WO2013031820A1 - Matériau de couche isolante pour transistor à couche mince organique - Google Patents

Matériau de couche isolante pour transistor à couche mince organique Download PDF

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WO2013031820A1
WO2013031820A1 PCT/JP2012/071813 JP2012071813W WO2013031820A1 WO 2013031820 A1 WO2013031820 A1 WO 2013031820A1 JP 2012071813 W JP2012071813 W JP 2012071813W WO 2013031820 A1 WO2013031820 A1 WO 2013031820A1
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group
insulating layer
film transistor
thin film
organic thin
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PCT/JP2012/071813
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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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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • 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]
    • H10K10/468—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

Definitions

  • the present invention relates to a material suitable for forming an insulating layer of an organic thin film transistor.
  • 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.
  • the organic semiconductor compound used for forming the organic semiconductor layer of the field effect organic thin film transistor is easily affected by the environment such as humidity and oxygen, and the transistor characteristics are likely to deteriorate with time due to humidity, oxygen and the like.
  • an overcoat insulating layer covering the entire element is formed to remove the organic semiconductor compound from contact with the outside air. It is essential to protect.
  • the organic semiconductor compound is coated and protected by a gate insulating layer.
  • an insulating layer material is used to form an overcoat insulating layer, a gate insulating layer, and the like that cover the organic semiconductor layer in the organic thin film transistor.
  • 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 organic thin film transistor insulating layer material is required to have excellent insulating properties and excellent dielectric breakdown strength when formed into a thin film.
  • an organic semiconductor layer is formed so as to overlap with a gate insulating layer. Therefore, the organic thin film transistor gate insulating layer material has an affinity with an organic semiconductor compound for forming an interface in close contact with the organic semiconductor layer, and the surface of the film formed from the organic thin film transistor gate insulating layer material on the organic semiconductor layer side. It is required to be flat.
  • Patent Document 1 describes that an epoxy resin and a silane coupling agent are used in combination as an organic thin film transistor gate insulating layer material.
  • a hydroxyl group produced during the curing reaction of an epoxy resin is reacted with a silane coupling agent. This is because the hydroxyl group enhances the hygroscopicity of the gate insulating layer material and impairs the stability of the transistor performance.
  • Non-Patent Document 1 describes that a resin obtained by thermally cross-linking polyvinylphenol and a melamine compound is used for the gate insulating layer.
  • a resin obtained by thermally cross-linking polyvinylphenol and a melamine compound is used for the gate insulating layer.
  • the hydroxyl group contained in polyvinylphenol is removed by crosslinking with a melamine compound, and at the same time the film strength is increased.
  • the pentacene TFT having this gate insulating layer has a small hysteresis and exhibits durability against gate bias stress.
  • Non-Patent Document 2 describes that polyvinyl gate and a copolymer obtained by copolymerizing vinyl phenol and methyl methacrylate are used for the gate insulating layer.
  • the hydroxyl group of vinylphenol interacts with the carbonyl group of methyl methacrylate to reduce the polarity of the entire film.
  • the pentacene TFT having this gate insulating layer has a small hysteresis and exhibits stable electrical characteristics.
  • the organic thin film transistor having the conventional gate insulating layer has a threshold voltage ( The absolute value and hysteresis of Vth) are large.
  • benzyldiethyldithiocarbamate (Ph-CH 2 -SCSNEt 2 ), a kind of iniferter, dissociates the bond between benzyl carbon and sulfur reversibly when irradiated with ultraviolet light, and the benzyl radical (Ph-CH 2. ) And diethyldithiocarbamyl radical (.SCSNEt 2 ).
  • the bond between benzyl carbon and sulfur is reversibly dissociated by heat.
  • the benzyl radical functions as a polymerization initiator for the vinyl monomer
  • the diethyldithiocarbamyl radical caps the polymerization terminal. Therefore, radical polymerization can proceed to many monomers in a living manner by selecting irradiation conditions (intensity, time) and solution conditions (monomer concentration, monomer / initiator ratio).
  • 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 absolute value of threshold voltage and small hysteresis.
  • the absolute value and hysteresis of the threshold voltage (Vth) of the organic thin film transistor can be reduced by forming the gate insulating layer using a specific resin composition capable of forming a crosslinked structure.
  • the present invention has the formula (1)
  • R 1 represents a hydrogen atom or a methyl group.
  • R 2 and R 3 each independently represents a monovalent organic group having 1 to 20 carbon atoms.
  • the hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom.
  • R aa represents a connecting portion that connects the main chain and the side chain of the polymer compound and may have a fluorine atom.
  • R represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
  • the hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom.
  • a represents an integer of 0 or 1
  • n represents an integer of 1 to 5.
  • the organic thin-film transistor insulating-layer material containing is provided.
  • the said double bond compound (B) is a low molecular double bond compound (B-1) containing two or more double bonds, and two repeating units containing a double bond. It is at least one selected from the group consisting of the polymer double bond compound (B-2) contained above.
  • the low molecular double bond compound (B-1) is represented by the formula (2)
  • R 4 and R 5 each independently represents a monovalent organic group having 1 to 20 carbon atoms.
  • the hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom.
  • the low molecular double bond compound (B-1) is represented by the formula (5)
  • R 8 to R 12 and R 17 to R 21 each independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
  • the hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom.
  • R 13 to R 16 each independently represents a monovalent organic group having 1 to 20 carbon atoms.
  • the hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom.
  • R dd , R ee and R ff each independently represents a divalent organic group having 1 to 20 carbon atoms.
  • a hydrogen atom in the divalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom.
  • p1, p2 and p3 each independently represents an integer of 0 or 1. ] It is a low molecular double bond compound represented by these.
  • the polymer double bond compound (B-2) has the formula (3)
  • R 6 represents a hydrogen atom or a methyl group.
  • R bb represents a connecting part that connects the main chain and the side chain of the polymer compound and may have a fluorine atom.
  • b represents an integer of 0 or 1.
  • R 7 represents a hydrogen atom or a methyl group.
  • R ′ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
  • the hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom.
  • R cc represents a connecting portion that connects the main chain and the side chain of the polymer compound and may have a fluorine atom.
  • c represents an integer of 0 or 1.
  • m represents an integer of 1 to 5. When there are a plurality of R ′, they may be the same or different.
  • It is a polymeric double bond compound containing the at least 1 sort (s) of repeating unit chosen from the group which consists of a repeating unit represented by these.
  • the present invention also provides an organic thin film transistor having an organic thin film transistor insulating layer formed using the organic thin film transistor insulating layer material.
  • the organic thin film transistor insulating layer is a gate insulating layer.
  • the present invention also provides a display member comprising the organic thin film transistor.
  • the present invention also provides a display including the display member.
  • An organic thin film transistor having an insulating layer formed using the organic thin film transistor insulating layer material of the present invention has a low absolute value of threshold voltage and low hysteresis.
  • 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 includes a polymer compound (A) containing a dithiocarbamylmethylphenyl group (—Ph—CH 2 —SCSNR 2 R 3 ) substituted with R 2 and R 3 , It is characterized by containing a binding compound (B). Since the dithiocarbamylmethylphenyl group in the polymer compound (A) and the double bond in the double bond compound (B) react in a living manner, a cured film having a high crosslinking density is formed. When the crosslink density of the organic thin film transistor insulating layer is increased, the movement of the molecular structure is suppressed, and the polarization of the insulating layer is suppressed. When the polarization of the insulating layer is suppressed, for example, when used as a gate insulating layer, the absolute value of the threshold voltage of the organic thin film transistor is lowered, and the operation accuracy is improved.
  • A a polymer compound (A) containing a di
  • the polymer compound (A) is, for example, a polymer compound having a repeating unit represented by the above formula (1).
  • R 1 represents a hydrogen atom or a methyl group. In one certain form, R ⁇ 1 > is a hydrogen atom.
  • R represents a monovalent organic group having 1 to 20 carbon atoms.
  • the hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom.
  • the gate insulating layer formed from the material has low polarity, and there are few components that are easily polarized even when a gate voltage is applied, and the polarization of the gate insulating layer is suppressed. Is done.
  • the organic thin film transistor insulating layer material of the present invention fluorine atoms are not an essential component.
  • the surface of the organic thin film transistor insulating layer containing no fluorine is excellent in affinity with an organic material.
  • the adhesion between the two becomes good. In that case, the flatness of the surface of the formed organic semiconductor layer is improved.
  • an insulating layer coating solution containing the organic thin film transistor insulating layer material and a solution containing no fluorine is applied to a bank having a lyophilic portion and a liquid repellent portion.
  • the movement of the insulating layer coating liquid to the liquid repellent portion of the bank can be suppressed.
  • the film and the organic thin film transistor insulating layer have excellent affinity.
  • a uniform organic semiconductor layer can be formed.
  • 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.
  • Groups, and aromatic hydrocarbon groups having 6 to 20 carbon atoms including straight-chain hydrocarbon groups having 1 to 6 carbon atoms, branched hydrocarbon groups having 3 to 6 carbon atoms, and 3 to 6 carbon atoms.
  • a cyclic hydrocarbon group and an aromatic hydrocarbon group having 6 to 20 carbon atoms are preferred.
  • a hydrogen atom in the group may be substituted with an alkyl group, a chlorine atom, a bromine atom, an iodine atom or the like.
  • the monovalent organic group having 1 to 20 carbon atoms which may be substituted with a fluorine atom include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutyl group, tert-Butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentynyl, cyclohexynyl, trifluoromethyl, trifluoroethyl, phenyl, naphthyl, anthryl, tolyl, xylyl Group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, diethylphenyl group, triethylphenyl group, propylphenyl group, butylphenyl group, methylnaphthy
  • R aa represents a connecting part that connects the main chain and the side chain of the polymer compound and may have a fluorine atom.
  • the connecting portion may be a divalent group having a structure that does not exhibit reactivity under environmental conditions for crosslinking the organic thin film transistor insulating layer material of the present invention.
  • the linking moiety include a bond composed of a divalent organic group having 1 to 20 carbon atoms, an ether bond (—O—), a ketone bond (—CO—), and an ester bond (—COO—, —OCO—).
  • Amide bond (—NHCO—, —CONH—), urethane bond (—NHCOO—, —OCONH—) and a combination of these bonds.
  • a represents an integer of 0 or 1. In one certain form, a is 0.
  • 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.
  • Examples of the divalent organic group having 1 to 20 carbon atoms include a divalent linear aliphatic hydrocarbon group having 1 to 20 carbon atoms and a divalent branched aliphatic hydrocarbon group having 3 to 20 carbon atoms.
  • a divalent linear aliphatic hydrocarbon group having 1 to 6 carbon atoms a divalent branched aliphatic hydrocarbon group having 3 to 6 carbon atoms, and a divalent cyclic hydrocarbon group having 3 to 6 carbon atoms.
  • a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may be substituted with an alkyl group or the like is preferable.
  • Examples of the divalent aliphatic hydrocarbon group and the divalent cyclic 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, a dimethylpropylene group, Examples include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, and a cyclohexylene group.
  • Examples of the divalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may be substituted with an alkyl group include, for example, a phenylene group, a naphthylene group, an anthrylene group, a dimethylphenylene group, a trimethylphenylene group, an ethylenephenylene group, Diethylenephenylene group, triethylenephenylene group, propylenephenylene group, butylenephenylene group, methylnaphthylene group, dimethylnaphthylene group, trimethylnaphthylene group, vinylnaphthylene group, ethenylnaphthylene group, methylanthrylene group, and An ethylanthrylene group may be mentioned.
  • R 2 and R 3 each independently represent a monovalent organic group having 1 to 20 carbon atoms.
  • the hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom.
  • Definitions and specific examples of monovalent organic groups having 1 to 20 carbon atoms represented by R 2 and R 3 are the definitions and specific examples of monovalent organic groups having 1 to 20 carbon atoms represented by R described above. Is the same.
  • R ⁇ 2 > and R ⁇ 3 > is an ethyl group.
  • n represents an integer of 1 to 5. In one certain form, n is 1.
  • the polymer compound (A) of the present invention may have a side chain group having a double bond. This is because the number of reaction sites of the dithiocarbamylmethylphenyl group increases and the crosslink density of the cured film increases.
  • the polymer compound (A) is a high polymer containing at least one repeating unit selected from the group consisting of the repeating unit represented by the above formula (3) and the repeating unit represented by the above formula (4).
  • the molecular compound (A-1) is preferable.
  • R 6 represents a hydrogen atom or a methyl group. In some one aspect, R 6 is a methyl group.
  • R bb represents a linking moiety that links the main chain and the side chain of the polymer compound and may have a fluorine atom.
  • the definition and specific examples of the linking moiety represented by R bb are the same as the definition and specific examples of the linking moiety represented by R aa described above.
  • R bb is a bond represented by —COO—CH 2 CH 2 —.
  • b represents an integer of 0 or 1. In one certain form, b is 1.
  • R 7 represents a hydrogen atom or a methyl group. In some one aspect, R 7 is a methyl group.
  • R cc represents a connecting part that connects the main chain and the side chain of the polymer compound and may have a fluorine atom.
  • the definition and specific examples of the connecting part represented by R cc are the same as the definition and specific examples of the connecting part represented by R aa described above.
  • R cc is a bond represented by —COO—CH 2 CH 2 —NH—CO—NH—.
  • c represents an integer of 0 or 1. In one certain form, c is 1.
  • n represents an integer of 1 to 5. In one certain form, m is 1.
  • R ′ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
  • the hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom.
  • the definition and specific examples of the monovalent organic group having 1 to 20 carbon atoms represented by R ′ are the same as the definition and specific examples of the monovalent organic group having 1 to 20 carbon atoms represented by R described above. is there.
  • R ' is a hydrogen atom.
  • the polymer compound (A) used in the present invention is obtained by, for example, a method in which a polymerizable monomer that is a raw material of the repeating unit represented by the formula (1) is polymerized using a photopolymerization initiator or a thermal polymerization initiator. Can be manufactured.
  • Examples of the polymerizable monomer that is a raw material of the repeating unit represented by the formula (1) include N, N-diethyldithiocarbamylmethylstyrene.
  • 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
  • carbonyl compounds such as luketal, benzyl diethy
  • 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 compound that serves as a radical polymerization initiator.
  • the polymer compound (A) has the formula
  • R, R 1 , R aa , a and n are as defined above, and X is a halogen atom.
  • the polymer compound (A) having a side chain group having a double bond includes, for example, a polymerizable monomer that is a raw material of the repeating unit represented by the formula (1) Produced by a method in which a polymerizable monomer having active hydrogen is copolymerized using a photopolymerization initiator or a thermal polymerization initiator and then reacted with a compound containing a functional group that reacts with active hydrogen and a terminal double bond. I can do it.
  • Active hydrogen refers to a hydrogen atom bonded to an atom other than a carbon atom such as an oxygen atom, a nitrogen atom and a sulfur atom.
  • Examples of the polymerizable monomer having active hydrogen include: 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxyphenyl acrylate, Acrylic acid-2-hydroxyphenylethyl 2-aminoethyl methacrylate, methacrylic acid-2-hydroxyethyl, methacrylic acid-2-hydroxypropyl, methacrylic acid-3-hydroxypropyl, methacrylic acid-2-hydroxybutyl 4-hydroxyphenyl methacrylate, 2-hydroxyphenyl ethyl methacrylate, 4-aminostyrene, 4-allylaniline, 4-aminophenyl vinyl ether, 4- (N-phenylamino) phenyl allyl ether, 4- (N Methylamino) phenyl allyl ether, 4-aminophenyl allyl ether, allylamine, 2-aminoethyl acrylate, 4-hydroxy
  • Examples of the compound containing a functional group that reacts with active hydrogen and a terminal double bond include acryloyl chloride, methacryloyl chloride, acrylic anhydride, methacrylic anhydride, 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate, Examples include 4-vinylbenzoyl chloride and 4-vinylphenyl isocyanate.
  • the polymer compound (A) and the polymer compound (A-1) polymerize a polymerizable monomer other than a polymerizable monomer that is a raw material of the repeating unit represented by the formula (1) and a polymerizable monomer having active hydrogen. Sometimes it may be added and manufactured.
  • Additional polymerizable monomers used include, for example, monomers having a double bond and an isocyanato group blocked with a blocking agent or an isothiocyanate group blocked with a blocking agent, acrylates and derivatives thereof, Acrylic esters and derivatives thereof, styrene and derivatives thereof, vinyl acetate and derivatives thereof, methacrylonitrile and derivatives thereof, acrylonitrile and derivatives thereof, vinyl esters of organic carboxylic acids and derivatives thereof, allyl esters of organic carboxylic acids and derivatives thereof, fumar Dialkyl esters of acids and derivatives thereof, dialkyl esters of maleic acid and derivatives thereof, dialkyl esters of itaconic acid and derivatives thereof, N-vinylamide derivatives of organic carboxylic acids, terminal unsaturated hydrocarbons and derivatives thereof, and , Organogermanium derivatives containing an unsaturated hydrocarbon group.
  • the type of polymerizable monomer used additionally is appropriately selected according to the characteristics required for the insulating layer. From the viewpoint of excellent durability against solvents and reducing the hysteresis of organic thin film transistors, monomers that have high molecular density and form a hard film are selected in films containing these compounds, such as styrene and styrene derivatives. . Further, from the viewpoint of adhesion to the adjacent surface of the insulating layer such as the gate electrode or the surface of the substrate, the polymer compounds (A) and (A) such as methacrylic acid ester and derivatives thereof, acrylic acid ester and derivatives thereof, and the like. A monomer that imparts plasticity to -1) is selected.
  • Examples of the monomer having an isocyanate group blocked with the blocking agent and a double bond include 2- [O- [1′-methylpropylideneamino] carboxyamino] ethyl-methacrylate and 2- [N -[1 ', 3'-dimethylpyrazolyl] carbonylamino] ethyl-methacrylate.
  • Examples of the monomer having an isothiocyanate group blocked with the blocking agent and a double bond include 2- [O- [1′-methylpropylideneamino] thiocarboxyamino] ethyl-methacrylate and 2- [ N- [1 ′, 3′-dimethylpyrazolyl] thiocarbonylamino] ethyl-methacrylate.
  • the acrylic acid esters and derivatives thereof may be monofunctional acrylates or polyfunctional acrylates although the amount of use is limited.
  • acrylic acid esters and derivatives thereof include methyl acrylate, ethyl acrylate, acrylic acid-n-propyl, isopropyl acrylate, acrylic acid-n-butyl, acrylic acid isobutyl, acrylic acid-sec-butyl, and acrylic acid.
  • the methacrylic acid esters and derivatives thereof may be monofunctional methacrylates, and may be polyfunctional methacrylates although there are restrictions on the amount used.
  • Examples of methacrylic acid esters and derivatives thereof include, for example, methyl methacrylate, ethyl methacrylate, methacrylic acid-n-propyl, isopropyl methacrylate, methacrylic acid-n-butyl, isobutyl methacrylate, -Sec-butyl acrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, Ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4-butanediol dimethacryl
  • styrene and its derivatives examples include styrene, 2,4-dimethyl- ⁇ -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, and 2,5-dimethylstyrene.
  • vinyl esters of organic carboxylic acids and derivatives thereof include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, and divinyl adipate.
  • allyl esters of organic carboxylic acids and derivatives thereof include allyl acetate, allyl benzoate, diallyl adipate, diallyl terephthalate, diallyl isophthalate, and diallyl phthalate.
  • dialkyl ester of fumaric acid and its derivatives examples include dimethyl fumarate, diethyl fumarate, diisopropyl fumarate, di-sec-butyl fumarate, diisobutyl fumarate, di-n-butyl fumarate, di-2 fumarate. -Ethylhexyl and dibenzyl fumarate.
  • dialkyl ester of maleic acid and its derivatives examples include dimethyl maleate, diethyl maleate, diisopropyl maleate, di-sec-butyl maleate, diisobutyl maleate, di-n-butyl maleate, di-2 maleate -Ethylhexyl and dibenzyl maleate.
  • Dialkyl esters of itaconic acid and derivatives thereof include, for example, dimethyl itaconate, diethyl itaconate, diisopropyl itaconate, di-sec-butyl itaconate, diisobutyl itaconate, di-n-butyl itaconate, di-2 itaconate -Ethylhexyl and dibenzyl itaconate.
  • N-vinylamide derivatives of organic carboxylic acids examples include N-methyl-N-vinylacetamide.
  • terminal unsaturated hydrocarbons and derivatives thereof examples include 1-butene, 1-pentene, 1-hexene, 1-octene, vinylcyclohexane, vinyl chloride, and allyl alcohol.
  • Examples of the organic germanium derivative containing an unsaturated hydrocarbon group include allyltrimethylgermanium, allyltriethylgermanium, allyltributylgermanium, trimethylvinylgermanium, and triethylvinylgermanium.
  • acrylic acid alkyl ester methacrylic acid alkyl ester, styrene, acrylonitrile, methacrylonitrile and allyltrimethylgermanium are preferable.
  • the charged molar ratio of the monomer serving as the raw material of the repeating unit represented by the formula (1) is preferably 0.1 mol% or more and 50 mol% or less, more preferably 1 mol among all the monomers involved in the polymerization. % Or more and 30 mol% or less.
  • the weight average molecular weight in terms of polystyrene of the polymer compound (A) and the polymer compound (A-1) is preferably from 3,000 to 1,000,000, more preferably from 5,000 to 500,000.
  • the polymer compound (A) and the polymer compound (A-1) may be linear, branched or cyclic.
  • polymer compound (A) examples include poly (N, N-diethyldithiocarbamylmethylstyrene-co-styrene-co- [2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl- Methacrylate]), poly (N, N-diethyldithiocarbamylmethylstyrene-co-styrene-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]), poly (N, N-diethyldithiocarbamylmethylstyrene-co-styrene-co-acrylonitrile-co- [2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly (N, N-diethyldithiocarbamylmethylsty
  • polymer compound (A-1) examples include poly (N, N-diethyldithiocarbamylmethylstyrene-co-2-methacryloyloxyethyl methacrylate-co-styrene-co- [2- [O- (1 ′ -Methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly (N, N-diethyldithiocarbamylmethylstyrene-co-2-methacryloyloxyethyl methacrylate-co-styrene-co- [2- [1'- (3 ', 5'-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]), poly (N, N-diethyldithiocarbamylmethylstyrene-co-2-methacryloyloxyethyl methacrylate-co-styrene-co-acrylon
  • the double bond compound (B) is preferably a compound having a terminal double bond, and more preferably a compound having two or more terminal double bonds.
  • a terminal double bond means the double bond located in the terminal of the chain
  • the chain portion may be a main chain or a branched chain of the compound.
  • the double bond compound (B) may be a low molecular compound or a high molecular compound.
  • the double bond compound (B) includes a divalent organic group represented by the above formula (2), that is, a divalent organic group having a structure in which a disubstituted carbylene group is bonded to an oxycarbonyloxylene group and It is a low molecular double bond compound (B-1) containing at least one double bond.
  • the organic group represented by the above formula (2) is decomposed when an acid is acted thereon. Therefore, when used with a photoacid generator, the organic thin film transistor insulating layer material of the present invention can exhibit a positive photosensitive function.
  • R 4 and R 5 each independently represents a monovalent organic group having 1 to 20 carbon atoms.
  • the hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom.
  • the definition and specific examples of the monovalent organic group having 1 to 20 carbon atoms represented by R 4 and R 5 are the definition and specific examples of the monovalent organic group having 1 to 20 carbon atoms represented by R described above. Is the same.
  • R 4 and R 5 are methyl groups.
  • a preferred example of the double bond compound (B-1) is a low molecular double bond compound represented by the above formula (5).
  • R 8 to R 12 and R 17 to R 21 represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
  • the hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom.
  • the definition and specific examples of the monovalent organic group having 1 to 20 carbon atoms represented by R 8 to R 12 and R 17 to R 21 are the monovalent organic groups having 1 to 20 carbon atoms represented by R described above. The definition and specific examples of the group are the same.
  • R 8 to R 12 and R 17 to R 21 are hydrogen atoms.
  • R 13 to R 16 represent a monovalent organic group having 1 to 20 carbon atoms.
  • the hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom.
  • the definition and specific examples of the monovalent organic group having 1 to 20 carbon atoms represented by R 13 to R 16 are the definition and specific examples of the monovalent organic group having 1 to 20 carbon atoms represented by R described above. Is the same. In one certain form, R 13 to R 16 are methyl groups.
  • R dd , R ee and R ff each independently represent a divalent organic group having 1 to 20 carbon atoms.
  • a hydrogen atom in the divalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom.
  • 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.
  • Examples of the divalent organic group having 1 to 20 carbon atoms include a divalent linear aliphatic hydrocarbon group having 1 to 20 carbon atoms and a divalent branched aliphatic hydrocarbon group having 3 to 20 carbon atoms.
  • a divalent linear aliphatic hydrocarbon group having 1 to 6 carbon atoms a divalent branched aliphatic hydrocarbon group having 3 to 6 carbon atoms, and a divalent cyclic hydrocarbon group having 3 to 6 carbon atoms.
  • a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may be substituted with an alkyl group or the like is preferable.
  • Examples of the divalent aliphatic hydrocarbon group and the divalent cyclic 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, a dimethylpropylene group, Examples include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, and a cyclohexylene group.
  • Examples of the divalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may be substituted with an alkyl group include, for example, a phenylene group, a naphthylene group, an anthrylene group, a dimethylphenylene group, a trimethylphenylene group, an ethylenephenylene group, Diethylenephenylene group, triethylenephenylene group, propylenephenylene group, butylenephenylene group, methylnaphthylene group, dimethylnaphthylene group, trimethylnaphthylene group, vinylnaphthylene group, ethenylnaphthylene group, methylanthrylene group, and An ethylanthrylene group may be mentioned.
  • p1, p2 and p3 each independently represent an integer of 0 or 1. In one embodiment, p1 is 1, p2 is 1, and p3 is 1.
  • the double bond compound (B-1) is prepared, for example, by reacting bromophenyl chloroformate with 2,5-dimethylhexane-2,5-diol in the presence of a deoxidizing agent, It can be produced by a method of coupling the reaction intermediate and vinylphenylboronic acid.
  • Examples of the double bond compound (B-1) include 2,3-bis (4′-vinylbiphenyl-4-oxycarbonyloxy) butane and 2,5-bis (4′-vinylbiphenyl-4-oxycarbonyl). Oxy) hexane.
  • the double bond compound (B) includes at least one repeating unit selected from the group consisting of a repeating unit represented by the above formula (3) and a repeating unit represented by the above formula (4).
  • This is a polymer double bond compound (B-2) to be contained.
  • the definitions of R 6 , R bb and b are the same as described above.
  • the definitions of R 7 , R cc , R ′, c and m are the same as described above.
  • the polymer double bond compound (B-2) is obtained by, for example, polymerizing a polymerizable monomer having active hydrogen using a photopolymerization initiator or a thermal polymerization initiator, and then reacting with a functional group that reacts with active hydrogen and a terminal group. It can be produced by a method of reacting with a compound containing a heavy bond.
  • the meaning of the polymerizable monomer having active hydrogen is the same as described above.
  • the definition of the compound containing a functional group that reacts with active hydrogen and a terminal double bond is the same as described above.
  • the polymer double bond compound (B-2) may be produced by adding a polymerizable monomer other than the polymerizable monomer having active hydrogen during the polymerization.
  • the addition amount of the double bond compound (B) contained in the organic thin film transistor insulating layer material of the present invention is 0.1 to about 0.1 to the amount of the repeating unit having the first functional group in the polymer compound (A). 1.0 equivalent is preferable, and 0.3 to 5 equivalent is more preferable. When the addition amount of the double bond compound (B) is outside the above range, the formation of the crosslinked structure may be insufficient.
  • the organic thin film transistor insulating layer material of the present invention includes a solvent for mixing and viscosity adjustment, a crosslinking agent used for crosslinking the polymer compound (A) and the polymer compound (A-1), and a combination with the crosslinking agent.
  • Additives used in the process may be included.
  • Solvents used include ether solvents such as tetrahydrofuran and diethyl ether, aliphatic hydrocarbon solvents such as hexane, alicyclic hydrocarbon solvents such as cyclohexane, unsaturated hydrocarbon solvents such as pentene, and aromatic carbonization such as xylene.
  • Examples thereof include a hydrogen solvent, a ketone solvent such as acetone, an acetate solvent such as butyl acetate, an alcohol solvent such as isopropyl alcohol, a halogen solvent such as chloroform, and a mixed solvent of these solvents.
  • the catalyst for promoting a crosslinking reaction, a sensitizer, a leveling agent, a viscosity modifier, etc. can be used.
  • Examples of the catalyst for promoting the crosslinking reaction include a photoacid generator, a thermal acid generator, and a photocationic polymerization initiator.
  • a photoacid generator or a thermal acid generator examples include diazomethane derivatives, triazine derivatives, iodonium salts, and sulfonium salts.
  • the diazomethane derivative examples include bis (cyclohexylsulfonyl) diazomethane.
  • triazine derivatives examples include 2-methyl-4,6-ditrichloromethyl-triazine.
  • the iodonium salt include tolylcumyl iodonium tetrakis (pentafluorophenyl) borate.
  • the sulfonium salt include triphenylsulfonium trifluoromethanesulfonate.
  • crosslinking agent examples include divinylbenzene, trimethylolpropane trimethacrylate, and ethylene glycol dimethacrylate.
  • 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. Among the insulating layers of organic thin film transistors, it is preferably used for forming an overcoat layer or a gate insulating layer.
  • the organic thin film transistor insulating layer material is preferably an organic thin film transistor overcoat layer composition or an organic thin film transistor gate insulating layer composition, and more preferably an organic thin film transistor gate insulating layer material.
  • FIG. 1 is a schematic cross-sectional view showing the structure of a bottom gate top contact organic thin film transistor according to 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 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.
  • the organic thin film transistor insulating layer material of the present invention is suitably used for forming a gate insulating layer as an organic thin film transistor gate insulating layer material. Moreover, it can also be used for forming an overcoat layer as an organic thin film transistor overcoat layer material.
  • 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 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.
  • the organic thin film transistor insulating layer material of the present invention is suitably used for forming a gate insulating layer as an organic thin film transistor gate insulating layer material. Moreover, it can also be used for forming an overcoat layer as an organic thin film transistor overcoat layer material.
  • a solvent or the like is added to prepare an insulating layer coating solution, and the insulating layer coating solution is placed under the gate insulating layer or overcoat layer. It is performed by applying to the surface of the layer located, drying and curing.
  • the organic solvent used in the insulating layer coating solution is not particularly limited as long as it dissolves the organic thin film transistor insulating layer material, but is preferably an organic solvent having a boiling point of 100 ° C. to 200 ° C. at normal pressure. .
  • organic solvent examples include 2-heptanone (boiling point 151 ° C.) and propylene glycol monomethyl ether acetate (boiling point 146 ° C.).
  • a leveling agent, a surfactant, a curing catalyst, and the like can be added to the insulating layer coating solution as necessary.
  • the organic thin film transistor insulating layer material of the present invention can also be used for forming a gate insulating layer as an organic thin film transistor gate insulating layer composition.
  • the insulating layer coating solution can be applied onto the gate electrode by a known method such as spin coating, die coating, screen printing, or ink jet.
  • the formed coating layer is dried as necessary. Drying here means removing the solvent contained in the applied resin composition.
  • the dried coating layer is then cured.
  • Curing means that the organic thin film transistor insulating layer material is crosslinked. Cross-linking of the transistor insulating layer material is performed, for example, by applying electromagnetic wave irradiation or heat to the coating layer.
  • the organic thin film transistor insulating layer material of the present invention When the organic thin film transistor insulating layer material of the present invention is irradiated with electromagnetic wave or electron beam or applied with heat, the N, N-dialkyldithiocarbamyl group is eliminated and the generated radical reacts with the double bond in the double bond compound. A crosslinked structure is formed.
  • the organic thin film transistor insulating layer of the present invention is a step of applying a liquid containing an organic thin film transistor insulating layer material to a base material to form a coating layer on the base material; and irradiating the coating layer with an electromagnetic wave or an electron beam. It can form with the formation method including a process.
  • the organic thin film transistor insulating layer of the present invention is a step of applying a liquid containing an organic thin film transistor insulating layer material to a base material to form a coating layer on the base material; and a step of applying heat to the coating layer Can be formed by a forming method including:
  • the organic thin film transistor insulating layer of the present invention is a step of applying a liquid containing an organic thin film transistor insulating layer material to a base material to form a coating layer on the base material; irradiating the coating layer with an electromagnetic wave or an electron beam And a step of applying heat to the coating layer.
  • the coating layer When heat is applied to the coating layer, the coating layer is heated to a temperature of about 80 to 250 ° C., preferably about 100 to 230 ° C., and maintained for about 5 to 120 minutes, preferably about 10 to 60 minutes. If the heating temperature is too low or the heating time is too short, the insulating layer is not sufficiently crosslinked, and if the heating temperature is too high or the heating time is too long, the insulating layer may be damaged.
  • the irradiation conditions are adjusted in consideration of the degree of crosslinking and damage of the insulating layer.
  • the application condition is adjusted in consideration of the cross-linking of the insulating layer and the degree of damage.
  • the wavelength of the electromagnetic wave to be irradiated is preferably 450 nm or less, more preferably 150 to 410 nm.
  • the organic thin film transistor insulating layer material may be insufficiently crosslinked.
  • electromagnetic waves ultraviolet rays are preferable.
  • 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. Heating can be performed using a heater, an oven, or the like.
  • 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, and octadecyltrimethoxysilane.
  • the substrate 1, gate electrode 2, source electrode 5, drain electrode 6 and organic semiconductor layer 4 may be composed of commonly used materials and methods. Resin or plastic plates, films, glass plates, silicon plates, etc. are used as the material of the substrate. As the electrode material, chromium, gold, silver, aluminum, molybdenum, or the like is used, and the electrode is formed by a known method such as a vapor deposition method, a sputtering method, a printing method, or an ink jet method.
  • a ⁇ -conjugated polymer is used as the organic semiconductor compound for forming the organic semiconductor layer 4.
  • polypyrroles, polythiophenes, polyanilines, polyallylamines, fluorenes, polycarbazoles, polyindoles, poly (P -Phenylene vinylene) and the like can be used.
  • 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 Etc. can be used.
  • the organic semiconductor layer can be formed, for example, by adding a solvent or the like if necessary for the organic semiconductor compound, preparing an organic semiconductor coating solution, applying the organic semiconductor coating solution on the gate insulating layer, and applying the organic semiconductor coating solution to the organic semiconductor coating solution. This is done by drying.
  • the resin constituting the gate insulating layer has a benzene ring and has an affinity for an organic semiconductor compound. Therefore, a uniform and flat interface is formed between the organic semiconductor layer and the gate insulating layer by the coating and drying method.
  • the solvent used in the organic semiconductor coating solution is not particularly limited as long as it dissolves or disperses the organic semiconductor, but is preferably a solvent having a boiling point of 50 ° C. to 200 ° C. at normal pressure.
  • the solvent include chloroform, toluene, anisole, 2-heptanone, and propylene glycol monomethyl ether acetate.
  • the organic semiconductor coating liquid can be applied onto the gate insulating layer by a known method such as spin coating, die coating, screen printing, and ink jet, in the same manner as the insulating layer coating liquid.
  • the organic thin film transistor of the present invention may be coated with an overcoat material for the purpose of protecting the organic thin film transistor and improving the smoothness of the surface.
  • the insulating layer manufactured using the organic thin film transistor insulating layer material of the present invention can be laminated with a flat film or the like, and a laminated structure can be easily formed. Moreover, an organic electroluminescent element can be suitably mounted on the insulating layer.
  • a display member having an organic thin film transistor can be suitably produced using the organic thin film transistor insulating layer material of the present invention.
  • a display provided with a display member can be manufactured using the display member having the organic thin film transistor.
  • the organic thin film transistor insulating layer material of the present invention can also be used for forming a layer included in a transistor other than an insulating layer and a layer included in an organic electroluminescence element.
  • the high molecular compound 1 has the following repeating unit.
  • the numbers in parentheses indicate the mole fraction of repeating units.
  • the high molecular compound 2 has the following repeating unit. The numbers in parentheses indicate the mole fraction of repeating units.
  • the mixture was vigorously stirred and heated to reflux for 24 hours.
  • the viscous reaction mixture was poured into 500 mL of acetone to precipitate a fibrous yellow polymer.
  • the polymer was collected by filtration, washed with acetone and dried in a vacuum oven at 60 ° C. overnight.
  • the resulting polymer is referred to as polymer compound 3.
  • the high molecular compound 3 has the following repeating unit. n indicates the number of repeating units.
  • the flask was washed with 100 ml of toluene, and the washing solution was transferred to a separatory funnel. After the aqueous layer was separated, 50 ml of ion exchange water was added to wash the organic layer with water, and the aqueous layer was separated. After repeating the water washing step three times, the organic layer was separated and dried over anhydrous magnesium sulfate. After completion of drying, anhydrous magnesium sulfate was filtered off, and the filtrate was concentrated on a rotary evaporator.
  • reaction solution was returned to room temperature, and the reaction mixture was transferred to a 500 ml separatory funnel.
  • the flask was washed with 100 ml of toluene, and the washing solution was transferred to a separatory funnel. After the aqueous layer was separated, 50 ml of ion exchange water was added to wash the organic layer with water, and the aqueous layer was separated. After repeating the water washing step three times, the organic layer was separated and dried over anhydrous magnesium sulfate. After drying, anhydrous magnesium sulfate was filtered off, and the filtrate was concentrated with a rotary evaporator and reprecipitated with methanol. The precipitate was filtered and dried to obtain polymer compound 4 as a gray powder. The yield of the high molecular compound 4 was 1.83g.
  • the high molecular compound 4 has the following repeating unit. The numbers in parentheses indicate the mole fraction of repeating units.
  • Example 1 (Production of organic thin film transistor insulating layer material and field effect organic thin film transistor)
  • a 10 ml sample bottle 0.4 g of the polymer compound 2 obtained in Synthesis Example 2, 0.04 g of the double bond compound 1 obtained in Synthesis Example 4 and 3.60 g of propylene glycol monomethyl ether acetate are stirred and stirred. Then, a uniform coating solution 1 as an organic thin film transistor insulating layer material was prepared.
  • the obtained coating solution was filtered using a membrane filter having a pore size of 0.2 ⁇ m, and the filtrate was spin-coated on a glass substrate with a chromium electrode, and then dried at 100 ° C. for 1 minute on a hot plate. Then, it baked at 200 degreeC for 30 minutes on the hotplate in nitrogen, and obtained the gate insulating layer.
  • the polymer compound 3 is dissolved in xylene as a solvent to prepare a solution (organic semiconductor composition) having a concentration of 0.5% by weight, and the solution is filtered through a membrane filter to prepare a coating solution. did.
  • the obtained coating solution is applied on the gate insulating layer by a spin coating method to form an active layer having a thickness of about 30 nm, and then, on the active layer by a vacuum deposition method using a metal mask,
  • a field effect organic thin film transistor was manufactured by forming a source electrode and a drain electrode (having a laminated structure in the order of molybdenum oxide and gold from the active layer side) having a channel length of 20 ⁇ m and a channel width of 2 mm.
  • the field effect organic thin film transistor thus fabricated has the transistor characteristics of a vacuum probe (BCT22MDC-5-5) under the condition that the gate voltage Vg is changed to 20 to -40V and the source-drain voltage Vsd is changed to 0 to -40V.
  • HT-SCU manufactured by Nagase Electronic Equipments Service Co., LTD.
  • the hysteresis of the field effect organic thin film transistor is that the source-drain voltage Vsd is ⁇ 40 V, and the threshold voltage Vth1 and the gate voltage Vg when the gate voltage Vg is changed from 20 V to ⁇ 40 V are changed from ⁇ 40 V to 20 V. It was expressed as a voltage difference from the threshold voltage Vth2. The results are shown in Table 1.
  • Example 2 (Production of organic thin film transistor insulating layer material and field effect organic thin film transistor)
  • a 10 ml sample bottle 0.4 g of the polymer compound 2 obtained in Synthesis Example 2, 0.04 g of the double bond compound 1 obtained in Synthesis Example 4, and 0.04 g of the polymer compound 4 obtained in Synthesis Example 5 were added.
  • 04 g and 4.10 g of propylene glycol monomethyl ether acetate were added and dissolved while stirring to prepare a uniform coating solution 2 as an organic thin film transistor insulating layer material.
  • a field effect organic thin film transistor was prepared in the same manner as in Example 1 except that the coating solution 2 was used instead of the coating solution 1, and the transistor characteristics were measured. The results are shown in Table 1.
  • Example 3 (Production of organic thin film transistor insulating layer material and field effect organic thin film transistor)
  • a photoacid generator (trade name: CPI-210S, Sunapro Co., Ltd.) (0.012 g) and propylene glycol monomethyl ether acetate (1.8 g) were added and dissolved while stirring to prepare a uniform coating solution 3 as an organic thin film transistor insulating layer material.
  • the obtained coating solution 3 was filtered using a membrane filter having a pore size of 0.2 ⁇ m, and the filtrate was spin-coated on a glass substrate with a chromium electrode, and then dried at 100 ° C. for 1 minute on a hot plate. Thereafter, UV light (wavelength 365 nm) was irradiated at 600 mJ / cm 2 using an aligner (manufactured by Canon; PLA-521) and baked in nitrogen at 200 ° C. for 30 minutes to obtain a gate insulating layer. The thickness of the obtained gate insulating layer was 406 nm.
  • a field effect organic thin film transistor was prepared in the same manner as in Example 1 except that the gate insulating layer was prepared, and the transistor characteristics were measured. The results are shown in Table 1.
  • Example 4 (Production of organic thin film transistor insulating layer material and field effect organic thin film transistor)
  • a photoacid generator (trade name: CPI-210S, Sunapro Co., Ltd.) (0.011 g) and propylene glycol monomethyl ether acetate (1.8 g) were added and dissolved while stirring to prepare a uniform coating solution 4 as an organic thin film transistor insulating layer material.
  • a field effect organic thin film transistor was prepared in the same manner as in Example 3 except that the coating solution 4 was used instead of the coating solution 3, and the transistor characteristics were measured. The results are shown in Table 1.
  • the thickness of the obtained gate insulating layer was 421 nm.
  • ⁇ Comparative Example 1> Manufacture of field-effect organic thin-film transistors
  • a field effect organic thin film transistor was prepared in the same manner as in Example 1 except that the coating solution 5 was used instead of the coating solution 1, and the transistor characteristics were measured. The results are shown in Table 1.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Thin Film Transistor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un matériau de couche isolante pour transistor à couche mince organique à l'aide duquel il est possible de fabriquer un transistor à couche mince organique présentant une faible hystérésis et une faible tension de seuil. Le matériau de couche isolante pour transistor à couche mince organique selon la présente invention comporte (A) un composé à haut poids moléculaire contenant un groupe thiocarbamate de benzyle (-Ph-CH2-SCSNR2) dans une molécule, et (B) un composé à liaisons doubles insaturées qui contient au moins deux liaisons doubles insaturées dans la molécule.
PCT/JP2012/071813 2011-09-01 2012-08-29 Matériau de couche isolante pour transistor à couche mince organique WO2013031820A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008244022A (ja) * 2007-03-26 2008-10-09 Kyushu Univ 有機半導体素子およびその製造方法
JP2010010608A (ja) * 2008-06-30 2010-01-14 Sumitomo Chemical Co Ltd 有機薄膜トランジスタ及びその製造方法、並びにこの有機トランジスタを用いたディスプレイ用部材及びディスプレイ
JP2011038062A (ja) * 2008-08-28 2011-02-24 Sumitomo Chemical Co Ltd 樹脂組成物、ゲート絶縁層及び有機薄膜トランジスタ

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008244022A (ja) * 2007-03-26 2008-10-09 Kyushu Univ 有機半導体素子およびその製造方法
JP2010010608A (ja) * 2008-06-30 2010-01-14 Sumitomo Chemical Co Ltd 有機薄膜トランジスタ及びその製造方法、並びにこの有機トランジスタを用いたディスプレイ用部材及びディスプレイ
JP2011038062A (ja) * 2008-08-28 2011-02-24 Sumitomo Chemical Co Ltd 樹脂組成物、ゲート絶縁層及び有機薄膜トランジスタ

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