WO2013187507A1 - Film d'isolation et transistor organique en film mince utilisant ledit film - Google Patents

Film d'isolation et transistor organique en film mince utilisant ledit film Download PDF

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Publication number
WO2013187507A1
WO2013187507A1 PCT/JP2013/066493 JP2013066493W WO2013187507A1 WO 2013187507 A1 WO2013187507 A1 WO 2013187507A1 JP 2013066493 W JP2013066493 W JP 2013066493W WO 2013187507 A1 WO2013187507 A1 WO 2013187507A1
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active energy
energy ray
insulating film
group
compound
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PCT/JP2013/066493
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English (en)
Japanese (ja)
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正義 高武
大塚　俊一
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Dic株式会社
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Priority to JP2014521432A priority Critical patent/JP5664828B2/ja
Publication of WO2013187507A1 publication Critical patent/WO2013187507A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
    • 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 an insulating film for active energy ray-curable semiconductor for insulating film and an organic thin film transistor manufacturing method using the same.
  • the insulating film is one of the most important components in the functional layer of the printed organic transistor.
  • Polysilsesquioxane compounds which are organic-inorganic hybrid materials, are attracting attention as insulating materials that can be applied in wet processes and have performance equivalent to that of inorganic insulating films used in conventional silicon processes. Has been.
  • Patent Document 1 A method in which a non-reactive polysilsesquioxane is mixed with a monomer containing a (meth) acryloyl group, which is coated on a support and irradiated with active energy rays to form an insulating film (Patent Document 1) ) And active energy ray-curable compositions (Patent Document 2) containing a silsesquioxane containing a (meth) acryloyl group, a urethane (meth) acrylate oligomer, and a monofunctional (meth) acrylate. Yes.
  • Non-patent Document 1 an active energy ray-curable composition containing a silsesquioxane containing a (meth) acryloyl group and an acrylate ester of tris (2-hydroxylethyl) isocyanuric acid is also known. .
  • the ink described in Patent Document 1 has an advantage that an insulating film can be obtained in a short time at a low temperature, the ink itself has substantially no activity on polysilsesquioxane which does not have crosslinkability by active energy rays.
  • An energy ray polymerizable (meth) acrylic acid ester compound is mixed, and the insulating film obtained therefrom is interspersed with the polysilsesquioxane molecules in the polymer network of the active energy ray polymerizable compound. The insulating film is trapped and dispersed.
  • the insulating film has the greatest influence on the thin film transistor (TFT) characteristics, but in the insulating film obtained from the ink of Patent Document 1, there is no covalent bond between the polysilsesquioxane molecule and the polymer molecule. For this reason, the excellent characteristics that polysilsesquioxane is supposed to have are not sufficiently drawn out, for example, only an organic thin film transistor having poor field effect mobility and ON / OFF ratio can be obtained. Is inherent.
  • Non-Patent Document 1 The cured product of the composition described in Non-Patent Document 1 is not used as an insulating film, and a polymer film with a bifunctional (meth) acrylate having a cyclic structure is assumed to be applied to an organic thin film transistor The field effect mobility and the ON / OFF ratio were still unsatisfactory.
  • the technical problem to be solved by the present invention is that it has a high field-effect mobility, an ON / OFF ratio, a normally-off threshold voltage (Vth) with little fluctuation, and an excellent performance that can withstand practical use.
  • An object of the present invention is to provide an insulating film formed by active energy ray curing that enables the formation of an organic transistor.
  • the inventors of the present invention have intensively studied in view of the above-described practical use, and use a compound containing a specific active energy ray polymerizable double bond in combination with a silsesquioxane compound having active energy ray polymerizability.
  • the present invention has been completed by finding that a highly practical transistor having a high degree and an ON / OFF ratio, which is normally off, has little fluctuation in threshold voltage (Vth), and has excellent characteristic stability can be formed.
  • an active energy ray-curable ink comprising an active energy ray polymerizable group (A) having an active energy ray polymerizable group and a crosslinking promoting compound (B) having two or more active energy ray polymerizable groups as essential components is used as an active energy ray.
  • A active energy ray polymerizable group
  • B crosslinking promoting compound
  • the semiconductor insulating film cross-linked with The film thickness is in the range of 0.1 ⁇ m to 5 ⁇ m
  • An insulating film for semiconductor, wherein the water contact angle of the surface of the film is 85 ° to 115 °, 2.
  • the active energy ray polymerizable group of the silsesquioxane compound (A) having an active energy ray polymerizable group is a (meth) acryloyl group or an oxetanyl group.
  • the crosslinking accelerator compound (B) having two or more active energy ray polymerizable groups is a compound having 3 to 6 (meth) acryloyl groups, or a maleimide compound. Or 2. Insulating films for semiconductors, 4).
  • the active energy ray-curable ink contains an active energy ray-polymerizable fluorosurfactant. ⁇ 3.
  • the insulating film of the present invention can be applied as a gate insulating film, an interlayer insulating film, a protective film or the like of a thin film transistor.
  • a gate insulating film of an organic transistor such as a TFT
  • it has excellent field effect mobility and ON / OFF ratio, is normally off, and has a threshold voltage with little variation.
  • Organic transistors can be formed.
  • the transistor of the present invention uses a crosslinked insulating film in a substantially non-heated / short-time manner by active energy rays such as UV, EB, and visible light, so that there is no thermal damage to the film substrate and the like.
  • active energy rays such as UV, EB, and visible light
  • the insulating film of the present invention is an active energy ray comprising, as essential components, a silsesquioxane compound (A) having an active energy ray polymerizable group and a crosslinking promoting compound (B) having two or more active energy ray polymerizable groups.
  • Silsesquioxane means a trifunctional polysiloxane represented by the unit composition formula (RSiO 3/2 ) n, and the R is well known that has a methyl group and / or a phenyl group.
  • Polysiloxanes, so-called silicones are represented by the unit composition formula R 2 SiO, silicas are likewise represented by SiO 2, and these are clearly distinguished by definition from silsesquioxanes, It is located between silicone and silica.
  • silsesquioxane structure a random structure, a complete cage structure, a ladder structure, an incomplete cage structure, and the like are known.
  • the silsesquioxane compound described in the present invention is not limited to such a structure, and may be a single product of these structures, a mixture of compounds, or a structure in which a plurality of these structures are connected. It may be a compound.
  • the silsesquioxane compound (A) having an active energy ray-polymerizable group used for forming the insulating film of the present invention may have a silsesquioxane structure as a main skeleton, for example, a silicone structure in the same molecule. You may have.
  • a silicone structure a dimethylsiloxane structure is preferable in that the surface energy of the cured product can be reduced to obtain a liquid-repellent surface.
  • the cissesquioxane compound has a so-called active energy ray functional group that directly or indirectly forms a crosslinked structure by an active energy ray such as UV, EB, or xenon lamp light.
  • these functional groups include (meth) acryloyl group, oxetane group, epoxy group, thiol group, maleimide group, various alkylene groups such as methylene and ethylene, isocyanate group, hydroxyl group, alkoxysilyl group and the like.
  • These silsesquioxane compounds having a functional group may be used alone, may be a mixture of silsesquioxane compounds having different functional groups, or may have different functional groups in the same molecule.
  • cissesquioxane having a (meth) acryloyl group or an oxetane group as a functional group is excellent in storage stability and crosslinkability upon irradiation with active energy rays.
  • silsesquioxane compound containing a (meth) acryloyl group for example, MAC grade or AC grade of Toa Gosei Co., Ltd. SQ series can be used.
  • the MAC grade is a silsesquioxane compound containing a methacryloyl group, and specific examples include MAC-SQ TM-100, MAC-SQ SI-20, MAC-SQ HDM, and the AC grade is Are silsesquioxane compounds containing an acryloyl group, and specific examples thereof include, for example, AC-SQ TA-100, AC-SQ SI-20, and the like.
  • silsesquioxane compound having an oxetanyl group as a functional group for example, OX grade of Toa Gosei Co., Ltd. SQ series can be used. Specific examples include OX-SQ SI-20, OX-SQ ME-20, OX-SQ HDX, and the like.
  • a polystyrene equivalent value measured using a gel permeation chromatography (GPC) method can be adopted.
  • a nuclear magnetic resonance spectrum method focusing on a hydrogen atom ( 1 H) or a silicon atom ( 29 Si) is an extremely useful method.
  • the number of adjacent oxygen atoms to which silicon atoms are bonded can be quantified.
  • the mass content of silsesquioxane in all cross-linking components of the insulating film for semiconductor of the present invention is preferably 30% to 80%, more preferably 40% to 70%.
  • the content of the silsesquioxane structure is less than this range, the high frequency response of the insulating film is lowered, which is not preferable.
  • the silsesquioxane structure is larger than this and the remaining crosslinking auxiliary component is 20% or less, the crosslinking density of the insulating film is not sufficient, and the voltage resistance and solvent resistance of the film are lowered, which is not preferable.
  • the semiconductor insulating film of the present invention is characterized in that it is crosslinked and cured by active energy rays, but if necessary, heat treatment such as pre-cure and post-cure can be performed.
  • the insulating film for semiconductor of the present invention is a polymerized crosslinked film having a reaction rate of active energy ray polymerizable groups of 85% or more, and includes toluene, xylene, chloroform, THF, acetone, mesitylene, chlorobenzene, dichlorobenzene, mesitylene, It is characterized by having substantial resistance to organic semiconductor solvents such as hydrocarbons, aromatics, and halogens such as tetralin and anisole.
  • the reaction rate of the active energy ray polymerizable group can be easily confirmed by IR measurement of the cured film. *
  • the insulating film for a semiconductor essentially comprises a silsesquioxane compound (A) having an active energy ray polymerizable group and a crosslinking promoting compound (B) containing at least two active energy ray polymerizable groups in the molecule. It is a polymer film obtained by subjecting active energy ray-curable ink as a component to active energy ray polymerization.
  • a crosslinking accelerating compound (B) containing two or more active energy ray-polymerizable groups in the molecule By mixing the silsesquioxane compound (A) having an active energy ray-polymerizable group with a crosslinking accelerating compound (B) containing two or more active energy ray-polymerizable groups in the molecule, the active energy ray is substantially increased.
  • a stronger cross-linking structure can be formed than only by curing, and film quality required for a semiconductor insulating film such as thin film forming property and solvent resistance can be realized.
  • the active energy ray polymerizable group of the crosslinking accelerating compound (B) mentioned here has a so-called functional group that directly or indirectly forms a crosslinked structure by active energy rays such as UV, EB, xenon lamp light, etc. To do.
  • these functional groups include (meth) acryloyl group, oxetanyl group, epoxy group, thiol group, maleimide group, various alkylene groups such as methylene and ethylene, isocyanate group, hydroxyl group, alkoxysilyl group and the like.
  • Which functional group has a bifunctional or higher functional crosslinking accelerator (B) depends on the reactivity with the active energy ray-polymerizable group of the silsesquioxane compound used in the present invention and the type of active energy ray to be applied. It can be selected as appropriate.
  • silsesquioxane compound (A) having a (meth) acryloyl group as a functional group When the silsesquioxane compound (A) having a (meth) acryloyl group as a functional group is used, a bifunctional or higher functional crosslinking accelerator (B) having a (meth) acryloyl group, a thiol group, and a maleimide group can be suitably applied. .
  • crosslinking accelerating compound (B) having a (meth) acryloyl group various epoxy acrylates, various urethane acrylates, various polyester acrylates, various polybutadiene acrylates, various silicone acrylates, various amino resin acrylates, and the like can be used.
  • these compounds include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, tetramethylene ether glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane or alkylene oxide addition thereof.
  • cyclic structure such as (meth) acrylate, pentaerythritol or its alkylene oxide adduct tetra (meth) acrylate containing three polymerizable double bonds that do not have a cyclic structure such as tri (meth) acrylate.
  • polymerizable double bonds having no cyclic structure such as (meth) acrylate containing 4 polymerizable double bonds, dipentaerythritol or hexa (meth) acrylate of its alkylene oxide adduct (Meta) Acry And two or more polymerizable double bonds having a cyclic structure such as an adduct of tris (2-hydroxylethyl) isocyanuric acid, an acrylate ester of isophorone diisocyanate and hydroxyethyl (meth) acrylate.
  • a cyclic structure such as an adduct of tris (2-hydroxylethyl) isocyanuric acid, an acrylate ester of isophorone diisocyanate and hydroxyethyl (meth) acrylate.
  • Styrene compounds such as acrylate, styrene, ⁇ -methylstyrene, t-butylstyrene, methyl (meth) acrylate, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, ( Compounds containing one (meth) acryloyl group such as (meth) acrylic acid esters such as stearyl methacrylate and benzyl (meth) acrylate, polyether (meth) acrylate, polyester (meth) acrylate, polyurethane 100 molecular weight, such as (meth) acrylate Examples include oligo (meth) acrylates exceeding 0.
  • bi- or more functional crosslinking accelerating compound (B) having a thiol group as a functional group examples include trimethylol ethane tris (3-mercaptobutyrate) trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercapto) Butyrate), 1,4 bis (3-mercaptobutyloxy) butane and the like can be suitably used.
  • a crosslinking accelerator compound (B) having an epoxy group or a vinyl ether group as a functional group can be preferably used.
  • examples of such compounds include bisphenol A type epoxy, bisphenol BA type epoxy, bisphenol F type epoxy, bisphenol AD type epoxy, phenol novolac type epoxy, cresol novolak type epoxy, alicyclic epoxy, fluorene type epoxy, naphthalene type epoxy, Examples thereof include glycidyl ester compounds, glycidyl amine compounds, heterocyclic epoxies, ⁇ -olefin epoxies, and the like.
  • the alicyclic epoxy compound can be suitably applied because an excellent cured film can be obtained.
  • alicyclic epoxy examples include 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate and its ⁇ -caprolactone modified product, bis- (3,4 epoxycyclohexylmethyl) adipate, diepoxy limonene and the like. It can be used suitably.
  • Oxetane compounds such as methyl ⁇ oxetane, vinyl compounds such as diallyl phthalate, divinylethylene urea, divinyl adipate, ethylene glycol, trimethylolpropane, various polyether polyols, various polyester polyols, and various caprolactone polyols can be applied.
  • a compound containing a vinyl ether group and an epoxy group in the same molecule, a reactive compound having a propenyl ether group and an epoxy group, and the like can be applied.
  • Hybridization is performed by, for example, mixing a radical curable component such as an acroyl group-containing compound and a radical curing initiator as necessary with a cationic curable composition containing an epoxy compound, an oxetane compound, a vinyl compound or the like as a reactive compound. Is obtained.
  • acroyl group-containing compound examples include compounds having a cationic polymerizable vinyl ether and a radical polymerizable acroyl group in the same molecule, such as (meth) acrylic acid (vinyloxy) ether.
  • the silsesquioxane compound containing the (meth) acryloyl group and / or oxetanyl group of the present invention is used in combination with a maleimide compound as the crosslinking accelerator compound (B).
  • a mixture of a silsesquioxane compound containing a (meth) acryloyl group and a maleimide compound is an active energy ray, and even when UV light is used, a cross-linked and cured semiconductor without substantially using a photopolymerization initiator described later. It is possible to obtain an insulating film for use.
  • the present inventors have found that when the present insulating film is applied to a gate insulating film of an organic transistor, the field effect mobility of the organic transistor is remarkably improved, and the present invention has been achieved.
  • maleimide compounds (B) examples include 4,4′-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, and 4-methyl-1,3-phenylene bismaleimide. 1,6-bismaleimide- (2,2,4-trimethyl) hexane, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide, maleimide acrylate, etc. may be used. I can do it.
  • n and n each independently represent an integer of 1 to 5, and m + n is 6 or less.
  • R 11 and R 12 each independently represent a hydrocarbon bond selected from the group consisting of an alkylene group, a cycloalkylene group, and a cycloalkylalkylene group.
  • G 1 and G 2 each independently represent an ester bond represented by —COO— or —OCO—.
  • R 2 is an average molecular weight in which at least one organic group selected from the group consisting of a linear alkylene group, a branched alkylene group, and a cycloalkylene group is bound by at least one bond selected from the group consisting of an ether bond and an ester bond 100 to 100,000 (poly) ether linkage chains or (poly) ester linkage chains).
  • the maleimide compound represented by the general formula (2) is applied.
  • k represents an integer of ⁇ 10
  • n represents a value selected so that the number average molecular weight of the polyether chain is in the range of 100 to 100,000.
  • the semiconductor insulating film of the present invention is characterized in that the film surface is liquid repellent.
  • the liquid repellency can be substituted by the dynamic contact angle of water on the film surface.
  • the insulating film of the present invention is characterized in that the dynamic contact angle of water on the film surface is 85 ° to 115 °, more preferably 90 ° to 110 °.
  • the semiconductor insulating film of the present invention may contain various surface energy adjusting agents such as silicone surfactants and fluorine surfactants in the film. By adding such a surface energy adjusting agent, the smoothness and liquid repellency of the film surface can be improved.
  • fluorine-based surfactants are more preferable because they are excellent in compatibility with organic semiconductors and not only improve film quality such as liquid repellency and surface smoothness, but also improve the electrical characteristics of organic transistors.
  • Preferred fluorosurfactants include a linear perfluoroalkyl group, a perfluoroalkylene bond, or a perfluorooxyfluoroalkyl group or a perfluorooxyfluoroalkylene bond in the molecule, and the fluoroalkyl chain length is C4 or more and less than 8 nonionic fluorosurfactant.
  • a copolymer of perfluoroalkyl group-containing (meth) acrylate or perfluorooxyfluoroalkyl group-containing (meth) acrylate and another copolymerizable monomer can be used.
  • Nonionic fluorosurfactants having a perfluoroalkyl group with a carbon chain length of C4 or more include, for example, MegaFuck F-482, MegaFuck F-470 (R-08), MegaFuck F-472SF, MegaFuck R-30, Megafuck F-484, Megafuck F-486, Megafuck F-172D, Megafuck F178RM, Megafuck F555 (all of which are manufactured by DIC Corporation).
  • an active energy ray-polymerizable fluorosurfactant is most preferable. Since this fluorosurfactant is formed on the surface of the insulating film for semiconductors of the present invention, a polymer film based on a copolymer with a fluorosurfactant having a polymerizable double bond is formed on the surface of the insulating film. A transistor having excellent bleed resistance to other constituent elements in contact with an insulating film forming the transistor, for example, an organic semiconductor layer and having stable electric characteristics over time can be formed. Specific examples of such a fluorosurfactant having a polymerizable double bond include Megafac RS-75 and RS-72-K (all of which are manufactured by DIC Corporation). . The above surfactant can be used, for example, in an amount of 0.01 to 10 parts per 100 parts in total of the compounds (A) and (B) in terms of mass.
  • the active energy ray-curable compound ink for forming an insulating film for a semiconductor of the present invention can be polymerized and cured by irradiation with an active energy ray to obtain an insulating polymer film.
  • an active energy ray high active energy rays such as electron rays and X-rays can be used in addition to ultraviolet rays and visible rays.
  • a photopolymerization initiator suitable for the functional group of the polymerization system can be added as necessary.
  • silsesquioxane compound (A) and / or the crosslinking accelerator compound (B) having a (meth) acryloyl group as a functional group is used to form the insulating film for organic semiconductor of the present invention
  • hydrogen abstraction type photopolymerization It is preferable to add an initiator and / or a decay type photopolymerization initiator.
  • examples of the aromatic ketone include benzophenones, Michler ketones, xanthenes, thioxanthones, and anthraquinones.
  • examples of the decay type photopolymerization initiator include benzoin alkyl ethers, 2,2-dialkoxy-2-phenylacetophenones, acetophenones, acyloxime esters, azo compounds, organic sulfur compounds, acylphosphine. Examples thereof include oxides and diketones.
  • a compound having a site functioning as a hydrogen abstraction type photopolymerization initiator and a site functioning as a decay type photopolymerization initiator in the same molecule for example, ⁇ -aminoacetophenones can also be used as the photopolymerization initiator.
  • diaryliodonium salt When using a silsesquioxane compound (A) having an oxetanyl group or an epoxy group as a functional group and / or a crosslinking promoting compound (B), a diaryliodonium salt, a triarylsulfonium salt, an aromatic diazonium salt, an iron arene complex, etc. Can be used. Among these, diaryliodonium salts are preferable because they are excellent in curability (curing speed, curing depth, coating film adhesion) and can be cured not only by photocationic polymerization but also by thermal cationic polymerization.
  • a counter anion when the cationic polymerization initiator is an onium salt compound a hexafluoroantimonate anion, a hexafluorophosphate anion, a tetrakis (pentafluorophenyl) borate anion, and the like are preferable.
  • photosensitizers such as phenothiazine derivatives, xanthone derivatives, thioxanthone derivatives, aminobenzoic acid derivatives, polycyclic aromatic compounds such as anthracene, phenanthrene, and perylene, or combinations thereof may be added, and protons may be supplied. You may add the polyhydric alcohol compound etc. which act as a raw material.
  • the addition amount of these photopolymerization initiators can be 0.05% by mass or more and 6% by mass or less, more preferably 0.2% by mass or more and 3% by mass or less of the total amount of the active energy ray polymerizable compound.
  • an organic solvent can be used in combination.
  • organic solvents include aliphatic hydrocarbon organic solvents such as pentane, hexane, heptane, octane, decane, dodecane, isopentane, isohexane, isooctane, cyclohexane, methylcyclohexane, and cyclopentane, benzene, toluene, o -Aromatic hydrocarbon solvents such as xylene, m-xylene, p-xylene, ethylbenzene, mesitylene, naphthalene, cyclohexylbenzene, diethylbenzene, methyl formate, ether formate, propyl formate,
  • the present invention is also characterized in that the gate insulating film of the thin film transistor is a copolymer obtained by crosslinking and polymerizing the silsesquioxane compound (A) and the crosslinking accelerating compound (B) by irradiating the active energy ray of the present invention.
  • a thin film transistor is provided.
  • the substrate of the thin film transistor examples include silicon, glass, metal, and synthetic resin. From the viewpoint of light weight and excellent flexibility, the thickness is preferably 50 to 500 ⁇ m, and the synthetic resin of 80 to 300 ⁇ m. It is preferable to use a film or a sheet.
  • a synthetic resin film or sheet examples include films or sheets of polyester, polycarbonate, polyimide, polyamide, polyolefin, polyphenylene ether, polyphenylene sulfide, and the like such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN). Can be mentioned.
  • Examples of the coating method for forming the gate insulating film of the present invention include offset printing, gravure printing, gravure offset printing, flexographic printing, screen printing machine, reverse printing, roll coating, gravure coating, slit coating, bar coating, and spinner coating.
  • the law etc. can be used.
  • the coating film thickness may be adjusted so that the film thickness after curing is 0.1 ⁇ m to 2 ⁇ m, and the cured film thickness is preferably 0.3 ⁇ m to 2.0 ⁇ m.
  • the coating film thickness may be adjusted so that the film thickness after curing is 2 ⁇ m to 5 ⁇ m.
  • the ink coating film of the present invention formed on the substrate is polymerized and crosslinked by irradiation with active energy rays
  • various light sources that emit the above-mentioned active energy rays can be used.
  • examples of ultraviolet rays include high pressure mercury lamps, ultra high pressure mercury lamps, ultraviolet fluorescent lamps, germicidal lamps, carbon arc lamps, xenon lamps, metal halide lamps, ozoneless UV lamps, and LEDs.
  • the xenon lamp can be used as a flash lamp to use light in the entire wavelength region.
  • active energy ray irradiation can be performed under an inert gas such as nitrogen or a rare gas.
  • an electron beam is preferable because the crosslink density of the insulating film can be easily increased.
  • the amount of UV irradiation is not particularly limited as long as a polymer film without coloring such as damage to the support itself or yellowing is formed, but it is preferably 30 to 1000 mJ / cm 2 .
  • the amount of electron beam irradiation is not particularly limited, but is preferably 10 to 200 kGy, and more preferably 10 to 100 kGy.
  • a thin film transistor having a desired layer structure can be easily obtained regardless of the layer structure.
  • a specific thin film transistor structure for example, only a lateral transistor having a bottom gate bottom contact (BGBC) structure, a bottom gate top contact (BGTC), a top gate top contact (TGTC), or a top gate bottom contact (TGBC) structure.
  • BGBC bottom gate bottom contact
  • BGTC bottom gate top contact
  • TGTC top gate top contact
  • TGBC top gate bottom contact
  • various vertical organic thin film transistors for example, only a lateral transistor having a bottom gate bottom contact (BGBC) structure, a bottom gate top contact (BGTC), a top gate top contact (TGTC), or a top gate bottom contact (TGBC) structure.
  • the method for producing the thin film transistor of the present invention is not particularly limited as long as the insulating film of the present invention is included in the constituent elements of the transistor, but not only the insulating film but all the layers are continuously formed by the printing process. In order to increase the productivity of the organic thin film transistor, it is preferable to form the film.
  • a semiconductor ink, a conductive ink, and an ink for forming a protective film are used. It is done.
  • Examples of coating and printing methods for printing and forming thin film transistors using these inks include offset printing, gravure printing, gravure offset printing, flexographic printing, screen printing machines, reverse printing, roll coating, gravure coating, slit coating, and bar coating.
  • a spinner coating method or the like can be used.
  • a modification method of the printed ink thin film to the transistor functional layer a modification method suitable for the characteristics of the ink used and the formation of various thin film transistor structures can be selected.
  • a method for modifying conductive ink or semiconductor ink for example, oven heating drying / firing, electron beam firing, plasma firing, high-frequency electromagnetic wave firing, light firing using a xenon lamp or the like can be applied.
  • Organic and inorganic semiconductor materials can be applied as semiconductor materials to be included in the semiconductor ink.
  • organic semiconductor materials include low molecular weight organic semiconductors such as phthalocyanine derivatives, porphyrin derivatives, naphthalenetetracarboxylic acid diimide derivatives, fullerene derivatives, pentacene and pentacentriisopropylsilyl (TIPS) pentacene, fluorinated pentacene and other derivatives, fluorine Polycyclic aromatic compounds such as tetracene, perylene, tetracene, pyrene, phenanthrene, coronene and derivatives thereof, oligothiophene and derivatives thereof, thiazole derivatives, fullerene derivatives, other thiophenes such as benzothienobenzothiophene, phenylene, vinylene, etc.
  • One or more soluble acene compounds such as various low molecular semiconductors combined, TIPS pen
  • polythiophene polymer such as polythiophene, poly (3-hexylthiophene) (P3HT), PQT-12, thiophene-thienothiophene copolymer such as B10TTT, PB12TTT, PB14TTT, and fluorene such as F8T2.
  • polymers phenylene vinylene polymers such as paraphenylene vinylene, arylamine polymers such as polytriarylamine, and the like can be suitably used.
  • solution-soluble Si semiconductor precursors that can be modified to inorganic semiconductors by heat treatment or irradiation with active energy rays such as EB and Xe flash lamps, oxides such as IGZO, YGZO, and ZnO A semiconductor precursor pair or the like can be applied.
  • Solvents applicable to inking organic and inorganic semiconductor materials only need to be able to dissolve the semiconductor materials at room temperature or with some heating, have appropriate volatility, and form an organic semiconductor thin film after volatilization of the solvent.
  • These organic solvents can be used.
  • surface energy regulators such as silica, titanium oxide, zirconia, and other inorganic particles, polymers such as polystyrene and polymethyl methacrylate, and silicone-based and fluorine-based surfactants are added to these solutions.
  • fluorosurfactants for crystalline semiconductor solutions can be used suitably because they can improve not only the ink property improvement effect but also the properties of the semiconductor film formed by drying the ink, such as field effect mobility. it can.
  • the conductive ink examples include, in a suitable solvent, metal particles such as gold, silver, copper, nickel, zinc, aluminum, calcium, magnesium, iron, platinum, palladium, tin, chromium, lead, silver / Alloys of these metals such as palladium, thermally decomposable metal compounds that give a conductive metal by thermal differentiation at relatively low temperatures, such as silver oxide, organic silver, and organic gold, zinc oxide (ZnO), indium tin oxide (ITO), etc.
  • Conductive metal oxide particles may be included as a conductive component, or a conductive polymer such as polyethylenedioxythiophene / polystyrene sulfonic acid (PEDOT / PSS) or polyaniline may be included.
  • PEDOT / PSS polyethylenedioxythiophene / polystyrene sulfonic acid
  • PEDOT / PSS polyaniline
  • the active energy ray-curable ink for insulating film of the present invention may contain other insulating materials if necessary.
  • insulating materials include epoxy resins, polyimide resins, polyvinyl pyrrolidone resins, polyvinyl alcohol resins, acrylonitrile resins, methacryl resins, polyamide resins, polyvinyl phenol resins, phenol resins, polyamide imide resins, Fluorine resin, melamine resin, urethane resin, polyester resin, alkyd resin, etc. can be applied.
  • these may be used alone or in combination of two or more, and if necessary, constitutions such as high relative dielectric constant particles such as alumina fine particles, silica fine particles and tantalum oxide fine particles, and low relative dielectric constant particles such as hollow silica fine particles Ingredients may be added.
  • high relative dielectric constant particles such as alumina fine particles, silica fine particles and tantalum oxide fine particles
  • low relative dielectric constant particles such as hollow silica fine particles
  • Ingredients may be added.
  • high relative dielectric constant particles such as alumina fine particles, silica fine particles and tantalum oxide fine particles
  • low relative dielectric constant particles such as hollow silica fine particles
  • Ingredients may be added.
  • limiting in the solvent applicable to insulating ink The above organic solvents can be used. Further, various silicone-based and fluorine-based surfactants can be added to the insulating ink as necessary.
  • the protective film ink for forming the protective film may be any ink that can form a film excellent in barrier properties such as light, oxygen, water, ions, etc. by modification treatment by heating, light, electron beam, drying or the like.
  • a silane compound, silazane compound, magnesium alkoxide compound, aluminum alkoxide compound, or tantalum alkoxide compound that forms an inorganic film by treatment can be used.
  • limiting in the solvent applicable to protective film ink The above organic solvents can be used. If necessary, various surfactants such as silicone and fluorine can be added to the protective film ink.
  • AC-SQ SI-20 Silsesquioxane represented by unit composition formula (RSiO 3/2 ) n having a (meth) acryloyl group as a functional group and unit composition formula R 2 SiO manufactured by Toa Gosei Co., Ltd.
  • Polysiloxane copolymer compound QX-SQ SI-20 Silsesquioxane represented by unit composition formula (RSiO 3/2 ) n having an oxetanyl group as a functional group, manufactured by Toagosei Co., Ltd., and unit composition 2-polysiloxane copolymer compound represented by the formula R 2 SiO: AC-SQ TA100: Sil represented by unit composition formula (RSiO 3/2 ) n having a (meth) acryloyl group as a functional group, manufactured by Toagosei Co., Ltd.
  • silsesquioxane compound OX-SQ-TX100 manufactured by Toagosei Co., unit composition formula having an oxetanyl group (RSiO 3/2) represented by n That silsesquioxane compound bismaleimide compound:
  • M4004 Miramar 4004 (EO-modified pentaerythritol tetraacrylate) manufactured by Toyo Chemical Co., Ltd.
  • EDG Diethylene glycol monomethyl ether
  • PGMAc Propylene glycol monomethyl ether acetate
  • TMP Trimethylolpropane celoxide 2021P: 3,4-epoxycyclohexenylmethyl-3, '4'-epoxycyclohexene carboxylate
  • Karenz MT PE1 made by Daicel Corporation Erythritol tetrakis (3-mercaptobutyrate)
  • CPI-100P Photo-cationic polymerization initiator F-556 manufactured by San Apro Co., Ltd.
  • DIC surfactant RS-72-K Polymeric fluorosurfactant manufactured by DIC Corporation
  • the dynamic contact angle of water on the film surfaces of Examples 1 to 8 and Comparative Examples 1 to 3 was such that an insulating ink before curing was applied on a glass plate to a thickness of 1 ⁇ m after curing with a spin coater.
  • the irradiation amount is 55 KGy
  • the coating is cured by irradiation to 260 mJ using a high-pressure Hg lamp.
  • the dynamic contact angle between the water droplet and the coating film was measured while dripping water on the cured coating film prepared with an automatic contact angle meter DSA100 manufactured by the company under the condition of 30 ⁇ L / min.
  • the solvent resistance of the cured film was evaluated by immersing acetone in a cotton swab and rubbing the same portion (length: about 10 mm) on the surface of the cured coating up to 25 reciprocations, and visually evaluating the occurrence of scratches and traces.
  • “O” indicates that there is no generation of scratches after 25 reciprocations
  • “x” indicates a film generated within 25 times.
  • a transistor characteristic measuring element having a bottom gate bottom contact (BGBC) structure was manufactured as follows, and field effect mobility ( cm 2 / Vs), ON / OFF ratio, and threshold voltage (Vth). The results are shown in Tables 3 and 4.
  • a gate electrode was formed by forming a Cr film on a non-alkali glass by sputtering and etching it into a desired pattern.
  • UV ultraviolet irradiation
  • the ink was polymerized and cured to form an organic gate insulating layer having a thickness of about 1 ⁇ m.
  • (4) To a 0.2% by mass solution of polyhexylthiophene (P3HT) in chloroform / xylene 1/1, a surfactant manufactured by DIC Co., Ltd. is added so as to be 0.01% by mass, and an organic semiconductor ink is added. Prepared.
  • P3HT polyhexylthiophene
  • the insulating layer with the source and drain electrodes prepared previously is pressed against the coated film,
  • the semiconductor coating film was transferred onto the insulating layer, and a P3HT semiconductor layer having a film thickness of about 50 nm was formed on the insulating layer to produce a BGBC transistor.
  • the gate insulating film and the semiconductor film straddling the Cr gate electrode on the substrate are shaved with a cutter knife so that each transistor element formed on each independent Cr gate electrode is separated one by one, and each of them is used for characteristic measurement. A single element was formed.
  • the fabricated device was heat-treated in a glove box at 150 ° C. for about 10 minutes, and the electrical characteristics of the device were measured using a semiconductor parameter measuring device (Keithley 4200). Field effect mobility, ON / OFF The threshold voltage (Vth) was determined by a known method.
  • the insulating film of the present invention can be applied as a gate insulating film, an interlayer insulating film, a protective film or the like of a thin film transistor.
  • the insulating film of the present invention When the insulating film of the present invention is applied as a gate insulating film of an organic transistor such as a TFT, it has a high field effect mobility and an ON / OFF ratio, is normally off, and has a small threshold voltage (Vth) fluctuation.
  • Vth threshold voltage
  • the organic thin film transistor of the present invention uses the crosslinked insulating film of the present invention that exhibits high performance transistor characteristics formed substantially in a non-heated / short time by active energy rays such as UV, EB, and visible light. Therefore, a flexible and highly reliable organic TFT can be easily formed by printing using an inexpensive film such as PET without causing thermal damage to the film substrate or the like on which the transistor is formed.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Thin Film Transistor (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Formation Of Insulating Films (AREA)

Abstract

La présente invention concerne un film d'isolation durci par un rayon d'énergie active et qui permet la formation d'un transistor organique qui présente une grande mobilité d'effet de champ, un rapport Marche/Arrêt élevé et d'excellentes performances pratiques, tout en étant normalement hors tension et exempt de variations de la tension seuil (Vth). En utilisant un composé de silsesquioxane polymérisable par un rayon d'énergie active en combinaison avec un composé contenant une liaison double polymérisable par un rayon d'énergie active spécifique, et en formant un film mince ayant un angle de contact avec l'eau de 85 à 115° en polymérisant ces composés au moyen d'un rayon d'énergie active, le film mince ainsi formé peut présenter une mobilité d'effet de champ et un rapport Marche/Arrêt excellents pour un film d'isolation de grille destiné à des transistors organiques en film mince en plus d'excellentes propriétés d'isolation de film mince et d'une excellente résistance aux solvants. Ce film mince permet la formation d'un transistor hautement pratique qui est normalement hors tension et exempt de variations de la tension seuil (Vth) tout en offrant d'excellentes caractéristiques de stabilité.
PCT/JP2013/066493 2012-06-15 2013-06-14 Film d'isolation et transistor organique en film mince utilisant ledit film WO2013187507A1 (fr)

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WO2017199902A1 (fr) * 2016-05-16 2017-11-23 Dic株式会社 Encre d'impression offset inverse durcissable par rayons d'énergie active
WO2018097284A1 (fr) * 2016-11-28 2018-05-31 国立大学法人 奈良先端科学技術大学院大学 Substrat de transistor à couche mince comprenant un film protecteur et son procédé de production
WO2019187988A1 (fr) * 2018-03-28 2019-10-03 日本板硝子株式会社 Produit durci de composition de résine, stratifié et composition de résine

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WO2017199902A1 (fr) * 2016-05-16 2017-11-23 Dic株式会社 Encre d'impression offset inverse durcissable par rayons d'énergie active
WO2018097284A1 (fr) * 2016-11-28 2018-05-31 国立大学法人 奈良先端科学技術大学院大学 Substrat de transistor à couche mince comprenant un film protecteur et son procédé de production
JPWO2018097284A1 (ja) * 2016-11-28 2019-10-17 国立大学法人 奈良先端科学技術大学院大学 保護膜を具備する薄膜トランジスタ基板およびその製造方法
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TWI573194B (zh) 2017-03-01
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TW201405660A (zh) 2014-02-01

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