WO2011158929A1 - Matériau pour couche isolante réticulable par une énergie optique pour transistor organique en film mince, couche isolante d'enrobage et transistor organique en film mince - Google Patents

Matériau pour couche isolante réticulable par une énergie optique pour transistor organique en film mince, couche isolante d'enrobage et transistor organique en film mince Download PDF

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WO2011158929A1
WO2011158929A1 PCT/JP2011/063895 JP2011063895W WO2011158929A1 WO 2011158929 A1 WO2011158929 A1 WO 2011158929A1 JP 2011063895 W JP2011063895 W JP 2011063895W WO 2011158929 A1 WO2011158929 A1 WO 2011158929A1
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group
film transistor
insulating layer
thin film
organic thin
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English (en)
Japanese (ja)
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公 矢作
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住友化学株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F216/14—Monomers containing only one unsaturated aliphatic radical
    • C08F216/1458—Monomers containing nitrogen
    • 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 a potential-jump barrier or a surface barrier
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/468—Insulated gate field-effect transistors [IGFETs] characterised by the gate dielectrics
    • H10K10/471—Insulated gate field-effect transistors [IGFETs] characterised by the gate dielectrics the gate dielectric comprising only organic materials
    • 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
    • H10K85/10—Organic polymers or oligomers
    • H10K85/141—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE

Definitions

  • the present invention relates to a material suitable for forming an insulating layer included in an organic thin film transistor, and particularly to a material suitable for forming an overcoat insulating layer.
  • organic thin film transistors can be manufactured at a lower temperature than inorganic semiconductors
  • plastic substrates and films can be used as the substrate, and by using such a substrate, a flexible, lightweight and hardly breakable element can be obtained.
  • an element can be manufactured by application of a solution containing an organic material or film formation using a printing method, and a large number of elements can be manufactured on a large-area substrate at low cost.
  • a voltage applied to a gate electrode acts on a semiconductor layer through a gate insulating layer to control on / off of a drain current. Therefore, a gate insulating layer is formed between the gate electrode and the semiconductor layer.
  • organic semiconductor compounds used in field effect organic thin film transistors are easily affected by the environment such as humidity and oxygen, and the transistor characteristics are likely to deteriorate over time due to humidity, oxygen and the like.
  • an overcoat insulating layer is formed to cover the entire element structure, and the organic semiconductor compound is separated from the outside air. It is essential to protect against contact.
  • the organic semiconductor compound is coated and protected by a gate insulating layer.
  • a resin composition is used to form an overcoat insulating layer, a gate insulating layer, and the like that cover an organic semiconductor layer.
  • an insulating layer or an insulating film of an organic thin film transistor such as the overcoat insulating layer and the gate insulating layer is referred to as an organic thin film transistor insulating layer.
  • a material used for forming the organic thin film transistor insulating layer is referred to as an organic thin film transistor insulating layer material.
  • the material here is a concept including an amorphous material such as a polymer compound, a composition containing the polymer compound, a resin, and a resin composition.
  • Patent Document 1 the performance of an organic field effect transistor is affected by components or materials other than the organic semiconductor that constitutes the organic field effect transistor, and the use of a low dielectric constant material as a gate insulating layer enables organic performance. It is described that the hysteresis of the field effect transistor is lowered and the threshold voltage is also lowered.
  • amorphous polypropylene, low dielectric constant fluoropolymer such as “TEFLON AF” (trade name) manufactured by DuPont
  • tetrafluoroethylene-based co-polymer such as “CYTOP” (trade name) manufactured by Asahi Glass Co., Ltd. Polymers and the like are used.
  • the organic field effect transistor using the conventional organic thin film transistor insulating layer has a problem that the absolute value of the threshold voltage (Vth) is large.
  • An object of the present invention is to provide an organic thin film transistor insulating layer material capable of producing an organic thin film transistor having a small threshold voltage absolute value.
  • the present invention has the formula (1)
  • X represents a hydrogen atom, a fluorine atom, a chlorine atom or a monovalent organic group having 1 to 20 carbon atoms.
  • a hydrogen atom in the monovalent organic group may be substituted with a fluorine atom.
  • X ′ represents a chlorine atom, a bromine atom or an iodine atom.
  • R 1 and R 2 each independently represents a divalent organic group having 1 to 20 carbon atoms. A hydrogen atom in the divalent organic group may be substituted with a fluorine atom.
  • R ′ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. A hydrogen atom in the monovalent organic group may be substituted with a fluorine atom.
  • a and b each independently represents an integer of 0 to 20.
  • c represents an integer of 1 to 5.
  • X ′′ represents a chlorine atom, a bromine atom or an iodine atom.
  • R 3 and R 4 each independently represents a divalent organic group having 1 to 20 carbon atoms.
  • the hydrogen atom therein may be substituted with a fluorine atom.
  • R ′′ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
  • a hydrogen atom in the monovalent organic group may be substituted with a fluorine atom.
  • d and e each independently represents an integer of 0 to 20.
  • f represents an integer of 1 to 5.
  • X ′ ′′ represents a chlorine atom, a bromine atom or an iodine atom.
  • R 5 represents a divalent organic group having 1 to 20 carbon atoms. A hydrogen atom in the divalent organic group may be substituted with a fluorine atom.
  • R ′ ′′ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. A hydrogen atom in the monovalent organic group may be substituted with a fluorine atom.
  • g represents an integer of 0 to 20, and h represents an integer of 1 to 5.
  • R 6 represents a divalent organic group having 1 to 20 carbon atoms.
  • a hydrogen atom in the divalent organic group may be substituted with a fluorine atom.
  • R 7 to R 13 each independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
  • a hydrogen atom in the monovalent organic group may be substituted with a fluorine atom.
  • j represents an integer of 0 to 20.
  • the organic thin-film transistor insulating-layer material containing the high molecular compound (A) which has at least 1 sort (s) of repeating unit selected from the group consisting of the repeating unit represented by these is provided.
  • the said organic thin-film transistor insulating-layer material further contains the organic solvent (B).
  • the present invention also provides an organic thin film transistor insulating layer formed using any one of the above organic thin film transistor insulating layer materials.
  • the said organic thin-film transistor insulating layer is an overcoat insulating layer.
  • the present invention also provides an organic thin film transistor having any one of the organic thin film transistor insulating layers described above.
  • the organic thin film transistor is a bottom gate top contact organic thin film transistor or a bottom gate bottom contact organic thin film transistor.
  • the present invention also provides a display member including the organic thin film transistor.
  • the present invention also provides a display including the display member.
  • An organic thin film transistor manufactured using the organic thin film transistor insulating layer material of the present invention has a small threshold voltage absolute value.
  • the “polymer compound” refers to a compound having a structure in which a plurality of the same structural units are repeated in the molecule, and includes a so-called dimer.
  • the organic thin film transistor insulating layer material of the present invention contains a polymer compound (A) having a structural unit containing a fluorine atom.
  • the organic thin film transistor insulating layer material of the present invention contains a solvent, an additive, or the like for mixing or viscosity adjustment, if necessary.
  • the polymer compound (A) includes a repeating unit containing a fluorine atom and a functional group that absorbs light energy or electron beam energy to cause a dimerization reaction (referred to as “photodimerization reactive group” in this specification). Having a repeating unit.
  • the insulating layer formed using the organic thin film transistor insulating layer material has low polarity, and polarization of the insulating layer is suppressed. Further, when the photodimerization reactive group is dimerized and a crosslinked structure is formed inside the insulating layer, the movement of molecules in the insulating layer is suppressed, and the polarization of the insulating layer is suppressed. When an insulating layer in which polarization is suppressed is used, the absolute value or hysteresis of the threshold voltage of the organic thin film transistor is lowered, and the operation accuracy is improved.
  • the photodimerization reactive group is a functional group that generates a carbo radical when absorbing light energy or electron beam energy.
  • Carbo radicals can be easily dimerized by radical coupling to form a crosslinked structure inside the insulating layer.
  • the photodimerization reactive group is a functional group that can perform a concerted reaction when absorbing light energy or electron beam energy.
  • Functional groups that can perform a concerted reaction can be dimerized by cycloaddition with each other to form a crosslinked structure inside the insulating layer.
  • the photodimerization reactive group may also react when the organic thin film transistor insulating layer material is formed by the photopolymerization method. Is preferred.
  • Preferable light that the photodimerization reactive group absorbs is ultraviolet light, for example, light having a wavelength of 400 nm or less, preferably 150 to 380 nm.
  • “Dimerization” here means that two molecules of an organic compound are chemically bonded.
  • the molecules to be bound may be the same or different.
  • the chemical structures of the functional groups involved in dimerization in the two molecules to be dimerized may be the same or different.
  • the functional group preferably has a structure and a combination that cause a photodimerization reaction without using a reaction aid such as a catalyst and an initiator. This is because contact with the residue of the reaction aid may cause deterioration of surrounding organic materials.
  • Preferred examples of the photodimerization reactive group include an aryl group in which a hydrogen atom is substituted with a halomethyl group, a vinyl group in which the hydrogen atom at the 2-position is substituted with an aryl group, and an ⁇ in which the hydrogen atom at the ⁇ -position is substituted with an aryl group , ⁇ -unsaturated carbonyl group, and ⁇ , ⁇ -unsaturated carbonyloxy group in which the hydrogen atom at the ⁇ -position is substituted with an aryl group.
  • a phenyl group in which a hydrogen atom is substituted with a halomethyl group a vinyl group in which a hydrogen atom at the 2-position is substituted with a phenyl group, an ⁇ , ⁇ -unsaturated carbonyl group in which a hydrogen atom at the ⁇ -position is substituted with a phenyl group, An ⁇ , ⁇ -unsaturated carbonyloxy group in which the hydrogen atom at the ⁇ -position is substituted with a phenyl group is preferred.
  • a vinyl group in which the hydrogen atom at the 2-position is substituted with an aryl group or a phenyl group an ⁇ , ⁇ -unsaturated carbonyl group in which the hydrogen atom at the ⁇ -position is substituted with an aryl group or a phenyl group, and a hydrogen atom at the ⁇ -position
  • an ⁇ , ⁇ -unsaturated carbonyloxy group substituted with an aryl group or a phenyl group a 2 + 2 cyclization reaction occurs when irradiated with ultraviolet rays or an electron beam, and the organic thin film transistor insulating layer material is crosslinked.
  • the repeating unit having a group containing a fluorine atom is preferably a repeating unit represented by the above formula (1).
  • the repeating unit having a photodimerization reactive group is preferably any of the repeating units represented by the above formulas (2) to (5).
  • X represents a hydrogen atom, a fluorine atom, a chlorine atom or a monovalent organic group having 1 to 20 carbon atoms.
  • a hydrogen atom in the monovalent organic group may be substituted with a fluorine atom.
  • X is a hydrogen atom.
  • the monovalent organic group having 1 to 20 carbon atoms may be linear, branched or cyclic, and may be saturated or unsaturated.
  • Examples of the monovalent organic group having 1 to 20 carbon atoms include a linear hydrocarbon group having 1 to 20 carbon atoms, a branched hydrocarbon group having 3 to 20 carbon atoms, and a cyclic hydrocarbon having 3 to 20 carbon atoms.
  • a hydrogen atom in the group may be substituted with an alkyl group, a halogen atom or the like.
  • Examples of the monovalent organic group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, isopropyl group, isobutyl group, tertiary butyl group, cyclopropyl group, cyclobutyl group, Cyclopentyl group, cyclohexyl group, cyclopentynyl group, cyclohexylinyl group, trifluoromethyl group, trifluoroethyl group, phenyl group, naphthyl group, anthryl group, tolyl group, xylyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl Group, diethylphenyl group, triethylphenyl group, propylphenyl group, butylphenyl group, methylnaphthyl group, dimethylnaphthy
  • R ′ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
  • a hydrogen atom in the monovalent organic group may be substituted with a fluorine atom.
  • R 1 and R 2 each independently represents a divalent organic group having 1 to 20 carbon atoms.
  • a hydrogen atom in the divalent organic group may be substituted with a fluorine atom.
  • R 1 is preferably an alkylene group.
  • X ′ represents a chlorine atom, a bromine atom or an iodine atom.
  • a and b each independently represents an integer of 0 to 20.
  • c represents an integer of 1 to 5.
  • Examples of the monovalent organic group having 1 to 20 carbon atoms include the same groups as the monovalent organic group represented by X.
  • the divalent organic group having 1 to 20 carbon atoms may be linear, branched or cyclic, and may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
  • a divalent linear aliphatic hydrocarbon group having 1 to 20 carbon atoms a divalent branched aliphatic hydrocarbon group having 3 to 20 carbon atoms
  • a divalent cyclic aliphatic carbon group having 3 to 20 carbon atoms examples thereof include a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may be substituted with a hydrogen group, an alkyl group or the like.
  • a divalent linear hydrocarbon group having 1 to 6 carbon atoms a divalent branched hydrocarbon group having 3 to 6 carbon atoms, a divalent cyclic hydrocarbon group having 3 to 6 carbon atoms, an alkyl group, etc.
  • a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may be substituted with is preferable.
  • the divalent aliphatic hydrocarbon group and the divalent cyclic aliphatic hydrocarbon group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, an isopropylene group, an isobutylene group, and a dimethylpropylene group. , Cyclopropylene group, cyclobutylene group, cyclopentylene group, cyclohexylene group and the like.
  • Examples of the divalent aromatic hydrocarbon group having 6 to 20 carbon atoms include phenylene group, naphthylene group, anthrylene group, dimethylphenylene group, trimethylphenylene group, ethylenephenylene group, diethylenephenylene group, triethylenephenylene group, and propylenephenylene group.
  • R 1 is a butylene group
  • X ′ is a chlorine atom
  • R ′ is a hydrogen atom
  • a and c are 1, and b is 0.
  • R ′′ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
  • the hydrogen atom in the monovalent organic group may be substituted with a fluorine atom.
  • 3 and R 4 are each independently a hydrogen atom in the representative.
  • An alkylene group is preferable.
  • X ′′ represents a chlorine atom, a bromine atom or an iodine atom.
  • d and e each independently represents an integer of 0 to 20.
  • f represents an integer of 1 to 5.
  • Examples of the monovalent organic group having 1 to 20 carbon atoms include the same groups as the monovalent organic group represented by X.
  • Examples of the divalent organic group having 1 to 20 carbon atoms include the same groups as the divalent organic group represented by R 1 .
  • R 3 is a butylene group
  • X ′′ is a chlorine atom
  • R ′′ is a hydrogen atom
  • d and f are 1, e is 0.
  • R ′ ′′ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
  • a hydrogen atom in the monovalent organic group may be substituted with a fluorine atom.
  • R 5 represents a divalent organic group having 1 to 20 carbon atoms.
  • a hydrogen atom in the divalent organic group may be substituted with a fluorine atom.
  • X ′′ ′ represents a chlorine atom, a bromine atom or an iodine atom.
  • g represents an integer of 0 to 20, and h represents an integer of 1 to 5.
  • Examples of the monovalent organic group having 1 to 20 carbon atoms include the same groups as the monovalent organic group represented by X.
  • Examples of the divalent organic group having 1 to 20 carbon atoms include the same groups as the divalent organic group represented by R 1 .
  • X ′ ′′ is a chlorine atom
  • R ′ ′′ is a hydrogen atom
  • g is 0, and h is 1.
  • R 7 to R 13 represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. A hydrogen atom in the monovalent organic group may be substituted with a fluorine atom.
  • R 6 represents a divalent organic group having 1 to 20 carbon atoms. A hydrogen atom in the divalent organic group may be substituted with a fluorine atom.
  • j represents an integer of 0 to 20. Examples of the monovalent organic group having 1 to 20 carbon atoms include the same groups as the monovalent organic group represented by X. Examples of the divalent organic group having 1 to 20 carbon atoms include the same groups as the divalent organic group represented by R 1 .
  • R 7 to R 13 are hydrogen atoms
  • R 6 is a butylene group
  • j is 1.
  • the polymer compound (A) is, for example, a polymerizable monomer that is a raw material for the repeating unit represented by the formula (1) and a raw material for the repeating unit that is represented by any one of the formulas (2) to (5). It can be produced by a method in which a polymerizable monomer is copolymerized using a photopolymerization initiator or a thermal polymerization initiator.
  • Examples of the polymerizable monomer that is a raw material for the repeating unit represented by the formula (1) include trifluoroethylene, 1,1,2-trifluoropropylene, and chlorotrifluoroethylene.
  • Examples of the polymerizable monomer that is a raw material of the repeating unit represented by the formula (2) include 4- (3′-chloromethylphenylaminocarbonyloxy) butyl vinyl ether.
  • Examples of the polymerizable monomer that is a raw material for the repeating unit represented by the formula (3) include 4- (3′-chloromethylphenylcarbonyloxy) butyl vinyl ether.
  • Examples of the polymerizable monomer that is a raw material of the repeating unit represented by the formula (4) include 3-chloromethylphenyl vinyl ether. Vinyl cinnamate etc. are mentioned as a polymerizable monomer used as the raw material of the repeating unit represented by Formula (5).
  • photopolymerization initiator examples include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 4-isopropyl-2-hydroxy-2-methylpropiophenone, 2-hydroxy- 2-methylpropiophenone, 4,4′-bis (diethylamino) benzophenone, benzophenone, methyl (o-benzoyl) benzoate, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, -Phenyl-1,2-propanedione-2- (o-benzoyl) oxime, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin octyl ether, benzyl, benzyl dimethyl Ruketaru, benzyl diethyl ketal, carbonyl compounds
  • the wavelength of light irradiated to the polymerizable monomer is 360 nm or more, preferably 360 to 450 nm.
  • the thermal polymerization initiator may be any radical polymerization initiator, such as 2,2′-azobisisobutyronitrile, 2,2′-azobisisovaleronitrile, 2,2 ′. -Azobis (2,4-dimethylvaleronitrile), 4,4'-azobis (4-cyanovaleric acid), 1,1'-azobis (cyclohexanecarbonitrile), 2,2'-azobis (2-methylpropane) ), Azo compounds such as 2,2′-azobis (2-methylpropionamidine) dihydrochloride, ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, acetylacetone peroxide, isobutyl peroxide Oxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxy , Diacyl peroxides such as o-methylbenzoyl peroxide,
  • the polymer compound (A) may be produced as follows. That is, a polymerizable monomer that is a raw material of the repeating unit represented by the formula (1) and a polymerizable monomer that is a raw material of the repeating unit represented by the formula (6), or represented by the formula (1) Using a photopolymerization initiator or a thermal polymerization initiator, a polymerizable monomer that is a raw material of the repeating unit, a polymerizable monomer that is a raw material of the repeating unit represented by formula (6), and another polymerizable monomer To obtain a copolymer.
  • the resulting copolymer is a polymer compound having a repeating unit containing a fluorine atom and a repeating unit containing a hydroxyl group.
  • a commercially available polymer compound may be used. Specific examples of the above-mentioned polymer compound commercially available include “Lumiflon LF906N”, “Lumiflon LF200F”, and “Lumiflon LF810” manufactured by Asahi Glass Co., Ltd.
  • the hydroxyl group contained in the polymer compound is protected using a compound that reacts with the hydroxyl group to give a photodimerization reactive group.
  • R 14 represents a divalent organic group having 1 to 20 carbon atoms.
  • a hydrogen atom in the divalent organic group may be substituted with a fluorine atom.
  • the compound that reacts with the hydroxyl group is specifically a compound that can form a pendant group represented by any one of formulas (2) to (5) by reacting with the hydroxyl group.
  • Examples of such compounds include 2-chloromethylphenyl isocyanate, 3-chloromethylphenyl isocyanate, 3-chloromethylbenzoyl chloride, 4-chloromethylbenzoyl chloride, cinnamoyl chloride, and 2- (2′-chloromethylphenyl) ethyl.
  • the polymer compound used in the present invention may be produced by adding a polymerizable monomer other than the polymerizable monomer used as a raw material for the repeating units represented by the above formulas (1) to (5) during the polymerization. .
  • Examples of the other polymerizable monomers include unsaturated hydrocarbons and derivatives thereof, vinyl ether derivatives and the like.
  • the kind of the other polymerizable monomer is appropriately selected according to characteristics required for an insulating layer such as an overcoat insulating layer.
  • Another preferred form of the polymerizable monomer is a monomer having no active hydrogen-containing group such as an alkyl group.
  • unsaturated hydrocarbons and derivatives thereof examples include 1-butene, 1-pentene, 1-hexene, 1-octene, vinylcyclohexane, vinyl chloride, allyl alcohol and the like.
  • vinyl ether derivatives include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether, and phenyl vinyl ether.
  • butyl vinyl ether and cyclohexyl vinyl ether are preferable.
  • the amount of the polymerizable monomer used as the raw material of the repeating unit represented by the formula (1) is adjusted so that the amount of fluorine introduced into the polymer compound (A) becomes an appropriate amount.
  • the amount of fluorine introduced into the polymer compound (A) is preferably 1 to 60% by mass, more preferably 5 to 50% by mass, and further preferably 5 to 40% by mass with respect to the mass of the polymer compound. It is. When the amount of fluorine is less than 1% by mass or more than 60% by mass, compatibility with the organic solvent (B) may be deteriorated and it may be difficult to prepare a resin composition.
  • the amount of the polymerizable monomer used as the raw material of the repeating unit represented by the above formulas (2) to (6) is adjusted so that the amount of the photodimerization reactive group introduced into the polymer compound (A) becomes an appropriate amount. Is done.
  • the amount of the photodimerization reactive group introduced into the polymer compound (A) is preferably 0.01 to 1 mol%, more preferably 0.05 to 0.5 mol%, based on the mass of the polymer compound. More preferably, it is 0.08 to 0.2 mol%.
  • the amount of the photodimerization reactive group is less than 0.01 mol%, the crosslinking inside the insulating layer becomes insufficient, and the absolute value of the threshold voltage of the organic thin film transistor may increase.
  • the amount of the photodimerization reactive group exceeds 1 mol%, the amount of fluorine in the insulating layer decreases, and the absolute value of the threshold voltage of the organic thin film transistor may increase.
  • the polymer compound (A) has a weight average molecular weight of preferably 3,000 to 1,000,000, more preferably 5,000 to 500,000, and may be linear, branched or cyclic.
  • polymer compound (A) examples include poly (trifluoroethylene-co-butyl vinyl ether-co-4- [3′-chloromethylphenylaminocarbonyloxy] butyl vinyl ether), poly (trifluoro Ethylene-co-butyl vinyl ether-co-4- [3'-chloromethylphenylcarbonyloxy] butyl vinyl ether), poly (trifluoroethylene-co-4-hydroxybutyl vinyl ether-co-3-chloromethylphenyl vinyl ether), poly (Trifluoroethylene-co-4-hydroxybutyl vinyl ether-co-vinyl cinnamate) and the like.
  • Organic solvent (B) is not particularly limited as long as it dissolves the polymer compound (A), for example, but is preferably an organic solvent having a boiling point of 60 ° C. to 200 ° C. at normal pressure.
  • examples of the organic solvent include 2-heptanone, propylene glycol monomethyl ether acetate, 2,3,4,5,6-pentafluorotoluene, octafluorotoluene, 1-butanol and the like.
  • a leveling agent, surfactant, etc. can be added to an organic solvent (B) as needed.
  • the organic thin film transistor insulating material polymer compound (A) and, if necessary, the solvent and additives for mixing and viscosity adjustment are mixed to obtain the organic thin film transistor insulating layer material of the present invention.
  • the organic thin film transistor insulating layer material of the present invention may contain an organic solvent (B).
  • the catalyst for promoting a crosslinking reaction, a leveling agent, a viscosity modifier, etc. can be used.
  • the content of the organic solvent (B) is preferably 100 to 3000 parts by weight, and 150 to 2000 parts by weight with respect to 100 parts by weight of the polymer compound (A). More preferably.
  • the organic thin film transistor insulating layer material of the present invention is a composition used for forming an insulating layer contained in an organic thin film transistor.
  • the material is preferably used for forming an overcoat insulating layer or a gate insulating layer of an organic thin film transistor.
  • the organic thin film transistor insulating layer material used for forming the overcoat insulating layer is referred to as an organic thin film transistor overcoat insulating layer material.
  • An organic thin film transistor insulating layer material used for forming the gate insulating layer is referred to as an organic thin film gate insulating layer material.
  • the organic thin film transistor insulating layer material of the present invention is particularly preferably used for forming an overcoat insulating layer of an organic thin film transistor.
  • the overcoat insulating layer formed using the organic thin film transistor overcoat insulating layer material of the present invention is excellent in insulation and airtightness. Therefore, the organic thin film transistor having the overcoat insulating layer can be stably driven even in the atmosphere.
  • FIG. 1 is a schematic cross-sectional view showing the structure of a bottom gate top contact type organic thin film transistor which is an embodiment of the present invention.
  • the organic thin film transistor includes a substrate 1, a gate electrode 2 formed on the substrate 1, a gate insulating layer 3 formed on the gate electrode 2, an organic semiconductor layer 4 formed on the gate insulating layer 3, A source electrode 5 and a drain electrode 6 formed on the organic semiconductor layer 4 with a channel portion interposed therebetween, and an overcoat insulating layer 7 covering the entire element are provided.
  • a bottom gate top contact type organic thin film transistor includes, for example, a gate electrode formed on a substrate, a gate insulating layer formed on the gate electrode, an organic semiconductor layer formed on the gate insulating layer, and a source electrode formed on the organic semiconductor layer. It can be manufactured by forming a drain electrode and forming an overcoat insulating layer.
  • FIG. 2 is a schematic cross-sectional view showing the structure of a bottom gate bottom contact type organic thin film transistor which is an embodiment of the present invention.
  • a substrate 1 a gate electrode 2 formed on the substrate 1, a gate insulating layer 3 formed on the gate electrode 2, and a channel portion on the gate insulating layer 3 are formed.
  • a source electrode 5 and a drain electrode 6, an organic semiconductor layer 4 formed on the source electrode 5 and the drain electrode 6, and an overcoat insulating layer 7 covering the entire element are provided.
  • a bottom gate bottom contact type organic thin film transistor includes, for example, a gate electrode formed on a substrate, a gate insulating layer formed on the gate electrode, a source electrode and a drain electrode formed on the gate insulating layer, and a source electrode and a drain electrode. It can be manufactured by forming an organic semiconductor layer thereon and forming an overcoat insulating layer.
  • a solvent is added to prepare an insulating layer coating solution, and the insulating layer coating solution is applied to the gate insulating layer or overcoat insulating layer. It is performed by applying, drying and curing on the surface of the underlying layer. The cured insulating layer may be further dried.
  • a leveling agent, a surfactant, a curing catalyst, a sensitizer, and the like can be added to the insulating layer coating solution as necessary.
  • the insulating layer coating solution can be applied onto the gate electrode by known spin coating, die coater, screen printing, ink jet or the like.
  • the formed coating layer is dried as necessary. Drying here means removing the solvent of the applied resin composition.
  • Curing means that the polymer compound (A) is crosslinked.
  • Crosslinking of the polymer compound (A) is performed by irradiating the coating layer with light or an electron beam. This is because crosslinking is formed by radical coupling reaction or cyclization reaction of the photodimerization reactive group of the polymer compound (A).
  • the photodimerization reactive group is an aryl group or a phenyl group substituted with a halomethyl group
  • these groups are bonded to each other by irradiation with light or electron beams, preferably ultraviolet rays or electron beams.
  • the wavelength of the irradiated light is 360 nm or less, preferably 150 to 300 nm. When the wavelength of the irradiated light exceeds 360 nm, the polymer compound (A) may not be sufficiently crosslinked.
  • the photodimerization reactive group is a vinyl group in which the hydrogen atom at the 2-position is substituted with an aryl group or a phenyl group, the ⁇ , ⁇ -unsaturated carbonyl group in which the hydrogen atom at the ⁇ -position is substituted with an aryl group or a phenyl group, and the ⁇ -position Are ⁇ , ⁇ -unsaturated carbonyloxy groups substituted with an aryl group or a phenyl group, these groups are bonded to each other by irradiation with light or an electron beam, preferably ultraviolet rays or an electron beam. To do.
  • the wavelength of the irradiated light is 400 nm or less, preferably 150 to 380 nm. When the wavelength of the irradiated light exceeds 400 nm, the polymer compound (A) may not be sufficiently crosslinked.
  • Irradiation with ultraviolet rays can be performed using, for example, an exposure apparatus used for manufacturing a semiconductor or a UV lamp used for curing a UV curable resin.
  • the electron beam irradiation can be performed using, for example, a micro electron beam irradiation tube. Other irradiation conditions are appropriately determined according to the type and amount of the photodimerization reactive group.
  • a self-assembled monolayer may be formed on the gate insulating layer.
  • the self-assembled monolayer can be formed, for example, by treating the gate insulating layer with a solution obtained by dissolving 1 to 10% by weight of an alkylchlorosilane compound or an alkylalkoxysilane compound in an organic solvent.
  • alkylchlorosilane compound examples include methyltrichlorosilane, ethyltrichlorosilane, butyltrichlorosilane, decyltrichlorosilane, and octadecyltrichlorosilane.
  • alkylalkoxysilane compound examples include methyltrimethoxysilane, ethyltrimethoxysilane, butyltrimethoxysilane, decyltrimethoxysilane, octadecyltrimethoxysilane and the like.
  • the substrate 1, the gate electrode 2, the source electrode 5, the drain electrode 6, and the organic semiconductor layer 4 that constitute the organic thin film transistor may be formed of materials and methods that are usually used.
  • a resin or plastic plate or film, a glass plate, a silicon plate, or the like is used as the substrate material.
  • the material of the electrode chromium, gold, silver, aluminum or the like is used, and it is formed by a known method such as a vapor deposition method, a sputtering method, a printing method, or an ink jet method.
  • ⁇ -conjugated polymers are widely used.
  • polypyrroles, polythiophenes, polyanilines, polyallylamines, fluorenes, polycarbazoles, polyindoles, poly (P-phenylene vinylene) s may be used. it can.
  • low-molecular substances having solubility in organic solvents for example, polycyclic aromatic derivatives such as pentacene, phthalocyanine derivatives, perylene derivatives, tetrathiafulvalene derivatives, tetracyanoquinodimethane derivatives, fullerenes, carbon nanotubes Can be used.
  • specific examples include condensates of 9,9-di-n-octylfluorene-2,7-di (ethylene boronate) and 5,5′-dibromo-2,2′-bithiophene. .
  • the formation of the organic semiconductor layer is performed, for example, by adding an organic semiconductor coating solution by adding a solvent or the like if necessary for the organic semiconductor, and applying and drying this on the gate insulating layer.
  • the solvent used is not particularly limited as long as it dissolves or disperses the organic semiconductor, but preferably has a boiling point of 50 ° C. to 200 ° C. at normal pressure.
  • the solvent include chloroform, toluene, anisole, 2-heptanone, propylene glycol monomethyl ether acetate and the like.
  • the organic semiconductor coating liquid can be applied onto the gate insulating layer by a known spin coating, die coater, screen printing, ink jet, or the like, similarly to the insulating layer coating liquid.
  • a display member having an organic thin film transistor can be suitably produced using the organic thin film transistor of the present invention.
  • a display including the display member can be suitably produced.
  • Synthesis example 1 (Synthesis of polymer compound 1) Asahi Glass Co., Ltd. “Lumiflon LF906N” (trade name) 65.5% xylene solution (OH value: 118 mg KOH / g) 21.50 g, propylene glycol monomethyl ether acetate 50 ml, stir bar with Dimroth and three-way cock Into a 200 ml three-necked flask. The solution in the flask was stirred using a magnetic stirrer to prepare a reaction mixture.
  • “Lumiflon LF906N” (trade name) is a polymer compound having a repeating unit represented by the formula (2-a) and a repeating unit represented by the formula (3-a).
  • X represents a fluorine atom, a chlorine atom or a trifluoromethyl group.
  • R 15 represents an alkylene group.
  • the high molecular compound 1 has the following repeating unit.
  • R 15 represents an alkylene group.
  • Synthesis example 2 (Synthesis of polymer compound 2) Under an inert atmosphere, 2,7-bis (1,3,2-dioxaborolan-2-yl) -9,9-dioctylfluorene (5.20 g), bis (4-bromophenyl)-(4-secondary butylphenyl) ) -Amine (4.50 g), palladium acetate (2.2 mg), tri (2-methylphenyl) phosphine (15.1 mg), methyltrioctylammonium chloride (0.91 g) (manufactured by Aldrich, “Aliquat 336” ( Trade name)) and toluene (70 ml) were mixed and heated to 105 ° C.
  • n in the following formula represents the degree of polymerization.
  • the polymer compound 2 had a polystyrene-reduced weight average molecular weight of 2.6 ⁇ 10 5 .
  • Synthesis example 3 (Synthesis of polymer compound 3) 2,3,4,5,6-pentafluorostyrene (Aldrich) 2.00 g, 2,2′-azobis (2-methylpropionitrile) 0.01 g, 2,3,4,5,6-penta Fluorotoluene (Aldrich) 3.00 g was put in a 50 ml pressure vessel (Ace), bubbled with argon, sealed, and polymerized in an oil bath at 60 ° C. for 24 hours. A 2,3,4,5,6-pentafluorotoluene solution of molecular compound 3 was obtained.
  • n in the following formula represents the degree of polymerization.
  • Synthesis example 4 (Synthesis of polymer compound 4) “Lumiflon LF200F” (trade name) (OH value: 45 mg KOH / g) 16.00 g, Asahi Glass Co., Ltd., 200 ml of toluene, 2.50 g of triethylamine, a stirrer, a 300 ml three-neck flask with a Jimroth and a three-way cock Put in. The solution in the flask was stirred using a magnetic stirrer to prepare a reaction mixture. To the resulting reaction mixture, 3.80 g of cinnamoyl chloride (manufactured by Tokyo Kasei) was added at room temperature (25 ° C.).
  • the flask containing the reaction mixture was immersed in an oil bath and reacted at 100 ° C. for 5 hours. After completion of the reaction, the reaction mixture cooled to room temperature (25 ° C.) was transferred to a separatory funnel, washed with an aqueous sodium carbonate solution, and then washed with water. After washing with water, the organic layer was separated, and the organic layer was dried using anhydrous magnesium sulfate, and then the solvent was distilled off using a rotary evaporator to obtain polymer compound 4 which was a viscous solid.
  • “Lumiflon LF200F” (trade name) is a polymer compound having a repeating unit represented by the formula (2-a) and a repeating unit represented by the formula (3-a).
  • X represents a fluorine atom, a chlorine atom or a trifluoromethyl group.
  • R 15 represents an alkylene group.
  • the high molecular compound 4 has the following repeating unit.
  • R 15 represents an alkylene group.
  • Example 1 (Preparation of organic thin film transistor insulating layer material 1) 2.00 g of the polymer compound 1 was dissolved in 8.00 g of propylene glycol monomethyl ether acetate and filtered through a membrane filter having a pore diameter of 0.45 ⁇ m to prepare an organic thin film transistor insulating layer material 1.
  • the polymer compound 2 was dissolved in xylene as a solvent to prepare a solution (organic semiconductor composition) having a concentration of 0.5% by weight, and this was filtered through a membrane filter to prepare a coating solution.
  • the obtained coating solution containing the polymer compound 2 is applied on a bottom gate bottom contact element (manufactured by Kyodo Inter) by a spin coating method and dried in nitrogen at 200 ° C. for 10 minutes to obtain an active layer having a thickness of about 60 nm. Formed.
  • an organic thin film transistor insulating layer material 1 which is an organic thin film transistor overcoat insulating layer material is applied onto the obtained active layer by a spin coating method, dried at 100 ° C. for 10 minutes in nitrogen, and UV / ozone in argon. After irradiating with ultraviolet rays (wavelength 254 nm) for 1 minute using a stripper (Model UV-1, manufactured by Samco), it is further dried at 200 ° C. for 30 minutes in nitrogen to form an overcoat insulating layer having a thickness of about 3.4 ⁇ m. Then, a field effect organic thin film transistor 1 was produced.
  • Example 2 (Preparation of organic thin film transistor insulating layer material 2) 2.00 g of the polymer compound 4 was dissolved in 8.00 g of 2,3,4,5,6-pentafluorotoluene and filtered through a membrane filter having a pore diameter of 0.45 ⁇ m to prepare an organic thin film transistor insulating layer material 2.
  • the polymer compound 2 was dissolved in xylene as a solvent to prepare a solution (organic semiconductor composition) having a concentration of 0.5% by weight, and this was filtered through a membrane filter to prepare a coating solution.
  • the obtained coating solution containing the polymer compound 2 is applied on a bottom gate bottom contact element (manufactured by Kyodo Inter) by a spin coating method and dried in nitrogen at 200 ° C. for 10 minutes to obtain an active layer having a thickness of about 60 nm. Formed.
  • an organic thin film transistor insulating layer material 2 which is an organic thin film transistor overcoat insulating layer material is applied onto the obtained active layer by a spin coating method, dried in nitrogen at 100 ° C. for 10 minutes, and aligned (PLA-521;
  • An overcoat insulating layer having a thickness of about 3.4 ⁇ m was formed by irradiating ultraviolet rays (wavelength 365 nm) of 6000 mJ / cm 2 using Canon, to produce a field effect organic thin film transistor 2.
  • Comparative Example 1 (Production of field-effect organic thin-film transistors) Instead of organic thin film transistor insulating layer material 1, 1.00 g of 2,3,4,5,6-pentafluorotoluene is added to 1.00 g of 2,3,4,5,6-pentafluorotoluene solution of polymer compound 3.
  • a field effect organic thin film transistor was prepared in the same manner as in Example 2 except that the organic thin film transistor insulating layer material 3 prepared by adding and filtering through a membrane filter having a pore diameter of 0.45 ⁇ m was used. It was measured. The thickness of the overcoat insulating layer was about 6 ⁇ m.
  • the absolute value of the threshold voltage was 40 V or more, and the device was not driven under the conditions where the gate voltage Vg was changed to 20 to ⁇ 40 V and the source-drain voltage Vsd was changed to 0 to ⁇ 40 V.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Thin Film Transistor (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un matériau pour couche isolante pour transistor organique en film mince, qui permet la production d'un transistor organique en film mince caractérisé par une tension de seuil de faible valeur absolue. Plus spécifiquement, l'invention concerne un matériau pour couche isolante pour transistor organique en film mince, caractérisé en ce qu'il contient un composé polymère (A) doté d'un motif répété contenant un groupe d'atomes de fluor et un autre motif répété contenant un groupe fonctionnel qui absorbe l'énergie optique ou l'énergie d'un faisceau d'électrons et provoque une réaction de dimérisation.
PCT/JP2011/063895 2010-06-17 2011-06-17 Matériau pour couche isolante réticulable par une énergie optique pour transistor organique en film mince, couche isolante d'enrobage et transistor organique en film mince WO2011158929A1 (fr)

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Cited By (1)

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WO2016100983A1 (fr) * 2014-12-19 2016-06-23 Polyera Corporation Compositions photoréticulables, diélectriques structurés en couche mince à constante k élevée et dispositifs associés

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JP6161636B2 (ja) * 2012-02-07 2017-07-12 フレックステラ， インコーポレイテッドＦｌｅｘｔｅｒｒａ， Ｉｎｃ． 光硬化性高分子材料および関連電子デバイス
JP5980522B2 (ja) * 2012-02-17 2016-08-31 住友化学株式会社 有機薄膜トランジスタ絶縁層材料

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JPH1160992A (ja) * 1997-08-22 1999-03-05 Asahi Glass Co Ltd 紫外線硬化性被覆用組成物
WO2010024238A1 (fr) * 2008-08-28 2010-03-04 住友化学株式会社 Composition de résine, couche d’isolation de grille et transistor à couches minces organiques

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JP2005513788A (ja) * 2001-12-19 2005-05-12 アベシア・リミテッド 有機誘電体を有する有機電界効果トランジスタ
JP2003201464A (ja) * 2002-01-09 2003-07-18 Asahi Glass Co Ltd 表面を被覆されたシーリング材およびシーリング材表面被覆用組成物
JP5137296B2 (ja) * 2004-03-19 2013-02-06 三菱化学株式会社 電界効果トランジスタ
JP2007322869A (ja) * 2006-06-02 2007-12-13 Kyushu Univ 表示装置
KR101581065B1 (ko) * 2008-04-24 2015-12-29 메르크 파텐트 게엠베하 전자 디바이스

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JPS61101083A (ja) * 1984-10-24 1986-05-19 Matsushita Electric Ind Co Ltd 太陽電池モジユ−ル
JPH1160992A (ja) * 1997-08-22 1999-03-05 Asahi Glass Co Ltd 紫外線硬化性被覆用組成物
WO2010024238A1 (fr) * 2008-08-28 2010-03-04 住友化学株式会社 Composition de résine, couche d’isolation de grille et transistor à couches minces organiques

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016100983A1 (fr) * 2014-12-19 2016-06-23 Polyera Corporation Compositions photoréticulables, diélectriques structurés en couche mince à constante k élevée et dispositifs associés

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