WO2011004688A1 - Phthalocyanine compounds - Google Patents
Phthalocyanine compounds Download PDFInfo
- Publication number
- WO2011004688A1 WO2011004688A1 PCT/JP2010/060334 JP2010060334W WO2011004688A1 WO 2011004688 A1 WO2011004688 A1 WO 2011004688A1 JP 2010060334 W JP2010060334 W JP 2010060334W WO 2011004688 A1 WO2011004688 A1 WO 2011004688A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- phthalocyanine compound
- oxide
- octakis
- och
- phthalocyanine
- Prior art date
Links
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 title claims abstract description 41
- -1 phthalocyanine compound Chemical class 0.000 claims description 87
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 125000003545 alkoxy group Chemical group 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 239000011358 absorbing material Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 238000010521 absorption reaction Methods 0.000 abstract description 25
- 238000000034 method Methods 0.000 abstract description 22
- 238000010438 heat treatment Methods 0.000 abstract description 18
- 230000031700 light absorption Effects 0.000 abstract description 14
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 238000004528 spin coating Methods 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 35
- 229940125773 compound 10 Drugs 0.000 description 26
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 26
- 125000001424 substituent group Chemical group 0.000 description 20
- 239000010408 film Substances 0.000 description 19
- 239000004065 semiconductor Substances 0.000 description 18
- 239000002904 solvent Substances 0.000 description 18
- 239000000758 substrate Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000000862 absorption spectrum Methods 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 239000010409 thin film Substances 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 7
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 7
- 229940125797 compound 12 Drugs 0.000 description 7
- 229910001935 vanadium oxide Inorganic materials 0.000 description 7
- 125000004793 2,2,2-trifluoroethoxy group Chemical group FC(CO*)(F)F 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 229910003437 indium oxide Inorganic materials 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 5
- 229910052751 metal Chemical class 0.000 description 5
- 239000002184 metal Chemical class 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 238000001771 vacuum deposition Methods 0.000 description 5
- ZQEKILIEWQFART-UHFFFAOYSA-N 1,4-bis(2,2,2-trifluoroethoxy)cyclohexa-3,5-diene-1,2-dicarbonitrile Chemical compound FC(COC1(C#N)C(C#N)C=C(C=C1)OCC(F)(F)F)(F)F ZQEKILIEWQFART-UHFFFAOYSA-N 0.000 description 4
- IGKCQDUYZULGBM-UHFFFAOYSA-N 2,2,2-trifluoroethyl 4-methylbenzenesulfonate Chemical compound CC1=CC=C(S(=O)(=O)OCC(F)(F)F)C=C1 IGKCQDUYZULGBM-UHFFFAOYSA-N 0.000 description 4
- STTGYIUESPWXOW-UHFFFAOYSA-N 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline Chemical compound C=12C=CC3=C(C=4C=CC=CC=4)C=C(C)N=C3C2=NC(C)=CC=1C1=CC=CC=C1 STTGYIUESPWXOW-UHFFFAOYSA-N 0.000 description 4
- MPAIWVOBMLSHQA-UHFFFAOYSA-N 3,6-dihydroxybenzene-1,2-dicarbonitrile Chemical compound OC1=CC=C(O)C(C#N)=C1C#N MPAIWVOBMLSHQA-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000012790 confirmation Methods 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000005240 physical vapour deposition Methods 0.000 description 4
- 239000002985 plastic film Substances 0.000 description 4
- 229920006255 plastic film Polymers 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 229910003472 fullerene Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 description 2
- 238000007611 bar coating method Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000007756 gravure coating Methods 0.000 description 2
- 238000007733 ion plating Methods 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000011112 polyethylene naphthalate Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 150000003681 vanadium Chemical class 0.000 description 2
- IBYSTTGVDIFUAY-UHFFFAOYSA-N vanadium monoxide Chemical compound [V]=O IBYSTTGVDIFUAY-UHFFFAOYSA-N 0.000 description 2
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- 125000004797 2,2,2-trichloroethoxy group Chemical group ClC(CO*)(Cl)Cl 0.000 description 1
- IPXKNSIIPLVCLB-UHFFFAOYSA-N 2-(3,3,3-trifluoropropylperoxycarbonyl)benzoic acid Chemical compound C1=CC=C(C(=C1)C(=O)O)C(=O)OOCCC(F)(F)F IPXKNSIIPLVCLB-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910021549 Vanadium(II) chloride Inorganic materials 0.000 description 1
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 125000004783 dichloromethoxy group Chemical group ClC(O*)Cl 0.000 description 1
- 125000004786 difluoromethoxy group Chemical group [H]C(F)(F)O* 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 238000013086 organic photovoltaic Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920006391 phthalonitrile polymer Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 125000004784 trichloromethoxy group Chemical group ClC(O*)(Cl)Cl 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- ITAKKORXEUJTBC-UHFFFAOYSA-L vanadium(ii) chloride Chemical compound Cl[V]Cl ITAKKORXEUJTBC-UHFFFAOYSA-L 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/06—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide
- C09B47/067—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile
- C09B47/0675—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile having oxygen or sulfur linked directly to the skeleton
Definitions
- the present invention relates to phthalocyanine compounds and the like useful as materials for photoelectric conversion elements, optical recording media, optical filters and the like.
- a phthalocyanine compound is an organic semiconductor that is chemically stable and has a narrow band gap. It is known that a thin film of a phthalocyanine compound having such characteristics is formed and used as an organic photovoltaic element or a near-infrared absorbing material (for example, Patent Document 1 and Patent Document 2).
- the phthalocyanine compound Since the phthalocyanine compound is generally insoluble in a solvent, it is usually thinned by a vacuum deposition method or the like. However, in Patent Document 2, a phthalocyanine compound having a specific substituent has solubility in a solvent. It is disclosed to show.
- phthalocyanine compounds are used according to various uses, there is a problem that there are few phthalocyanine compounds having desirable characteristics and the range of material selection is narrow depending on the use.
- some phthalocyanine compounds exhibit solubility in a solvent as described above, but are preferably used as a P-type organic semiconductor material that is soluble in a solvent and can absorb near-infrared light. Has not been obtained yet.
- an object of the present invention is to provide a phthalocyanine compound or the like that can be formed by a simple process and has a desirable absorption region as a material for a photoelectric conversion element or the like.
- the phthalocyanine compound in the present invention is a phthalocyanine compound represented by the following general formula (I), wherein R1 to R8 are linear halogenated alkoxy groups having 5 or less carbon atoms, or 5 carbon atoms. It represents one of the following branched alkoxy groups. These substituents R1 to R8 may be the same or different.
- R1 to R8 in the above general formula (I) are preferably selected from the group of 1a to 1g represented by the following chemical formula (II).
- the light absorbing material of the present invention is characterized by containing the above-mentioned phthalocyanine compound.
- the light absorbing material is preferably formed into a film and heated at a temperature of more than 60 ° C. and not more than 150 ° C.
- the photoelectric conversion element of the present invention is characterized by including a photoelectric conversion layer containing the above-described light absorbing material.
- a phthalocyanine compound or the like that is soluble in a solvent, can be formed by a simple process such as a coating method, and has a desirable absorption region as a material for a photoelectric conversion element or the like.
- FIG. 1 shows the molecular formula of the phthalocyanine compound of the present invention.
- the phthalocyanine compound 10 of the present invention contains vanadium oxide (VO) as a central metal compound and substituents R1 to R8.
- the substituents R1 to R8 are either a linear halogenated alkoxy group having 5 or less carbon atoms or a branched alkoxy group having 5 or less carbon atoms, and may be the same or different. Good.
- the straight-chain halogenated alkoxy group having 5 or less carbon atoms is a group in which a part of methoxy group, ethoxy group, propoxy group, butoxy group or pentyloxy group is halogenated.
- halogen element fluorine (F) or chlorine (Cl) is preferable.
- phthalocyanine compound examples include 1,4,5,8,9,12,13,16-octakis (monofluoromethoxy) phthalocyaninatovanadium oxide, 1,4,5,8,9,12, 13,16-octakis (difluoromethoxy) phthalocyaninatovanadium oxide, 1,4,5,8,9,12,13,16-octakis (trifluoromethoxy) phthalocyaninatovanadium oxide, 1,4,5,8 , 9,12,13,16-octakis (monochloromethoxy) phthalocyaninatovanadium oxide, 1,4,5,8,9,12,13,16-octakis (dichloromethoxy) phthalocyaninatovanadium oxide, 1,4 , 5,8,9,12,13,16-octakis (trichloromethoxy) phthalocyanine Tovanadium oxide, 1,4,5,8,9,12,13,16-octakis (2-
- substituents R1 to R8 are preferably selected from the group of 1a to 1g represented by the following chemical formula (II).
- the substituents R1 to R8 selected from the group of 1a to 1g may be the same or different. That is, the above-mentioned compounds having the same substituents R1 to R8, for example, 1,4,5,8,9,12,13,16-octakis (2,2,2-trifluoroethoxy) phthalocyaninato Vanadium oxide, 1,4,5,8,9,12,13,16-octakis (2,2,2-trichloroethoxy) phthalocyaninatovanadium oxide, 1,4,5,8,9,12,13, 16-octakis (3,3,3-trifluoropropoxy) phthalocyaninatovanadium oxide, 1,4,5,8,9,12,13,16-octakis (3,3,3-trichloropropoxy) phthalocyaninato Vanadium oxide, 1,4,5,8,9,12,13,16-octakis-iso-propoxyphthalocyaninatovanadium oxide, 1, , 5,8,
- the phthalocyanine compound 10 has excellent solubility in organic solvents. It is considered that the solubility in organic solvents is mainly brought about by the substituents R1 to R8. That is, the solubility of the phthalocyanine compound 10 is improved by having a linear halogenated alkoxy group having 5 or less carbon atoms or a branched alkoxy group having 5 or less carbon atoms as a substituent. From the viewpoint of improving solubility, the substituent is more preferably selected from the group of 1a to 1g represented by the chemical formula (II), and a halogenated alkoxy such as 2,2,2-trifluoroethoxy group (1a). Particularly preferred is a group.
- the phthalocyanine compound 10 is light absorptive and can particularly efficiently absorb near infrared light. It is considered that the absorption of near infrared light is mainly due to the high crystallinity of the phthalocyanine compound 10.
- the crystallinity of the phthalocyanine compound 10 is that the oxygen ion of vanadium oxide at the center protrudes to one of the planes of the phthalocyanine compound 10 having a substantially planar structure, and the carbon number of the substituent R is suppressed to 5 or less. Is brought about by being.
- the absorption wavelength preferably has a maximum absorption wavelength in the wavelength region of 700 to 1100 nm, and more preferably has a maximum absorption wavelength in the wavelength region of 800 to 1000 nm.
- the phthalocyanine compound 10 When the phthalocyanine compound 10 is used as a light absorbing material, it is preferable to form a film (hereinafter sometimes referred to as a thin film).
- the method for forming the film is not limited. However, since the phthalocyanine compound 10 has excellent solubility in an organic solvent, it can be formed by a coating method.
- the coating method is a method in which the phthalocyanine compound 10 is dissolved in a suitable solvent to form a coating solution, and the coating solution is applied to a substrate to form a film.
- Solvents used include alcohols such as methyl alcohol and ethyl alcohol, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate and butyl acetate, hydrocarbons such as toluene and xylene, dichloromethane, chloroform, chlorobenzene and the like. Examples thereof include halogenated hydrocarbons.
- the concentration of the phthalocyanine compound 10 in the solvent is preferably 0.01 to 20% by mass.
- the substrate for example, a glass plate, a plastic film or the like can be used.
- the plastic film include films made of polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, polyvinyl chloride, polystyrene, and polyimide.
- the thickness of the substrate is about 10 ⁇ m to 5 mm.
- a gas barrier layer or a conductive layer may be provided on these substrates.
- the gas barrier layer include a layer made of silica or silicon nitride
- the conductive layer include a layer made of indium oxide, tin oxide, tin-doped indium oxide (ITO), or zinc oxide.
- Examples of the method for applying the coating liquid to the substrate include a spin coating method, a bar coating method, a gravure coating method, and a spray coating method. After applying the coating solution by these methods, the film of the phthalocyanine compound is formed by heating as necessary to remove the solvent.
- the thickness of the formed film is not particularly limited and may be determined according to the application and purpose, but is usually about 10 nm to 10 ⁇ m. Note that a vacuum deposition method, a sputtering method, or the like can also be used as a film formation method.
- the heating temperature is preferably higher than 60 ° C. and 150 ° C. or lower.
- the heating method is not limited, and it can be performed by a method such as using a hot plate or an oven (a constant temperature bath).
- the heating time is about 1 minute to 1 hour, preferably about 2 minutes to 30 minutes.
- the heating atmosphere may be air, or may be under reduced pressure, filled with nitrogen or an inert gas. Moreover, you may perform simultaneously drying and heat processing of a coating film.
- FIG. 2 is a light absorption spectrum of the phthalocyanine compound 101a of the present invention (described later).
- the light absorption spectrum of the phthalocyanine compound 101a differs between the solution and the film. That is, in the case of a solution, the maximum absorption wavelength is in the vicinity of 740 nm as shown by the broken line, whereas in the case of a film, the maximum absorption wavelength is about 836 nm as shown by the solid line.
- the film-like phthalocyanine compound 101a is obtained by applying a coating solution to a glass substrate to form a thin film and heating at 150 ° C.
- the thin-film phthalocyanine compound 101a has a light absorption spectrum shown by a solid line in FIG. 2, but the light absorption spectrum is changed by heating.
- the solution in FIG. 2 uses chlorobenzene as a solvent. And about chlorobenzene, since absorption is not recognized by 740 nm vicinity, it can be said that the change of the maximum absorption wavelength in FIG. 2 originates in the phthalocyanine compound 101a.
- FIG. 3 shows changes in the light absorption spectrum when the heating temperature of the thinned phthalocyanine compound 101a shown in FIG. 2 is changed.
- the heating temperature when heated at 60 ° C., it has a light absorption spectrum (dashed line) close to a solution.
- the heating temperature is 80 ° C.
- the absorption intensity peak shifts to the near infrared region.
- the maximum absorption wavelength shows almost the same value as in the case of 80 ° C. while shifting to the near infrared region, and has a stable absorption intensity peak. It can be seen that it is.
- the phthalocyanine compound 101a can be suitably used in a field where an absorption band in the near infrared region is required.
- the fall of absorption intensity is recognized as shown in figure. For this reason, it is preferable to heat the phthalocyanine compound 101a in a temperature range exceeding 60 ° C. and 150 ° C. or less.
- the phthalocyanine compound 101a when the thin film of the phthalocyanine compound 101a after heating is observed with a microscope, a birefringent domain exhibiting high crystallinity is observed. This also suggests that the phthalocyanine compound 101a is crystallized by heating and has an absorption band in the near infrared region when it has a crystal structure.
- the phthalocyanine compound 10 can be performed using a known method for producing a phthalocyanine compound, but it is preferable to use a cyclization reaction using a phthalonitrile compound and a metal salt. Hereinafter, the manufacturing method of the phthalocyanine compound 10 using a cyclization reaction is demonstrated.
- 1,4-bis (2,2,2-trifluoroethoxy) phthalonitrile (by reaction of dicyanohydroquinone and 2,2,2-trifluoroethyl tosylate) Compound 12) is synthesized.
- This synthesis is performed by adding dicyanohydroquinone and 2,2,2-trifluoroethyl tosylate in a solvent such as N, N-dimethylformamide (DMF) and stirring at 80 to 130 ° C. for about 1 to 60 hours. Is called.
- a solvent such as N, N-dimethylformamide (DMF)
- DMF N, N-dimethylformamide
- 2,2,2-trifluoroethyl tosylate can be obtained, for example, by the method described in paragraph 0360 of JP-A-2005-84584.
- the obtained compound 12 can be separated, washed and purified by a known method.
- the obtained compound 12, vanadium salt and urea are added to a solvent such as benzonitrile and dichlorobenzene, and stirred at 100 to 170 ° C. for about 10 to 120 minutes.
- the compound 101a which is one of the phthalocyanine compounds 10 that is, 1, 4, 5, 8, 9, 12, 13, 16-octakis (2,2,2-trifluoroethoxy) Phthalocyaninatovanadium oxide
- the vanadium salt vanadium dichloride, vanadium trichloride, vanadium pentoxide, or the like can be used.
- the obtained 1,4,5,8,9,12,13,16-octakis (2,2,2-trifluoroethoxy) phthalocyaninatovanadium oxide can be separated, washed and purified by known methods. Can do.
- the phthalocyanine compound having —OCH 2 CF 3 as a substituent has been described.
- the —OCH 2 CF 3 of the compound 12 may be another linear halogenated alkoxy group having 5 or less carbon atoms, or the number of carbon atoms. If the branched alkoxy group is 5 or less, the phthalocyanine compound 10 having those substituents can be obtained.
- the photoelectric conversion layer of the present invention includes a light absorbing material containing the phthalocyanine compound 10.
- the photoelectric conversion element generally has two electrodes, that is, an anode and a cathode, and has a structure including a photoelectric conversion layer between them. At least one of the anode and the cathode needs to transmit light, but the anode is usually a light-transmitting electrode.
- Examples of the conductive material for forming the anode include indium oxide, tin oxide, tin-doped indium oxide (ITO), iridium oxide, zinc oxide, and gallium-doped zinc oxide. However, the conductivity and transparency are good. Tin-doped indium oxide (ITO) and gallium-doped zinc oxide are preferred. Examples of the conductive material for forming the cathode include metals such as platinum, gold, aluminum, iridium, and chromium, and carbon nanotubes.
- the anode and the cathode can be obtained, for example, by forming a layer made of a conductive material on a substrate or a photoelectric conversion layer by a PVD (physical vapor deposition) method such as vacuum deposition, sputtering, or ion plating.
- a glass plate or a plastic film is preferable.
- the plastic film include films made of polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, polyvinyl chloride, polystyrene, and polyimide.
- the thickness of the substrate is about 10 ⁇ m to 5 mm.
- the thickness of the anode and the cathode is preferably 10 to 500 nm, respectively.
- the photoelectric conversion layer is a layer having a function of absorbing light and converting light energy into electric energy.
- a layer in which a p-type semiconductor layer and an n-type semiconductor layer are stacked may be used.
- the phthalocyanine compound is a p-type semiconductor, and the phthalocyanine compound 10 of the present invention functions as a p-type semiconductor layer in such a photoelectric conversion layer.
- the n-type semiconductor may be an inorganic semiconductor or an organic semiconductor.
- the inorganic semiconductor include silicon doped with arsenic or phosphorus
- examples of the organic semiconductor include fullerene and fullerene derivatives such as [6,6] -phenyl-C 61 -methyl butyrate (PCBM).
- an intrinsic semiconductor (i-type semiconductor) layer may be provided between the p-type semiconductor layer and the n-type semiconductor layer. Conversion efficiency can be improved by making a photoelectric converting layer into such a structure.
- Each layer constituting the photoelectric conversion layer is formed by a coating method such as PVD (physical vapor deposition) such as vacuum deposition, sputtering, ion plating, spin coating method, bar coating method, gravure coating method, spray coating method, etc. can do.
- the thickness of the photoelectric conversion layer is preferably 10 nm to 3 ⁇ m.
- a buffer layer may be provided in the photoelectric conversion element.
- the buffer layer include a layer containing bathocuproine (2,9-dimethyl-4,7diphenyl-1,10-phenanthroline) as a hole blocking material.
- This buffer layer (hole blocking material) is usually provided between the n-type semiconductor layer and the cathode.
- a photoelectric conversion element a solar cell, an optical sensor, etc. are mentioned, for example.
- Solubility test The phthalocyanine compound was added to each solvent and stirred so that the concentration of the phthalocyanine compound was 10% by mass, the solubility of the phthalocyanine compound was visually observed, and the solubility was observed depending on the presence or absence of undissolved substances. .
- Dichloromethane, chloroform, chlorobenzene, tetrahydrofuran, acetone, ethyl acetate, and toluene were used as the solvent. Measurement was performed using a light absorption spectrophotometer (“UV-3101PC” manufactured by Shimadzu Corporation). Confirmation of crystallinity It was observed at a magnification of 10 using a polarizing microscope (OLYMPUS "BX51").
- Example 1 As shown in the reaction formula (1) in FIG. 4, 1,4-bis (2,2,2-trifluoroethoxy) phthalonitrile (Compound 12) was synthesized from dicyanohydroquinone (manufactured by Tokyo Chemical Industry Co., Ltd.). That is, a solution obtained by dissolving 2.3 g of metal sodium in 80 ml of methanol (solvent) at room temperature under a nitrogen stream was added to 8.0 g of dicyanohydroquinone, stirred at room temperature for 30 minutes, and unreacted methanol was removed under reduced pressure. Removed.
- dicyanohydroquinone manufactured by Tokyo Chemical Industry Co., Ltd.
- phthalocyanine compound 101a 1,4,5,8,9,12,13,16-octakis (2,2,2-trifluoroethoxy) phthalocyaninatovanadium oxide. It was confirmed that there was. The evaluation result of this phthalocyanine compound 101a is shown.
- the phthalocyanine compound 101a is crystallized by heating and has an absorption band in the near infrared region when it has a crystal structure.
- a photoelectric conversion element was produced and evaluated using the obtained phthalocyanine compound 101a.
- ITO glass cleaned by cleaning and UV (ultraviolet light) -ozone treatment transparent conductive glass having a tin-doped indium oxide (ITO) film formed on a glass substrate, resistance value 14 ⁇ / sq) ITO film (anode
- the obtained phthalocyanine compound 101a was laminated to a thickness of 50 nm under the conditions of a pressure of 3.3 ⁇ 10 ⁇ 4 Pa and a deposition rate of 0.4 K / sec.
- fullerene manufactured by Nano-C
- fullerene as an n-type organic semiconductor on the phthalocyanine compound 101a layer so as to have a thickness of 50 nm under the conditions of a pressure of 1.1 ⁇ 10 ⁇ 4 Pa and a deposition rate of 0.5 kg / sec. Laminated.
- bathocuproin As a hole blocking agent was laminated on the fullerene layer to a thickness of 10 nm under the conditions of 8.5 ⁇ 10 ⁇ 5 Pa and a deposition rate of 0.4 kg / sec.
- a silver (Nihon Kojun Kagaku Co., Ltd.) silver as a cathode was stacked on the bathocuproine layer at a thickness of 8.2 ⁇ 10 ⁇ 5 Pa and a deposition rate of 0.4 ⁇ / sec to produce a photoelectric conversion element.
- a photoelectric conversion element was irradiated with light from the ITO glass side using a tungsten lamp (100 W) and the current value at the time of short circuit was measured, a current value of 27.4 ⁇ A was obtained, and a photoelectric conversion element showing good characteristics was obtained. Obtained.
- Comparative Example 1 In Comparative Example 1 in which the central metal is copper and Comparative Example 2 in which the central metal compound is dichlorotin, the phthalocyanine compound having the same substituent R as the phthalocyanine compound 101a has an absorption band in the near infrared region. It was confirmed not to.
- the phthalocyanine compound 10 can be formed into a film by a coating method such as spin coating which is simpler than the conventional vapor deposition method. Moreover, since the phthalocyanine compound 10 of the present invention has light absorption performance, it can be suitably used for photovoltaic elements such as organic thin-film solar cells and optical sensors, optical recording media, and the like.
- the phthalocyanine compound 10 can easily shift the absorption band to the near infrared region by heat treatment. Therefore, the phthalocyanine compound 10 satisfies the performance particularly required in the field of P-type organic semiconductor materials, and can be said to be useful in this respect.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Photovoltaic Devices (AREA)
- Thermal Transfer Or Thermal Recording In General (AREA)
Abstract
Disclosed are phthalocyanine compounds, which are to be subjected to film formation and then heating. When the temperature of the heating is raised from 60°C to 80°C, 150°C or 200°C, the light absorption bands of the phthalocyanine compounds are shifted to the near-infrared region. Therefore, the phthalocyanine compounds are suitable for use in fields wherein an absorption band in the near-infrared region is necessitated. Further, the phthalocyanine compounds exhibit excellent solubility in organic solvents and thus can be easily formed into films by spin coating or other simple methods.
Description
本発明は、光電変換素子、光記録媒体、光フィルター等の材料として有用なフタロシアニン化合物等に関する。
The present invention relates to phthalocyanine compounds and the like useful as materials for photoelectric conversion elements, optical recording media, optical filters and the like.
フタロシアニン化合物は、化学的に安定であって狭いバンドギャップを有する有機半導体である。このような特徴を有するフタロシアニン化合物の薄膜を形成し、有機光起電力素子、あるいは近赤外線吸収材料として用いることが知られている（例えば、特許文献１および特許文献２）。
A phthalocyanine compound is an organic semiconductor that is chemically stable and has a narrow band gap. It is known that a thin film of a phthalocyanine compound having such characteristics is formed and used as an organic photovoltaic element or a near-infrared absorbing material (for example, Patent Document 1 and Patent Document 2).
フタロシアニン化合物は、一般的に溶媒に対して不溶性であるため、通常、真空蒸着法などにより薄膜化されているが、特許文献２には特定の置換基を有するフタロシアニン化合物が溶媒への溶解性を示すことが開示されている。
Since the phthalocyanine compound is generally insoluble in a solvent, it is usually thinned by a vacuum deposition method or the like. However, in Patent Document 2, a phthalocyanine compound having a specific substituent has solubility in a solvent. It is disclosed to show.
フタロシアニン化合物を真空蒸着法などにより薄膜化する場合、比較的大規模な装置と複雑な工程が必要となる。このため、フタロシアニン化合物を成膜して光電変換層等を製造する際には、コストが増大し、大面積化が困難になるといった問題が生じ得る。
When a phthalocyanine compound is thinned by a vacuum deposition method or the like, a relatively large-scale apparatus and a complicated process are required. For this reason, when manufacturing a photoelectric converting layer etc. by forming a phthalocyanine compound into a film, the problem that a cost increases and enlargement of an area becomes difficult may arise.
また、各種用途に応じて様々なフタロシアニン化合物が使用されているものの、用途によっては、望ましい特徴を兼ね備えたフタロシアニン化合物が少なく、材料選択の幅が狭いという問題もある。例えば、一部のフタロシアニン化合物は、上述のように溶媒への溶解性を示すものの、溶媒に可溶であるとともに近赤外光を吸収可能なＰ型有機半導体の材料として好適に用いられるフタロシアニン化合物は、未だ得られていない。
In addition, although various phthalocyanine compounds are used according to various uses, there is a problem that there are few phthalocyanine compounds having desirable characteristics and the range of material selection is narrow depending on the use. For example, some phthalocyanine compounds exhibit solubility in a solvent as described above, but are preferably used as a P-type organic semiconductor material that is soluble in a solvent and can absorb near-infrared light. Has not been obtained yet.
そこで本発明は、簡易な工程により成膜が可能であるとともに、光電変換素子などの材料として望ましい吸収域を有するフタロシアニン化合物等を提供することを目的とする。
Therefore, an object of the present invention is to provide a phthalocyanine compound or the like that can be formed by a simple process and has a desirable absorption region as a material for a photoelectric conversion element or the like.
本発明におけるフタロシアニン化合物は、下記一般式（Ｉ）で表されるフタロシアニン化合物であって、式中Ｒ１～Ｒ８は、炭素数が５以下の直鎖状のハロゲン化アルコキシ基、あるいは炭素数が５以下の分岐状のアルコキシ基のいずれかを表す。これらの置換基Ｒ１～Ｒ８は、それぞれ同一であっても異なっていてもよい。
The phthalocyanine compound in the present invention is a phthalocyanine compound represented by the following general formula (I), wherein R1 to R8 are linear halogenated alkoxy groups having 5 or less carbon atoms, or 5 carbon atoms. It represents one of the following branched alkoxy groups. These substituents R1 to R8 may be the same or different.
The phthalocyanine compound in the present invention is a phthalocyanine compound represented by the following general formula (I), wherein R1 to R8 are linear halogenated alkoxy groups having 5 or less carbon atoms, or 5 carbon atoms. It represents one of the following branched alkoxy groups. These substituents R1 to R8 may be the same or different.
上述の一般式（Ｉ）中のＲ１～Ｒ８は、下記化学式（II）で示される１ａから１ｇの群から選択されることが好ましい。
［化学式（II）］
１ａ：－ＯＣＨ２ＣＦ３
１ｂ：－ＯＣＨ２ＣＨ２ＣＦ３
１ｃ：－ＯＣＨ２ＣＣｌ３
１ｄ：－ＯＣＨ２ＣＨ２ＣＣｌ３
１ｅ：－ＯＣＨ（ＣＨ３）２
１ｆ：－ＯＣＨ２ＣＨ（ＣＨ３）２
１ｇ：－ＯＣＨ２ＣＨ２ＣＨ（ＣＨ３）２ R1 to R8 in the above general formula (I) are preferably selected from the group of 1a to 1g represented by the following chemical formula (II).
[Chemical formula (II)]
1a: —OCH 2 CF 3
1b: —OCH 2 CH 2 CF 3
1c: —OCH 2 CCl 3
1d: —OCH 2 CH 2 CCl 3
1e: —OCH (CH 3 ) 2
1f: —OCH 2 CH (CH 3 ) 2
1 g: —OCH 2 CH 2 CH (CH 3 ) 2
［化学式（II）］
１ａ：－ＯＣＨ２ＣＦ３
１ｂ：－ＯＣＨ２ＣＨ２ＣＦ３
１ｃ：－ＯＣＨ２ＣＣｌ３
１ｄ：－ＯＣＨ２ＣＨ２ＣＣｌ３
１ｅ：－ＯＣＨ（ＣＨ３）２
１ｆ：－ＯＣＨ２ＣＨ（ＣＨ３）２
１ｇ：－ＯＣＨ２ＣＨ２ＣＨ（ＣＨ３）２ R1 to R8 in the above general formula (I) are preferably selected from the group of 1a to 1g represented by the following chemical formula (II).
[Chemical formula (II)]
1a: —OCH 2 CF 3
1b: —OCH 2 CH 2 CF 3
1c: —OCH 2 CCl 3
1d: —OCH 2 CH 2 CCl 3
1e: —OCH (CH 3 ) 2
1f: —OCH 2 CH (CH 3 ) 2
1 g: —OCH 2 CH 2 CH (CH 3 ) 2
本発明の光吸収材料は、上述のフタロシアニン化合物を含むことを特徴とする。光吸収材料は、膜状にして６０℃を超え１５０℃以下の温度で加熱することが好ましい。
The light absorbing material of the present invention is characterized by containing the above-mentioned phthalocyanine compound. The light absorbing material is preferably formed into a film and heated at a temperature of more than 60 ° C. and not more than 150 ° C.
本発明の光電変換素子は、上述の光吸収材料を含む光電変換層を備えたことを特徴とする。
The photoelectric conversion element of the present invention is characterized by including a photoelectric conversion layer containing the above-described light absorbing material.
本発明によれば、溶媒可溶性であり、塗布法などの簡易な工程により成膜が可能であるとともに、光電変換素子などの材料として望ましい吸収域を有するフタロシアニン化合物等を実現できる。
According to the present invention, it is possible to realize a phthalocyanine compound or the like that is soluble in a solvent, can be formed by a simple process such as a coating method, and has a desirable absorption region as a material for a photoelectric conversion element or the like.
以下、本発明のフタロシアニン化合物につき説明する。図１は、本発明のフタロシアニン化合物の分子式を示す図である。
Hereinafter, the phthalocyanine compound of the present invention will be described. FIG. 1 shows the molecular formula of the phthalocyanine compound of the present invention.
本発明のフタロシアニン化合物１０は、中心金属化合物としてのバナジウムオキサイド（ＶＯ）と、置換基Ｒ１～Ｒ８とを含む。置換基Ｒ１～Ｒ８は、炭素数が５以下の直鎖状のハロゲン化アルコキシ基、あるいは炭素数が５以下の分岐状のアルコキシ基のいずれかであり、それぞれ同一であっても異なっていてもよい。
The phthalocyanine compound 10 of the present invention contains vanadium oxide (VO) as a central metal compound and substituents R1 to R8. The substituents R1 to R8 are either a linear halogenated alkoxy group having 5 or less carbon atoms or a branched alkoxy group having 5 or less carbon atoms, and may be the same or different. Good.
炭素数が５以下の直鎖状のハロゲン化アルコキシ基は、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基あるいはペンチルオキシ基の一部がハロゲン化されたものである。ハロゲン元素としては、フッ素（Ｆ）又は塩素（Ｃｌ）が好ましい。フタロシアニン化合物は具体的な例としては、１，４，５，８，９，１２，１３，１６－オクタキス（モノフルオロメトキシ）フタロシアニナトバナジウムオキサイド、１，４，５，８，９，１２，１３，１６－オクタキス（ジフルオロメトキシ）フタロシアニナトバナジウムオキサイド、１，４，５，８，９，１２，１３，１６－オクタキス（トリフルオロメトキシ）フタロシアニナトバナジウムオキサイド、１，４，５，８，９，１２，１３，１６－オクタキス（モノクロロメトキシ）フタロシアニナトバナジウムオキサイド、１，４，５，８，９，１２，１３，１６－オクタキス（ジクロロメトキシ）フタロシアニナトバナジウムオキサイド、１，４，５，８，９，１２，１３，１６－オクタキス（トリクロロメトキシ）フタロシアニナトバナジウムオキサイド、１，４，５，８，９，１２，１３，１６－オクタキス（２－モノフルオロエトキシ）フタロシアニナトバナジウムオキサイド、１，４，５，８，９，１２，１３，１６－オクタキス（２，２－ジフルオロエトキシ）フタロシアニナトバナジウムオキサイド、１，４，５，８，９，１２，１３，１６－オクタキス（２，２，２－トリフルオロエトキシ）フタロシアニナトバナジウムオキサイド、１，４，５，８，９，１２，１３，１６－オクタキス（２－モノクロロエトキシ）フタロシアニナトバナジウムオキサイド、１，４，５，８，９，１２，１３，１６－オクタキス（２，２－ジクロロエトキシ）フタロシアニナトバナジウムオキサイド、１，４，５，８，９，１２，１３，１６－オクタキス（２，２，２－トリクロロエトキシ）フタロシアニナトバナジウムオキサイド、１，４，５，８，９，１２，１３，１６－オクタキス（３－モノフルオロプロポキシ）フタロシアニナトバナジウムオキサイド、１，４，５，８，９，１２，１３，１６－オクタキス（３，３－ジフルオロプロポキシ）フタロシアニナトバナジウムオキサイド、１，４，５，８，９，１２，１３，１６－オクタキス（３，３，３－トリフルオロプロポキシ）フタロシアニナトバナジウムオキサイド、１，４，５，８，９，１２，１３，１６－オクタキス（３－モノクロロプロポキシ）フタロシアニナトバナジウムオキサイド、１，４，５，８，９，１２，１３，１６－オクタキス（３，３－ジクロロプロポキシ）フタロシアニナトバナジウムオキサイド、１，４，５，８，９，１２，１３，１６－オクタキス（３，３，３－トリクロロプロポキシ）フタロシアニナトバナジウムオキサイド、１，４，５，８，９，１２，１３，１６－オクタキス（４－モノフルオロブトキシ）フタロシアニナトバナジウムオキサイド、１，４，５，８，９，１２，１３，１６－オクタキス（４，４－ジフルオロブトキシ）フタロシアニナトバナジウムオキサイド、１，４，５，８，９，１２，１３，１６－オクタキス（４，４，４－トリフルオロブトキシ）フタロシアニナトバナジウムオキサイド、１，４，５，８，９，１２，１３，１６－オクタキス（４－モノクロロブトキシ）フタロシアニナトバナジウムオキサイド、１，４，５，８，９，１２，１３，１６－オクタキス（４，４－ジクロロブトキシ）フタロシアニナトバナジウムオキサイド、１，４，５，８，９，１２，１３，１６－オクタキス（４，４，４－トリクロロブトキシ）フタロシアニナトバナジウムオキサイド、１，４，５，８，９，１２，１３，１６－オクタキス（５－モノフルオロペンチルオキシ）フタロシアニナトバナジウムオキサイド、１，４，５，８，９，１２，１３，１６－オクタキス（５，５－ジフルオロエペンチルオキシ）フタロシアニナトバナジウムオキサイド、１，４，５，８，９，１２，１３，１６－オクタキス（５，５，５－トリフルオロペンチルオキシ）フタロシアニナトバナジウムオキサイド、１，４，５，８，９，１２，１３，１６－オクタキス（５－モノクロロペンチルオキシ）フタロシアニナトバナジウムオキサイド、１，４，５，８，９，１２，１３，１６－オクタキス（５，５－ジクロロペンチルオキシ）フタロシアニナトバナジウムオキサイド、１，４，５，８，９，１２，１３，１６－オクタキス（５，５，５－トリクロロペンチルオキシ）フタロシアニナトバナジウムオキサイド、１，４，５，８，９，１２，１３，１６－オクタキス－ｉｓｏ－プロポキシフタロシアニナトバナジウムオキサイド、１，４，５，８，９，１２，１３，１６－オクタキス－ｉｓｏ－ブトキシフタロシアニナトバナジウムオキサイド、１，４，５，８，９，１２，１３，１６－オクタキス－ｔｅｒｔ－ブトキシフタロシアニナトバナジウムオキサイド、１，４，５，８，９，１２，１３，１６－オクタキス－ｉｓｏ－ペンチルオキシフタロシアニナトバナジウムオキサイド、１，４，５，８，９，１２，１３，１６－オクタキス－ネオペンチルオキシフタロシアニナトバナジウムオキサイド等があげられる。
The straight-chain halogenated alkoxy group having 5 or less carbon atoms is a group in which a part of methoxy group, ethoxy group, propoxy group, butoxy group or pentyloxy group is halogenated. As the halogen element, fluorine (F) or chlorine (Cl) is preferable. Specific examples of the phthalocyanine compound include 1,4,5,8,9,12,13,16-octakis (monofluoromethoxy) phthalocyaninatovanadium oxide, 1,4,5,8,9,12, 13,16-octakis (difluoromethoxy) phthalocyaninatovanadium oxide, 1,4,5,8,9,12,13,16-octakis (trifluoromethoxy) phthalocyaninatovanadium oxide, 1,4,5,8 , 9,12,13,16-octakis (monochloromethoxy) phthalocyaninatovanadium oxide, 1,4,5,8,9,12,13,16-octakis (dichloromethoxy) phthalocyaninatovanadium oxide, 1,4 , 5,8,9,12,13,16-octakis (trichloromethoxy) phthalocyanine Tovanadium oxide, 1,4,5,8,9,12,13,16-octakis (2-monofluoroethoxy) phthalocyaninatovanadium oxide, 1,4,5,8,9,12,13,16- Octakis (2,2-difluoroethoxy) phthalocyaninatovanadium oxide, 1,4,5,8,9,12,13,16-octakis (2,2,2-trifluoroethoxy) phthalocyaninatovanadium oxide, 1 , 4,5,8,9,12,13,16-octakis (2-monochloroethoxy) phthalocyaninatovanadium oxide, 1,4,5,8,9,12,13,16-octakis (2,2- Dichloroethoxy) phthalocyaninatovanadium oxide, 1,4,5,8,9,12,13,16-octakis (2,2,2- Lichloroethoxy) phthalocyaninatovanadium oxide, 1,4,5,8,9,12,13,16-octakis (3-monofluoropropoxy) phthalocyaninatovanadium oxide, 1,4,5,8,9, 12,13,16-octakis (3,3-difluoropropoxy) phthalocyaninatovanadium oxide, 1,4,5,8,9,12,13,16-octakis (3,3,3-trifluoropropoxy) phthalate Russian ninato vanadium oxide, 1,4,5,8,9,12,13,16-octakis (3-monochloropropoxy) phthalocyaninatovanadium oxide, 1,4,5,8,9,12,13,16- Octakis (3,3-dichloropropoxy) phthalocyaninatovanadium oxide, 1,4,5,8,9,1 2,13,16-octakis (3,3,3-trichloropropoxy) phthalocyaninatovanadium oxide, 1,4,5,8,9,12,13,16-octakis (4-monofluorobutoxy) phthalocyaninato Vanadium oxide, 1,4,5,8,9,12,13,16-octakis (4,4-difluorobutoxy) phthalocyaninatovanadium oxide, 1,4,5,8,9,12,13,16- Octakis (4,4,4-trifluorobutoxy) phthalocyaninatovanadium oxide, 1,4,5,8,9,12,13,16-octakis (4-monochlorobutoxy) phthalocyaninatovanadium oxide, 1,4 , 5,8,9,12,13,16-octakis (4,4-dichlorobutoxy) phthalocyaninatovanadium 1,4,5,8,9,12,13,16-octakis (4,4,4-trichlorobutoxy) phthalocyaninatovanadium oxide, 1,4,5,8,9,12,13,16 Octakis (5-monofluoropentyloxy) phthalocyaninatovanadium oxide, 1,4,5,8,9,12,13,16-octakis (5,5-difluoroepentyloxy) phthalocyaninatovanadium oxide, 1 , 4,5,8,9,12,13,16-octakis (5,5,5-trifluoropentyloxy) phthalocyaninatovanadium oxide, 1,4,5,8,9,12,13,16- Octakis (5-monochloropentyloxy) phthalocyaninatovanadium oxide, 1,4,5,8,9,12,13,16-octa (5,5-dichloropentyloxy) phthalocyaninatovanadium oxide, 1,4,5,8,9,12,13,16-octakis (5,5,5-trichloropentyloxy) phthalocyaninatovanadium oxide, 1,4,5,8,9,12,13,16-octakis-iso-propoxyphthalocyaninatovanadium oxide, 1,4,5,8,9,12,13,16-octakis-iso-butoxyphthalocyanine Ninato vanadium oxide, 1,4,5,8,9,12,13,16-octakis-tert-butoxyphthalocyaninatovanadium oxide, 1,4,5,8,9,12,13,16-octakis-iso -Pentyloxyphthalocyaninatovanadium oxide, 1,4,5,8,9,12,13,16-o Examples include kutakis-neopentyloxyphthalocyaninatovanadium oxide.
ここで、置換基Ｒ１～Ｒ８は、下記化学式（II）で表わされる１ａから１ｇの群から選択されることが好ましい。
［化学式（II）］
１ａ：－ＯＣＨ２ＣＦ３
１ｂ：－ＯＣＨ２ＣＨ２ＣＦ３
１ｃ：－ＯＣＨ２ＣＣｌ３
１ｄ：－ＯＣＨ２ＣＨ２ＣＣｌ３
１ｅ：－ＯＣＨ（ＣＨ３）２
１ｆ：－ＯＣＨ２ＣＨ（ＣＨ３）２
１ｇ：－ＯＣＨ２ＣＨ２ＣＨ（ＣＨ３）２ Here, the substituents R1 to R8 are preferably selected from the group of 1a to 1g represented by the following chemical formula (II).
[Chemical formula (II)]
1a: —OCH 2 CF 3
1b: —OCH 2 CH 2 CF 3
1c: —OCH 2 CCl 3
1d: —OCH 2 CH 2 CCl 3
1e: —OCH (CH 3 ) 2
1f: —OCH 2 CH (CH 3 ) 2
1 g: —OCH 2 CH 2 CH (CH 3 ) 2
［化学式（II）］
１ａ：－ＯＣＨ２ＣＦ３
１ｂ：－ＯＣＨ２ＣＨ２ＣＦ３
１ｃ：－ＯＣＨ２ＣＣｌ３
１ｄ：－ＯＣＨ２ＣＨ２ＣＣｌ３
１ｅ：－ＯＣＨ（ＣＨ３）２
１ｆ：－ＯＣＨ２ＣＨ（ＣＨ３）２
１ｇ：－ＯＣＨ２ＣＨ２ＣＨ（ＣＨ３）２ Here, the substituents R1 to R8 are preferably selected from the group of 1a to 1g represented by the following chemical formula (II).
[Chemical formula (II)]
1a: —OCH 2 CF 3
1b: —OCH 2 CH 2 CF 3
1c: —OCH 2 CCl 3
1d: —OCH 2 CH 2 CCl 3
1e: —OCH (CH 3 ) 2
1f: —OCH 2 CH (CH 3 ) 2
1 g: —OCH 2 CH 2 CH (CH 3 ) 2
１ａから１ｇの群から選択される置換基Ｒ１～Ｒ８は、それぞれ同一であってもよいし異なっていてもよい。すなわち、置換基Ｒ１～Ｒ８がいずれも同一である上述の化合物、例えば、１，４，５，８，９，１２，１３，１６－オクタキス（２，２，２－トリフルオロエトキシ）フタロシアニナトバナジウムオキサイド、１，４，５，８，９，１２，１３，１６－オクタキス（２，２，２－トリクロロエトキシ）フタロシアニナトバナジウムオキサイド、１，４，５，８，９，１２，１３，１６－オクタキス（３，３，３－トリフルオロプロポキシ）フタロシアニナトバナジウムオキサイド、１，４，５，８，９，１２，１３，１６－オクタキス（３，３，３－トリクロロプロポキシ）フタロシアニナトバナジウムオキサイド、１，４，５，８，９，１２，１３，１６－オクタキス－ｉｓｏ－プロポキシフタロシアニナトバナジウムオキサイド、１，４，５，８，９，１２，１３，１６－オクタキス－ｉｓｏ－ブトキシフタロシアニナトバナジウムオキサイド、１，４，５，８，９，１２，１３，１６－オクタキス－ｉｓｏ－ペンチルオキシフタロシアニナトバナジウムオキサイド等には限定されない。例えば、１，４，５，８，９，１２，１３，１６位の置換基Ｒ１～Ｒ８として、上述の１ａから１ｇのうちいずれかを重複させても良い。
The substituents R1 to R8 selected from the group of 1a to 1g may be the same or different. That is, the above-mentioned compounds having the same substituents R1 to R8, for example, 1,4,5,8,9,12,13,16-octakis (2,2,2-trifluoroethoxy) phthalocyaninato Vanadium oxide, 1,4,5,8,9,12,13,16-octakis (2,2,2-trichloroethoxy) phthalocyaninatovanadium oxide, 1,4,5,8,9,12,13, 16-octakis (3,3,3-trifluoropropoxy) phthalocyaninatovanadium oxide, 1,4,5,8,9,12,13,16-octakis (3,3,3-trichloropropoxy) phthalocyaninato Vanadium oxide, 1,4,5,8,9,12,13,16-octakis-iso-propoxyphthalocyaninatovanadium oxide, 1, , 5,8,9,12,13,16-octakis-iso-butoxyphthalocyaninatovanadium oxide, 1,4,5,8,9,12,13,16-octakis-iso-pentyloxyphthalocyaninatovanadium It is not limited to oxide or the like. For example, as the substituents R1 to R8 at the 1,4,5,8,9,12,13,16 positions, any one of the above 1a to 1g may be overlapped.
フタロシアニン化合物１０は、有機溶媒に対する溶解性に優れている。有機溶媒に対する溶解性は、主として置換基Ｒ１～Ｒ８によりもたらされると考えられる。すなわち、炭素数が５以下の直鎖状のハロゲン化アルコキシ基、あるいは炭素数が５以下の分岐状のアルコキシ基を置換基として有することにより、フタロシアニン化合物１０の溶解性が向上されている。溶解性向上の観点では、置換基は、前記化学式（II）で表わされる１ａから１ｇの群から選ばれることがより好ましく、２，２，２－トリフルオロエトキシ基（１ａ）などのハロゲン化アルコキシ基であることが特に好ましい。
The phthalocyanine compound 10 has excellent solubility in organic solvents. It is considered that the solubility in organic solvents is mainly brought about by the substituents R1 to R8. That is, the solubility of the phthalocyanine compound 10 is improved by having a linear halogenated alkoxy group having 5 or less carbon atoms or a branched alkoxy group having 5 or less carbon atoms as a substituent. From the viewpoint of improving solubility, the substituent is more preferably selected from the group of 1a to 1g represented by the chemical formula (II), and a halogenated alkoxy such as 2,2,2-trifluoroethoxy group (1a). Particularly preferred is a group.
フタロシアニン化合物１０は、光吸収性であり、特に近赤外光を効率的に吸収することができる。近赤外光の吸収は、主としてフタロシアニン化合物１０の高い結晶性によるものと考えられる。フタロシアニン化合物１０の結晶性は、中心にあるバナジウムオキサイドの酸素イオンが、概ね平面構造をとるフタロシアニン化合物１０の平面の一方に突出していること、および置換基Ｒの炭素数が５以下に抑えられていることにより、もたらされている。仮に、炭素数が５よりも多い嵩高い置換基Ｒを設けた場合、置換基Ｒが立体障害となり、フタロシアニン化合物１０の結晶性が低下すると考えられる。また、図１に示すように、置換基Ｒ１～Ｒ８が１、４、５、８、９、１２、１３、１６位に設けられていることも、フタロシアニン化合物１０の優れた結晶性に寄与していると考えられる。フタロシアニン化合物１０の結晶化を立体的に妨げ易い、２、３位等に設けられた置換基Ｒを含んでいないためである。吸収波長としては、７００～１１００ｎｍの波長領域に極大吸収波長を有することが好ましく、８００～１０００ｎｍの波長領域に極大吸収波長を有することがより好ましい。
The phthalocyanine compound 10 is light absorptive and can particularly efficiently absorb near infrared light. It is considered that the absorption of near infrared light is mainly due to the high crystallinity of the phthalocyanine compound 10. The crystallinity of the phthalocyanine compound 10 is that the oxygen ion of vanadium oxide at the center protrudes to one of the planes of the phthalocyanine compound 10 having a substantially planar structure, and the carbon number of the substituent R is suppressed to 5 or less. Is brought about by being. If a bulky substituent R having more than 5 carbon atoms is provided, it is considered that the substituent R becomes a steric hindrance and the crystallinity of the phthalocyanine compound 10 is lowered. Further, as shown in FIG. 1, the fact that the substituents R1 to R8 are provided at positions 1, 4, 5, 8, 9, 12, 13, 16 contributes to the excellent crystallinity of the phthalocyanine compound 10. It is thought that. This is because it does not contain a substituent R provided at the 2, 3-position or the like, which tends to sterically hinder crystallization of the phthalocyanine compound 10. The absorption wavelength preferably has a maximum absorption wavelength in the wavelength region of 700 to 1100 nm, and more preferably has a maximum absorption wavelength in the wavelength region of 800 to 1000 nm.
フタロシアニン化合物１０を光吸収材料として用いる場合は、膜状にすること（以下、薄膜化ということがある）が好ましい。膜の形成方法は限定されないが、フタロシアニン化合物１０は有機溶媒への溶解性が優れているので、塗布法により形成することが可能である。塗布法は、適当な溶媒にフタロシアニン化合物１０を溶解して塗布液とし、塗布液を基板に塗布して膜を形成する方法である。用いられる溶媒としては、メチルアルコール、エチルアルコール等のアルコール類、アセトン、メチルエチルケトン等のケトン類、酢酸エチル、酢酸ブチル等のエステル類、トルエン、キシレン等の炭化水素類、ジクロロメタン、クロロホルム、クロロベンゼン等のハロゲン化炭化水素等が挙げられる。フタロシアニン化合物１０の溶媒中の濃度は、０．０１～２０質量％であることが好ましい。
When the phthalocyanine compound 10 is used as a light absorbing material, it is preferable to form a film (hereinafter sometimes referred to as a thin film). The method for forming the film is not limited. However, since the phthalocyanine compound 10 has excellent solubility in an organic solvent, it can be formed by a coating method. The coating method is a method in which the phthalocyanine compound 10 is dissolved in a suitable solvent to form a coating solution, and the coating solution is applied to a substrate to form a film. Solvents used include alcohols such as methyl alcohol and ethyl alcohol, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate and butyl acetate, hydrocarbons such as toluene and xylene, dichloromethane, chloroform, chlorobenzene and the like. Examples thereof include halogenated hydrocarbons. The concentration of the phthalocyanine compound 10 in the solvent is preferably 0.01 to 20% by mass.
基板としては、例えば、ガラス板、プラスチックフィルム等を用いることができる。プラスチックフィルムとしては、ポリエチレン、ポリプロピレン等のポリオレフィン、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート等のポリエステル、ポリ塩化ビニル、ポリスチレン、ポリイミド等からなるフィルムが挙げられる。基板の厚さは、１０μｍ～５ｍｍ程度である。また、これらの基板にはガスバリア層や導電層が設けられていてもよい。ガスバリア層としては、例えば、シリカや窒化珪素からなる層が挙げられ、導電層としては、酸化インジウム、酸化錫、錫ドープ酸化インジウム（ＩＴＯ）や酸化亜鉛からなる層が挙げられる。
As the substrate, for example, a glass plate, a plastic film or the like can be used. Examples of the plastic film include films made of polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, polyvinyl chloride, polystyrene, and polyimide. The thickness of the substrate is about 10 μm to 5 mm. In addition, a gas barrier layer or a conductive layer may be provided on these substrates. Examples of the gas barrier layer include a layer made of silica or silicon nitride, and examples of the conductive layer include a layer made of indium oxide, tin oxide, tin-doped indium oxide (ITO), or zinc oxide.
塗布液を基板に塗布する方法としては、例えば、スピンコート法、バーコート法、グラビアコート法、スプレーコート法等があげられる。これらの方法で塗布液を塗布した後、必要により加熱して溶媒を除去することによりフタロシアニン化合物の膜が形成される。形成された膜の厚さは特に限定されず、用途や目的に応じて決めればよいが、通常１０ｎｍ～１０μｍ程度である。なお、膜の形成方法として、真空蒸着法やスパッタリング法などを用いることも可能である。
Examples of the method for applying the coating liquid to the substrate include a spin coating method, a bar coating method, a gravure coating method, and a spray coating method. After applying the coating solution by these methods, the film of the phthalocyanine compound is formed by heating as necessary to remove the solvent. The thickness of the formed film is not particularly limited and may be determined according to the application and purpose, but is usually about 10 nm to 10 μm. Note that a vacuum deposition method, a sputtering method, or the like can also be used as a film formation method.
また、薄膜化したフタロシアニン化合物１０を加熱することも好ましい。加熱を行うことによって、フタロシアニン化合物１０の最大吸収波長をシフトさせることができる。加熱温度は６０℃を超えて１５０℃以下で行うことが好ましい。加熱方法は限定されず、ホットプレートやオーブン（恒温槽）を用いるなどの方法で行うことができる。加熱時間は、１分～１時間、好ましくは２分～３０分程度である。加熱雰囲気は大気中でもよいし、減圧下、窒素あるいは不活性ガス充填下でよい。また、塗布膜の乾燥と熱処理を同時に行ってもよい。
It is also preferable to heat the thinned phthalocyanine compound 10. By performing the heating, the maximum absorption wavelength of the phthalocyanine compound 10 can be shifted. The heating temperature is preferably higher than 60 ° C. and 150 ° C. or lower. The heating method is not limited, and it can be performed by a method such as using a hot plate or an oven (a constant temperature bath). The heating time is about 1 minute to 1 hour, preferably about 2 minutes to 30 minutes. The heating atmosphere may be air, or may be under reduced pressure, filled with nitrogen or an inert gas. Moreover, you may perform simultaneously drying and heat processing of a coating film.
ここで、フタロシアニン化合物１０の光吸収スペクトルについて説明する。図２は、本発明のフタロシアニン化合物１０１ａ（後出）の光吸収スペクトルである。図２に示すように、フタロシアニン化合物１０１ａの光吸収スペクトルは、溶液と膜状とで異なる。すなわち、溶液であるときには、破線で示されるように７４０ｎｍ付近に極大吸収波長があるのに対し、膜状であるときには、実線で示されるように極大吸収波長が約８３６ｎｍとなっている。なお、膜状のフタロシアニン化合物１０１ａは、ガラス基板に塗布液を塗布して薄膜化し、１５０℃で加熱したものである。
Here, the light absorption spectrum of the phthalocyanine compound 10 will be described. FIG. 2 is a light absorption spectrum of the phthalocyanine compound 101a of the present invention (described later). As shown in FIG. 2, the light absorption spectrum of the phthalocyanine compound 101a differs between the solution and the film. That is, in the case of a solution, the maximum absorption wavelength is in the vicinity of 740 nm as shown by the broken line, whereas in the case of a film, the maximum absorption wavelength is about 836 nm as shown by the solid line. The film-like phthalocyanine compound 101a is obtained by applying a coating solution to a glass substrate to form a thin film and heating at 150 ° C.
さらに、薄膜状のフタロシアニン化合物１０１ａは、図２の実線に示される光吸収スペクトルを有しているが、加熱によって光吸収スペクトルが変化する。なお図２の溶液は、溶媒としてクロロベンゼンを用いたものである。そしてクロロベンゼンについては、７４０ｎｍ付近に吸収が認められることはないため、図２における極大吸収波長の変化は、フタロシアニン化合物１０１ａに起因しているといえる。
Furthermore, the thin-film phthalocyanine compound 101a has a light absorption spectrum shown by a solid line in FIG. 2, but the light absorption spectrum is changed by heating. The solution in FIG. 2 uses chlorobenzene as a solvent. And about chlorobenzene, since absorption is not recognized by 740 nm vicinity, it can be said that the change of the maximum absorption wavelength in FIG. 2 originates in the phthalocyanine compound 101a.
図３は、図２に示した薄膜化したフタロシアニン化合物１０１ａの加熱温度を変更した場合の光吸収スペクトルの変化を示したものである。図３に示すように、６０℃で加熱した場合は、溶液状に近い光吸収スペクトル（破線）を有する。そして、加熱温度を８０℃とすると、吸収強度のピークが近赤外領域にシフトする。さらに、加熱温度を１５０℃、２００℃とした場合も、極大吸収波長は近赤外領域にシフトしつつ８０℃の場合とほぼ同じ値を示しており、安定した吸収強度のピークを有するフタロシアニン化合物であることがわかる。このためフタロシアニン化合物１０１ａは、近赤外領域の吸収帯が必要とされる分野で好適に用いられ得る。なお、２００℃で加熱すると、図示されたように、吸収強度の低下が認められる。このため、６０℃を超え、１５０℃以下の温度範囲でフタロシアニン化合物１０１ａを加熱することが好ましい。
FIG. 3 shows changes in the light absorption spectrum when the heating temperature of the thinned phthalocyanine compound 101a shown in FIG. 2 is changed. As shown in FIG. 3, when heated at 60 ° C., it has a light absorption spectrum (dashed line) close to a solution. When the heating temperature is 80 ° C., the absorption intensity peak shifts to the near infrared region. Further, even when the heating temperature is 150 ° C. and 200 ° C., the maximum absorption wavelength shows almost the same value as in the case of 80 ° C. while shifting to the near infrared region, and has a stable absorption intensity peak. It can be seen that it is. Therefore, the phthalocyanine compound 101a can be suitably used in a field where an absorption band in the near infrared region is required. In addition, when it heats at 200 degreeC, the fall of absorption intensity is recognized as shown in figure. For this reason, it is preferable to heat the phthalocyanine compound 101a in a temperature range exceeding 60 ° C. and 150 ° C. or less.
なお、加熱後のフタロシアニン化合物１０１ａの薄膜を顕微鏡で観察すると、高い結晶性を示す複屈折性のドメインが観測される。このことからも、フタロシアニン化合物１０１ａは、加熱によって結晶化され、結晶構造を有するときに近赤外領域に吸収帯を有するものと考えられる。
In addition, when the thin film of the phthalocyanine compound 101a after heating is observed with a microscope, a birefringent domain exhibiting high crystallinity is observed. This also suggests that the phthalocyanine compound 101a is crystallized by heating and has an absorption band in the near infrared region when it has a crystal structure.
フタロシアニン化合物１０は、公知のフタロシアニン化合物の製造方法を利用して行うことができるが、フタロニトリル化合物と金属塩を用いた環化反応を利用することが好ましい。以下、環化反応を利用したフタロシアニン化合物１０の製造方法を説明する。
The phthalocyanine compound 10 can be performed using a known method for producing a phthalocyanine compound, but it is preferable to use a cyclization reaction using a phthalonitrile compound and a metal salt. Hereinafter, the manufacturing method of the phthalocyanine compound 10 using a cyclization reaction is demonstrated.
図４の反応式（１）に示すように、ジシアノハイドロキノンと２，２，２－トリフルオロエチルトシレートの反応により、１，４－ビス（２，２，２－トリフルオロエトキシ）フタロニトリル（化合物１２）を合成する。この合成は、Ｎ，Ｎ－ジメチルホルムアミド（ＤＭＦ）などの溶媒中に、ジシアノハイドロキノンと２，２，２－トリフルオロエチルトシレートを加え、８０～１３０℃で１～６０時間程度撹拌して行われる。なお、２，２，２－トリフルオロエチルトシレートは、例えば、特開２００５－８４５８４号公報の段落０３６０に記載された方法により得ることができる。また、得られた化合物１２は公知の方法により分離、洗浄及び精製することができる。
As shown in the reaction formula (1) in FIG. 4, 1,4-bis (2,2,2-trifluoroethoxy) phthalonitrile (by reaction of dicyanohydroquinone and 2,2,2-trifluoroethyl tosylate) Compound 12) is synthesized. This synthesis is performed by adding dicyanohydroquinone and 2,2,2-trifluoroethyl tosylate in a solvent such as N, N-dimethylformamide (DMF) and stirring at 80 to 130 ° C. for about 1 to 60 hours. Is called. Incidentally, 2,2,2-trifluoroethyl tosylate can be obtained, for example, by the method described in paragraph 0360 of JP-A-2005-84584. Moreover, the obtained compound 12 can be separated, washed and purified by a known method.
次に、図５に示されるように、ベンゾニトリル、ジクロロベンゼンなどの溶媒に、得られた化合物１２、バナジウム塩及び尿素(Ｕｒｅａ)を加え、１００～１７０℃で１０分から１２０分程度撹拌することにより、上述のフタロシアニン化合物１０（図１参照）の一つである化合物１０１ａ、すなわち、１、４、５、８、９、１２、１３、１６－オクタキス（２，２，２－トリフルオロエトキシ）フタロシアニナトバナジウムオキサイドを合成することができる。バナジウム塩としては、二塩化バナジウム、三塩化バナジウム、五酸化バナジウム等を用いることができる。得られた１、４、５、８、９、１２、１３、１６－オクタキス（２，２，２－トリフルオロエトキシ）フタロシアニナトバナジウムオキサイドは、公知の方法により、分離、洗浄及び精製することができる。
Next, as shown in FIG. 5, the obtained compound 12, vanadium salt and urea (Urea) are added to a solvent such as benzonitrile and dichlorobenzene, and stirred at 100 to 170 ° C. for about 10 to 120 minutes. Thus, the compound 101a which is one of the phthalocyanine compounds 10 (see FIG. 1), that is, 1, 4, 5, 8, 9, 12, 13, 16-octakis (2,2,2-trifluoroethoxy) Phthalocyaninatovanadium oxide can be synthesized. As the vanadium salt, vanadium dichloride, vanadium trichloride, vanadium pentoxide, or the like can be used. The obtained 1,4,5,8,9,12,13,16-octakis (2,2,2-trifluoroethoxy) phthalocyaninatovanadium oxide can be separated, washed and purified by known methods. Can do.
ここで、置換基として－ＯＣＨ２ＣＦ３を有するフタロシアニン化合物について説明したが、化合物１２の－ＯＣＨ２ＣＦ３を他の炭素数が５以下の直鎖状のハロゲン化アルコキシ基、あるいは炭素数が５以下の分岐状のアルコキシ基とすれば、それらの置換基を有するフタロシアニン化合物１０を得ることができる。
Here, the phthalocyanine compound having —OCH 2 CF 3 as a substituent has been described. However, the —OCH 2 CF 3 of the compound 12 may be another linear halogenated alkoxy group having 5 or less carbon atoms, or the number of carbon atoms. If the branched alkoxy group is 5 or less, the phthalocyanine compound 10 having those substituents can be obtained.
次に、本発明の光電変換素子について説明する。本発明の光電変換層は、フタロシアニン化合物１０を含む光吸収材料を備えている。光電変換素子は、一般に二つの電極、すなわち陽極と陰極を有し、それらの間に光電変換層を備えた構造を有している。陽極または陰極のうち少なくとも一方が光を透過する必要があるが、通常、陽極を光透過性電極とする。
Next, the photoelectric conversion element of the present invention will be described. The photoelectric conversion layer of the present invention includes a light absorbing material containing the phthalocyanine compound 10. The photoelectric conversion element generally has two electrodes, that is, an anode and a cathode, and has a structure including a photoelectric conversion layer between them. At least one of the anode and the cathode needs to transmit light, but the anode is usually a light-transmitting electrode.
陽極を形成する導電材料としては、酸化インジウム、酸化錫、錫ドープ酸化インジウム（ＩＴＯ）、酸化イリジウム、酸化亜鉛、ガリウムドープ酸化亜鉛などが挙げられるが、導電性及び透明性が良好であることから、錫ドープ酸化インジウム（ＩＴＯ）、ガリウムドープ酸化亜鉛が好ましい。また、陰極を形成する導電材料としては、白金、金、アルミニウム、イリジウム、クロムなどの金属、カーボンナノチューブ等が挙げられる。
Examples of the conductive material for forming the anode include indium oxide, tin oxide, tin-doped indium oxide (ITO), iridium oxide, zinc oxide, and gallium-doped zinc oxide. However, the conductivity and transparency are good. Tin-doped indium oxide (ITO) and gallium-doped zinc oxide are preferred. Examples of the conductive material for forming the cathode include metals such as platinum, gold, aluminum, iridium, and chromium, and carbon nanotubes.
陽極及び陰極は、例えば、基板あるいは光電変換層上に、真空蒸着、スパッタリング、イオンプレーティング等のＰＶＤ（物理気相蒸着）の手法によって導電材料からなる層を形成することにより得られる。基板としては、ガラス板やプラスチックフィルムが好ましい。プラスチックフィルムとしては、ポリエチレン、ポリプロピレン等のポリオレフィン、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート等のポリエステル、ポリ塩化ビニル、ポリスチレン、ポリイミド等からなるフィルムが挙げられる。基板の厚さは、１０μｍ～５ｍｍ程度である。陽極及び陰極の厚さは、それぞれ１０～５００ｎｍであることが好ましい。
The anode and the cathode can be obtained, for example, by forming a layer made of a conductive material on a substrate or a photoelectric conversion layer by a PVD (physical vapor deposition) method such as vacuum deposition, sputtering, or ion plating. As the substrate, a glass plate or a plastic film is preferable. Examples of the plastic film include films made of polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, polyvinyl chloride, polystyrene, and polyimide. The thickness of the substrate is about 10 μm to 5 mm. The thickness of the anode and the cathode is preferably 10 to 500 nm, respectively.
光電変換層は、光を吸収し光エネルギーを電気エネルギーに変換する機能を有する層であり、例えば、ｐ型半導体層とｎ型半導体層を積層したものが挙げられる。フタロシアニン化合物はｐ型半導体であり、本発明のフタロシアニン化合物１０は、このような光電変換層においてｐ型半導体層として機能する。
The photoelectric conversion layer is a layer having a function of absorbing light and converting light energy into electric energy. For example, a layer in which a p-type semiconductor layer and an n-type semiconductor layer are stacked may be used. The phthalocyanine compound is a p-type semiconductor, and the phthalocyanine compound 10 of the present invention functions as a p-type semiconductor layer in such a photoelectric conversion layer.
なお、ｎ型半導体は無機半導体であっても有機半導体であってもよい。無機半導体としては砒素あるいはリンをドープしたシリコン、有機半導体としては、フラーレン、[６，６]－フェニル－Ｃ６１－酪酸メチル（ＰＣＢＭ）などのフラーレン誘導体が挙げられる。
The n-type semiconductor may be an inorganic semiconductor or an organic semiconductor. Examples of the inorganic semiconductor include silicon doped with arsenic or phosphorus, and examples of the organic semiconductor include fullerene and fullerene derivatives such as [6,6] -phenyl-C 61 -methyl butyrate (PCBM).
光電変換層には、真性半導体（ｉ型半導体）層をｐ型半導体層とｎ型半導体層との間に設けてもよい。光電変換層をこのような構成とすることにより変換効率を向上させることができる。
In the photoelectric conversion layer, an intrinsic semiconductor (i-type semiconductor) layer may be provided between the p-type semiconductor layer and the n-type semiconductor layer. Conversion efficiency can be improved by making a photoelectric converting layer into such a structure.
光電変換層を構成する各層は、例えば、真空蒸着、スパッタリング、イオンプレーティングなどのＰＶＤ（物理気相蒸着）、スピンコート法、バーコート法、グラビアコート法、スプレーコート法等の塗布法により形成することができる。光電変換層の厚さは、１０ｎｍ～３μｍであることが好ましい。
Each layer constituting the photoelectric conversion layer is formed by a coating method such as PVD (physical vapor deposition) such as vacuum deposition, sputtering, ion plating, spin coating method, bar coating method, gravure coating method, spray coating method, etc. can do. The thickness of the photoelectric conversion layer is preferably 10 nm to 3 μm.
また、光電変換素子にはバッファ層を設けてもよい。バッファ層としては、正孔ブロッキング材としてのバソクプロイン（２，９－ジメチル－４，７ジフェニル－１，１０－フェナントロリン）を含む層が挙げられる。このバッファ層（正孔ブロッキング材）は、通常、ｎ型半導体層と陰極の間に設けられる。光電変換素子としては、例えば、太陽電池や光センサー等が挙げられる。
Further, a buffer layer may be provided in the photoelectric conversion element. Examples of the buffer layer include a layer containing bathocuproine (2,9-dimethyl-4,7diphenyl-1,10-phenanthroline) as a hole blocking material. This buffer layer (hole blocking material) is usually provided between the n-type semiconductor layer and the cathode. As a photoelectric conversion element, a solar cell, an optical sensor, etc. are mentioned, for example.
以下、実施例を挙げて本発明を更に詳細に説明するが、本発明は、以下の実施例になんら限定されるものではない。
なお、化合物の構造の確認、溶解性、光吸収性及び結晶性の測定・評価は以下の通り行った。
化合物の構造の確認
１Ｈ ＮＭＲ測定及びＩＲ測定により確認した。１Ｈ ＮＭＲ測定は、核磁気共鳴装置（ＮＭＲ）（Ｂｒｕｋｅｒ社製、「Ａｖａｎｃｅ５００」）を用い、ＩＲ測定は、フーリエ変換赤外吸収（ＦＴ－ＩＲ）測定装置（ＰＥＲＫＩＮ ＥＬＭＥＲ社製、「ＳＰＥＣＴＲＵＭ ＯＮＥ」）を用いて、臭化カリウム（ＫＢｒ）錠剤法により測定した。
溶解性試験
フタロシアニン化合物の濃度が１０質量％になるように、それぞれの溶媒にフタロシアニン化合物を加えて撹拌し、フタロシアニン化合物の溶解性を目視で観察し、未溶解物の有無により溶解性を観察した。溶媒として、ジクロロメタン、クロロホルム、クロロベンゼン、テトラヒドロフラン、アセトン、酢酸エチル、トルエンを用いた。
光吸収性
分光光度計（株式会社島津製作所製、「ＵＶ－３１０１ＰＣ」）を用いて測定した。
結晶性の確認
偏光顕微鏡（オリンパス株式会社製 「ＢＸ５１」）を用いて倍率１０倍で観察した。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, this invention is not limited to a following example at all.
In addition, confirmation of the structure of the compound, and measurement / evaluation of solubility, light absorption and crystallinity were performed as follows.
Confirmation of compound structure
This was confirmed by 1 H NMR measurement and IR measurement. 1 H NMR measurement uses a nuclear magnetic resonance apparatus (NMR) (manufactured by Bruker, “Avance 500”), and IR measurement uses a Fourier transform infrared absorption (FT-IR) measuring apparatus (manufactured by PERKIN ELMER, “SPECTRUM ONE”. )) Was measured by the potassium bromide (KBr) tablet method.
Solubility test The phthalocyanine compound was added to each solvent and stirred so that the concentration of the phthalocyanine compound was 10% by mass, the solubility of the phthalocyanine compound was visually observed, and the solubility was observed depending on the presence or absence of undissolved substances. . Dichloromethane, chloroform, chlorobenzene, tetrahydrofuran, acetone, ethyl acetate, and toluene were used as the solvent.
Measurement was performed using a light absorption spectrophotometer (“UV-3101PC” manufactured by Shimadzu Corporation).
Confirmation of crystallinity It was observed at a magnification of 10 using a polarizing microscope (OLYMPUS "BX51").
なお、化合物の構造の確認、溶解性、光吸収性及び結晶性の測定・評価は以下の通り行った。
化合物の構造の確認
１Ｈ ＮＭＲ測定及びＩＲ測定により確認した。１Ｈ ＮＭＲ測定は、核磁気共鳴装置（ＮＭＲ）（Ｂｒｕｋｅｒ社製、「Ａｖａｎｃｅ５００」）を用い、ＩＲ測定は、フーリエ変換赤外吸収（ＦＴ－ＩＲ）測定装置（ＰＥＲＫＩＮ ＥＬＭＥＲ社製、「ＳＰＥＣＴＲＵＭ ＯＮＥ」）を用いて、臭化カリウム（ＫＢｒ）錠剤法により測定した。
溶解性試験
フタロシアニン化合物の濃度が１０質量％になるように、それぞれの溶媒にフタロシアニン化合物を加えて撹拌し、フタロシアニン化合物の溶解性を目視で観察し、未溶解物の有無により溶解性を観察した。溶媒として、ジクロロメタン、クロロホルム、クロロベンゼン、テトラヒドロフラン、アセトン、酢酸エチル、トルエンを用いた。
光吸収性
分光光度計（株式会社島津製作所製、「ＵＶ－３１０１ＰＣ」）を用いて測定した。
結晶性の確認
偏光顕微鏡（オリンパス株式会社製 「ＢＸ５１」）を用いて倍率１０倍で観察した。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, this invention is not limited to a following example at all.
In addition, confirmation of the structure of the compound, and measurement / evaluation of solubility, light absorption and crystallinity were performed as follows.
Confirmation of compound structure
This was confirmed by 1 H NMR measurement and IR measurement. 1 H NMR measurement uses a nuclear magnetic resonance apparatus (NMR) (manufactured by Bruker, “
Solubility test The phthalocyanine compound was added to each solvent and stirred so that the concentration of the phthalocyanine compound was 10% by mass, the solubility of the phthalocyanine compound was visually observed, and the solubility was observed depending on the presence or absence of undissolved substances. . Dichloromethane, chloroform, chlorobenzene, tetrahydrofuran, acetone, ethyl acetate, and toluene were used as the solvent.
Measurement was performed using a light absorption spectrophotometer (“UV-3101PC” manufactured by Shimadzu Corporation).
Confirmation of crystallinity It was observed at a magnification of 10 using a polarizing microscope (OLYMPUS "BX51").
（実施例１）
図４の反応式（１）に示されるように、ジシアノハイドロキノン（東京化成株式会社製）から１，４－ビス（２，２，２－トリフルオロエトキシ）フタロニトリル（化合物１２）を合成した。すなわち、窒素気流下、室温で、金属ナトリウム２．３ｇをメタノール（溶媒）８０ｍｌに溶解させた溶液を、ジシアノハイドロキノン８．０ｇに加え、室温で３０分間撹拌し、減圧下において未反応のメタノールを除去した。これに２，２，２－トリフルオロエチルトシレート４０．０ｇ及び溶媒としてＮ，Ｎ－ジメチルホルムアミド（ＤＭＦ）を加え、１２０℃に昇温して４８時間、撹拌した。この反応混合物を室温まで冷却後、氷水に注加し、生じた固体をろ過して集めた後に、エタノールで洗浄した。こうして得られた固体をエタノール／へキサン（混合溶媒）から再結晶し、５０℃で６時間、減圧乾燥した。こうして、１１．７ｇの１，４－ビス（２，２，２－トリフルオロエトキシ）フタロニトリル（化合物１２）を得た（収率７０％）。 Example 1
As shown in the reaction formula (1) in FIG. 4, 1,4-bis (2,2,2-trifluoroethoxy) phthalonitrile (Compound 12) was synthesized from dicyanohydroquinone (manufactured by Tokyo Chemical Industry Co., Ltd.). That is, a solution obtained by dissolving 2.3 g of metal sodium in 80 ml of methanol (solvent) at room temperature under a nitrogen stream was added to 8.0 g of dicyanohydroquinone, stirred at room temperature for 30 minutes, and unreacted methanol was removed under reduced pressure. Removed. To this, 40.0 g of 2,2,2-trifluoroethyl tosylate and N, N-dimethylformamide (DMF) as a solvent were added, and the mixture was heated to 120 ° C. and stirred for 48 hours. The reaction mixture was cooled to room temperature, poured into ice water, and the resulting solid was collected by filtration and washed with ethanol. The solid thus obtained was recrystallized from ethanol / hexane (mixed solvent) and dried under reduced pressure at 50 ° C. for 6 hours. Thus, 11.7 g of 1,4-bis (2,2,2-trifluoroethoxy) phthalonitrile (Compound 12) was obtained (yield 70%).
図４の反応式（１）に示されるように、ジシアノハイドロキノン（東京化成株式会社製）から１，４－ビス（２，２，２－トリフルオロエトキシ）フタロニトリル（化合物１２）を合成した。すなわち、窒素気流下、室温で、金属ナトリウム２．３ｇをメタノール（溶媒）８０ｍｌに溶解させた溶液を、ジシアノハイドロキノン８．０ｇに加え、室温で３０分間撹拌し、減圧下において未反応のメタノールを除去した。これに２，２，２－トリフルオロエチルトシレート４０．０ｇ及び溶媒としてＮ，Ｎ－ジメチルホルムアミド（ＤＭＦ）を加え、１２０℃に昇温して４８時間、撹拌した。この反応混合物を室温まで冷却後、氷水に注加し、生じた固体をろ過して集めた後に、エタノールで洗浄した。こうして得られた固体をエタノール／へキサン（混合溶媒）から再結晶し、５０℃で６時間、減圧乾燥した。こうして、１１．７ｇの１，４－ビス（２，２，２－トリフルオロエトキシ）フタロニトリル（化合物１２）を得た（収率７０％）。 Example 1
As shown in the reaction formula (1) in FIG. 4, 1,4-bis (2,2,2-trifluoroethoxy) phthalonitrile (Compound 12) was synthesized from dicyanohydroquinone (manufactured by Tokyo Chemical Industry Co., Ltd.). That is, a solution obtained by dissolving 2.3 g of metal sodium in 80 ml of methanol (solvent) at room temperature under a nitrogen stream was added to 8.0 g of dicyanohydroquinone, stirred at room temperature for 30 minutes, and unreacted methanol was removed under reduced pressure. Removed. To this, 40.0 g of 2,2,2-trifluoroethyl tosylate and N, N-dimethylformamide (DMF) as a solvent were added, and the mixture was heated to 120 ° C. and stirred for 48 hours. The reaction mixture was cooled to room temperature, poured into ice water, and the resulting solid was collected by filtration and washed with ethanol. The solid thus obtained was recrystallized from ethanol / hexane (mixed solvent) and dried under reduced pressure at 50 ° C. for 6 hours. Thus, 11.7 g of 1,4-bis (2,2,2-trifluoroethoxy) phthalonitrile (Compound 12) was obtained (yield 70%).
１，４－ビス（２，２，２－トリフルオロエトキシ）フタロニトリル（化合物１２）５．０ｇを、尿素４０．０ｇおよび三塩化バナジウム１．６ｇと混合した。この反応混合物を撹拌しながら、１６０℃で約９０分間、加熱した。そして室温になるまで放冷した反応液に１Ｎ塩酸を１００ｍｌ加え、１００℃に加熱した。放冷後、生じた緑色固体をろ過して回収し、純水で十分に洗浄した後、酢酸エチルで抽出した。抽出した有機層を濃縮し、カラムクロマトグラフィー（シリカゲル、アセトン：へキサン＝１：１）で精製した。さらに、再結晶（エタノール／へキサン）を行い、２．０ｇの化合物を得た（収率４０％、融点：２９０℃（分解））。得られた化合物の１Ｈ ＮＭＲ測定及びＩＲ測定の結果を示す。
１Ｈ ＮＭＲ測定（重アセトン中）
８．９９ｐｐｍ（ｐｈＨ, ８Ｈ）、 ５．７８ｐｐｍ（－ＯＣＨ２ＣＦ, １６Ｈ）
金属を導入していないフタロシアニンに見られる－１．０ｐｐｍ付近の化学シフトは観測されなかった。
ＩＲ測定
酸化バナジウム（ＶＯ）の振動ピークに帰属する１００２ｃｍ－１が観測された。
これらの結果から、得られた化合物は、１、４、５、８、９、１２、１３、１６－オクタキス（２，２，２－トリフルオロエトキシ）フタロシアニナトバナジウムオキサイド（フタロシアニン化合物１０１ａ）であることが確認された。このフタロシアニン化合物１０１ａの評価結果を示す。 5.0 g of 1,4-bis (2,2,2-trifluoroethoxy) phthalonitrile (compound 12) was mixed with 40.0 g of urea and 1.6 g of vanadium trichloride. The reaction mixture was heated at 160 ° C. for about 90 minutes with stirring. Then, 100 ml of 1N hydrochloric acid was added to the reaction solution which had been allowed to cool to room temperature and heated to 100 ° C. After allowing to cool, the resulting green solid was collected by filtration, washed thoroughly with pure water, and extracted with ethyl acetate. The extracted organic layer was concentrated and purified by column chromatography (silica gel, acetone: hexane = 1: 1). Further, recrystallization (ethanol / hexane) was performed to obtain 2.0 g of a compound (yield 40%, melting point: 290 ° C. (decomposition)). The result of 1 H NMR measurement and IR measurement of the obtained compound is shown.
1 H NMR measurement (in heavy acetone)
8.99 ppm (phH, 8H), 5.78 ppm (—OCH 2 CF, 16H)
The chemical shift around −1.0 ppm observed in phthalocyanine into which no metal was introduced was not observed.
IR measurement 1002 cm −1 attributed to the vibration peak of vanadium oxide (VO) was observed.
From these results, the obtained compound was 1,4,5,8,9,12,13,16-octakis (2,2,2-trifluoroethoxy) phthalocyaninatovanadium oxide (phthalocyanine compound 101a). It was confirmed that there was. The evaluation result of this phthalocyanine compound 101a is shown.
１Ｈ ＮＭＲ測定（重アセトン中）
８．９９ｐｐｍ（ｐｈＨ, ８Ｈ）、 ５．７８ｐｐｍ（－ＯＣＨ２ＣＦ, １６Ｈ）
金属を導入していないフタロシアニンに見られる－１．０ｐｐｍ付近の化学シフトは観測されなかった。
ＩＲ測定
酸化バナジウム（ＶＯ）の振動ピークに帰属する１００２ｃｍ－１が観測された。
これらの結果から、得られた化合物は、１、４、５、８、９、１２、１３、１６－オクタキス（２，２，２－トリフルオロエトキシ）フタロシアニナトバナジウムオキサイド（フタロシアニン化合物１０１ａ）であることが確認された。このフタロシアニン化合物１０１ａの評価結果を示す。 5.0 g of 1,4-bis (2,2,2-trifluoroethoxy) phthalonitrile (compound 12) was mixed with 40.0 g of urea and 1.6 g of vanadium trichloride. The reaction mixture was heated at 160 ° C. for about 90 minutes with stirring. Then, 100 ml of 1N hydrochloric acid was added to the reaction solution which had been allowed to cool to room temperature and heated to 100 ° C. After allowing to cool, the resulting green solid was collected by filtration, washed thoroughly with pure water, and extracted with ethyl acetate. The extracted organic layer was concentrated and purified by column chromatography (silica gel, acetone: hexane = 1: 1). Further, recrystallization (ethanol / hexane) was performed to obtain 2.0 g of a compound (yield 40%, melting point: 290 ° C. (decomposition)). The result of 1 H NMR measurement and IR measurement of the obtained compound is shown.
1 H NMR measurement (in heavy acetone)
8.99 ppm (phH, 8H), 5.78 ppm (—OCH 2 CF, 16H)
The chemical shift around −1.0 ppm observed in phthalocyanine into which no metal was introduced was not observed.
IR measurement 1002 cm −1 attributed to the vibration peak of vanadium oxide (VO) was observed.
From these results, the obtained compound was 1,4,5,8,9,12,13,16-octakis (2,2,2-trifluoroethoxy) phthalocyaninatovanadium oxide (
＜溶解性試験＞
用いた全ての溶媒において未溶解物は見られず、良好な溶解性を示すことが確認された。
＜光吸収性＞
フタロシアニン化合物１０１ａを１０ｍｇ、クロロベンゼン０．７５ｍｌに溶解し、ガラス基板の表面に滴下した。そして基板を回転させることによりフタロシアニン化合物１０１ａのスピンコート成膜を行い、６０℃で１０分間乾燥してフタロシアニン化合物１０１ａを薄膜化した。乾燥後の膜厚は４０ｎｍであった。得られた薄膜を用いて、光吸収性の測定を行ったところ、極大吸収波長は７４０ｎｍであった。薄膜を８０℃、１５０℃、２００℃で１０分間加熱した後の極大吸収波長はいずれも８３６ｎｍであり、良好な近赤外線吸収性を示した。 <Solubility test>
In all of the solvents used, no undissolved product was found, and it was confirmed that good solubility was exhibited.
<Light absorption>
Thephthalocyanine compound 101a was dissolved in 10 mg and 0.75 ml of chlorobenzene, and dropped onto the surface of the glass substrate. Then, the spin coat film formation of the phthalocyanine compound 101a was performed by rotating the substrate, and the film was dried at 60 ° C. for 10 minutes to thin the phthalocyanine compound 101a. The film thickness after drying was 40 nm. When the light absorptivity was measured using the obtained thin film, the maximum absorption wavelength was 740 nm. The maximum absorption wavelength after heating the thin film for 10 minutes at 80 ° C., 150 ° C., and 200 ° C. was 836 nm, indicating good near infrared absorption.
用いた全ての溶媒において未溶解物は見られず、良好な溶解性を示すことが確認された。
＜光吸収性＞
フタロシアニン化合物１０１ａを１０ｍｇ、クロロベンゼン０．７５ｍｌに溶解し、ガラス基板の表面に滴下した。そして基板を回転させることによりフタロシアニン化合物１０１ａのスピンコート成膜を行い、６０℃で１０分間乾燥してフタロシアニン化合物１０１ａを薄膜化した。乾燥後の膜厚は４０ｎｍであった。得られた薄膜を用いて、光吸収性の測定を行ったところ、極大吸収波長は７４０ｎｍであった。薄膜を８０℃、１５０℃、２００℃で１０分間加熱した後の極大吸収波長はいずれも８３６ｎｍであり、良好な近赤外線吸収性を示した。 <Solubility test>
In all of the solvents used, no undissolved product was found, and it was confirmed that good solubility was exhibited.
<Light absorption>
The
＜結晶性の確認＞
溶解性試験と同様にして作成した薄膜を、８０℃、１５０℃、２００℃でそれぞれ加熱した後、偏光顕微鏡を用いて観察したところ、高い結晶性を示す複屈折性のドメインが観測され、フタロシアニン化合物１０１ａが、結晶性に優れることが確認された。なお、６０℃で乾燥したフタロシアニン化合物１０１ａでは、結晶性を示す複屈折性のドメインが観測されなかった。 <Confirmation of crystallinity>
When the thin films prepared in the same manner as in the solubility test were heated at 80 ° C., 150 ° C., and 200 ° C., respectively, and observed using a polarizing microscope, birefringent domains exhibiting high crystallinity were observed, and phthalocyanine It was confirmed that thecompound 101a was excellent in crystallinity. In the phthalocyanine compound 101a dried at 60 ° C., a birefringent domain exhibiting crystallinity was not observed.
溶解性試験と同様にして作成した薄膜を、８０℃、１５０℃、２００℃でそれぞれ加熱した後、偏光顕微鏡を用いて観察したところ、高い結晶性を示す複屈折性のドメインが観測され、フタロシアニン化合物１０１ａが、結晶性に優れることが確認された。なお、６０℃で乾燥したフタロシアニン化合物１０１ａでは、結晶性を示す複屈折性のドメインが観測されなかった。 <Confirmation of crystallinity>
When the thin films prepared in the same manner as in the solubility test were heated at 80 ° C., 150 ° C., and 200 ° C., respectively, and observed using a polarizing microscope, birefringent domains exhibiting high crystallinity were observed, and phthalocyanine It was confirmed that the
以上のことから、フタロシアニン化合物１０１ａは、加熱によって結晶化され、結晶構造を有するときに近赤外領域に吸収帯を有するものと考えられる。
From the above, it is considered that the phthalocyanine compound 101a is crystallized by heating and has an absorption band in the near infrared region when it has a crystal structure.
次に、得られたフタロシアニン化合物１０１ａを用いて光電変換素子を作製し、評価した。まず、洗浄及びＵＶ（紫外線）－オゾン処理を行って清浄化したＩＴＯガラス（ガラス基板に錫ドープ酸化インジウム（ＩＴＯ）膜を形成した透明導電性ガラス、抵抗値１４Ω／ｓｑ）のＩＴＯ膜（陽極）上に、得られたフタロシアニン化合物１０１ａを、圧力３．３×１０－４Ｐａ、堆積速度０．４Å／秒の条件下で、厚さ５０ｎｍになるように積層した。さらに、フタロシアニン化合物１０１ａ層上にｎ型有機半導体としてフラーレン（Ｎａｎｏ－Ｃ社製）を圧力１．１×１０－４Ｐａ、堆積速度０．５Å／秒の条件下で、厚さ５０ｎｍになるように積層した。さらに、フラーレン層上にホールブロッキング剤としてのバソクプロイン（株式会社オージェック）を８．５×１０－５Ｐａ、堆積速度０．４Å／秒の条件下で、厚さ１０ｎｍに積層した。バソクプロイン層に陰極として銀（日本高純度化学株式会社製）を８．２×１０－５Ｐａ、堆積速度０．４Å／秒の条件下で５０ｎｍ積層して光電変換素子を作製した。タングステンランプ（１００Ｗ）を用いてＩＴＯガラス側から光電変換素子に光を照射して短絡時の電流値を測定したところ、２７．４μＡの電流値が得られ、良好な特性を示す光電変換素子が得られた。
Next, a photoelectric conversion element was produced and evaluated using the obtained phthalocyanine compound 101a. First, ITO glass cleaned by cleaning and UV (ultraviolet light) -ozone treatment (transparent conductive glass having a tin-doped indium oxide (ITO) film formed on a glass substrate, resistance value 14Ω / sq) ITO film (anode The obtained phthalocyanine compound 101a was laminated to a thickness of 50 nm under the conditions of a pressure of 3.3 × 10 −4 Pa and a deposition rate of 0.4 K / sec. Further, fullerene (manufactured by Nano-C) as an n-type organic semiconductor on the phthalocyanine compound 101a layer so as to have a thickness of 50 nm under the conditions of a pressure of 1.1 × 10 −4 Pa and a deposition rate of 0.5 kg / sec. Laminated. Furthermore, bathocuproin (Aujek Co., Ltd.) as a hole blocking agent was laminated on the fullerene layer to a thickness of 10 nm under the conditions of 8.5 × 10 −5 Pa and a deposition rate of 0.4 kg / sec. A silver (Nihon Kojun Kagaku Co., Ltd.) silver as a cathode was stacked on the bathocuproine layer at a thickness of 8.2 × 10 −5 Pa and a deposition rate of 0.4 Å / sec to produce a photoelectric conversion element. When a photoelectric conversion element was irradiated with light from the ITO glass side using a tungsten lamp (100 W) and the current value at the time of short circuit was measured, a current value of 27.4 μA was obtained, and a photoelectric conversion element showing good characteristics was obtained. Obtained.
（比較例）
フタロシアニン化合物１０１ａと同じ置換基Ｒを有するフタロシアニン化合物であって、中心金属が銅である比較例１、および中心金属化合物がジクロロ錫である比較例２においては、近赤外領域に吸収帯を有さないことが確認された。また、置換基Ｒ１～Ｒ８（図１等参照）がいずれも水素である酸化バナジウムフタロシアニンの比較例３では、上述の溶解性試験で用いられた各溶媒に対する溶解性が、フタロシアニン化合物１０１ａよりも低かった。 (Comparative example)
In Comparative Example 1 in which the central metal is copper and Comparative Example 2 in which the central metal compound is dichlorotin, the phthalocyanine compound having the same substituent R as thephthalocyanine compound 101a has an absorption band in the near infrared region. It was confirmed not to. In Comparative Example 3 of vanadium oxide phthalocyanine in which all of substituents R1 to R8 (see FIG. 1 and the like) are hydrogen, the solubility in each solvent used in the above-described solubility test is lower than that of phthalocyanine compound 101a. It was.
フタロシアニン化合物１０１ａと同じ置換基Ｒを有するフタロシアニン化合物であって、中心金属が銅である比較例１、および中心金属化合物がジクロロ錫である比較例２においては、近赤外領域に吸収帯を有さないことが確認された。また、置換基Ｒ１～Ｒ８（図１等参照）がいずれも水素である酸化バナジウムフタロシアニンの比較例３では、上述の溶解性試験で用いられた各溶媒に対する溶解性が、フタロシアニン化合物１０１ａよりも低かった。 (Comparative example)
In Comparative Example 1 in which the central metal is copper and Comparative Example 2 in which the central metal compound is dichlorotin, the phthalocyanine compound having the same substituent R as the
以上のように本発明によれば、フタロシアニン化合物１０は、従来の蒸着法等よりも簡易なスピンコート等の塗布法により、成膜化することが可能である。また、本発明のフタロシアニン化合物１０は、光吸収性能を有するため、有機薄膜太陽電池や光センサーなどの光起電力素子、光記録媒体などに好適に使用することができる。
As described above, according to the present invention, the phthalocyanine compound 10 can be formed into a film by a coating method such as spin coating which is simpler than the conventional vapor deposition method. Moreover, since the phthalocyanine compound 10 of the present invention has light absorption performance, it can be suitably used for photovoltaic elements such as organic thin-film solar cells and optical sensors, optical recording media, and the like.
さらにフタロシアニン化合物１０は、加熱処理によって容易に吸収帯を近赤外領域にシフトできる。このためフタロシアニン化合物１０は、Ｐ型有機半導体材料の分野などで特に要求されている性能を満たしており、この点においても有用であるといえる。
Furthermore, the phthalocyanine compound 10 can easily shift the absorption band to the near infrared region by heat treatment. Therefore, the phthalocyanine compound 10 satisfies the performance particularly required in the field of P-type organic semiconductor materials, and can be said to be useful in this respect.
Claims (5)
- 下記一般式（Ｉ）で表されるフタロシアニン化合物：
（式中Ｒは、炭素数が５以下の直鎖状のハロゲン化アルコキシ基、あるいは炭素数が５以下の分岐状のアルコキシ基のいずれかを表す） Phthalocyanine compounds represented by the following general formula (I):
(In the formula, R represents either a linear halogenated alkoxy group having 5 or less carbon atoms or a branched alkoxy group having 5 or less carbon atoms) - 前記一般式（Ｉ）中のＲが下記化学式（II）で示される１ａから１ｇの群から選択されることを特徴とする請求項１に記載のフタロシアニン化合物。
［化学式（II）］
１ａ：－ＯＣＨ２ＣＦ３
１ｂ：－ＯＣＨ２ＣＨ２ＣＦ３
１ｃ：－ＯＣＨ２ＣＣｌ３
１ｄ：－ＯＣＨ２ＣＨ２ＣＣｌ３
１ｅ：－ＯＣＨ（ＣＨ３）２
１ｆ：－ＯＣＨ２ＣＨ（ＣＨ３）２
１ｇ：－ＯＣＨ２ＣＨ２ＣＨ（ＣＨ３）２ The phthalocyanine compound according to claim 1, wherein R in the general formula (I) is selected from the group of 1a to 1g represented by the following chemical formula (II).
[Chemical formula (II)]
1a: —OCH 2 CF 3
1b: —OCH 2 CH 2 CF 3
1c: —OCH 2 CCl 3
1d: —OCH 2 CH 2 CCl 3
1e: —OCH (CH 3 ) 2
1f: —OCH 2 CH (CH 3 ) 2
1 g: —OCH 2 CH 2 CH (CH 3 ) 2 - 請求項１に記載のフタロシアニン化合物を含むことを特徴とする光吸収材料。 A light-absorbing material comprising the phthalocyanine compound according to claim 1.
- 前記光吸収材料を膜状にして、６０℃を超え１５０℃以下の温度で加熱したことを特徴とする請求項３に記載の光吸収材料。 The light-absorbing material according to claim 3, wherein the light-absorbing material is formed into a film and heated at a temperature exceeding 60 ° C and not more than 150 ° C.
- 請求項３または請求項４のいずれかに記載の光吸収材料を含む光電変換層を備えたことを特徴とする光電変換素子。 A photoelectric conversion element comprising a photoelectric conversion layer containing the light-absorbing material according to claim 3.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010800269183A CN102471601B (en) | 2009-07-07 | 2010-06-18 | Phthalocyanine compounds |
| JP2011521871A JP4967074B2 (en) | 2009-07-07 | 2010-06-18 | Phthalocyanine compounds |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009160965 | 2009-07-07 | ||
| JP2009-160965 | 2009-07-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2011004688A1 true WO2011004688A1 (en) | 2011-01-13 |
Family
ID=43429112
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2010/060334 WO2011004688A1 (en) | 2009-07-07 | 2010-06-18 | Phthalocyanine compounds |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP4967074B2 (en) |
| KR (1) | KR20120112345A (en) |
| CN (1) | CN102471601B (en) |
| TW (1) | TWI476250B (en) |
| WO (1) | WO2011004688A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012167145A (en) * | 2011-02-10 | 2012-09-06 | Fujifilm Corp | Colored curable composition, and color filter |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1059974A (en) * | 1996-08-21 | 1998-03-03 | Yamamoto Chem Inc | Production of phthalocyanine compound |
| JP2000063693A (en) * | 1998-08-24 | 2000-02-29 | Nippon Shokubai Co Ltd | Preparation of phthalocyanine compound |
| JP2004240043A (en) * | 2003-02-04 | 2004-08-26 | Fuji Photo Film Co Ltd | Original plate for lithographic printing plate |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05295283A (en) * | 1991-06-19 | 1993-11-09 | Mitsui Toatsu Chem Inc | Colorant for filter and color filter containing the colorant |
| JPH11106386A (en) * | 1997-10-02 | 1999-04-20 | Ricoh Co Ltd | Production of metallophthalocyanines |
| JP4079234B2 (en) * | 1998-01-23 | 2008-04-23 | 株式会社リコー | Method for producing metal phthalocyanines |
| JP2002114790A (en) * | 2000-10-04 | 2002-04-16 | Nippon Shokubai Co Ltd | Method for purifying phthalocyanine compound and naphthalocyanine compound |
| JP4238822B2 (en) * | 2004-12-03 | 2009-03-18 | セイコーエプソン株式会社 | Pattern-formed substrate, electro-optical device, pattern-formed substrate manufacturing method, and electro-optical device manufacturing method |
| CN101255163A (en) * | 2008-03-14 | 2008-09-03 | 中国科学院长春应用化学研究所 | Soluble tetraalkyl phthalocyanine compound and preparation method thereof |
-
2010
- 2010-06-18 KR KR1020127000334A patent/KR20120112345A/en not_active Application Discontinuation
- 2010-06-18 WO PCT/JP2010/060334 patent/WO2011004688A1/en active Application Filing
- 2010-06-18 CN CN2010800269183A patent/CN102471601B/en active Active
- 2010-06-18 JP JP2011521871A patent/JP4967074B2/en active Active
- 2010-06-30 TW TW099121413A patent/TWI476250B/en active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1059974A (en) * | 1996-08-21 | 1998-03-03 | Yamamoto Chem Inc | Production of phthalocyanine compound |
| JP2000063693A (en) * | 1998-08-24 | 2000-02-29 | Nippon Shokubai Co Ltd | Preparation of phthalocyanine compound |
| JP2004240043A (en) * | 2003-02-04 | 2004-08-26 | Fuji Photo Film Co Ltd | Original plate for lithographic printing plate |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012167145A (en) * | 2011-02-10 | 2012-09-06 | Fujifilm Corp | Colored curable composition, and color filter |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2011004688A1 (en) | 2012-12-20 |
| TW201107427A (en) | 2011-03-01 |
| CN102471601B (en) | 2013-12-04 |
| TWI476250B (en) | 2015-03-11 |
| CN102471601A (en) | 2012-05-23 |
| JP4967074B2 (en) | 2012-07-04 |
| KR20120112345A (en) | 2012-10-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Fateev et al. | Solution processing of methylammonium lead iodide perovskite from γ-butyrolactone: crystallization mediated by solvation equilibrium | |
| CN101842917B (en) | Use of halogenated phthalocyanines | |
| EP2470543B1 (en) | Visible/nir photodetectors | |
| EP2962992B1 (en) | Fullerene derivative, organic solar cell using same, and manufacturing method thereof | |
| EP2310315A2 (en) | Film and device using layer based on ribtan material | |
| Cho et al. | Thermally durable nonfullerene acceptor with nonplanar conjugated backbone for high‐performance organic solar cells | |
| Li et al. | Effects of fused-ring regiochemistry on the properties and photovoltaic performance of n-type organic semiconductor acceptors | |
| US9362509B2 (en) | Aryloxy-phthalocyanines of group IV metals | |
| KR20130133903A (en) | Perylene tetracarboxylic acid bisimide derivative, n-type semiconductor, process for producing n-type semiconductor, and electronic device | |
| Simón Marqués et al. | Indeno [1, 2-b] thiophene End-capped Perylene Diimide: Should the 1, 6-Regioisomers be systematically considered as a byproduct? | |
| JP4967074B2 (en) | Phthalocyanine compounds | |
| WO2023142330A1 (en) | Fullerene derivative material and preparation method therefor and application thereof in perovskite solar cell | |
| Lozano-González et al. | Synthesis and Evaluation of the Semiconductor Behavior in Vanadium Indanone Derivatives Thin Films | |
| Wang et al. | Soluble hexamethyl-substituted subphthalocyanine as a dopant-free hole transport material for planar perovskite solar cells | |
| Yong et al. | Enhancement of Interfacial Properties by Indoloquinoxaline‐Based Small Molecules for Highly Efficient Wide‐Bandgap Perovskite Solar Cells | |
| JP5993054B1 (en) | Thin films exhibiting a wide absorption band, devices containing them, and their manufacturing methods | |
| Monzón González et al. | Design of Promising Uranyl (VI) Complexes Thin Films with Potential Applications in Molecular Electronics | |
| KR102573398B1 (en) | Composition for Solution Process for producing Hetero Metal Chalcogenide Thin film and Method for producing thin film using the same | |
| EP4383990A1 (en) | Materials for optoelectronic applications | |
| JP2022149441A (en) | Light adjusting material, light adjusting film, and light adjusting laminate body | |
| KR101624094B1 (en) | Aryloxy-phthalocyanines of group iii metals | |
| McGrath | Synthesis and characterization of novel asymmetrically substituted bisphenazines and their self assembling properties |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WWE | Wipo information: entry into national phase |
Ref document number: 201080026918.3 Country of ref document: CN |
|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 10796999 Country of ref document: EP Kind code of ref document: A1 |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 2011521871 Country of ref document: JP |
|
| ENP | Entry into the national phase |
Ref document number: 20127000334 Country of ref document: KR Kind code of ref document: A |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 10796999 Country of ref document: EP Kind code of ref document: A1 |