 / dye / electrolyte interface. Lower resistance provides higher Jsc value, small molecular weight allows adsorption at TiO 2 interface without problems of pore filling, allowing holes in dye molecules to move more rapidly to co-adsorbent material, consisting of TiO 2 By reducing the recombination of electrons occurring at the interface of the electrolyte containing the semiconductor layer and iodine it ultimately provides the effect of improving the photocurrent and photovoltage of the dye-sensitized solar cell.
또한, 본 발명의 정공전도특성을 발현하는 화합물은 가격이 저렴하여 태양전지의 효율을 향상시키는데 매우 유용하게 사용될 수 있다.In addition, the compound expressing the hole conduction characteristics of the present invention can be very useful to improve the efficiency of the solar cell is low cost.
도1은 염료감응 태양전지에서 정공전도특성을 갖는 공흡착체의 역할을 도식화하여 나타낸 것이다.
도2는 실시예 및 비교예에서 제조한 염료 용액을 TiO2필름에 흡착시켜서 측정한 UV-vis absorption spectra 그래프이다.
도3은 실시예 및 비교예에서 제조한 염료감응 태양전지의 전류-전압곡선 그래프이다.
도4는 실시예 및 비교예에서 제조한 염료감응 태양전지의 광전변환효율(IPCE) 그래프이다.
도5는 염료감응 태양전지 내에서의 전하이동 저항을 측정하기 위하여 1 sun(100mW/cm2) 조건하에서 AC 임피던스를 측정한 Nyquist plot이다.
도6은 실시예 및 비교예에서 제조한 염료 용액의 태양전지 내에서의 내부 저항을 구하기 위하여 설정한 등가회로를 나타낸다.
도7은 실시예 및 비교예에서 제조한 염료감응 태양전지의 전류-전압곡선 그래프이다.
도8은 실시예 및 비교예에서 제조한 염료감응 태양전지의 광전변환효율(IPCE) 그래프이다.Figure 1 illustrates the role of the co-adsorber having hole conductivity in the dye-sensitized solar cell.
FIG. 2 is a UV-vis absorption spectra graph measured by adsorbing dye solutions prepared in Examples and Comparative Examples onto TiO 2 films.
3 is a current-voltage curve graph of the dye-sensitized solar cells prepared in Examples and Comparative Examples.
Figure 4 is a graph of the photoelectric conversion efficiency (IPCE) of the dye-sensitized solar cells prepared in Examples and Comparative Examples.
FIG. 5 is a Nyquist plot measuring AC impedance under 1 sun (100 mW / cm 2 ) condition to measure charge transfer resistance in dye-sensitized solar cells. FIG.
Fig. 6 shows an equivalent circuit set to find the internal resistance in the solar cell of the dye solutions prepared in Examples and Comparative Examples.
7 is a current-voltage curve graph of the dye-sensitized solar cells prepared in Examples and Comparative Examples.
8 is a graph of photoelectric conversion efficiency (IPCE) of the dye-sensitized solar cells prepared in Examples and Comparative Examples.
본 발명은, 하기 화학식1로 표시되는 화합물에 관한 것이다: The present invention relates to a compound represented by the following general formula (1):
[화학식1][Chemical Formula 1]
상기 식에서In the above formula
R1, R2, R3, R4, R5 및 R6는 각각 독립적으로 수소; C1~C15의 알콕시로 치환 또는 비치환된 C1~C15의 알킬; C1~C15의 알킬로 치환 또는 비치환된 C1~C15의 알콕시; C1~C15의 알콕시로 치환된 C1~C15의 알콕시; C1~C15의 알콕시로 치환 또는 비치환된 C1~C15의 알킬, C1~C15의 알킬로 치환 또는 비치환된 C1~C15의 알콕시, 및 C1~C15의 알콕시로 치환된 C1~C15의 알콕시로 이루어진 군으로부터 선택되는 치환기로 치환 또는 비치환된 C5~C20의 아릴 또는 헤테로 아릴; 또는 C1~C15의 알콕시로 치환 또는 비치환된 C1~C15의 알킬, C1~C15의 알킬로 치환 또는 비치환된 C1~C15의 알콕시, 및 C1~C15의 알콕시로 치환된 C1~C15의 알콕시로 이루어진 군으로부터 선택되는 치환기로 치환 또는 비치환된 C6~C22의 아릴알킬 또는 헤테로 아릴알킬기이며;R1, R2, R3, R4, R5 and R6 are each independently hydrogen; C1 to C15 alkyl substituted or unsubstituted with C1 to C15 alkoxy; C1-C15 alkoxy optionally substituted with C1-C15 alkyl; C1 to C15 alkoxy substituted with C1 to C15 alkoxy; C1-C15 alkyl substituted or unsubstituted with C1-C15 alkoxy, C1-C15 alkoxy substituted or unsubstituted with C1-C15 alkyl, and C1-C15 alkoxy substituted with alkoxy of C1-C15 C5 ~ C20 aryl or hetero aryl unsubstituted or substituted with a substituent selected from the group; Or C1-C15 alkoxy substituted or unsubstituted with C1-C15 alkoxy, C1-C15 alkoxy substituted or unsubstituted with C1-C15 alkoxy, and C1-C15 alkoxy substituted with alkoxy of C1-C15 A C 6 -C 22 arylalkyl or hetero arylalkyl group unsubstituted or substituted with a substituent selected from the group consisting of;
R7은 결합 또는 부존재이며,R7 is a bond or absent,
R8 및 R9은 하나 또는 두개의 C1~C5의 알킬기로 치환 또는 비치환된 메틸렌기이거나 부존재이며; R8 and R9 are methylene groups unsubstituted or substituted with one or two C1 to C5 alkyl groups;
Ar은 C5~C20의 아릴 또는 헤테로 아릴이며, 상기 헤테로 아릴은 O, S 및 N으로 이루어진 군으로부터 선택되는 1~3개의 헤테로 원소를 포함하며;Ar is C5-C20 aryl or hetero aryl, wherein the hetero aryl comprises 1 to 3 hetero elements selected from the group consisting of O, S and N;
m은 0~5의 정수이고;m is an integer from 0 to 5;
단, 상기 Ar이 헤테로 아릴인 경우, R3, R4, R5 및 R6 중 하나 이상은 부존재하는 것일 수 있다. However, when Ar is hetero aryl, one or more of
상기 화학식1로 표시되는 화합물은 우수한 정공전도특성을 갖는다.
The compound represented by Chemical Formula 1 has excellent hole conductivity.
본 발명은, 하기 화학식2로 표시되는 화합물에 관한 것이다: The present invention relates to a compound represented by the following general formula (2):
[화학식2](2)
상기 식에서In the above formula
R1, R2, R10 및 R11은 각각 독립적으로 수소; C1~C15의 알콕시로 치환 또는 비치환된 C1~C15의 알킬; C1~C15의 알킬로 치환 또는 비치환된 C1~C15의 알콕시; C1~C15의 알콕시로 치환된 C1~C15의 알콕시; C1~C15의 알콕시로 치환 또는 비치환된 C1~C15의 알킬, C1~C15의 알킬로 치환 또는 비치환된 C1~C15의 알콕시, 및 C1~C15의 알콕시로 치환된 C1~C15의 알콕시로 이루어진 군으로부터 선택되는 치환기로 치환 또는 비치환된 C5~C20의 아릴 또는 헤테로 아릴; 또는 C1~C15의 알콕시로 치환 또는 비치환된 C1~C15의 알킬, C1~C15의 알킬로 치환 또는 비치환된 C1~C15의 알콕시, 및 C1~C15의 알콕시로 치환된 C1~C15의 알콕시로 이루어진 군으로부터 선택되는 치환기로 치환 또는 비치환된 C6~C22의 아릴알킬 또는 헤테로 아릴알킬기이며;R 1,
Ar은 C5~C20의 아릴 또는 헤테로 아릴이며, 상기 헤테로 아릴은 O, S 및 N으로 이루어진 군으로부터 선택되는 1~3개의 헤테로 원소를 포함하며;Ar is C5-C20 aryl or hetero aryl, wherein the hetero aryl comprises 1 to 3 hetero elements selected from the group consisting of O, S and N;
n은 1 내지 3의 정수이다. n is an integer of 1 to 3;
상기 화학식1로 표시되는 화합물은 우수한 정공전도특성을 갖는다.
The compound represented by Chemical Formula 1 has excellent hole conductivity.
상기 화학식1 또는 화학식2에 있어서, In Chemical Formula 1 or
각각의 치환기에 포함된 C1~C15의 알킬기로는 메틸, 에틸, 프로필, 부틸, 펜틸, 헥틸, 헵틸 또는 옥틸기 등이 바람직하고, C1~C15의 알콕시기로는 메톡시, 에톡시, 프로폭시, 부톡시, 펜톡시, 헥톡시 또는 헵톡시기 등이 바람직하다.As the alkyl group of C1 to C15 included in each substituent, methyl, ethyl, propyl, butyl, pentyl, hectyl, heptyl or octyl group and the like are preferable, and as the alkoxy group of C1 to C15, methoxy, ethoxy, propoxy, Butoxy, pentoxy, hexoxy or heptoxy groups are preferred.
예컨대, C1~C15의 알콕시로 치환된 C1~C15의 알킬기로는 부톡시메틸, 부톡시에틸, 헥톡시메틸, 헵톡시메틸 등을 들 수 있으며, C1~C15의 알킬로 치환된 C1~C15의 알콕시기로는 2-에틸헵틸옥시, 3-에틸헵틸옥시, 2-메틸부틸옥시, 2-에틸펜틸옥시, 3-에틸펜틸옥시기 등을 들 수 있으며, C1~C15의 알콕시로 치환된 C1~C15의 알콕시기로는 3-메톡시펜톡시, 3-에톡시펜톡시, 3-프로톡시펜톡시, 2-메톡시헥톡시, 2-에톡시헥톡시, 2-프로톡시헥톡시기 등을 들 수 있다.For example, C1-C15 alkyl group substituted with C1-C15 alkoxy may include butoxymethyl, butoxyethyl, hexoxymethyl, heptoxymethyl, and the like of C1-C15 substituted with alkyl of C1-C15. Examples of the alkoxy group include 2-ethylheptyloxy, 3-ethylheptyloxy, 2-methylbutyloxy, 2-ethylpentyloxy, and 3-ethylpentyloxy group, and C1 to C15 substituted with alkoxy of C1 to C15. Examples of the alkoxy group include 3-methoxypentoxy, 3-ethoxypentoxy, 3-propoxypentoxy, 2-methoxyhexoxy, 2-ethoxyhexoxy and 2-prooxyhexoxy group. .
또한, C5~C20의 아릴 또는 헤테로 아릴기, 및 C6~C22의 아릴알킬 또는 헤테로 아릴알킬기에 포함되는 아릴기 또는 헤테로 아릴기로는, 이에 한정되는 것은 아니나, 페닐, 나프틸, 티오페닐, 안트라실, 이미다졸, 피리딘, 옥사졸, 티아졸, 퀴놀린, 에닷(EDOT,3,4-ethylenedioxythiophene) 등을 들 수 있다. The aryl or heteroaryl group of C5 to C20 and the aryl or heteroaryl group of the C6 to C22 arylalkyl or heteroarylalkyl group include, but are not limited to, phenyl, naphthyl, thiophenyl, anthracyl , Imidazole, pyridine, oxazole, thiazole, quinoline, EDOT (3,4-ethylenedioxythiophene) and the like.
상기 Ar로는, 이에 한정되는 것은 아니지만, 페닐, 나프탈렌, 안트라센, 이미다졸, 피리딘, 옥사졸, 티아졸, 퀴놀린, 에닷(EDOT) 등을 들 수 있다. Examples of the Ar include, but are not limited to, phenyl, naphthalene, anthracene, imidazole, pyridine, oxazole, thiazole, quinoline and EDOT.
본 발명의 치환기들에 포함된 알킬기는 측쇄 또는 분지쇄 형태일 수 있다.
Alkyl groups included in the substituents of the present invention may be in the form of branched or branched chains.
본 발명의 정공전도특성을 갖는 화합물은 염료감응 태양전지에 있어서 데옥시콜린산(DCA)의 대용으로 사용될 수 있는 새로운 개념의 정공전도특성을 갖는 공흡착체로서, 염료의 응집을 방지하는 기능이 우수할 뿐만 아니라, 작은 분자량에 의해 TiO2 계면까지 침투하는 것이 가능하여 Pore filling 문제도 최소화하는 특징을 갖는다.
The compound having the hole conductivity of the present invention is a coadsorbent having a new concept of hole conductivity that can be used as a substitute for deoxycholic acid (DCA) in dye-sensitized solar cells. Not only is it excellent, it can penetrate to the TiO 2 interface by small molecular weight, which minimizes the pore filling problem.
이하에서, 본 발명의 신규한 화합물들의 구체예와 제조방법을 예를들어 설명한다. Hereinafter, specific examples and preparation methods of the novel compounds of the present invention will be described by way of example.
상기 화학식1 및 화학식2의 화합물의 구체적인 예로는 하기 화학식3 내지 화학식10의 화합물을 들을 수 있다. Specific examples of the compound of Formula 1 and
[화학식3](3)
상기 화학식3의 화합물은 카바졸을 포함하는 것을 특징으로 하며, 구조 내에 비공유 전자쌍을 갖는 질소 원자와 2중 결합을 포함하므로 정공의 수송능력이 우수하다.
The compound of
[화학식4][Chemical Formula 4]
상기 화학식4의 화합물은 트리페닐아민 구조를 포함하는 것을 특징으로 하며, 구조 내에 비공유 전자쌍을 갖는 질소 원자와 2중 결합을 포함하므로 정공의 수송능력이 우수하다.The compound of Formula 4 is characterized by having a triphenylamine structure. Since the compound contains a nitrogen atom and a double bond having a non-covalent electron pair in the structure, the hole transporting ability is excellent.
상기 화학식4의 화합물 중 2-(4-(비스(4-(2-에틸헥실옥시)페닐)아미노)페닐)아세트산은 하기의 반응식1에 의해 제조될 수 있다. 더 자세한 내용은 하기 실시예1 에서 설명된다.2- (4- (bis (4- (2-ethylhexyloxy) phenyl) amino) phenyl) acetic acid in the compound of Formula 4 may be prepared by the following Scheme 1. More details are described in Example 1 below.
[반응식1][Reaction Scheme 1]
[화학식5] [Chemical Formula 5]
상기 화학식5의 화합물은 트리페닐아민 구조를 포함하는 것을 특징으로 하며, 구조 내에 비공유 전자쌍을 갖는 질소 원자와 2중 결합을 포함하므로 정공의 수송능력이 우수하다.
The compound of
[화학식6] [Chemical Formula 6]
상기 화학식6의 화합물은 나프탈렌과 다이페닐 아민 구조를 포함하는 것을 특징으로 하며, 구조 내에 비공유 전자쌍을 갖는 질소 원자와 2중 결합을 포함하므로 정공의 수송능력이 우수하다.
The compound of
[화학식7] (7)
상기 화학식7의 화합물은 다이플루오렌과 페닐아민 구조를 포함하는 것을 특징으로 하며, 구조 내에 비공유 전자쌍을 갖는 질소 원자와 2중 결합을 포함하므로 정공의 수송능력이 우수하다.The compound of formula (7) is characterized in that it comprises a difluorene and phenylamine structure, because it contains a nitrogen bond and a double bond having a non-covalent electron pair in the structure is excellent in the hole transport ability.
상기 화학식7의 화합물 중 4-(비스(9,9-디메틸-9H-플루오렌-2-일)아미노)벤조산은 하기의 반응식2에 의해 제조될 수 있다. 더 자세한 내용은 하기 실시예2에서 설명된다.4- (bis (9,9-dimethyl-9H-fluoren-2-yl) amino) benzoic acid in the compound of Formula 7 may be prepared by the following
[반응식 2][Reaction Scheme 2]
[화학식8] [Chemical Formula 8]
상기 화학식8의 화합물은 카바졸을 포함하는 것을 특징으로 하며, 구조 내에 비공유 전자쌍을 갖는 질소 원자와 2중 결합을 포함하므로 정공의 수송능력이 우수하다.The compound of formula (8) is characterized by containing a carbazole. Since it contains a nitrogen atom having a non-covalent electron pair in the structure and a double bond, the hole transport ability is excellent.
상기 화학식8에 포함되는 화합물 중 4-(3,6-비스(4-(2-에틸헥실옥시)페닐)-9H-카바졸-9-일)벤조산은 하기의 반응식3에 의해 제조될 수 있다. 더 자세한 내용은 하기 실시예3에서 설명된다.4- (3,6-bis (4- (2-ethylhexyloxy) phenyl) -9H-carbazol-9-yl) benzoic acid in the compound of
[반응식 3]
[화학식9] [Chemical Formula 9]
상기 화학식9의 화합물은 카바졸을 포함하는 것을 특징으로 하며, 구조 내에 비공유 전자쌍을 갖는 질소 원자와 2중 결합을 포함하므로 정공의 수송능력이 우수하다.The compound of formula (9) is characterized by containing a carbazole. Since it contains a nitrogen atom and a double bond having a non-covalent electron pair in the structure, the hole transport ability is excellent.
[화학식10][Chemical formula 10]
[화학식11](11)
상기 화학식10 및 11의 화합물은 벤조산의 메타 위치에 두 개의 카바졸을 포함하는 것을 특징으로 하며, 구조 내에 비공유 전자쌍을 갖는 질소 원자와 2중 결합을 포함하므로 정공전도 능력이 우수하다. The compounds of
상기 화학식3 내지 화학식11에서, R1, R2, R3, R4, R5, R6, R10, R11 및 m의 정의는 상기 화학식1 및 화학식2에서 정의된 바와 같다.
In
상기 화학식1 및 화학식2의 화합물의 구체적인 예는 다음과 같다:Specific examples of the compound of Formula 1 and
4-(N,N-비스(4-(2-에틸헥실옥시)페닐)아미노)벤조산,4- (N, N-bis (4- (2-ethylhexyloxy) phenyl) amino) benzoic acid,
2-(4-(N,N-비스(4-(2-에틸헥실옥시)페닐)아미노)페닐)아세트산,2- (4- (N, N-bis (4- (2-ethylhexyloxy) phenyl) amino) phenyl) acetic acid,
4-(3,6-비스(4-부톡시페닐)-9H-카바졸-9-일)벤조산4- (3,6-bis (4-butoxyphenyl) -9H-carbazol-9-yl) benzoic acid
4-(N,N-비스(4-부톡시페닐)아미노)-2,3,5,6-테트라메틸벤조산,4- (N, N-bis (4-butoxyphenyl) amino) -2,3,5,6-tetramethylbenzoic acid,
4-(N,N-비스(4-부톡시페닐)아미노)-1-나프토산,4- (N, N-bis (4-butoxyphenyl) amino) -1-naphthoic acid,
4-(N,N-비스(9,9-디메틸-9H-플루오렌-2-일)아미노)벤조산,4- (N, N-bis (9,9-dimethyl-9H-fluoren-2-yl) amino) benzoic acid,
4-(3,6-비스(4-(2-에틸헥실옥시)페닐)-9H-카바졸-9-일)벤조산,4- (3,6-bis (4- (2-ethylhexyloxy) phenyl) -9H-carbazol-9-yl) benzoic acid,
3,5-비스[3,6-비스(4-부톡시페닐)-9H-카바졸-9-일]벤조산, 3,5-bis [3,6-bis (4-butoxyphenyl) -9H-carbazol-9-yl] benzoic acid,
3,5-비스[3,6-비스(4-(2-에틸헥실옥시)페닐)-9H-카바졸-9-일]벤조산,3,5-bis [3,6-bis (4- (2-ethylhexyloxy) phenyl) -9H-carbazol-9-yl] benzoic acid,
3,5-비스[4-(3,6-비스(4-부톡시페닐)-9H-카바졸-9-일)페닐]벤조산, 3,5-bis [4- (3,6-bis (4-butoxyphenyl) -9H-carbazol-9-yl) phenyl] benzoic acid,
3,5-비스[4-(3,6-비스(4-(2-에틸헥실옥시)페닐)-9H-카바졸-9-일)페닐]벤조산
3,5-bis [4- (3,6-bis (4- (2-ethylhexyloxy) phenyl) -9H-carbazol-9-yl) phenyl] benzoic acid
상기 화학식1 및 화학식2로 표시되는 화합물은 공흡착체로서 유용하게 사용될 수 있다. 따라서, 본 발명은 상기 화학식1 및 화학식2로 표시되는 화합물을 포함하는 전공전도특성을 갖는 공흡착체를 제공한다.
The compounds represented by Formula 1 and
또한, 본 발명은,Further, according to the present invention,
상기 전공전도특성을 갖는 공흡착체를 광흡수층에 포함하는 것을 특징으로 하는 염료감응 태양전지에 관한 것이다. It relates to a dye-sensitized solar cell, characterized in that it comprises a co-adsorbent having the electroconductive properties in the light absorption layer.
본 발명의 정공전도특성을 갖는 화합물을 광흡수층에 포함하는 염료감응 태양전지는 상기 공흡착체에 의한 홀전도성이 우수하여 염료의 재충전이 빨라지며, 염료간의 π-π스태킹(staking)이 방지되며, TiO2로 넘어간 전자가 전해질 또는 염료로 재결합되는 것을 방지하여 높은 JSC값과 높은 VOC값을 갖는다. The dye-sensitized solar cell including the compound having the hole conducting property of the present invention in the light absorbing layer has excellent hole conductivity by the co-adsorbent, so that dyes can be recharged quickly, and π-π stacking is prevented between dyes. Therefore, the electrons transferred to TiO 2 are prevented from recombining with the electrolyte or the dye, and thus have a high JSC value and a high V OC value.
본 발명에서 염료감응 태양전지는, 이에 한정되는 것은 아니나, 다음과 같은 구성을 가질 수 있다:In the present invention, the dye-sensitized solar cell is not limited thereto, but may have the following configuration:
전도성 투명 기판을 포함하는 제1전극;A first electrode comprising a conductive transparent substrate;
상기 제1전극의 어느 일면에 형성된 광흡수층;A light absorption layer formed on one surface of the first electrode;
상기 광흡수층이 형성된 제1전극에 대향하여 배치되는 제2전극; 및A second electrode disposed to face the first electrode on which the light absorption layer is formed; And
상기 제1전극과 제2전극 사이의 공간에 위치하는 전해질.
An electrolyte located in the space between the first electrode and the second electrode.
상기 태양전지를 구성하는 소재들을 예를 들어 설명하면 다음과 같다. Referring to the materials constituting the solar cell as an example.
전도성 투명 기판을 포함하는 제1전극은 인듐 틴 옥사이드, 플루오린 틴 옥사이드, ZnO- Ga2O3, ZnO-Al2O3 및 주석계 산화물로 이루어진 군에서 선택되는 1종 이상의 물질로 형성된 투광성 전극을 포함하는 유리 기판 또는 플라스틱 기판일 수 있다. The first electrode including the conductive transparent substrate is a translucent electrode formed of at least one material selected from the group consisting of indium tin oxide, fluorine tin oxide, ZnO-Ga 2 O 3 , ZnO-Al 2 O 3 and tin oxide It may be a glass substrate or a plastic substrate comprising a.
상기 광흡수층은 반도체 미립자, 염료, 정공전도특성을 갖는 화합물 등을 포함하며, 상기 반도체 미립자는, 이에 한정되는 것은 아니나, 이산화티탄(TiO2), 이산화주석(SnO2), 산화아연(ZnO) 등의 나노입자 산화물로 형성될 수 있다. 상기 반도체 미립자 상에 흡착되는 염료로는 가시광선 영역의 빛을 흡수할 수 있으며, 나노산화물 표면과 견고한 화학결합을 이루며, 열 및 광확적 안정성을 지니고 있는 것이라면 제한 없이 사용될 수 있다. 대표적인 예로서, 루테늄계 유기금속화합물을 들 수 있다. 그리고 상기 정공전도특성을 갖는 공흡착체는 빛을 흡수하여 전자를 내준 염료에 생긴 홀을 채우며 자신이 다시 홀이 되며, 다시금 전해질에 의하여 홀을 채운다.The light absorbing layer includes semiconductor fine particles, dyes, compounds having hole conducting properties, and the like, and the semiconductor fine particles include, but are not limited to, titanium dioxide (TiO 2 ), tin dioxide (SnO 2 ), and zinc oxide (ZnO). It may be formed of nanoparticle oxides. The dye adsorbed on the semiconductor fine particles may absorb light in the visible light region, form a strong chemical bond with the surface of the nanooxide, and may be used without limitation as long as it has thermal and optical stability. Representative examples include ruthenium-based organometallic compounds. In addition, the coadsorbent having the hole conduction property fills the hole formed in the dye that gives up electrons by absorbing light, and becomes a hole again, and fills the hole by the electrolyte again.
상기 제2전극으로는 상기 제1전극과 동일한 것이 사용될 수 있으며, 제1전극의 투광성 전극 상에 백금 등으로 집전층이 더 형성된 것이 사용될 수도 있다.
As the second electrode, the same electrode as the first electrode may be used, and a current collector layer further formed of platinum or the like may be used on the light transmitting electrode of the first electrode.
이하, 실시예를 통해 본 발명을 구체적으로 설명한다. 그러나, 이러한 실시예는 본 발명을 좀 더 명확하게 설명하기 위하여 제시되는 것일 뿐, 본 발명의 범위를 제한하는 목적으로 제시되는 것은 아니다. 본 발명의 범위는 후술하는 특허청구범위의 기술적 사상에 의해 정해질 것이다.
Hereinafter, the present invention will be described in detail by way of examples. However, these embodiments are provided to explain the present invention more clearly and not to limit the scope of the present invention. The scope of the invention will be defined by the technical spirit of the claims below.
실시예.Examples.
사용된 시약Reagents Used
테트라하이드로퓨란, 아세토나이트릴, 황산, 톨루엔, 메탄올, 아세트산, 에탄올, 아세톤, 에틸아세테이트, 헥산, 디클로로메탄은 동양화학사 제품을 사용하였다. Tetrahydrofuran, acetonitrile, sulfuric acid, toluene, methanol, acetic acid, ethanol, acetone, ethyl acetate, hexane and dichloromethane were used by Dongyang Chemical.
2-에톡시에탄올, 디메틸 설폭사이드, 1,2-디클로로벤젠, 디메틸 설페이트, N,N-디메틸 포름아마이드, 2-이소프로폭시-4,4,5,5-테트라메틸-1,3,2-디옥사보로란(2-isopropoxy-4,4,5,5-테트라메틸-1,3,2-dioxaborolane), N-브로모숙신이미드, 설파민산(sulfamic acid), 아염소산나트륨(sodium chlorite), 염화포스포릴, 염화구리(I), 1,10-펜안트롤린(1,10-phenanthroline), 수산화칼륨, 탄산칼륨(potassium carbonate), 요오드, 오르토과요오드산(orthoperiodic acid), 요오드화메틸, 메틸 4-브로모벤조에이트, Cu-브론즈, 19-crown-6, N-부틸리튬, 탄산나트륨, 수산화나트륨, 중탄산나트륨, 황산나트륨, 9H-플루오렌, 4-요오드페놀, 3-(브로모메틸)헥산, 카바졸, 4-플루오로벤조나이트릴, 포타슘-tert-부톡사이드, 3,5-다이브로모벤조나이트릴, 1,2-디메틸-3-프로필이미다졸리움 요오드, LiI, I2, 테트라부틸암모늄 헥사플루오로포스페이트는 Aldrich사 제품을 구입하여 사용하였다. 2-ethoxyethanol, dimethyl sulfoxide, 1,2-dichlorobenzene, dimethyl sulfate, N, N-dimethyl formamide, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2 Dioxaborolane (2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane), N -bromosuccinimide, sulfamic acid, sodium chlorite ( sodium chlorite, phosphoryl chloride, copper chloride (I), 1,10-phenanthroline, potassium hydroxide, potassium carbonate, iodine, orthorioriodic acid, iodide Methyl, methyl 4-bromobenzoate, Cu-bronze, 19-crown-6, N-butyllithium, sodium carbonate, sodium hydroxide, sodium bicarbonate, sodium sulfate, 9H-fluorene, 4-iodinephenol, 3- (bromo Methyl) hexane, carbazole, 4-fluorobenzonitrile, potassium-tert-butoxide, 3,5-dibromobenzonitrile, 1,2-dimethyl-3-propylimidazolium iodine, LiI, I 2 tetrabutylammonium hexafluoro flu A phosphate was used to purchase from Aldrich.
상기의 시약들은 별다른 정제과정 없이 사용하였다.
The reagents were used without any purification.
합성된 화합물의 확인방법Confirmation method of synthesized compound
모든 새로운 화합물은 1H-NMR과 13C-NMR 그리고 FT-IR로 구조를 확인하였다. 1H-NMR은 Varian 300 분광기를 사용하여 기록하였고, 모든 화학적 이동도는 내부 표준물질인 테트라메틸 실란에 대해 ppm 단위로 기록하였다. IR 스펙트럼은 Perkin-Elmer Spectrometer를 사용하여 KBr 펠렛으로 측정하였다.All new compounds were identified by 1 H-NMR, 13 C-NMR and FT-IR. 1 H-NMR was recorded using a
실시예1: 4-디(4-(2-에틸헥실옥시)페닐)아미노벤조산의 합성Example 1: Synthesis of 4-di (4- (2-ethylhexyloxy) phenyl) aminobenzoic acid
1-1: 1-(2-에틸헥실옥시)-4-요오도벤젠의 합성1-1: Synthesis of 1- (2-ethylhexyloxy) -4-iodobenzene
250 mL 둥근 플라스크에 4-요오도페놀(요오도페놀, 15 g, 68.18 mmol), K2CO3(24.5 g, 177.26 mmol), DMF 70 mL를 넣고 2시간 동안 환류, 교반한 후, 2-에틸헥실브로마이드(17.12 g, 88.63 mmol)을 주사기를 사용하여 첨가한 후 24시간 동안 환류, 교반하였다. 반응이 종결되면 온도를 상온으로 내리고, 70 mL의 2몰 HCl 수용액으로 산처리 한 후 메틸렌 클로라이드로 추출 하고, 증류수로 여러 번 세척하였다. 유기층은 MgSO4 로 건조한 후 감압 하에서 용매를 제거하고, 관크로마토그래피(실리카, CH2Cl2:헥산 = 3:2)로 생성물을 분리하였다. 수득률은 93 %이었다.In a 250 mL round flask, add 4-iodophenol (iodophenol, 15 g, 68.18 mmol), K 2 CO 3 (24.5 g, 177.26 mmol), and 70 mL of DMF, reflux for 2 hours, and stir. Ethylhexylbromide (17.12 g, 88.63 mmol) was added using a syringe and then refluxed and stirred for 24 hours. After the reaction was completed, the temperature was lowered to room temperature, acidified with 70 mL of 2 mol HCl aqueous solution, extracted with methylene chloride, and washed with distilled water several times. The organic layer was dried over MgSO 4 , the solvent was removed under reduced pressure, and the product was separated by column chromatography (silica, CH 2 Cl 2 : hexane = 3: 2). Yield 93%.
1H NMR(CDCl3. ppm): δ7.55-7.52(d, 2H, Ar-H), 6.69-6.66(d, 2H, Ar-H), 3.80-3.79(d, 2H, CH2-O), 1.73-1.67(m, 1H,(CH2)3-H), 1.53-1.28(m, 8H, -CH2), 0.97-0.88(t, 6H, -CH3).
1 H NMR (CDCl 3 ppm): δ 7.55-7.52 (d, 2H, Ar-H), 6.69-6.66 (d, 2H, Ar-H), 3.80-3.79 (d, 2H, CH 2 -O ), 1.73-1.67 (m, 1H, (CH 2 ) 3 -H), 1.53-1.28 (m, 8H, -CH 2 ), 0.97-0.88 (t, 6H, -CH 3 ).
1-2: 4-디(4-(2-에틸헥실옥시)페닐)아미노벤젠의 합성1-2: Synthesis of 4-di (4- (2-ethylhexyloxy) phenyl) aminobenzene
250 mL 둥근 플라스크에 4-(2-에틸헥실옥시)벤질요오다이드(19.03 g, 59.06 mmol), 아닐린(2.5 g, 26.84 mmol), 염화구리(0.27 g, 2.68 mmol), 1,10-펜안트롤린(0.48 g, 2.68 mmol), KOH(9.04g, 161.07 mmol)를 넣고 질소 하에서 주사기로 정제된 톨루엔 20 mL를 첨가한 후, 125℃에서 24시간 동안 환류, 교반하였다. 반응이 종료되면 온도를 상온으로 내리고, 톨루엔으로 추출하여 증류수로 여러 번 세척하였다. 유기층은 MgSO4로 건조한 후 감압 하에서 용매를 제거하고, 관크로마토그래피(실리카, CH2Cl2: 헥산 = 2:3)로 생성물을 분리하였다. 수득률은 80%이었다.4- (2-ethylhexyloxy) benzyl iodide (19.03 g, 59.06 mmol), aniline (2.5 g, 26.84 mmol), copper chloride (0.27 g, 2.68 mmol), 1,10- in a 250 mL round flask Phenanthroline (0.48 g, 2.68 mmol) and KOH (9.04 g, 161.07 mmol) were added, and 20 mL of toluene purified by syringe under nitrogen was added thereto, followed by reflux and stirring at 125 ° C. for 24 hours. After the reaction was completed, the temperature was lowered to room temperature, extracted with toluene, and washed several times with distilled water. The organic layer was dried over MgSO 4 , the solvent was removed under reduced pressure, and the product was separated by column chromatography (silica, CH 2 Cl 2 : hexane = 2: 3). Yield was 80%.
1H NMR(CDCl3. ppm): δ7.23-7.21(t, 1H, Ar-H), 6.85-6.81(t, 2H, Ar-H), 6.79-6.75(d, 4H, Ar-H), 6.63-6.61(d, 2H, Ar-H), 6.55-6.52(d, 4H, Ar-H), 3.80-3.79(d, 4H, CH2-O), 1.73-1.67(m, 2H,(CH2)3-H), 1.53-1.28(m, 16H, -CH2), 0.97-0.88(t, 12H, -CH3).
1 H NMR (CDCl 3 ppm. ): Δ7.23-7.21 (t, 1H, Ar-H), 6.85-6.81 (t, 2H, Ar-H), 6.79-6.75 (d, 4H, Ar-H) , 6.63-6.61 (d, 2H, Ar -H), 6.55-6.52 (d, 4H, Ar-H), 3.80-3.79 (d, 4H, CH 2 -O), 1.73-1.67 (m, 2H, ( CH 2 ) 3 -H), 1.53-1.28 (m, 16H, -CH 2 ), 0.97-0.88 (t, 12H, -CH 3 ).
1-3: 4-디(4-(2-에틸헥실옥시)페닐)아미노벤즈알데히드의 합성 1-3: Synthesis of 4-di (4- (2-ethylhexyloxy) phenyl) aminobenzaldehyde
250 mL 슈렝크 플라스크에 4-(2-에틸헥실옥시)-N-(4-(2-에틸헥실옥시)페닐)-N-페닐벤젠아민(5g, 20.38mmol)이 담긴 적하 깔대기을 장치하고 진공으로 건조하였다. 건조가 완료되면 질소 환류 하에서 주사기를 사용하여 POCl3(3.28g, 21.04 mmol), DMF 30 mL를 플라스크에 첨가 하였다. 그 후 적하 깔대기에 20 mL의 DMF를 추가로 첨가 한 후 0℃에서 천천히 적하 하였다. 적하가 완료된 후 90℃에서 24시간 동안 환류, 교반하였다. 반응이 종료되면 온도를 상온으로 내리고, MC로 추출하여 증류수로 세척하였다. 유기층을 MgSO4로 건조한 후 감압 하에서 용매를 제거하고, 관크로마토그래피(실리카, CH2Cl2: 헥산 = 2:3)로 생성물을 분리하였다. 수득률은 80%이었다.A 250 mL Schlenk flask was equipped with a dropping funnel containing 4- (2-ethylhexyloxy) -N- (4- (2-ethylhexyloxy) phenyl) -N-phenylbenzeneamine (5 g, 20.38 mmol). Dried in vacuo. When drying was complete, POCl 3 (3.28 g, 21.04 mmol) and 30 mL of DMF were added to the flask using a syringe under nitrogen reflux. Thereafter, 20 mL of DMF was further added to the dropping funnel, and then slowly added dropwise at 0 ° C. After the dropping was completed, the mixture was refluxed and stirred at 90 ° C for 24 hours. After the reaction was completed, the temperature was lowered to room temperature, extracted with MC, and washed with distilled water. The organic layer was dried over MgSO 4 , the solvent was removed under reduced pressure, and the product was separated by column chromatography (silica, CH 2 Cl 2 : hexane = 2: 3). Yield was 80%.
1 H NMR(CDCl3. ppm): δ9.9(s, 1H, H-C=O), 7.09-7.07(d, 2H, Ar-H), 6.85-6.82(d, 2H, Ar-H), 6.77-6.74(d, 4H, Ar-H), 6.54-6.52(d, 4H, Ar-H), 3.80-3.79(d, 4H, CH2-O), 1.73-1.67(m, 2H,(CH2)3-H), 1.53-1.28(m, 16H, -CH2), 0.97-0.88(t, 12H, -CH3).
1 H NMR (CDCl 3 ppm. ): Δ9.9 (s, 1H, HC = O), 7.09-7.07 (d, 2H, Ar-H), 6.85-6.82 (d, 2H, Ar-H), 6.77 -6.74 (d, 4H, Ar- H), 6.54-6.52 (d, 4H, Ar-H), 3.80-3.79 (d, 4H, CH 2 -O), 1.73-1.67 (m, 2H, (
1-4: 4-디(4-(2-에틸헥실옥시)페닐)아미노벤조산의 합성1-4: Synthesis of 4-di (4- (2-ethylhexyloxy) phenyl) aminobenzoic acid
4-디(4-(2-에틸헥실옥시페닐)아미노벤즈알데히드와 아염소산나트륨(NaClO2)을 아세톤에 넣고 0℃에서 천천히 교반시켰다. 그리고 다시 설파믹산과 물을 넣어주면서 실온에서 12시간 교반 시켰다. 물과 에틸아세테이트로 추출하여 유기층을 MgSO4로 건조한 후 감압 하에서 용매를 제거하고, 관크로마토그래피(실리카, CH2Cl2)로 생성물을 분리하였다. 수득률은 80%이었다.4-di (4- (2-ethylhexyloxyphenyl) aminobenzaldehyde and sodium chlorite (NaClO 2 ) were added to acetone and stirred slowly at 0 ° C. Then, the mixture was stirred at room temperature for 12 hours while adding sulfamic acid and water. After extraction with water and ethyl acetate, the organic layer was dried over MgSO 4 , the solvent was removed under reduced pressure, and the product was separated by column chromatography (silica, CH 2 Cl 2 ) .The yield was 80%.
1 H NMR(CDCl3. ppm): δ12.7(s, 1H, H-O-C=O), δ7.09-7.07(d, 2H, Ar-H), 6.85-6.82(d, 2H, Ar-H), 6.77-6.74(d, 4H, Ar-H), 6.54-6.52(d, 4H, Ar-H), 4.61(s, 2H, CH2), 3.80-3.79(d, 4H, CH2-O), 1.73-1.67(m, 2H,(CH2)3-H), 1.53-1.28(m, 16H, -CH2), 0.97-0.88(t, 12H, -CH3). 1 H NMR (CDCl 3 ppm): δ 12.7 (s, 1H, HOC = O), 7.07.09-7.07 (d, 2H, Ar-H), 6.85-6.82 (d, 2H, Ar-H) , 6.77-6.74 (d, 4H, Ar-H), 6.54-6.52 (d, 4H, Ar-H), 4.61 (s, 2H, CH 2 ), 3.80-3.79 (d, 4H, CH 2 -O) , 1.73-1.67 (m, 2H, (CH 2 ) 3 -H), 1.53-1.28 (m, 16H, -CH 2 ), 0.97-0.88 (t, 12H, -CH 3 ).
실시예 2: 4-(비스(9,9-디메틸-9H-플루오렌-2-일)아미노)벤조산의 합성Example 2: Synthesis of 4- (bis (9,9-dimethyl-9H-fluoren-2-yl) amino) benzoic acid
2-1: 2-요오도 플루오렌의 합성2-1: Synthesis of 2-iodofluorene
플루오렌(30.0 g, 180 mmol)을 끓는 용매(아세틱산:물:황산/100:20:3(v/v/v))에 녹인 후 퍼아이오딕산 디하이드레이트(8.0 g, 45 mmol)와 요오드(23.0 g, 91.0 mmol)를 첨가하였다. 65℃에서 4시간 교반 후 생성된 침전물을 여과한 후 여과물을 2N 소듐카보네이트 수용액과 물로 세척하였다. 생성된 결정은 헥산에서 재결정하였다. 수득률은 72%이었다. Fluorene (30.0 g, 180 mmol) is dissolved in a boiling solvent (acetic acid: water: sulfuric acid / 100: 20: 3 (v / v / v)), followed by periodic dihydrate (8.0 g, 45 mmol) and iodine (23.0 g, 91.0 mmol) was added. After stirring at 65 ° C. for 4 hours, the resulting precipitate was filtered and the filtrate was washed with 2N aqueous sodium carbonate solution and water. The resulting crystals were recrystallized in hexane. Yield 72%.
1H NMR(300 MHz, CDCl3) δ(TMS, ppm): 3.81(2H, s, -CH2), 7.31(2H, m, Ar-H), 7.44(2H, m, Ar-H), 7.66(1H, d, Ar-H), 7.73(1H, d, Ar-H), 7.85(1H, s, Ar-H).
1 H NMR (300 MHz, CDCl 3 ) δ (TMS, ppm): 3.81 (2H, s, -CH 2), 7.31 (2H, m, Ar-H), 7.44 (2H, m, Ar-H), 7.66 (1H, d, Ar-H), 7.73 (1H, d, Ar-H), 7.85 (1H, s, Ar-H).
2-2: 9,9-디메틸-2-요오도 플루오렌의 합성2-2: Synthesis of 9,9-dimethyl-2-iodo fluorene
2-요오도 플루오렌(25.0 g, 85.6 mmol)이 녹아 있는 냉각된 무수 테트라하이드로퓨란에 포타슘터트부톡사이드(21.8 g, 0.19 mol)를 첨가한 후 실온에서 1.5.시간 교반한다. 메틸요오드(28.2 g, 0.19 mol)를 첨가한 후 두 시간 교반하였다. 생성된 요오드화칼륨을 여과한 후 감압하에 용매를 제거하고 이를 실리카 컬럼 크로마토그래피(헥산)로 정제하였다. 수득률은 70%이었다.Potassium tertbutoxide (21.8 g, 0.19 mol) is added to the cooled anhydrous tetrahydrofuran in which 2-iodo fluorene (25.0 g, 85.6 mmol) is dissolved, followed by stirring at room temperature for 1.5 hours. Methyl iodine (28.2 g, 0.19 mol) was added and stirred for 2 hours. The resulting potassium iodide was filtered off, and the solvent was removed under reduced pressure, which was then purified by silica column chromatography (hexane). Yield was 70%.
1H NMR(300 MHz, CDCl3) δ(TMS, ppm): 1.47(6H, s, -CH3), 7.31(2H, m, Ar-H)), 7.45(2H, m, Ar-H), 7.66(1H, d, Ar-H), 7.73(1H, d, Ar-H), 7.85(1H, s, Ar-H).
1 H NMR (300 MHz, CDCl 3 ) δ (TMS, ppm): 1.47 (6H, s, -CH 3 ), 7.31 (2H, m, Ar-H)), 7.45 (2H, m, Ar-H) , 7.66 (1H, d, Ar-H), 7.73 (1H, d, Ar-H), 7.85 (1H, s, Ar-H).
2-3: 메틸 4-(비스(9,9-디메틸-9H-플루오렌-2-일)아미노)벤조에이트의 합성2-3: Synthesis of Methyl 4- (bis (9,9-dimethyl-9H-fluoren-2-yl) amino) benzoate
상기에서 얻은 9,9-디메틸-2-요오도 플루오렌(5.00 g, 15.6 mmol), 메틸-4-아미노 벤조에이트(1.00 g, 6.62 mol), 구리-주석 합금(0.12 g, 0.66 mmol), 18-크라운-6(0.180 g, 0.68 mmol), 포타슘 카보네이트(4.1 g, 29.6 mmol)을 1,2-디클로로벤젠에 녹인 후 2일 동안 환류, 교반하였다. 반응이 종결된 후, 혼합물을 디클로로메탄과 물로 수회 추출한 후 유기층을 무수 마그네슘설페이트로 건조하고, 여과한 후, 감압하에 용매를 제거하고 이를 실리카 컬럼 크로마토그래피(디클로로메탄-헥산=2:1)로 정제하였다. 수득률은 59%이었다.9,9-dimethyl-2-iodo fluorene (5.00 g, 15.6 mmol), methyl-4-amino benzoate (1.00 g, 6.62 mol), copper-tin alloy (0.12 g, 0.66 mmol) obtained above, 18-crown-6 (0.180 g, 0.68 mmol) and potassium carbonate (4.1 g, 29.6 mmol) were dissolved in 1,2-dichlorobenzene and refluxed and stirred for 2 days. After the reaction was completed, the mixture was extracted several times with dichloromethane and water, and then the organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure, which was then purified by silica column chromatography (dichloromethane-hexane = 2: 1). Purified. Yield 59%.
1H NMR(300 MHz, CDCl3) δ(TMS, ppm): 1.43(12H, s, -CH3), 3.89(3H, s, -CH3), 7.31(4H, m, Ar-H)), 7.45(2H, m, Ar-H), 7.66(6H, m, Ar-H), 7.73(4H, d, Ar-H), 7.85(2H, d, Ar-H).
1 H NMR (300 MHz, CDCl 3 ) δ (TMS, ppm): 1.43 (12H, s, -CH 3 ), 3.89 (3H, s, -CH 3 ), 7.31 (4H, m, Ar-H)) 7.45 (2H, m, Ar-H), 7.66 (6H, m, Ar-H), 7.73 (4H, d, Ar-H), 7.85 (2H, d, Ar-H).
2-4: 4-(비스(9,9-디메틸-9H-플루오렌-2-일)아미노)벤조산의 합성2-4: Synthesis of 4- (bis (9,9-dimethyl-9H-fluoren-2-yl) amino) benzoic acid
250 mL 플라스크에 상기에서 얻은 메틸 4-(비스(9,9-디메틸-9H-플루오렌-2-일)아미노)벤조에이트(300 mg, 0.58 mmol), KOH(330 mg, 5.88 mmol), THF-에탄올(1:1) 100 mL, 증류수 30 mL를 넣고 하루동안 환류, 교반하였다. 반응이 종결되면 온도를 상온으로 내리고, 진한 염산을 첨가하여 용액을 PH 2로 맞추었다. 이 용액을 CH2Cl2로 추출하고, 유기층을 중탄산나트륨(sodium bicarbonate) 수용액과 물로 수회 세척하고, 무수 황산나트륨으로 건조하였다. 감압하에서 용매를 제거하고, 생성물을 속성 관크로마토그래피(실리카, CH2Cl2 : EA = 3 : 2)로 분리하였다. 분리된 생성물을 차가운 에탄올로 세척하고, 진공 하에서 건조하였다. 수득률은 80%이었다.In a 250 mL flask, methyl 4- (bis (9,9-dimethyl-9H-fluoren-2-yl) amino) benzoate (300 mg, 0.58 mmol), KOH (330 mg, 5.88 mmol), THF obtained above. 100 mL of ethanol (1: 1) and 30 mL of distilled water were added thereto, and the mixture was refluxed and stirred for one day. At the end of the reaction, the temperature was lowered to room temperature and the solution was adjusted to P
1H NMR(300 MHz, CDCl3) δ(TMS, ppm): 1.43(12H, s, -CH3), 7.31(4H, m, Ar-H)), 7.45(2H, m, Ar-H), 7.66(6H, m, Ar-H), 7.73(4H, d, Ar-H), 7.85(2H, d, Ar-H).
1 H NMR (300 MHz, CDCl 3 ) δ (TMS, ppm): 1.43 (12H, s, -CH 3 ), 7.31 (4H, m, Ar-H)), 7.45 (2H, m, Ar-H) , 7.66 (6H, m, Ar-H), 7.73 (4H, d, Ar-H), 7.85 (2H, d, Ar-H).
실시예 3: 4-(3,6-비스(4-(2-에틸헥실옥시)페닐)-9H-카바졸-9-일)벤조산의 합성Example 3: Synthesis of 4- (3,6-bis (4- (2-ethylhexyloxy) phenyl) -9H-carbazol-9-yl) benzoic acid
3-1: 1-브로모-4-(2-에틸헥실옥시)벤젠의 합성3-1: Synthesis of 1-bromo-4- (2-ethylhexyloxy) benzene
4-브로모페놀(5g,28.8mmol) 및 K2CO3(9.99g,43.2mmol)를 아세토나이트릴(30ml) 안에 넣고 실온에서 1시간 교반후에 3-(브로모메틸)헵탄(6.67g,34.6mmol)을 천천히 적하하고 23시간 동안 실온에서 교반시켰다. 반응 후 물과 에틸아세테이트를 넣고 추출하여 MgSO4 넣고 건조시킨 후, 관크로마토그래피(n-헥산/DCM=2/1)로 생성물을 분리하였다. 수득율은 67%(5.52g)이었다.4-bromophenol (5 g, 28.8 mmol) and K 2 CO 3 (9.99 g, 43.2 mmol) were added to acetonitrile (30 ml) and stirred at room temperature for 1 hour, followed by 3- (bromomethyl) heptane (6.67 g, 34.6 mmol) was slowly added dropwise and stirred at room temperature for 23 hours. After the reaction, water and ethyl acetate were added, followed by extraction, followed by drying with MgSO 4. The product was separated by column chromatography ( n -hexane / DCM = 2/1). Yield was 67% (5.52 g).
1HNMR(300MHz,CDCl3)δ7.55-7.52(d, 2H, Ar-H), 6.69-6.66(d, 2H, Ar-H), 3.80-3.79(d, 2H, CH2-O),1.73-1.67(m,1H,(CH2)3-H),1.53-1.28(m,8H,-CH2),0.97-0.88(t,6H,-CH3) 1 HNMR (300MHz, CDCl 3 ) δ7.55-7.52 (d, 2H, Ar-H), 6.69-6.66 (d, 2H, Ar-H), 3.80-3.79 (d, 2H, CH 2 -O), 1.73-1.67 (m, 1H, (CH 2 ) 3 -H), 1.53-1.28 (m, 8H, -CH 2 ), 0.97-0.88 (t, 6H, -CH 3 )
3-2: 2-(4-(2-에틸헥실옥시)페닐)-4,4,5,5-테트라메틸-1,3,2-디옥사보로란의 합성3-2: Synthesis of 2- (4- (2-ethylhexyloxy) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane
상기에서 얻은 1-브로모-4-(2-에틸헥실옥시)벤젠(5.52g, 19.4 mmol)을 THF(150 ml)에 넣고 -78℃에서 n-BuLi(1.61g, 25.2mmol, 2.5Min, n-hexane)를 적하시켰다. 1시간 교반후에 2-이소프로폭시-4,4,5,5-테트라메틸-1,3,2-디옥사보로란(4.32 g, 23.2 mmol)을 반응물에 다시 적하하고 1시간 동안 교반한후, 실온에서 12시간 동안 더 교반시켰다. 반응 종료 후 용매를 제거하고 반응물을 물과 에틸 아세테이트로 추출하고, MgSO4로 건조한 후에 관크로마토그래피(n-헥산/DCM=3/1)로 생성물을 분리하였다. 수득율은 92%(5.9g)이었다.1-Bromo-4- (2-ethylhexyloxy) benzene (5.52 g, 19.4 mmol) obtained above was added to THF (150 ml) and n- BuLi (1.61 g, 25.2 mmol, 2.5 Min at -78 ° C). , n- hexane) was added dropwise. After stirring for 1 hour, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4.32 g, 23.2 mmol) was added dropwise to the reaction and stirred for 1 hour. Then further stirred at room temperature for 12 hours. After completion of the reaction, the solvent was removed, the reaction was extracted with water and ethyl acetate, dried over MgSO 4 and the product was separated by column chromatography ( n -hexane / DCM = 3/1). The yield was 92% (5.9 g).
1HNMR(300MHz,CDCl3)δ7.55-7.52(d, 2H, Ar-H), 6.69-6.66(d, 2H, Ar-H), 3.80-3.79(d, 2H, CH2-O),1.73-1.67(m,1H,(CH2)3-H),1.53-1.28(m,8H,-CH2),1.28-1.32(s,12H,-CH3)1.53-1.28(m,8H,-CH2),0.97-0.88(t,6H,-CH3) 1 HNMR (300MHz, CDCl 3 ) δ7.55-7.52 (d, 2H, Ar-H), 6.69-6.66 (d, 2H, Ar-H), 3.80-3.79 (d, 2H, CH 2 -O), 1.73-1.67 (m, 1H, (CH 2 ) 3 -H), 1.53-1.28 (m, 8H, -CH 2 ), 1.28-1.32 (s, 12H, -CH 3 ) 1.53-1.28 (m, 8H, -CH 2 ), 0.97-0.88 (t, 6H, -CH 3 )
3-3: 4-(9H-카바졸-9-일)벤조나이트릴의 합성3-3: Synthesis of 4- (9H-carbazol-9-yl) benzonitrile
9H-카바졸(3 g, 17.94 mmol)을 K2CO3(8.22g,26.91mmol)와 DMSO(30ml)에 넣고 실온에서 1시간 교반시킨 후, 4-플루오로벤조나이트릴(2.61g,21.5mmol)을 적하시키고 150℃ 12시간 동안 교반시켰다. 반응 종료후 용매를 제거하고 물과 에틸 아세테이트로 추출한 후, MgSO4로 건조하고 관크로마토그리피(n-헥산/EtOAc=2/1)로 생성물을 분리하였다. 수득율은 94%(4.5g)이었다.9H-carbazole (3 g, 17.94 mmol) was added to K 2 CO 3 (8.22 g, 26.91 mmol) and DMSO (30 ml), and stirred at room temperature for 1 hour, followed by 4-fluorobenzonitrile (2.61 g, 21.5). mmol) was added dropwise and stirred at 150 ° C. for 12 hours. After completion of the reaction, the solvent was removed, extracted with water and ethyl acetate, dried over MgSO 4 and the product was separated by tube chromatography ( n -hexane / EtOAc = 2/1). The yield was 94% (4.5 g).
1HNMR(300MHz,CDCl3) 8.13(d, Ar-H, 2H), 7.44(d, Ar-H, 2H), 7.38(m, Ar-H, 2H), 7.32(d, Ar-H, 2H), 7.27(m, Ar-H, 2H), 7.10(d, Ar-H, 2H) 1 HNMR (300 MHz, CDCl 3 ) 8.13 (d, Ar-H, 2H), 7.44 (d, Ar-H, 2H), 7.38 (m, Ar-H, 2H), 7.32 (d, Ar-H, 2H ), 7.27 (m, Ar-H, 2H), 7.10 (d, Ar-H, 2H)
3-4: 4-(3,6-디브로모-9H-카바졸-9-일)벤조나이트릴의 합성3-4: Synthesis of 4- (3,6-dibromo-9H-carbazol-9-yl) benzonitrile
4-(9H-카바졸-9-일)벤조나이트릴(4.5 g, 16.8 mmol)을 THF(50 ml)에 녹이고 N-브로모숙신이미드(5.9g,33.9mmol)를 넣어주었다. 실온에서 4시간 반응시킨 후, 용매를 날리고 물과 에틸 아세테이트로 추출하였다. 상기 추출물을 MgSO4로 건조시킨 후, 관크로마토그래피(n-헥산/EtOAc=4/1)로 분리하였다. 수득률은 90%(6.5g)이었다.4- (9H-carbazol-9-yl) benzonitrile (4.5 g, 16.8 mmol) was dissolved in THF (50 ml) and N -bromosuccinimide (5.9 g, 33.9 mmol) was added thereto. After 4 hours of reaction at room temperature, the solvent was removed and extracted with water and ethyl acetate. The extract was dried over MgSO 4 and then separated by column chromatography ( n -hexane / EtOAc = 4/1). The yield was 90% (6.5 g).
1HNMR(300MHz,CDCl3)δ7.01-7.03(d,-Ar,4H),7.48-7.51(d,-Ar,2H), 8.27(s,-Ar,2H) 1 HNMR (300MHz, CDCl 3 ) δ7.01-7.03 (d, -Ar, 4H), 7.48-7.51 (d, -Ar, 2H), 8.27 (s, -Ar, 2H)
3-5: 4-(3,6-비스(4-(2-에틸헥실옥시)페닐)-9H-카바졸-9-일)벤조나이트릴의 합성3-5: Synthesis of 4- (3,6-bis (4- (2-ethylhexyloxy) phenyl) -9H-carbazol-9-yl) benzonitrile
4-(3,6-디브로모-9H-카바졸-9-일)벤조나이트릴(3.0g, 7.04 mmol)과 2-(4-(2-에틸헥실옥시)페닐)-4,4,5,5-테트라메틸-1,3,2-디옥사보로란(4.68 g, 14.08mmol), 탄산나트륨(1.87 g, 10.56 mmol), 및 테트라키스(트리페닐포스핀)팔라듐(Pd(PPh3)4)(0.68g,0.35mmol)을 톨루엔/테트라히드로퓨란/H2O/에탄올(3:1:1:1(v/v/v/v)) 100ml에 넣고 질소하에서 녹인 후 80℃에서 12시간동안 환류 교반시켰다. 반응물질을 물과 에틸 아세테이트로 추출한 후 MgSO4로 건조시킨 후, 관크로마토그래피(n-hexane/EtOAc=3/1)로 분리하였다. 수득율은 60%(2.9g)이었다.4- (3,6-dibromo-9H-carbazol-9-yl) benzonitrile (3.0 g, 7.04 mmol) and 2- (4- (2-ethylhexyloxy) phenyl) -4,4 , 5,5-tetramethyl-1,3,2-dioxaborolane (4.68 g, 14.08 mmol), sodium carbonate (1.87 g, 10.56 mmol), and tetrakis (triphenylphosphine) palladium (Pd (PPh 3 ) 4 ) (0.68g, 0.35mmol) was added to 100ml of toluene / tetrahydrofuran / H 2 O / ethanol (3: 1: 1: 1 (v / v / v / v)) and dissolved under nitrogen. It was stirred at reflux for 12 hours. The reaction mass was extracted with water and ethyl acetate, dried over MgSO 4 , and separated by column chromatography ( n- hexane / EtOAc = 3/1). Yield was 60% (2.9 g).
1HNMR(300MHz,CDCl3)δ7.55-7.52(d, 2H, Ar-H), 6.69-6.66(d, 2H, Ar-H), 3.80-3.79(d, 2H, CH2-O),1.73-1.67(m,1H,(CH2)3-H),1.53-1.28(m,8H,-CH2),0.97-0.88(t,6H,-CH3),δ 7.01-7.03(d, -Ar, 4H), 7.48-7.51(d, -Ar, 2H), 7.63-7.65(m, -Ar, 6H), 8.27(s, -Ar, 2H).
1 HNMR (300MHz, CDCl 3 ) δ7.55-7.52 (d, 2H, Ar-H), 6.69-6.66 (d, 2H, Ar-H), 3.80-3.79 (d, 2H, CH 2 -O), 1.73-1.67 (m, 1H, (CH 2 ) 3 -H), 1.53-1.28 (m, 8H, -CH 2 ), 0.97-0.88 (t, 6H, -CH 3 ), δ 7.01-7.03 (d, -Ar, 4H), 7.48-7.51 (d, -Ar, 2H), 7.63-7.65 (m, -Ar, 6H), 8.27 (s, -Ar, 2H).
3-6: 4-(3,6-비스(4-(2-에틸헥실옥시)페닐)-9H-카바졸-9-일)벤조산의 합성3-6: Synthesis of 4- (3,6-bis (4- (2-ethylhexyloxy) phenyl) -9H-carbazol-9-yl) benzoic acid
4-(3,6-비스(4-(2-에틸헥실옥시)페닐)-9H-카바졸-9-일)벤조나이트릴(2.9 g, 4.28 mmol)와 수산화나트륨(0.51g, 12.85 mmol)을 2-에톡시에탄올/H2O(2:1(v/v)) 20ml에 넣고 80℃에서 24시간 동안 교반시켰다. 물과 에틸 아세테이트로 추출한 후, MgSO4로 건조시키고 관크로마토그래피(n-헥산/EtOAc=2/1)로 분리하였다. 수득율은 94%(4.5g)이었다.4- (3,6-bis (4- (2-ethylhexyloxy) phenyl) -9H-carbazol-9-yl) benzonitrile (2.9 g, 4.28 mmol) and sodium hydroxide (0.51 g, 12.85 mmol) ) Was added to 20 ml of 2- ethoxyethanol / H 2 O (2: 1 (v / v)) and stirred at 80 ° C. for 24 hours. Extracted with water and ethyl acetate, dried over MgSO 4 and separated by column chromatography ( n -hexane / EtOAc = 2/1). The yield was 94% (4.5 g).
1HNMR(300MHz,CDCl3)δ7.55-7.52(d, 2H, -Ar), 6.69-6.66(d, 2H, -Ar), 3.80-3.79(d, 2H, CH2-O),1.73-1.67(m,1H,(CH2)3-H),1.53-1.28(m,8H,-CH2),0.97-0.88(t,6H,-CH3),δ 7.01-7.03(d, -Ar, 4H), 7.48-7.51(d, -Ar, 2H), 7.63-7.65(m, -Ar, 6H), 8.27(s, -Ar, 2H),(s, OH, H)
1 HNMR (300MHz, CDCl 3 ) δ7.55-7.52 (d, 2H, -Ar), 6.69-6.66 (d, 2H, -Ar), 3.80-3.79 (d, 2H, CH 2 -O), 1.73- 1.67 (m, 1H, (CH 2 ) 3 -H), 1.53-1.28 (m, 8H, -CH 2 ), 0.97-0.88 (t, 6H, -CH 3 ), δ 7.01-7.03 (d, -Ar , 4H), 7.48-7.51 (d, -Ar, 2H), 7.63-7.65 (m, -Ar, 6H), 8.27 (s, -Ar, 2H), (s, OH, H)
실시예 4: 3,5-비스(3,6-비스(4-메톡시페닐)-9H-카바졸-9-일)벤조산의 합성Example 4: Synthesis of 3,5-bis (3,6-bis (4-methoxyphenyl) -9H-carbazol-9-yl) benzoic acid
4-1: 3,5-디(9H-카바졸-9-일)벤조나이트릴의 합성4-1: Synthesis of 3,5-di (9H-carbazol-9-yl) benzonitrile
9H-카바졸(6.4 g, 40.00 mmol)을 K2CO3(10.6g,76.64mmol), CuI(0.91g, 4.79mmol), 3,5-디브로모벤조나이트릴(5 g, 19.16mmol), 18-crown-6(1.01g, 3.83mmol)과 O-다이클로로벤젠(40mL)을 넣고 180℃에서 24시간 동안 교반시켰다. 반응 종료 후 거름종이로 염과 Cu를 거른 후에 용매를 제거하고 물과 에틸 아세테이트로 추출한 후, MgSO4로 건조하고 관크로마토그리피(n-헥산/EtOAc=2/1)로 생성물을 분리하였다. 수득율은 60%(4.9g)이었다.9H-carbazole (6.4 g, 40.00 mmol) in K 2 CO 3 (10.6 g, 76.64 mmol), CuI (0.91 g, 4.79 mmol), 3,5-dibromobenzonitrile (5 g, 19.16 mmol) , 18-crown-6 (1.01 g, 3.83 mmol) and O -dichlorobenzene (40 mL) were added thereto and stirred at 180 ° C. for 24 hours. After completion of the reaction, the salt and Cu were filtered through a filter paper, the solvent was removed, extracted with water and ethyl acetate, dried over MgSO 4 , and the product was separated by tube chromatography ( n -hexane / EtOAc = 2/1). Yield was 60% (4.9 g).
1HNMR(300MHz,CDCl3) 8.13(d, -Ar, 4H), 7.50(s, -Ar, 3H), 7.08-7.20(d, -Ar, 8H) 7.27(m, -Ar, 4H)
1 HNMR (300MHz, CDCl 3 ) 8.13 (d, -Ar, 4H), 7.50 (s, -Ar, 3H), 7.08-7.20 (d, -Ar, 8H) 7.27 (m, -Ar, 4H)
4-2: 3,5-비스(3,6-디브로모-9H-카바졸-9-일)벤조나이트릴의 합성4-2: Synthesis of 3,5-bis (3,6-dibromo-9H-carbazol-9-yl) benzonitrile
3,5-디(9H-카바졸-9-일)벤조나이트릴(4.9 g, 16.8 mmol)을 THF(50 ml)에 녹이고 N-브로모숙신이미드(8.25g, 46.34mmol)를 넣어주었다. 실온에서 4시간 반응시킨 후, 용매를 날리고 물과 에틸 아세테이트로 추출하였다. 상기 추출물을 MgSO4로 건조시킨 후, 관크로마토그래피(n-헥산/EtOAc=4/1)로 분리하였다. 수득률은 80%(6.8g)이었다.3,5-di (9H-carbazol-9-yl) benzonitrile (4.9 g, 16.8 mmol) was dissolved in THF (50 ml) and N -bromosuccinimide (8.25 g, 46.34 mmol) was added thereto. . After 4 hours of reaction at room temperature, the solvent was removed and extracted with water and ethyl acetate. The extract was dried over MgSO 4 and then separated by column chromatography ( n -hexane / EtOAc = 4/1). Yield was 80% (6.8 g).
1HNMR(300MHz,CDCl3) 8.21(d, -Ar, 4H), 7.50(s, -Ar, 3H), 7.25-7.29(d, Ar-H, 8H)
1 HNMR (300MHz, CDCl 3 ) 8.21 (d, -Ar, 4H), 7.50 (s, -Ar, 3H), 7.25-7.29 (d, Ar-H, 8H)
4-3: 4-메톡시페닐보론산의 합성4-3: Synthesis of 4-methoxyphenylboronic acid
1-브로모-4-메톡시벤젠(15.0g, 80.2mmole)을 테트라하이드로퓨란 150ml에 녹이고 -78℃로 온도를 유지하면서 부틸리튬(5.65g, 88.2mmole)을 천천히 적가한 후 1시간 동안 교반시켰다. 같은 온도에서 트리메틸보레이트(16.7g, 160.4mmole)를 천천히 적가한 후 1시간동안 교반 시킨 후, 실온에서 밤새 교반하였다. 반응 종료후 6M-HCl로 pH를 2로 맞추고 물과 에틸아세테이트로 추출한 후 유기용매와 수용액층을 분리하고 유기용매층을 무수 마그네슘 설페이트로 건조시키고 여과하였다. 유기용매를 증발시키고 잔류물을 소량의 에테르에 녹인 후 0℃에서 n-헥산을 적가하여 결정으로 석출시켜 여과하고 건조시켰다. 수득률은 66%(8.0g)이었다.Dissolve 1-bromo-4-methoxybenzene (15.0g, 80.2mmole) in 150ml of tetrahydrofuran, slowly add dropwise butyllithium (5.65g, 88.2mmole) dropwise for 1 hour while maintaining the temperature at -78 ° C. I was. Trimethyl borate (16.7 g, 160.4 mmol) was slowly added dropwise at the same temperature, followed by stirring for 1 hour, followed by stirring at room temperature overnight. After completion of the reaction, the pH was adjusted to 2 with 6M-HCl, extracted with water and ethyl acetate, the organic solvent and the aqueous layer were separated, and the organic solvent layer was dried over anhydrous magnesium sulfate and filtered. The organic solvent was evaporated, the residue was dissolved in a small amount of ether, and n-hexane was added dropwise at 0 ° C. to precipitate crystals, filtered and dried. The yield was 66% (8.0 g).
1H NMR(300MHz, CDCl3) δ 3.81(s, -OCH3, 3H), 6.89-6.91(d, -Ar, 2H), 7.72-7.74(d, -Ar, 2H)
1 H NMR (300 MHz, CDCl 3 ) δ 3.81 (s, -OCH 3 , 3H), 6.89-6.91 (d, -Ar, 2H), 7.72-7.74 (d, -Ar, 2H)
4-4: 3,5-비스(3,6-비스(4-메톡시페닐)-9H-카바졸-9-일)벤조나이트릴의 합성4-4: Synthesis of 3,5-bis (3,6-bis (4-methoxyphenyl) -9H-carbazol-9-yl) benzonitrile
3,5-비스(3,6-디브로모-9H-카바졸-9-일)벤조나이트릴(6.8g, 15.69mmole), 4-메톡시페닐보론산(10.75g, 64.31mmol), 탄산칼륨(17.34g, 125.49mmole), 테트라키스(트리페닐포스포린)팔라듐(0)(3.63g, 3.14mmole)을 THF/H2O(10:3) 100ml에 녹이고 80℃에서 반응 종료 후 물과 에틸아세테이트로 추출한 후, 무수 마그네슘 설페이트로 건조시키고 여과한 후, 유기용매를 증발시키고 관크로마토그래피(n-헥산/EtOAc=2/1)로 분리하였다. 수득률은 54%(7.3g)이었다.3,5-bis (3,6-dibromo-9H-carbazol-9-yl) benzonitrile (6.8 g, 15.69 mmol), 4-methoxyphenylboronic acid (10.75 g, 64.31 mmol), carbonic acid Potassium (17.34g, 125.49mmole) and tetrakis (triphenylphosphorine) palladium (0) (3.63g, 3.14mmole) are dissolved in 100ml of THF / H 2 O (10: 3) and after completion of the reaction at 80 ° C, After extraction with ethyl acetate, drying with anhydrous magnesium sulfate and filtration, the organic solvent was evaporated and separated by column chromatography ( n -hexane / EtOAc = 2/1). The yield was 54% (7.3 g).
1HNMR(300MHz,CDCl3) 8.21(d, -Ar, 4H), 7.50(s, -Ar, 3H), 7.25-7.29(d, -Ar, 8H), 3.8(s, CH3-O, 12H), 6.89-6.91(d, -Ar, 8H), 7.72-7.74(d, -Ar, 8H)
1 HNMR (300MHz, CDCl 3 ) 8.21 (d, -Ar, 4H), 7.50 (s, -Ar, 3H), 7.25-7.29 (d, -Ar, 8H), 3.8 (s, CH 3 -O, 12H ), 6.89-6.91 (d, -Ar, 8H), 7.72-7.74 (d, -Ar, 8H)
4-5: 3,5-비스(3,6-비스(4-메톡시페닐)-9H-카바졸-9-일)benzoic acid의 합성 4-5: Synthesis of 3,5-bis (3,6-bis (4-methoxyphenyl) -9H-carbazol-9-yl) benzoic acid
3,5-비스(3,6-비스(4-메톡시페닐)-9H-카바졸-9-일)벤조나이트릴(7.3 g, 7.93 mmol)와 수산화나트륨(0.95g, 23.78 mmol)을 2-에톡시에탄올/H2O(2:1(v/v)) 40ml에 넣고 80℃에서 24시간 동안 교반시켰다. 물과 에틸 아세테이트로 추출한 후, MgSO4로 건조시키고 관크로마토그래피(n-헥산/EtOAc=3/1)로 분리하였다. 수득율은 80%(5.5g)이었다.3,5-bis (3,6-bis (4-methoxyphenyl) -9H-carbazol-9-yl) benzonitrile (7.3 g, 7.93 mmol) and sodium hydroxide (0.95 g, 23.78 mmol) It was added to 40 ml of ethoxyethanol / H 2 O (2: 1 (v / v)) and stirred at 80 ° C. for 24 hours. Extracted with water and ethyl acetate, dried over MgSO 4 and separated by column chromatography ( n -hexane / EtOAc = 3/1). Yield was 80% (5.5 g).
1HNMR(300MHz,CDCl3) 8.21(d, -Ar, 4H), 7.50(s, -Ar, 3H), 7.25-7.29(d, Ar-H, 8H), 3.8(s, CH3-O, 12H), 6.89-6.91(d, -Ar, 8H), 7.72-7.74(d, -Ar, 8H), 12.7(s, OH, H)
1 HNMR (300 MHz, CDCl 3 ) 8.21 (d, -Ar, 4H), 7.50 (s, -Ar, 3H), 7.25-7.29 (d, Ar-H, 8H), 3.8 (s, CH 3 -O, 12H), 6.89-6.91 (d, -Ar, 8H), 7.72-7.74 (d, -Ar, 8H), 12.7 (s, OH, H)
실시예 5: 9-[3,5-비스(페닐)-3,6-비스(4-메톡시페닐))-9H-카바졸-9-일]벤조산의 합성Example 5: Synthesis of 9- [3,5-bis (phenyl) -3,6-bis (4-methoxyphenyl))-9H-carbazol-9-yl] benzoic acid
5-1: 4-메톡시페닐보론산의 합성5-1: Synthesis of 4-methoxyphenylboronic acid
1-브로모-4-메톡시벤젠(15.0g, 80.2mmole)을 테트라하이드로퓨란 150ml에 녹이고 -78℃로 온도를 유지하면서 부틸리튬(5.65g, 88.2mmole)을 천천히 적가한 후 1시간 교반시켰다. 같은 온도에서 트리메틸보레이트(16.7g, 160.4mmole)를 천천히 적가한 후, 1시간동안 교반 시킨고 실온에서 밤새 교반하였다. 반응 종료후 6M-HCl로 pH를 2로 맞추고 물과 에틸아세테이트로 추출한 후 유기용매와 수용액층을 분리하고 유기용매층을 무수 마그네슘 설페이트로 건조시키고 여과하였다. 유기용매를 증발시키고 잔류물을 소량의 에테르에 녹인 후, 0℃에서 n-헥산을 적가하여 결정으로 석출시켜 여과하고 건조시켰다. 수득률은 66%(8.0g)이었다.1-bromo-4-methoxybenzene (15.0g, 80.2mmole) was dissolved in 150ml of tetrahydrofuran and slowly added dropwise butyllithium (5.65g, 88.2mmole) while maintaining the temperature at -78 ° C and stirred for 1 hour. . Trimethyl borate (16.7 g, 160.4 mmol) was slowly added dropwise at the same temperature, followed by stirring for 1 hour, followed by stirring at room temperature overnight. After completion of the reaction, the pH was adjusted to 2 with 6M-HCl, extracted with water and ethyl acetate, the organic solvent and the aqueous layer were separated, and the organic solvent layer was dried over anhydrous magnesium sulfate and filtered. The organic solvent was evaporated and the residue was dissolved in a small amount of ether. Then, n-hexane was added dropwise at 0 ° C. to precipitate crystals, filtered and dried. The yield was 66% (8.0 g).
1H NMR(300MHz, CDCl3) δ 3.81(s, -OCH3, 3H), 6.89-6.91(d, -Ar, 2H), 7.72-7.74(d, -Ar, 2H)
1 H NMR (300 MHz, CDCl 3 ) δ 3.81 (s, -OCH 3 , 3H), 6.89-6.91 (d, -Ar, 2H), 7.72-7.74 (d, -Ar, 2H)
5-2: 5-시아노-1,3-페닐렌디보론산의 합성5-2: Synthesis of 5-cyano-1,3-phenylenediboronic acid
3,5-디브로모벤조나이트릴(15.0g, 57.49mmole)을 테트라하이드로퓨란 150ml에 녹이고 -100℃로 온도를 유지하면서 부틸리튬(8.10g, 126.48mmole)을 천천히 적가한 후 1시간 동안 교반시켰다. 같은 온도에서 트리메틸보레이트(23.90g, 229.96mmole)를 천천히 적가한 후 1시간동안 교반 시킨고 실온에서 밤새 교반하였다. 반응 종료후 6M-HCl로 pH를 2로 맞추고 물과 에틸아세테이트로 추출한 후 유기용매와 수용액층을 분리하고 유기용매층을 무수 마그네슘 설페이트로 건조시키고 여과하였다. 유기용매를 증발시키고 잔류물을 소량의 에테르에 녹인 후 0℃에서 n-헥산을 적가하여 결정으로 석출시켜 여과하고 건조시켰다. 수득률은 74%(8.0g)이었다.Dissolve 3,5-dibromobenzonitrile (15.0g, 57.49mmole) in 150ml of tetrahydrofuran, slowly add dropwise butyllithium (8.10g, 126.48mmole) while maintaining the temperature at -100 ° C, and stir for 1 hour. I was. Trimethyl borate (23.90 g, 229.96 mmol) was slowly added dropwise at the same temperature, stirred for 1 hour, and stirred overnight at room temperature. After completion of the reaction, the pH was adjusted to 2 with 6M-HCl, extracted with water and ethyl acetate, the organic solvent and the aqueous layer were separated, and the organic solvent layer was dried over anhydrous magnesium sulfate and filtered. The organic solvent was evaporated, the residue was dissolved in a small amount of ether, and n-hexane was added dropwise at 0 ° C. to precipitate crystals, filtered and dried. The yield was 74% (8.0 g).
1H NMR(300MHz, CDCl3) δ 7.54(s, -Ar, 3H), 2.0(s, OH, 4H)
1 H NMR (300 MHz, CDCl 3 ) δ 7.54 (s, -Ar, 3H), 2.0 (s, OH, 4H)
5-3: 3,6-디브로모-9H-카바졸의 합성5-3: Synthesis of 3,6-dibromo-9H-carbazole
카바졸(5.0 g, 29.9 mmol)을 THF(50 ml)에 녹이고 N-브로모숙신이미드(11.18g, 62.80mmol)를 넣어주었다. 실온에서 4시간 반응시킨 후, 용매를 날리고 물과 에틸 아세테이트로 추출하였다. 상기 추출물을 MgSO4로 건조시킨 후, 관크로마토그래피(n-헥산/EtOAc=4/1)로 분리하였다. 수득률은 83%(8.1g)이었다.Carbazole (5.0 g, 29.9 mmol) was dissolved in THF (50 ml) and N -bromosuccinimide (11.18 g, 62.80 mmol) was added thereto. After 4 hours of reaction at room temperature, the solvent was removed and extracted with water and ethyl acetate. The extract was dried over MgSO 4 and then separated by column chromatography ( n -hexane / EtOAc = 4/1). Yield was 83% (8.1 g).
1HNMR(300MHz,CDCl3) 8.21(d, -Ar, 2H), 7.25-7.29(d, -Ar, 4H), 11.70(s, N-H, H)
1 HNMR (300MHz, CDCl 3 ) 8.21 (d, -Ar, 2H), 7.25-7.29 (d, -Ar, 4H), 11.70 (s, NH, H)
5-4: 3,6-비스(4-메톡시페닐)-9H-카바졸의 합성5-4: Synthesis of 3,6-bis (4-methoxyphenyl) -9H-carbazole
3,6-디브로모-9H-카바졸(8.1g, 24.92mmole), 4-메톡시페닐보론산(8.75g, 52.34mmol), 탄산칼륨(10.33g, 77.77mmole), 테트라키스(트리페닐포스포린)팔라듐(0)(2.88g, 2.49mmole)을 THF/톨루엔/에탄올/H2O(비피비=1:1:1:1) 100ml에 녹이고 80℃에서 반응 종료 후 물과 에틸아세테이트로 추출한 후 무수 마그네슘 설페이트로 건조시키고 여과한 후, 유기용매를 증발시키고 관크로마토그래피(n-헥산/EtOAc=3/1)로 분리하였다. 수득률은 54%(7.3g)이었다.3,6-dibromo--9H- carbazole (8.1g, 24.92mmole), 4- methoxyphenyl boronic acid (8.75g, 52.34mmol), potassium carbonate (10.33g, 77.77mmole), tetrakis (triphenyl Phosphorin) palladium (0) (2.88 g, 2.49 mmol) was dissolved in 100 ml of THF / toluene / ethanol / H 2 O (BP ratio = 1: 1: 1: 1) and the reaction was completed at 80 ° C. with water and ethyl acetate. After extraction, dried over anhydrous magnesium sulfate and filtered, the organic solvent was evaporated and separated by column chromatography ( n -hexane / EtOAc = 3/1). The yield was 54% (7.3 g).
1HNMR(300MHz,CDCl3) 8.21(d, -Ar, 2H), 7.25-7.29(d, -Ar, 4H), 3.8(s, CH3-O, 12H), 7.02(d, -Ar, 2H), 7.65(d, -Ar, 2H), 11.70(s, N-H, H)
1 HNMR (300MHz, CDCl 3 ) 8.21 (d, -Ar, 2H), 7.25-7.29 (d, -Ar, 4H), 3.8 (s, CH 3 -O, 12H), 7.02 (d, -Ar, 2H ), 7.65 (d, -Ar, 2H), 11.70 (s, NH, H)
5-5: 3,6-비스(4-메톡시페닐)-9-페닐-9H-카바졸의 합성5-5: Synthesis of 3,6-bis (4-methoxyphenyl) -9-phenyl-9H-carbazole
3,6-비스(4-메톡시페닐)-9H-카바졸(7.3 g, 19.24 mmol)을 K2CO3(5.32g,38.48mmol), CuI(0.44g, 2.31mmol), 브로모벤젠(3.32 g, 21.16mmol), 18-crown-6(0.51g, 1.91mmol)과 O-다이클로로벤젠(50mL)넣고 180℃에서 24시간 동안 교반시켰다. 반응 종료 후 거름종이로 염과 Cu를 거른 후에 용매를 제거하고 물과 에틸 아세테이트로 추출한 후, MgSO4로 건조하고 관크로마토그리피(n-헥산/EtOAc=3/1)로 생성물을 분리하였다. 수득율은 74%(6.5g)이었다.3,6-bis (4-methoxyphenyl) -9H-carbazole (7.3 g, 19.24 mmol) was dissolved in K 2 CO 3 (5.32 g, 38.48 mmol), CuI (0.44 g, 2.31 mmol), bromobenzene ( 3.32 g, 21.16 mmol), 18-crown-6 (0.51 g, 1.91 mmol), and O -dichlorobenzene (50 mL) were added and stirred at 180 ° C. for 24 hours. After completion of the reaction, the salt and Cu were filtered through a filter paper, the solvent was removed, extracted with water and ethyl acetate, dried over MgSO 4 , and the product was separated by tube chromatography ( n -hexane / EtOAc = 3/1). Yield was 74% (6.5 g).
1HNMR(300MHz,CDCl3) 8.21(d, -Ar, 2H), 7.25-7.29(d, -Ar, 4H), 3.8(s, CH3-O, 12H), 7.02(d, -Ar, 2H), 7.65(d, -Ar, 2H), 7.55(m, -Ar, 2H), 7.50(m, -Ar, H), 7.30(d, -Ar, 2H)
1 HNMR (300MHz, CDCl 3 ) 8.21 (d, -Ar, 2H), 7.25-7.29 (d, -Ar, 4H), 3.8 (s, CH 3 -O, 12H), 7.02 (d, -Ar, 2H ), 7.65 (d, -Ar, 2H), 7.55 (m, -Ar, 2H), 7.50 (m, -Ar, H), 7.30 (d, -Ar, 2H)
5-6: 9-(4-브로모페닐)-3,6-비스(4-메톡시페닐)-9H-카바졸의 합성5-6: Synthesis of 9- (4-bromophenyl) -3,6-bis (4-methoxyphenyl) -9H-carbazole
3,6-비스(4-메톡시페닐)-9-페닐-9H-카바졸(6.5 g, 14.27 mmol)을 HBr(50ml)에 넣고 Br2(3.42g, 21.40mmol)를 적하 시킨후 12시간 동안 교반시켰다. 반응 종료 후 물과 에틸 아세테이트로 추출한 후, MgSO4로 건조하고 관크로마토그리피(n-헥산/EtOAc=2/1)로 생성물을 분리하였다. 수득율은 78%(6.0g)이었다.3,6-bis (4-methoxyphenyl) -9-phenyl-9H-carbazole (6.5 g, 14.27 mmol) was added to HBr (50 ml) and Br 2 (3.42 g, 21.40 mmol) was added dropwise thereto for 12 hours. Was stirred. After completion of the reaction, the mixture was extracted with water and ethyl acetate, dried over MgSO 4 , and the product was separated by tube chromatography ( n -hexane / EtOAc = 2/1). Yield was 78% (6.0 g).
1HNMR(300MHz,CDCl3) 8.21(d, -Ar, 2H), 7.25-7.29(d, -Ar, 4H), 3.8(s, CH3-O, 6H), 7.02(d, -Ar, 2H), 7.65(d, -Ar, 2H), 7.4(d, -Ar, 2H), 7.2(d, -Ar, 2H)
1 HNMR (300MHz, CDCl 3 ) 8.21 (d, -Ar, 2H), 7.25-7.29 (d, -Ar, 4H), 3.8 (s, CH 3 -O, 6H), 7.02 (d, -Ar, 2H ), 7.65 (d, -Ar, 2H), 7.4 (d, -Ar, 2H), 7.2 (d, -Ar, 2H)
5-7: 3,5-비스[4-(3,6-비스(4-메톡시페닐)-9H-카바졸-9-일)페닐]벤조나이트릴의 합성5-7: Synthesis of 3,5-bis [4- (3,6-bis (4-methoxyphenyl) -9H-carbazol-9-yl) phenyl] benzonitrile
9-(4-브로모페닐)-3,6-비스(4-메톡시페닐)-9H-카바졸(5.8g, 11.01mmole), 5-시아노-1,3-페닐렌디보론산(2.90g, 20.97mmol), 탄산칼륨(2.90g, 20.97mmole), 테트라키스(트리페닐포스포린)팔라듐(0)(0.61g, 0.52mmole)을 THF/톨루엔/에탄올/H2O(비피비=1:1:1:1) 100ml에 녹이고 80℃에서 반응 종료 후 물과 에틸아세테이트로 추출한 후, 무수 마그네슘 설페이트로 건조시키고 여과한 후 유기용매를 증발시키고 관크로마토그래피(n-헥산/EtOAc=2/1)로 분리하였다. 수득률은 75%(4.1g)이었다. 9- (4-bromophenyl) -3,6-bis (4-methoxyphenyl) -9H-carbazole (5.8 g, 11.01 mmol), 5-cyano-1,3-phenylenediboronic acid (2.90 g, 20.97 mmol), potassium carbonate (2.90 g, 20.97 mmol), tetrakis (triphenylphosphorine) palladium (0) (0.61 g, 0.52 mmol) and THF / toluene / ethanol / H 2 O (BP ratio = 1) : 1: 1: 1) After dissolving in 100ml, the reaction was completed at 80 ° C, extracted with water and ethyl acetate, dried over anhydrous magnesium sulfate, filtered and the organic solvent was evaporated and tube chromatography ( n -hexane / EtOAc = 2 / Separated by 1). Yield was 75% (4.1 g).
1HNMR(300MHz,CDCl3) 8.21(d, -Ar, 4H), 7.5(s, -Ar, 3H), 7.25-7.29(d, -Ar, 8H), 3.8(s, CH3-O, 12H), 7.02(d, -Ar, 4H), 7.65(d, -Ar, 4H), 7.4(d, -Ar, 4H), 7.2(d, -Ar, 4H)
1 HNMR (300MHz, CDCl 3 ) 8.21 (d, -Ar, 4H), 7.5 (s, -Ar, 3H), 7.25-7.29 (d, -Ar, 8H), 3.8 (s, CH 3 -O, 12H ), 7.02 (d, -Ar, 4H), 7.65 (d, -Ar, 4H), 7.4 (d, -Ar, 4H), 7.2 (d, -Ar, 4H)
5-8: 3,5-비스[4-(3,6-비스(4-메톡시페닐)-9H-카바졸-9-일)페닐]벤조산의 합성5-8: Synthesis of 3,5-bis [4- (3,6-bis (4-methoxyphenyl) -9H-carbazol-9-yl) phenyl] benzoic acid
3,5-비스[4-(3,6-비스(4-메톡시페닐)-9H-카바졸-9-일)페닐]벤조나이트릴(4.1 g, 4.06 mmol)과 수산화나트륨(0.32g, 8.12 mmol)을 2-에톡시에탄올/H2O(2:1(v/v)) 20ml에 넣고 80℃에서 24시간 동안 교반시켰다. 물과 에틸 아세테이트로 추출한 후, MgSO4로 건조시키고 관크로마토그래피(n-헥산/EtOAc=2/1)로 분리하였다. 수득율은 94%(4.5g)이었다.3,5-bis [4- (3,6-bis (4-methoxyphenyl) -9H-carbazol-9-yl) phenyl] benzonitrile (4.1 g, 4.06 mmol) and sodium hydroxide (0.32 g, 8.12 mmol) was added to 20 ml of 2- ethoxyethanol / H 2 O (2: 1 (v / v)) and stirred at 80 ° C. for 24 hours. Extracted with water and ethyl acetate, dried over MgSO 4 and separated by column chromatography ( n -hexane / EtOAc = 2/1). The yield was 94% (4.5 g).
1HNMR(300MHz,CDCl3) 8.21(d, -Ar, 4H), 7.5(s, -Ar, 3H), 7.25-7.29(d, -Ar, 8H), 3.8(s, CH3-O, 12H), 7.02(d, -Ar, 4H), 7.65(d, -Ar, 4H), 7.4(d, -Ar, 4H), 7.2(d, -Ar, 4H), 12.7(s, OH, H)
1 HNMR (300MHz, CDCl 3 ) 8.21 (d, -Ar, 4H), 7.5 (s, -Ar, 3H), 7.25-7.29 (d, -Ar, 8H), 3.8 (s, CH 3 -O, 12H ), 7.02 (d, -Ar, 4H), 7.65 (d, -Ar, 4H), 7.4 (d, -Ar, 4H), 7.2 (d, -Ar, 4H), 12.7 (s, OH, H)
실시예 6: 정공전도특성을 갖는 공흡착체를 함유하는 염료 용액의 제조 Example 6 Preparation of Dye Solution Containing Coadsorbent with Hole Conduction Properties
다음의 염료 및 정공전도특성을 갖는 공흡착체를 하기 주어진 농도가 되도록 에탄올에 용해하여 염료 용액을 제조하였다.A dye solution was prepared by dissolving the following dyes and coadsorbents having hole conduction properties in ethanol to a concentration given below.
NKX2677 염료[(주)林原生物化學硏究所 사 제품, 일본]: 0.3m몰(M) NKX2677 Dyestuff (manufactured by 林 原 生物化學 硏 究 所, Japan): 0.3mmol (M)
bEHCBA[4-(3,6-비스(4-(2-에틸헥실옥시)페닐)-9H- b EHCBA [4- (3,6-bis (4- (2-ethylhexyloxy) phenyl) -9H-
카바졸-9-일)벤조산, 실시예3의 화합물]: 10m몰(M)
Carbazol-9-yl) benzoic acid, compound of Example 3]: 10 mmol (M)
실시예 7~9: 정공전도특성을 갖는 공흡착체를 함유하는 염료 용액의 제조Examples 7-9: Preparation of Dye Solution Containing Coadsorbent With Hole Conductivity
0.3m몰(M) 농도의 염료에 대하여 각각 20m몰(M)농도(실시예7), 30m몰(M)농도(실시예8), 40m몰(M)농도(실시예9)의 bEHCBA[4-(3,6-비스(4-(2-에틸헥실옥시)페닐)-9H-카바졸-9-일)벤조산]을 용해한 것을 제외하고는 상기 실시예6와 동일한 방법으로 정공전도특성을 갖는 공흡착체를 함유한 염료 용액을 제조하였다.
0.3m moles (M) 20m each molar (M) concentrations relative to concentration of the dye (Example 7), 30m molar (M) concentration (Example 8), b EHCBA of 40m molar (M) concentration (Example 9) Hole conduction in the same manner as in Example 6, except that [4- (3,6-bis (4- (2-ethylhexyloxy) phenyl) -9H-carbazol-9-yl) benzoic acid] was dissolved. Dye solutions containing cosorbents with properties were prepared.
실시예 10: 정공전도특성을 갖는 공흡착체를 함유하는 염료 용액의 제조 Example 10 Preparation of Dye Solution Containing Coadsorbent with Hole Conductivity
다음의 염료 및 정공전도특성을 갖는 공흡착체를 하기 주어진 농도가 되도록 에탄올에 용해하여 염료 용액을 제조하였다.A dye solution was prepared by dissolving the following dyes and coadsorbents having hole conduction properties in ethanol to a concentration given below.
NKX2677 염료[(주)林原生物化學硏究所 사 제품, 일본]: 0.3m몰(M)NKX2677 Dyestuff (manufactured by 林 原 生物化學 硏 究 所, Japan): 0.3mmol (M)
4-(N,N-비스(9,9-디메틸-9H-플루오렌-2-일)아미노)벤조산(실시예2의 화합물): 10m몰(M)
4- (N, N-bis (9,9-dimethyl-9H-fluoren-2-yl) amino) benzoic acid ( compound of Example 2): 10 mmol (M)
비교예1: 정공전도특성을 갖는 공흡착체를 포함하지 않는 염료의 제조Comparative Example 1 Preparation of a Dye Without a Coadsorbent With a Hole Conductivity
0.3m몰(M) 농도의 NKX2677을 구입하여 염료로 사용하였다.
NKX2677 at 0.3 mmol (M) concentration was purchased and used as a dye.
비교예2: 염료와 기존에 DCA(deoxycholic acid)가 함유된 염료 용액의 제조Comparative Example 2: Preparation of dye solution containing dye and deoxycholic acid (DCA)
다음과 같은 염료 및 DCA를 주어진 농도가 되도록 에탄올에 용해하여 염료 용액을 제조하였다.A dye solution was prepared by dissolving the following dyes and DCA in ethanol to a given concentration.
NKX2677 염료[(주)林原生物化學硏究所 사 제품, 일본]: 0.3m몰(M)NKX2677 Dyestuff (manufactured by 林 原 生物化學 硏 究 所, Japan): 0.3mmol (M)
DCA: 40m몰(M)
DCA: 40mM (M)
실시예 11: 염료감응 태양전지의 제조 Example 11: Preparation of Dye-Sensitized Solar Cell
다음의 공정에 따라 염료감응 태양전지를 제조하였다.A dye-sensitized solar cell was manufactured according to the following procedure.
1.FTO 유리기판을 수산화나트륨 세정용액에 넣고 1시간 동안 초음파 세척한 후, 증류수와 에탄올을 이용하여 세척하고, 질소가소를 이용해 건조시켰다.1. Put the FTO glass substrate in a sodium hydroxide cleaning solution and ultrasonically cleaned for 1 hour, washed with distilled water and ethanol, and dried using nitrogen gas.
2.세척된 FTO 유리기판을 40mM 농도의 TiCl4 수용액에 담근 후에 70℃ 오븐에서 30분 간 가열하였다.2. The washed FTO glass substrate was immersed in a 40 mM TiCl 4 aqueous solution and then heated in a 70 ° C. oven for 30 minutes.
3.TiCl4 처리된 FTO 유리기판을 증류수와 에탄올을 이용하여 세척한 후, 질소 가스를 이용하여 건조시키고, 80℃ 오븐에서 10분 간 가열하였다.3. TiCl 4 treated FTO glass substrate was washed with distilled water and ethanol, dried using nitrogen gas and heated in an oven at 80 ° C. for 10 minutes.
4.이어서, TiCl4 처리된 FTO 유리기판에 13nm 입자 크기의 Ti02 페이스트를 닥터 블레이드(doctor blade) 방법으로 코팅하고, 상온에서(20°C) 2시간 동안 건조시켰다.4. Then, Ti0 4 paste of 13 nm particle size was coated on a TiCl 4 treated FTO glass substrate by a doctor blade method, and dried at room temperature (20 ° C.) for 2 hours.
5.Ti02가 코팅된 FTO 유리기판을 80℃ 오븐에서 2시간 동안 건조시켰다.5.Ti0 2 coated FTO glass substrate was dried in an 80 ° C. oven for 2 hours.
6.이어서, Ti02가 코팅된 FTO 유리기판을 가열로를 이용하여 서서히 온도를 올리면서 최대 500℃에서 30분간 소성시켰다.6. Subsequently, the TiO 2 coated FTO glass substrate was calcined at a maximum temperature of 500 ° C. for 30 minutes while gradually raising the temperature using a heating furnace.
7.상기 소성된 FTO 유리기판을 입자크기 400nm인 Ti02 페이스트를 닥터 블레이드 방법으로 코팅하였다. 그리고 상온에서(20℃) 2시간 동안 건조시킨 후, 가열로를 이용하여 서서히 온도를 올리면서 최대 500℃에서 30분간 소성시켰다.7. The fired FTO glass substrate was coated with a TiO 2 paste having a particle size of 400 nm by a doctor blade method. And after drying for 2 hours at room temperature (20 ℃), it was baked for 30 minutes at a maximum 500 ℃ while gradually raising the temperature using a heating furnace.
8.이어서, 상기 소성된 FTO 유리기판을 40mM TiCl4 수용액에 30분 동안 담근 후, 증류수와 에탄올을 이용하여 세척하고 질소가스를 이용하여 건조시키고, 80℃ 오븐에서 10분 동안 건조시켰다.8. Subsequently, the calcined FTO glass substrate was immersed in 40mM TiCl 4 aqueous solution for 30 minutes, washed with distilled water and ethanol, dried using nitrogen gas, and dried in an oven at 80 ° C. for 10 minutes.
9.이어서, 상기 건조된 FTO 유리기판을 히팅건(heating gun)을 이용하여 30분 동안 소결한 후에 상기 실시예6에서 제조된 염료 용액(EtOH)에 담궈 12시간 동안 염료와 정공전도특성을 갖는 공흡착체를 흡착시켰다. 9. Then, the dried FTO glass substrate was sintered for 30 minutes using a heating gun and then immersed in the dye solution (EtOH) prepared in Example 6 to have a dye and hole conductivity for 12 hours. The coadsorbent was adsorbed.
10.상기 염료가 흡착된 FTO 유리기판을 에탄올로 세척한 후, 질소가스를 이용하여 건조시켰다.10. The FTO glass substrate on which the dye was adsorbed was washed with ethanol and then dried using nitrogen gas.
11.FTO 유리기판(상대전극용)에 전해질을 주입하기 위한 지름 0.6mm의 두개 의 전해질 주입구를 만들었다.11. Two electrolyte injection holes with a diameter of 0.6 mm were made to inject the electrolyte into the FTO glass substrate (for the counter electrode).
12.이어서, FTO 유리기판을 H20/아세톤/HCl(부피비=4:4:2) 수용액에 1시간 동안 담가서 초음파 세척기로 세척하고, 70℃ 오븐에서 30분 동안 건조시켰다.12. Subsequently, the FTO glass substrate was immersed in an aqueous solution of H 2 O / acetone / HCl (volume ratio 4: 4: 2) for 1 hour, washed with an ultrasonic cleaner, and dried in an oven at 70 ° C. for 30 minutes.
13.이어서, FTO 유리기판을 Pt 용액(1mL 에탄올 용액에 2mg의 H2PtCl6을 녹임)으로 스핀 코팅한 후 히팅건을 이용하여 400℃에서 15분간 가열시켰다.13. Then, the FTO glass substrate was spin-coated with Pt solution (dissolved 2 mg of H 2 PtCl 6 in 1 mL ethanol solution) and then heated at 400 ° C. for 15 minutes using a heating gun.
14.상기에서 제조된 산화전극과 환원전극을 고분자 실링 필름(sealing film)을 이용하여 80℃로 가열된 핫프레스(hot press)를 이용하여 합체하였다.14. The anode and the cathode prepared above were coalesced using a hot press heated to 80 ° C. using a polymer sealing film.
15.합체된 셀에 진공펌프라인을 이용하여 이온성 전해질을 주입한다.15. Inject the ionic electrolyte into the combined cells using a vacuum pump line.
16.상기 셀에 전해질 주입구를 실링필름과 커버 글래스(cover glass)로 밀봉하였다.
16. The electrolyte injection hole was sealed in the cell with a sealing film and a cover glass.
실시예 12-14 염료감응 태양전지의 제조Example 12-14 Preparation of Dye-Sensitized Solar Cell
실시예6에서 제조된 정공전도특성을 갖는 공흡착체를 함유하는 염료 용액을 대체하여 각각 실시예7(실시예12의 태양전지), 실시예8(실시예13의 태양전지), 실시예9(실시예14의 태양전지), 실시예10(실시예15의 태양전지)에서 제조된 정공전도특성을 갖는 공흡착체를 함유하는 염료 용액을 사용한 것을 제외하고는 상기 실시예 9와 동일한 방법으로 태양전지를 제조하였다.
Example 7 (solar cell of Example 12), Example 8 (solar cell of Example 13), and Example 9 were substituted for the dye solution containing the coadsorbent having the hole conduction properties prepared in Example 6. (Solar cell of Example 14), Example 10 (Solar cell of Example 15) in the same manner as in Example 9 except for using a dye solution containing a coadsorbent having a hole conductivity characteristics A solar cell was prepared.
비교예3 및 4: 염료감응 태양전지의 제조 Comparative Examples 3 and 4: Preparation of Dye-Sensitized Solar Cell
상기 실시예4의 9단계에서, 실시예4에서 제조된 정공전도특성을 갖는 공흡착체를 함유하는 염료 용액 대신 각각 비교예1(비교예3의 태양전지), 비교예2(비교예4의 태양전지)에서 제조된 정공전도특성을 갖는 공흡착체를 함유하는 염료 용액을 사용한 것을 제외하고는 상기 실시예 9와 동일한 방법으로 태양전지를 제조하였다.
In
시험예 1: TiOTest Example 1: TiO 22 필름에 흡착된 정공전도특성을 갖는 공흡착체를 함유하는 염료, 정공전도특성을 갖는 공흡착체를 포함하지 않는 염료 및 DCA의 UV-vis 흡수 스펙트럼 분석UV-vis absorption spectra analysis of dyes containing coadsorbents with hole conduction properties adsorbed on the film, dyes without coadsorbents with hole conduction properties, and DCA
실시예6, 비교예1 및 비교예2에서 제조된 염료 용액을 TiO2필름에 딥핑하여 12시간 동안 흡착시켜 UV-vis absorption spectra로 확인하고 그 결과를 도2에 나타내었다.
The dye solutions prepared in Example 6, Comparative Example 1 and Comparative Example 2 were dipped into TiO 2 films and adsorbed for 12 hours to confirm by UV-vis absorption spectra, and the results are shown in FIG. 2.
시험예 2: 염료감응 태양전지의 성능 평가Test Example 2: Performance Evaluation of Dye-Sensitized Solar Cell
실시예11, 비교예3 및 비교예4에서 제조된 염료감응 태양전지를 사용하여 1 sun(100 mW/cm2) 일루미네이션(illumination) 조건에서 광전류-전압을 측정하고, 그 결과를 하기 표1에 나타내었다. 실시예11, 비교예3 및 비교예4의 염료감응 태양전지의 전류-전압곡선은 도3에 도시하였으며, 광전변환효율(IPCE)은 도4에 도시하였다.Using the dye-sensitized solar cells prepared in Example 11, Comparative Example 3 and Comparative Example 4 measured the photocurrent-voltage under 1 sun (100 mW / cm 2 ) illumination (illumination) conditions, the results are shown in Table 1 Indicated. The current-voltage curves of the dye-sensitized solar cells of Example 11, Comparative Example 3 and Comparative Example 4 are shown in FIG. 3, and the photoelectric conversion efficiency (IPCE) is shown in FIG.
상기 표1 및 도2 및 도3로부터 확인되는 바와 같이, 본 발명의 정공전도특성을 갖는 공흡착체(bEHCBA)를 포함하는 염료 용액을 사용한 태양전지의 경우, 1sun(100mW/cm2) 기준에서 V oc: 0.723 V, J sc: 15.02 mA/cm2, Fill factor: 0.72.36%, η: 7.86%를 나타내어, 정공전도특성을 갖는 공흡착체를 포함하지 않는 비교예3 및 비교예4와 비교하여 매우 현저한 성능을 나타냈다.
As can be seen from Table 1 and Figures 2 and 3, in the case of a solar cell using a dye solution containing a co-adsorbent ( b EHCBA) having a hole conductivity of the present invention, based on 1sun (100mW / cm 2 ) At V oc : 0.723 V, J sc : 15.02 mA / cm 2 , Fill factor: 0.72.36%, η : 7.86%, which was very remarkable in comparison with Comparative Example 3 and Comparative Example 4, which did not include a coadsorbent having hole conduction properties.
시험예 3: 염료감응 태양전지 셀의 내부 전하이동 저항 특성Test Example 3 Characteristics of Internal Charge Transfer Resistance of Dye-Sensitized Solar Cell
염료감응 태양전지의 내부 저항 특성을 알아보고, 염료감응 태양전지 내에서 전하이동 저항(charge transfer resistance)을 측정하기 위하여 1 sun(100mW/cm2) 조건하에서 AC 임피던스를 측정한 Nyquist plot를 도5에에 나타내었다. 이 때, 임피던스 fitting에 의하여 각각 계면의 내부 저항을 구하기 위하여 설정한 등가회로는 도6에 나타내었다. In order to investigate the internal resistance characteristics of dye-sensitized solar cells and to measure the charge transfer resistance in dye-sensitized solar cells, a Nyquist plot measuring AC impedance under 1 sun (100 mW / cm 2 ) is shown in FIG. 5. Indicated. At this time, an equivalent circuit set to obtain internal resistance of each interface by impedance fitting is shown in FIG.
도5에서 확인되는 바와 같이, 본 발명의 정공전도특성을 갖는 공흡착체(bEHCBA)를 포함하여 제조된 실시예11의 태양전지는 비교예3 및 비교예4의 셀들과 비교하여 TiO2/염료/전해질 계면에서 낮은 저항을 나타냈다. 이러한 낮은 저항은 전자의 빠른 이동을 가능하게 하여 염료감응 태양전지의 효율을 향상시킨다.
As can be seen in Figure 5, the solar cell of Example 11, including the co-adsorbent ( b EHCBA) having a hole conductivity of the present invention is compared to the cells of Comparative Example 3 and Comparative Example 4 TiO 2 / Low resistance at the dye / electrolyte interface. These low resistances enable fast transfer of electrons to improve the efficiency of the dye-sensitized solar cell.
시험예 4: 염료감응 태양전지의 성능 평가Test Example 4: Performance Evaluation of Dye-Sensitized Solar Cell
실시예15, 비교예3 및 비교예4에서 제조된 염료감응 태양전지를 사용하여 1 sun(100 mW/cm2) 일루미네이션(illumination) 조건에서 광전류-전압을 측정하고, 그 결과를 하기 표2에 나타내었다. 실시예15, 비교예3 및 비교예4의 염료감응 태양전지의 전류-전압곡선은 도7에 도시하였으며, 광전변환효율(IPCE)은 도8에 도시하였고, 염료감응 태양전지 내에서 전하이동 저항(charge transfer resistance)을 측정하기 위하여 1 sun(100mW/cm2) 조건하에서 AC 임피던스를 측정한 Nyquist plot를 도5에 나타내었다.Using the dye-sensitized solar cells prepared in Example 15, Comparative Example 3 and Comparative Example 4 measured the photocurrent-voltage under 1 sun (100 mW / cm 2 ) illumination (illumination) conditions, the results are shown in Table 2 Indicated. The current-voltage curves of the dye-sensitized solar cells of Example 15, Comparative Example 3 and Comparative Example 4 are shown in FIG. 7, the photoelectric conversion efficiency (IPCE) is shown in FIG. 8, and the charge transfer resistance in the dye-sensitized solar cell. In order to measure the charge transfer resistance, a Nyquist plot of measuring AC impedance under 1 sun (100 mW / cm 2 ) condition is shown in FIG. 5.
상기 표2에서 확인되는 바와 같이, 본 발명의 정공전도특성을 갖는 공흡착체(실시예15)를 포함하는 염료 용액을 사용한 태양전지의 경우, 1sun(100mW/cm2) 기준에서 V oc: 0.636 V, J sc: 17.60 mA/cm2, Fill factor: 73.60%, η: 8.24%를 나타내어, 정공전도특성을 갖는 공흡착체를 포함하지 않는 비교예3 및 비교예4의 태양전지와 비교하여 매우 현저한 성능을 나타냈다.As confirmed in Table 2, in the case of a solar cell using a dye solution containing a co-adsorbent (Example 15) having a hole conductivity of the present invention, V oc : 0.636 at 1sun (100mW / cm 2 ) reference V, J sc : 17.60 mA / cm 2 , Fill factor: 73.60%, η : 8.24%, which was very remarkable in comparison with the solar cells of Comparative Example 3 and Comparative Example 4, which did not include a coadsorbent having hole conductivity.
Claims (12)
[화학식1]
상기 식에서
R1 및 R2는 수소 또는 C1~C5의 알킬로 치환된 C4~C10의 알콕시기이며,
R3, R4, R5 및 R6는 수소이며,
R7은 결합 또는 부존재이며,
R8 및 R9은 두개의 C1~C4의 알킬기로 치환된 메틸렌기이거나 부존재이며,
Ar은 페닐기이며,
m은 0 이고, n은 1이고, o 및 p는 0 또는 1이다. Compound represented by the following formula (1):
[Chemical Formula 1]
In the above formula
R1 and R2 are hydrogen or C1-C5 alkoxy group substituted by C1-C5 alkyl,
R3, R4, R5 and R6 are hydrogen,
R7 is a bond or absent,
R8 and R9 are methylene groups substituted with two C1 to C4 alkyl groups or absent,
Ar is a phenyl group,
m is 0, n is 1, o and p are 0 or 1.
[화학식4]
[화학식7]
[화학식8]
상기 화학식4, 화학식7 및 화학식8에서 R1, R2 및 m의 정의는 화학식1과 동일하다. The compound according to claim 1, wherein the compound represented by Chemical Formula 1 is one compound selected from the group consisting of Chemical Formulas 4, 7, and 8:
[Chemical Formula 4]
(7)
[Chemical Formula 8]
In Formulas 4, 7 and 8, the definitions of R1, R2, and m are the same as those of Formula 1.
4-(N,N-비스(4-(2-에틸헥실옥시)페닐)아미노)벤조산,
4-(N,N-비스(9,9-디메틸-9H-플루오렌-2-일)아미노)벤조산, 또는
4-(3,6-비스(4-(2-에틸헥실옥시)페닐)-9H-카바졸-9-일)벤조산인 것을 특징으로 하는 화합물.The compound of claim 3, wherein the one compound selected from the group consisting of the compounds of Formulas 4, 7, and 8
4- (N, N-bis (4- (2-ethylhexyloxy) phenyl) amino) benzoic acid,
4- (N, N-bis (9,9-dimethyl-9H-fluoren-2-yl) amino) benzoic acid, or
4- (3,6-bis (4- (2-ethylhexyloxy) phenyl) -9H-carbazol-9-yl) benzoic acid.
전도성 투명 기판을 포함하는 제1전극;
상기 제1전극의 어느 일면에 형성된 광흡수층;
상기 광흡수층이 형성된 제1전극에 대향하여 배치되는 제2전극; 및
상기 제1전극과 제2전극 사이의 공간에 위치하는 전해질을 포함하는 것을 특징으로 하는 염료감응 태양전지.
The method of claim 11, wherein the dye-sensitized solar cell
A first electrode comprising a conductive transparent substrate;
A light absorption layer formed on one surface of the first electrode;
A second electrode disposed to face the first electrode on which the light absorption layer is formed; And
Dye-sensitized solar cell comprising an electrolyte located in the space between the first electrode and the second electrode.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/KR2011/009504 WO2012078005A2 (en) | 2010-12-10 | 2011-12-09 | Compounds having hole conducting property, co-adsorbent body comprising same, and dye-sensitized solar cell comprising the co-adsorbent body |
| EP11846378.5A EP2712859B1 (en) | 2010-12-10 | 2011-12-09 | Compounds having hole conducting property, co-adsorbent body comprising same, and dye-sensitized solar cell comprising the co-adsorbent body |
| JP2013543106A JP5914514B2 (en) | 2010-12-10 | 2011-12-09 | COMPOUND HAVING HOLE CONDUCTIVITY, COADSORBENT HAVING HOLE CONDUCTIVITY CONTAINING THE SAME, AND DYE-SENSITIZED SOLAR CELL CONTAINING THE SAME |
| EP13176063.9A EP2711949B9 (en) | 2010-12-10 | 2011-12-09 | Compounds having hole conducting property, co-adsorbent body comprising same, and dye-sensitized solar cell comprising the co-adsorbent body |
| EP13176064.7A EP2711359B1 (en) | 2010-12-10 | 2011-12-09 | Compounds having hole conducting property, co-adsorbent body comprising same, and dye-sensitized solar cell comprising the co-adsorbent body |
| EP13176066.2A EP2712860B1 (en) | 2010-12-10 | 2011-12-09 | Compound having hole conducting property, co-adsorbent body comprising same, and dye-sensitized solar cell comprising the co-adsorbent body |
| JP2014265001A JP5989080B2 (en) | 2010-12-10 | 2014-12-26 | COMPOUND HAVING HOLE CONDUCTIVITY, COADSORBENT HAVING HOLE CONDUCTIVITY CONTAINING THE SAME, AND DYE-SENSITIZED SOLAR CELL CONTAINING THE SAME |
| JP2014265000A JP5989079B2 (en) | 2010-12-10 | 2014-12-26 | COMPOUND HAVING HOLE CONDUCTIVITY, COADSORBENT HAVING HOLE CONDUCTIVITY CONTAINING THE SAME, AND DYE-SENSITIZED SOLAR CELL CONTAINING THE SAME |
| JP2014264999A JP5989078B2 (en) | 2010-12-10 | 2014-12-26 | COMPOUND HAVING HOLE CONDUCTIVITY, COADSORBENT HAVING HOLE CONDUCTIVITY CONTAINING THE SAME, AND DYE-SENSITIZED SOLAR CELL CONTAINING THE SAME |
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| KR20100062141 | 2010-06-29 | ||
| KR1020100062141 | 2010-06-29 |
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| KR1020120122604A Division KR101290406B1 (en) | 2010-06-29 | 2012-10-31 | Compounds with hole conducting property, their use as co-adsorbent materials, and dye-sensitized solar cell comprising the same |
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| KR1020120122604A KR101290406B1 (en) | 2010-06-29 | 2012-10-31 | Compounds with hole conducting property, their use as co-adsorbent materials, and dye-sensitized solar cell comprising the same |
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| KR101563558B1 (en) | 2012-05-23 | 2015-10-27 | 고려대학교 산학협력단 | Novel Tailor-made Hole-Conducting Coadsorbents for Highly Efficient Dye-sensitized Solar Cells |
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| JP5990385B2 (en) * | 2012-03-01 | 2016-09-14 | ユー・ディー・シー アイルランド リミテッド | Compound, material for organic electroluminescence device, charge transport material, organic electroluminescence device |
| DE202013012834U1 (en) | 2012-08-31 | 2020-03-19 | lDEMITSU KOSAN CO., LTD. | Aromatic amine derivative and organic electroluminescent element using the same |
| KR20200057886A (en) | 2018-11-16 | 2020-05-27 | 삼성디스플레이 주식회사 | Organic electroluminescence device and compound for organic electroluminescence device |
| KR20210056495A (en) | 2019-11-08 | 2021-05-20 | 삼성디스플레이 주식회사 | Organic electroluminescence device and aromatic compound for organic electroluminescence device |
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| TW201107333A (en) | 2009-08-28 | 2011-03-01 | Univ Nat Taipei Technology | A kind of organic compound and organic dye used in dye-sensitized solar cell thereof |
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| JP2004363103A (en) | 2003-06-03 | 2004-12-24 | Canon Inc | Bipolar asymmetric carbazole-group host material for electrophosphorescent guest-host organic light emitting device system |
| KR20080103680A (en) * | 2007-05-25 | 2008-11-28 | 고려대학교 산학협력단 | Novel organic dye containing n-arylcarbazole moiety and preparation thereof |
| WO2008146975A1 (en) | 2007-05-25 | 2008-12-04 | Dongjin Semichem Co., Ltd | Novel organic dye containing n-arylcarbazole moiety and preparation thereof |
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| KR101563558B1 (en) | 2012-05-23 | 2015-10-27 | 고려대학교 산학협력단 | Novel Tailor-made Hole-Conducting Coadsorbents for Highly Efficient Dye-sensitized Solar Cells |
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