CN102574806B - 苝四甲酰二亚胺衍生物 - Google Patents
苝四甲酰二亚胺衍生物 Download PDFInfo
- Publication number
- CN102574806B CN102574806B CN201080047762.7A CN201080047762A CN102574806B CN 102574806 B CN102574806 B CN 102574806B CN 201080047762 A CN201080047762 A CN 201080047762A CN 102574806 B CN102574806 B CN 102574806B
- Authority
- CN
- China
- Prior art keywords
- perylene
- formyl
- derivative
- tri
- exemplary compounds
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 title claims abstract description 37
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 title claims abstract description 33
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 abstract description 9
- 125000004093 cyano group Chemical group *C#N 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 125000005843 halogen group Chemical group 0.000 abstract description 3
- 125000005842 heteroatom Chemical group 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 abstract description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052711 selenium Inorganic materials 0.000 abstract description 2
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 abstract 1
- 239000011669 selenium Substances 0.000 abstract 1
- 229910052717 sulfur Inorganic materials 0.000 abstract 1
- 239000011593 sulfur Substances 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 29
- 239000004065 semiconductor Substances 0.000 description 21
- 239000010408 film Substances 0.000 description 17
- 239000003960 organic solvent Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 8
- -1 perylene tetracarboxylic acid acid anhydride Chemical class 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000010409 thin film Substances 0.000 description 6
- 238000004528 spin coating Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 230000005669 field effect Effects 0.000 description 3
- 230000008676 import Effects 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GTZOZDOTOWNSJH-UHFFFAOYSA-N [O].CCCCCCC Chemical compound [O].CCCCCCC GTZOZDOTOWNSJH-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 1
- FXIXKBWZQPKQLB-UHFFFAOYSA-N 3-butylsulfanylpropan-1-amine Chemical compound CCCCSCCCN FXIXKBWZQPKQLB-UHFFFAOYSA-N 0.000 description 1
- XLCJHZNTOSDPMV-UHFFFAOYSA-N 3-dodecylselanylpropan-1-amine Chemical compound CCCCCCCCCCCC[Se]CCCN XLCJHZNTOSDPMV-UHFFFAOYSA-N 0.000 description 1
- AJJBNKUPXKYSKX-UHFFFAOYSA-N 3-dodecylsulfanylpropan-1-amine Chemical compound CCCCCCCCCCCCSCCCN AJJBNKUPXKYSKX-UHFFFAOYSA-N 0.000 description 1
- YUANZDIYFLGXAB-UHFFFAOYSA-N 3-ethylsulfanylpropan-1-amine Chemical compound CCSCCCN YUANZDIYFLGXAB-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 240000004859 Gamochaeta purpurea Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 125000005447 octyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 230000000176 photostabilization Effects 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound 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 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
- C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
- C07D221/04—Ortho- or peri-condensed ring systems
- C07D221/18—Ring systems of four or more rings
-
- 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
- C09B5/00—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings
- C09B5/62—Cyclic imides or amidines of peri-dicarboxylic acids of the anthracene, benzanthrene, or perylene series
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
- H10K10/462—Insulated gate field-effect transistors [IGFETs]
- H10K10/484—Insulated gate field-effect transistors [IGFETs] characterised by the channel regions
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/621—Aromatic anhydride or imide compounds, e.g. perylene tetra-carboxylic dianhydride or perylene tetracarboxylic di-imide
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Thin Film Transistor (AREA)
- Photovoltaic Devices (AREA)
Abstract
本发明为一种苝四甲酰二亚胺衍生物,其特征在于,由下述通式(1)表示。其中,通式(1)中,R1表示碳原子数为1~20的分支或不分支的烷基,R2及R3独立地表示碳原子数为2~6的分支或不分支的烷基,X1及X2表示选自氧原子、硫原子及硒原子中的杂原子,Y表示卤原子或氰基,m表示0~4的数,并且n表示0~2的数。
Description
技术领域
本发明涉及具有特定的取代基的苝四甲酰二亚胺衍生物。
背景技术
以往,作为用于形成有机薄膜太阳能电池、有机晶体管或有机光导电体等的有机半导体材料,一直使用酞菁颜料、苝颜料、偶氮颜料等各种颜料衍生物。这些当中,苝颜料衍生物具有优异的半导体特性,已经公开了将苝骨架的一部分氰基化而提高了半导体特性的苝衍生物(专利文献1)、通过经氟化的烷基的导入而提高了耐久性的苝衍生物(专利文献2)等。
现有技术文献
专利文献
专利文献1:日本特表2007-527114号公报
专利文献2:日本特表2008-524846号公报
发明内容
发明所要解决的问题
然而,以往已知的各种苝颜料衍生物虽然与在可见光区域具有吸收的染料等相比,具有耐光性或耐热性等优异的特点,但未得到具有充分满足作为有机半导体材料的使用目的的特性的材料。
用于解决问题的手段
本发明者们为了改良用于有机薄膜太阳能电池、有机晶体管或有机光导电体等的有机半导体材料而进行研究,发现下述通式(1)、通式(2)或式(3)所示的具有特定的取代基的苝四甲酰二亚胺衍生物具有优异的特性,从而实现了本发明。
即,本发明提供一种苝四甲酰二亚胺衍生物,其特征在于,由下述通式(1)、通式(2)或式(3)表示,具有特定的取代基。
(其中,通式(1)中,R1表示碳原子数为1~20的分支或不分支的烷基,R2表示碳原子数为2~6的分支或不分支的烷基,R3表示碳原子数为2~6的分支或不分支的烷基,X1及X2表示选自氧原子、硫原子及硒原子中的杂原子,Y表示卤原子或氰基,m表示0~4的数,并且n表示0~2的数。)
(其中,通式(2)中,R1表示碳原子数为1~20的直链烷基,R2表示碳原子数为2~6的直链烷基,R3表示碳原子数为2~6的直链烷基,X1及X2表示氧原子,Y表示卤原子或氰基,m表示0~4的数,并且n表示0~2的数。)
发明效果
根据本发明,可提供显示出优异的半导体特性、并且当制成薄膜时耐久性优异、在有机溶剂中的溶解性高、能够应用于有用的有机半导体材料的苝四甲酰二亚胺衍生物。
附图说明
图1是例示化合物1的红外吸收光谱。
图2是例示化合物2的红外吸收光谱。
具体实施方式
接着列举出用于实施本发明的最佳方式对本发明进一步详细说明。本发明的具有特定的取代基的苝四甲酰二亚胺衍生物可通过公知的方法来合成。例如,只要使苝四羧酸酐在高沸点有机溶剂中与相应的胺类反应,导入带有本发明的特征的特定的取代基即可。或者通过将苝四甲酰二亚胺暂时制成钾盐后,与相应的卤代烷基反应,从而导入特定的取代基,由此也能得到本发明的苝四甲酰二亚胺衍生物。
作为在合成本发明的苝四甲酰二亚胺衍生物时使用的胺成分,可列举出以下的胺。可以使用例如3-甲氧基-正乙胺、3-甲氧基-正丙胺、3-乙氧基-正丙胺、4-乙氧基-正丁胺、5-(正丁氧基)-正戊胺、3-(正丁氧基)-正丙胺、3-(正丁氧基)-正己胺、3-(正庚氧基)-正丙胺、3-(异丁氧基)-正丙胺、3-(仲丁氧基)-正丙胺、3-(叔丁氧基)-正丙胺、3-(正辛氧基)-正丙胺、3-(正癸氧基)-正丙胺、3-(正十二烷氧基)-正丙胺、3-(正十四烷氧基)-正丙胺、3-(正二十烷氧基)-正丙胺、2-(2-乙氧基乙氧基)乙胺、2-(2-正丁氧基)乙胺、2-(2-正己氧基)乙胺、2-(2-正辛氧基)乙胺、2-(2-仲辛氧基)乙胺、2-(2-丁氧基丙氧基)丙胺、2-(2-(十二烷氧基)丙氧基)丙胺、3-(正丁基硫基)丙胺、3-(乙基硫基)丙胺、3-(正十二烷基硫基)丙胺、3-(正十二烷基硒基)丙胺等。
若考虑原材料的容易获得性和反应的容易性、以及所合成的苝四甲酰二亚胺衍生物的半导体特性等,优选使用3-甲氧基-正丙胺、3-乙氧基-正丙胺、5-(正丁氧基)-正戊胺、3-(正丁氧基)-正丙胺、3-(正丁氧基)-正己胺、3-(正庚氧基)-正丙胺、3-(正辛氧基)-正丙胺、3-(正癸氧基)-正丙胺、3-(正十二烷氧基)-正丙胺、3-(正十四烷氧基)-正丙胺、3-(正二十烷氧基)-正丙胺,尤其优选使用3-(正丁氧基)-正丙胺、3-(正十二烷氧基)-正丙胺。
作为在合成本发明的苝四甲酰二亚胺衍生物时使用的苝四羧酸酐,可列举出以下的苝四羧酸酐。例如可列举出无取代的3,4:9,10-苝四羧酸酐、1,7-二氰基-3,4:9,10-苝四羧酸酐、1,7-二氯-3,4:9,10-苝四羧酸酐、1,7-二氟-3,4:9,10-苝四羧酸酐、1,6,7,10-四氟-3,4:9,10-苝四羧酸酐等。这些当中,若考虑原材料的容易获得性和反应的容易性、以及所合成的苝四甲酰二亚胺衍生物的半导体特性等,优选使用在苝骨架上未导入取代基的无取代的苝四羧酸酐。
通常,当将苝四甲酰二亚胺衍生物用于有机太阳能电池和有机光半导体或有机晶体管等时,经常在高真空下蒸镀到基板上,是一般的方法。很大的原因之一是以往已知的苝四甲酰二亚胺衍生物基本不溶于有机溶剂。
相对于此,本发明的具有特定的取代基的苝四甲酰二亚胺衍生物与以往的衍生物不同,比较易溶于有机溶剂中。因此,本发明的衍生物可以在其制造时执行像柱色谱法那样的纯化手段,当应用于有机半导体材料时,也可以溶解到有机溶剂中通过旋涂等方法涂布到基板上,形成被膜(薄膜)。后述的表2中记载了使用与本发明的衍生物相关的例示化合物,各种溶剂中的薄膜形成的状态。在有机溶剂中的溶解特性意味着使苝四甲酰二亚胺衍生物向有机半导体材料等的应用飞跃提高。
以下,列举出显示半导体特性、并且显示在上述的有机溶剂中的溶解性的本发明的具有特定的取代基的苝四甲酰二亚胺衍生物的具体例子,通过分别确定了与上述通式(1)中的各符号相应的基团或原子的表1来表示。但是,它们是例示,本发明的苝四甲酰二亚胺衍生物并不限定于这些。这些化合物的制造方法依照后述的实施例1。
表1:通式(1)所示的苝四甲酰二亚胺衍生物的例子
上述例示的具有特定的取代基的本发明的苝四甲酰二亚胺衍生物比较易溶于例如下述列举的有机溶剂中。例如为氯仿、二氯乙烷、氯苯、二氯苯、三氯苯、氯萘等卤系烃溶剂、丙酮、甲乙酮、甲基异丁酮的酮系溶剂、乙酸乙酯、乙酸丁酯等酯系溶剂、二乙醚、二噁烷、四氢呋喃等醚系溶剂、甲苯、二甲苯、乙苯等芳香族系烃溶剂、环丁砜、N,N-二甲基甲酰胺、N-甲基-2-吡咯烷酮、二甲基亚砜等非质子系极性溶剂等。本发明的苝四甲酰二亚胺衍生物可以通过将上述列举的有机溶剂单独使用或者并用多种,从而制成适当浓度的溶液。因此,根据本发明的苝四甲酰二亚胺衍生物,通过使用其溶液,从而可以适用以往的衍生物所无法利用的旋涂法等溶液涂布法,通过该方法能够容易地形成均匀的薄膜。进而,本发明的苝四甲酰二亚胺衍生物由于具有充分的半导体特性,所以所形成的薄膜例如作为用于有机薄膜太阳能电池、有机晶体管或有机光导电体等的良好的有机半导体薄膜发挥功能。
为了确认本发明的具有特定的取代基的苝四甲酰二亚胺衍生物相对于有机溶剂的溶解性,对于之前列举的例示化合物1~17,使用各有机溶剂,以通过旋涂法在硅基板上形成薄膜的状态来进行判断。将结果示于表2中。其结果是,虽然根据通式(1)中的烷基的链长和杂原子不同而多少有些差异,但确认相对于有机溶剂显示良好的溶解性,能够适用旋涂法等溶液涂布法。
表2:例示化合物1~17在有机溶剂中的溶解性
<评价基准>以通过旋涂法在硅基板上形成薄膜的状态来进行判断
◎:能形成均匀的薄膜
○:通过对溶液进行加温,能形成均匀的薄膜
△:通过对溶液进行加温,能在基板上的一部分上形成薄膜
×:难以形成薄膜
实施例
以下列举出实施例对本发明进一步具体进行说明。各实施例中,分别合成了之前表1中示出的例示化合物1~17。
[实施例1]
(例示化合物1的合成)
将苝四羧酸酐3.92g和3-(正十二烷氧基)-正丙胺9.72g分散到咪唑40g中,在氮气流下160℃下搅拌4小时。冷却后,过滤,将过滤物依次用甲醇·稀盐酸、接着用水进行洗涤。然后,将过滤物干燥,得到5.90g的下述式(3)所示的N,N′-双(3-(正十二烷氧基)-正丙基)-3,4:9,10-苝四甲酰二亚胺作为例示化合物1(收率70%)。
关于上述得到的例示化合物1的各分析结果如下所示,通过这些分析,确认例示化合物1为上述的结构。
熔点:330℃附近(分解)
元素分析值( )内为理论值:C:76.88%(76.92%)、H:8.30%(8.37%)、N:3.25%(3.32%)
图1中示出红外吸收光谱。
[实施例2]
(例示化合物2的合成)
除了将实施例1中使用的3-(正十二烷氧基)-正丙胺9.72g替换成3-(正丁氧基)-正丙胺5.24g以外,通过与实施例1同样的方法,得到作为例示化合物2的4.95g的N,N′-双(3-(正丁氧基)-正丙基)-3,4:9,10-苝四甲酰二亚胺(收率80%)。关于所合成的例示化合物2的各分析结果如下所示,通过这些分析,确认例示化合物2为上述的化合物。
熔点:340℃附近(分解)
元素分析值( )内为理论值:C:73.81%(73.77%)、H:6.15%(6.19%)、N:4.49%(4.53%)
图2中示出红外吸收光谱。
[实施例3~17]
通过与实施例1及2同样的方法,分别合成了之前表1中所示结构的例示化合物3~17。并且,将所得到的各化合物的收率、熔点、紫外·可见光吸收光谱中的最大吸收波长示于表3中。对于实施例1及2中得到的例示化合物1、2,也测定最大吸收波长,将结果与收率及熔点一并示出。例示化合物3~17的紫外·可见光吸收光谱与例示化合物1、2大致相同。
以下表3中记载了各实施例中合成的例示化合物1~17的收率、最大吸收波长及熔点。
表3:各例示化合物的收率及特性
以下示出使用了本发明的苝四甲酰二亚胺衍生物的有机半导体的制作例。
[参考例1]
使用了例示化合物1(N,N′-双(3-(正十二烷氧基)-正丙基)-3,4:9,10-苝四甲酰二亚胺)的有机薄膜晶体管的制作
首先,准备了在表面具有成为栅极绝缘体层的氧化硅膜(厚度为200nm)的硅基板。由实施例1中得到的例示化合物1形成的有机半导体薄膜在氧化硅膜上通过真空蒸镀法(蒸镀速率2[nm/sec])以厚度达到30nm的方式成膜。接着,隔着荫罩,形成金电极的图案(30nm)作为源极/漏极电极,制成顶电极型有机薄膜晶体管。此时的通道长度、通道宽度分别设定为100μm、2000μm。
对于上述得到的晶体管,测定每个不同的栅极电压下的漏极电压和漏极电流。其结果是,在漏极电流-漏极电压曲线上见到明显的饱和区域,因此表示作为具有典型的n型特性的场效应晶体管进行驱动。由该曲线算出的电子迁移率为3.3×10-2cm2/Vs,阈值电压值为15V。
[参考例2]
将参考例1中使用的例示化合物1溶解到氯仿中,使其浓度达到0.25%,使用该溶液,利用旋涂机(1500转/分钟,40秒),在表面具有ITO电极的带氧化膜的硅基板上形成有机半导体薄膜,在真空中140℃下进行1小时的减压干燥。
对于上述得到的晶体管,与参考例1同样地测定晶体管特性。其结果是,表示作为具有典型的n型特性的场效应晶体管进行驱动。此外确认,电子迁移率为0.40cm2/Vs,阈值电压值为16V,得到与参考例1的通过真空蒸镀法来形成薄膜时相比半导体特性优异的晶体管。
[参考例3]
本参考例中,代替参考例1中使用的例示化合物1,使用实施例2中得到的例示化合物2(N,N′-双(3-(正丁氧基)-正丙基)-3,4:9,10-苝四甲酰二亚胺)。
与参考例1同样地制作了具有由例示化合物2形成的有机半导体层的顶电极型有机薄膜晶体管。并且,显示出作为具有典型的n型特性的场效应晶体管进行驱动。此外,电子迁移率为3.8×10-3cm2/Vs,阈值电压值为10V。
产业上的可利用性
根据本发明,可提供显示优异的半导体特性、并且当制成薄膜时耐久性优异、能够应用于有用的有机半导体材料的苝四甲酰二亚胺衍生物。此外,由本发明提供的上述苝四甲酰二亚胺衍生物显示出在有机溶剂中的溶解性,所以可期待能够通过溶液法来形成薄膜等,其实用性非常高。
Claims (1)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2009249127 | 2009-10-29 | ||
JP2009-249127 | 2009-10-29 | ||
PCT/JP2010/069277 WO2011052719A1 (ja) | 2009-10-29 | 2010-10-29 | ペリレンテトラカルボキシジイミド誘導体 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN102574806A CN102574806A (zh) | 2012-07-11 |
CN102574806B true CN102574806B (zh) | 2014-07-02 |
Family
ID=43922140
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201080047762.7A Active CN102574806B (zh) | 2009-10-29 | 2010-10-29 | 苝四甲酰二亚胺衍生物 |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP2471778B1 (zh) |
JP (1) | JP5643215B2 (zh) |
KR (1) | KR101491888B1 (zh) |
CN (1) | CN102574806B (zh) |
TW (1) | TWI431005B (zh) |
WO (1) | WO2011052719A1 (zh) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20140021014A (ko) * | 2011-05-11 | 2014-02-19 | 바스프 에스이 | 할로겐화 페릴렌계 반도체 물질 |
US8986842B2 (en) * | 2011-05-24 | 2015-03-24 | Ecole Polytechnique Federale De Lausanne (Epfl) | Color conversion films comprising polymer-substituted organic fluorescent dyes |
CN103764787A (zh) * | 2011-08-12 | 2014-04-30 | 巴斯夫欧洲公司 | 氟化苝基半导体材料 |
CN104557931B (zh) * | 2013-10-25 | 2016-08-17 | 济南大学 | N-吡啶基苝四甲酰二亚胺的制备及其光催化制氢性能 |
EP3193383B1 (en) * | 2014-09-01 | 2022-02-23 | FUJIFILM Corporation | Composition for forming organic semiconductor film, organic semiconductor film and method for manufacturing same, and organic semiconductor compound |
JP6995596B2 (ja) * | 2017-12-08 | 2022-01-14 | 住友化学株式会社 | 光電変換素子 |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1523475A (en) * | 1974-10-31 | 1978-08-31 | Basf Ag | Dyes of the perylene-3,4,9,10-tetracarboxylic acid diimide series |
US4156757A (en) * | 1976-08-13 | 1979-05-29 | Basf Aktiengesellschaft | Electrically conductive perylene derivatives |
EP0047027A1 (de) * | 1980-08-22 | 1982-03-10 | BBC Aktiengesellschaft Brown, Boveri & Cie. | Flüssigkristallmischung |
DE3235526A1 (de) * | 1982-09-25 | 1984-03-29 | Basf Ag, 6700 Ludwigshafen | Verfahren zur flaechenmaessigen konzentrierung von licht |
EP0061088B1 (de) * | 1981-03-20 | 1984-06-13 | BASF Aktiengesellschaft | Elektrophotographisches Aufzeichnungsmaterial |
DE3413418A1 (de) * | 1984-04-10 | 1985-10-17 | Basf Ag, 6700 Ludwigshafen | Farbstofflaser |
US4667036A (en) * | 1983-08-27 | 1987-05-19 | Basf Aktiengesellschaft | Concentration of light over a particular area, and novel perylene-3,4,9,10-tetracarboxylic acid diimides |
CN1980791A (zh) * | 2004-01-26 | 2007-06-13 | 西北大学 | 苝n-型半导体和相关器件 |
CN101353349A (zh) * | 2007-07-25 | 2009-01-28 | 中国科学院化学研究所 | 全氟烷基链取代的苝-3,4:9,10-四羧酸二酰亚胺类化合物及其制备方法 |
WO2009118742A1 (en) * | 2008-03-26 | 2009-10-01 | Yeda Research And Development Co. Ltd | Doubly reduced perylene-diimides and supramolecular polymers derived from perylene-diimides |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5774361A (en) * | 1980-08-22 | 1982-05-10 | Bbc Brown Boveri & Cie | Liquid crystal mixture and novel bichromophoric coloring matter |
US7326956B2 (en) | 2004-12-17 | 2008-02-05 | Eastman Kodak Company | Fluorine-containing N,N′-diaryl perylene-based tetracarboxylic diimide compounds as N-type semiconductor materials for thin film transistors |
-
2010
- 2010-10-29 CN CN201080047762.7A patent/CN102574806B/zh active Active
- 2010-10-29 TW TW099137147A patent/TWI431005B/zh active
- 2010-10-29 KR KR20127013355A patent/KR101491888B1/ko active IP Right Grant
- 2010-10-29 JP JP2011538496A patent/JP5643215B2/ja active Active
- 2010-10-29 EP EP10826849.1A patent/EP2471778B1/en active Active
- 2010-10-29 WO PCT/JP2010/069277 patent/WO2011052719A1/ja active Application Filing
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1523475A (en) * | 1974-10-31 | 1978-08-31 | Basf Ag | Dyes of the perylene-3,4,9,10-tetracarboxylic acid diimide series |
US4156757A (en) * | 1976-08-13 | 1979-05-29 | Basf Aktiengesellschaft | Electrically conductive perylene derivatives |
EP0047027A1 (de) * | 1980-08-22 | 1982-03-10 | BBC Aktiengesellschaft Brown, Boveri & Cie. | Flüssigkristallmischung |
EP0061088B1 (de) * | 1981-03-20 | 1984-06-13 | BASF Aktiengesellschaft | Elektrophotographisches Aufzeichnungsmaterial |
DE3235526A1 (de) * | 1982-09-25 | 1984-03-29 | Basf Ag, 6700 Ludwigshafen | Verfahren zur flaechenmaessigen konzentrierung von licht |
US4667036A (en) * | 1983-08-27 | 1987-05-19 | Basf Aktiengesellschaft | Concentration of light over a particular area, and novel perylene-3,4,9,10-tetracarboxylic acid diimides |
DE3413418A1 (de) * | 1984-04-10 | 1985-10-17 | Basf Ag, 6700 Ludwigshafen | Farbstofflaser |
CN1980791A (zh) * | 2004-01-26 | 2007-06-13 | 西北大学 | 苝n-型半导体和相关器件 |
CN101353349A (zh) * | 2007-07-25 | 2009-01-28 | 中国科学院化学研究所 | 全氟烷基链取代的苝-3,4:9,10-四羧酸二酰亚胺类化合物及其制备方法 |
WO2009118742A1 (en) * | 2008-03-26 | 2009-10-01 | Yeda Research And Development Co. Ltd | Doubly reduced perylene-diimides and supramolecular polymers derived from perylene-diimides |
Non-Patent Citations (11)
Title |
---|
Brian A. Gregg,等.Doping Molecular Semiconductors: n-Type Doping of a Liquid Crystal Perylene Diimide.《J.Am.Chem.Soc.》.2001,第123卷(第32期),7959-7960. |
Doping Molecular Semiconductors: n-Type Doping of a Liquid Crystal Perylene Diimide;Brian A. Gregg,等;《J.Am.Chem.Soc.》;20010721;第123卷(第32期);7959-7960 * |
Elijah Shirman,等.Stable Aromatic Dianion in Water.《The Journal of Physical Chemistry B》.2008,第112卷(第30期),8855-8858. |
Enhancing One-Dimensional Charge Transport through Intermolecular π-Electron Delocalization: Conductivity Improvement for Organic Nanobelts;Yanke Che,等;《J.Am.Chem.Soc》;20070428;第129卷(第20期);6354-6355 * |
Jeroen van Herrikhuyzen,等.Synthesis of n-Type Perylene Bisimide Derivatives and Their Orthogonal Self-Assembly with p-Type Oligo(p-phenylene vinylene)s.《J.Am.Chem.Soc.》.2004,第126卷(第32期),10021-10027. |
JP昭57-176046A 1982.10.29 |
RamakrishnaSamudrala,等.Synthesisofanon-cationic water-soluble perylenetetracarboxylic diimide and its interactions with G-quadruplex-forming DNA.《Bioorganic & Medicinal Chemistry》.2006 |
Stable Aromatic Dianion in Water;Elijah Shirman,等;《The Journal of Physical Chemistry B》;20080703;第112卷(第30期);8855-8858 * |
Synthesis of a non-cationic, water-soluble perylenetetracarboxylic diimide and its interactions with G-quadruplex-forming DNA;Ramakrishna Samudrala,等;《Bioorganic & Medicinal Chemistry》;20061010;第15卷(第1期);186-193 * |
Synthesis of n-Type Perylene Bisimide Derivatives and Their Orthogonal Self-Assembly with p-Type Oligo(p-phenylene vinylene)s;Jeroen van Herrikhuyzen,等;《J.Am.Chem.Soc.》;20040713;第126卷(第32期);10021-10027 * |
Yanke Che,等.Enhancing One-Dimensional Charge Transport through Intermolecular π-Electron Delocalization: Conductivity Improvement for Organic Nanobelts.《J.Am.Chem.Soc》.2007,第129卷(第20期),6354-6355. |
Also Published As
Publication number | Publication date |
---|---|
EP2471778B1 (en) | 2019-05-08 |
TWI431005B (zh) | 2014-03-21 |
KR101491888B1 (ko) | 2015-02-09 |
JP5643215B2 (ja) | 2014-12-17 |
JPWO2011052719A1 (ja) | 2013-03-21 |
TW201124413A (en) | 2011-07-16 |
EP2471778A1 (en) | 2012-07-04 |
KR20120085856A (ko) | 2012-08-01 |
EP2471778A4 (en) | 2013-04-17 |
CN102574806A (zh) | 2012-07-11 |
WO2011052719A1 (ja) | 2011-05-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102574806B (zh) | 苝四甲酰二亚胺衍生物 | |
Głowacki et al. | Air-stable organic semiconductors based on 6, 6′-dithienylindigo and polymers thereof | |
Usta et al. | Anthracenedicarboximide-based semiconductors for air-stable, n-channel organic thin-film transistors: materials design, synthesis, and structural characterization | |
JP5438363B2 (ja) | バンドギャップが広いことを特徴とする有機半導体材料 | |
Chen et al. | Asymmetric fused thiophenes for field-effect transistors: crystal structure–film microstructure–transistor performance correlations | |
Yenilmez et al. | Photosensitive field effect transistor based on metallo-phthalocyanines containing (4-pentylphenyl) ethynyl moieties | |
CN102714276A (zh) | 有机半导体材料、有机半导体薄膜以及有机薄膜晶体管 | |
KR20070035208A (ko) | 신규한 질소계 반도체 화합물 및 이를 이용한 소자 | |
KR102043043B1 (ko) | 신규 헤테로시클릭 형광 염료 및 그의 제조 방법 | |
Han et al. | Solution processable low bandgap thienoisoindigo-based small molecules for organic electronic devices | |
Bilgiçli et al. | Nonperipheral tetra phthalocyanines bearing alkyl chain moiety; Synthesis, characterization and fabrication of the OFET based on phthalocyanine | |
Bhagwat et al. | Viscosity-active D-π-A chromophores derived from benzo [b] thiophen-3 (2H)-one 1, 1-dioxide (BTD): Synthesis, photophysical, and NLO properties | |
Park et al. | [1] Benzothieno [3, 2-b][1] benzothiophene-based liquid crystalline organic semiconductor for solution-processed organic thin film transistors | |
Yutronkie et al. | Attaining air stability in high performing n-type phthalocyanine based organic semiconductors | |
Lee et al. | Synthesis and characterization of benzo [b] thieno [2, 3-d] thiophene (BTT) derivatives as solution-processable organic semiconductors for organic field-effect transistors | |
Duan et al. | Organic field-effect transistors based on two phenylene–thiophene oligomer derivatives with a biphenyl or fluorene core | |
Xia et al. | Triarylamino and tricyanovinyl end-capped oligothiophenes with reduced optical gap for photovoltaic applications | |
Xiao et al. | Synthesis, structure and material properties of thiopyranylidene-based asymmetrical squaraines | |
Hu et al. | New Core‐Expanded Naphthalene Diimides for n‐Channel Organic Thin Film Transistors | |
Yun et al. | Side chain engineering of [1] benzothieno [3, 2-b] benzothiophene (BTBT)-based semiconductors for organic field-effect transistors | |
Lu et al. | Fine-tuning the molecular energy levels by incorporating thiophene units onto the π-backbone of core-expanded naphthalene diimides | |
Chen et al. | Langmuir–Blodgett film of new phthalocyanine containing oxadiazol groups and its application in field-effect transistor | |
Tardío et al. | Rational Design of a Multifunctional Benzothiadiazole Derivative in Organic Photonics and Electronics | |
Melville et al. | Functionalization of commercial pigment Hostasol Red GG for incorporation into organic thin-film transistors | |
DE102019114456B4 (de) | Bispyranilidene, Dithiobispyranilidene und Diselenobispyranilidene und deren Verwendung |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant |