WO2014017323A1 - Encre conductrice pour impression en transparence, procédé de production de transistor à film mince, et transistor à film mince produit par ledit procédé - Google Patents

Encre conductrice pour impression en transparence, procédé de production de transistor à film mince, et transistor à film mince produit par ledit procédé Download PDF

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Publication number
WO2014017323A1
WO2014017323A1 PCT/JP2013/069184 JP2013069184W WO2014017323A1 WO 2014017323 A1 WO2014017323 A1 WO 2014017323A1 JP 2013069184 W JP2013069184 W JP 2013069184W WO 2014017323 A1 WO2014017323 A1 WO 2014017323A1
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ink
pattern
conductive
blanket
surface energy
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PCT/JP2013/069184
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English (en)
Japanese (ja)
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正義 高武
直 義原
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Dic株式会社
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Priority to JP2014526856A priority Critical patent/JPWO2014017323A1/ja
Publication of WO2014017323A1 publication Critical patent/WO2014017323A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/52—Electrically conductive inks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
    • H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
    • H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
    • H01L27/1259—Multistep manufacturing methods
    • H01L27/1292—Multistep manufacturing methods using liquid deposition, e.g. printing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
    • H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
    • H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
    • H01L27/1222—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs with a particular composition, shape or crystalline structure of the active layer
    • H01L27/1225—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs with a particular composition, shape or crystalline structure of the active layer with semiconductor materials not belonging to the group IV of the periodic table, e.g. InGaZnO

Definitions

  • the present invention relates to a conductive ink for forming a conductive pattern by a reverse printing method, a method for manufacturing a thin film transistor using the same, and a thin film transistor formed by such a method.
  • Patent Document 1 As a printing method for forming a fine pattern of several micrometers, a reversal printing method (see Patent Document 1) is attracting attention as a printing method different from conventional general relief printing, intaglio printing, planographic printing, and stencil printing. .
  • Patent Document 2 discloses a coating process in which a resin is applied to a silicone resin surface to form a coated surface, and a relief plate formed in a predetermined shape is pressed against the coated surface to transfer the resin to the convex portion of the relief plate.
  • a relief reversal printing method comprising a removing step and a transfer step for transferring the resin remaining on the coated surface to the substrate is disclosed, thereby forming a color filter with uniform ink film thickness and resist patterning. It has been shown that images with high definition and high resin flatness can be obtained.
  • Patent Document 2 (Paragraph 0009) also describes that a precision pattern forming method can be applied to patterning of a printed circuit board and patterning of an electric circuit as an alternative to photolithography.
  • Patent Document 3 discloses a conductor material having a volume resistivity of 1 ⁇ 10 ⁇ 4 ⁇ ⁇ cm or less, an insulator material having a volume resistivity of 1 ⁇ 10 10 ⁇ ⁇ cm or more, and a volume resistivity of 1 ⁇ 10 6. -3 ⁇ ⁇ cm or more of a resistor material, characterized in that the viscosity in the step of forming a coated surface by applying to the release surface of these functional materials is adjusted to 50 mPa ⁇ s or less A method of manufacturing a printed wiring board by a printing method is disclosed. However, there is no specific description of the ink composition required to achieve fine electrical patterns that can be formed by reverse printing and that can be used practically.
  • the ink composition has a viscosity and surface energy that can form a uniform ink film on a blanket, and is in contact with a relief printing plate.
  • the dryness, tackiness, and cohesive force are developed so that a complete printed pattern can be formed on the blanket, and the ink coating on the blanket is completely on the substrate to be printed.
  • the viscosity of the ink is 5 mPa ⁇ s or less
  • the surface energy is 25 mN / m or less
  • Patent Document 4 discloses in detail the ink composition necessary for forming a precise pattern by the reverse printing method, it is necessary for imparting excellent conductive properties to the pattern formed with the conductive pattern forming ink. There is no disclosure about the ink composition.
  • a binder component is substantially used as a relief printing ink that can form a fine conductive pattern without transfer failure by a relief printing method and can impart excellent conductivity by low-temperature baking.
  • conductive particles having a volume average particle size (Mv) of 10 to 700 nm, a release agent, a surface energy adjusting agent, and a solvent component are essential components, and the solvent component has a surface energy of 27 mN / m or more at 25 ° C.
  • the ink of the present invention has excellent reversal printing characteristics, and although the obtained fine pattern can obtain high conductivity by low-temperature baking, the process window of reversal printing is narrow and there is a problem in mass productivity.
  • JP 55-44813 A Japanese Patent Laid-Open No. 11-58921 JP-A-2005-57118 JP 2005-126608 A WO2008 / 111484
  • the ink disclosed in Patent Document 5 has a large atmosphere dependency of the waiting time (waiting time) until the removal of unnecessary patterns after the ink film is formed on the blanket, and the pattern formed on the blanket is covered. Strict time management and atmospheric environment management were necessary because the allowable time range (range) in which the entire transfer to the transfer body can be performed was narrow.
  • the present inventors have intensively studied in view of the above circumstances, and found that the above problems can be solved by including a specific surface energy adjusting agent and a specific amount of water in a conventional relief printing ink.
  • the invention has been completed.
  • the present invention relates to a conductive ink that does not contain a binder component for forming a conductive pattern by a letterpress reverse printing method, and the conductive particles having a volume average particle size (Mv) of 2 to 250 nm are Dispersed in a liquid medium comprising an organic solvent containing an energy adjusting agent and / or a silicon-based surface energy adjusting agent and containing 0.5 to 40% of water as an essential component with respect to the total liquid medium
  • Mv volume average particle size
  • the present invention provides an ink for letterpress reversal printing that exhibits electrical conductivity through interparticle fusion bonding.
  • the present invention also relates to a conductive ink which does not contain a binder component for forming a conductive pattern on a transfer medium by a letterpress reverse printing method, and has a volume average particle diameter (Mv) of 2 to 250 nm. Is dispersed in a liquid medium comprising an organic solvent containing a fluorine-based surface energy adjusting agent and / or a silicon-based surface energy adjusting agent and containing 0.5 to 40% of water as an essential component with respect to the total liquid medium.
  • a method for producing a thin film transistor comprising a step of forming a conductive pattern by a letterpress reversal printing method using a letterpress reversal printing ink that exhibits conductivity by melt bonding between particles. It is to provide.
  • the present invention provides a conductive ink which does not contain a binder component for forming a conductive pattern by a letterpress reverse printing method, and the conductive particles having a volume average particle diameter (Mv) of 2 to 250 nm are formed on a fluorine-based surface.
  • a liquid medium comprising an organic solvent containing an energy adjusting agent and / or a silicon-based surface energy adjusting agent and containing 0.5 to 40% of water as an essential component with respect to the total liquid medium
  • the present invention provides a thin film transistor containing a conductive pattern formed by a letterpress reversal printing method using an ink for letterpress reversal printing that exhibits conductivity by interparticle fusion bonding.
  • the ink for reversal printing of the present invention has wide process tolerance, is excellent in image pattern transferability, and can stably form a fine conductive pattern without defective transfer even in an actual production process. Further, by using the conductive ink of the present invention, a fine pattern formed by letterpress reversal printing can be imparted with excellent conductivity having a specific resistance of 1 ⁇ 10 ⁇ 5 ⁇ cm or less by heat treatment at low temperature and short time.
  • the thin film transistor manufacturing method of the present invention has excellent process tolerance, electrical conductivity, and reliability in the conductive pattern manufacturing process. You can enjoy the advantages. The obtained thin film transistor becomes more reliable.
  • the conductive ink of the present invention relates to a conductive ink for forming a conductive pattern by a letterpress reverse printing method.
  • the letterpress reverse printing method means forming a uniform ink film on the liquid repellent surface of the blanket, pressing the letterpress on the ink film surface, and removing the ink in the portion that contacts the letterpress from the blanket.
  • the ink remaining on the blanket is transferred to a transfer medium.
  • any known and commonly used rubber or elastomer can be used as long as the release surface of the blanket used for letterpress reverse printing has a uniform overall film thickness, excellent surface smoothness and a liquid-repellent surface.
  • the material for forming such a blanket release surface include silicone elastomers such as vinyl silicone rubber and fluorinated silicone rubber, various fluororesin elastomers, ethylene propylene rubber, and olefin elastomers.
  • silicone elastomers and fluorine elastomers can be suitably used because of their excellent liquid repellency and excellent pattern releasability.
  • silicone elastomers have appropriate liquid repellency, solvent resistance, and solvent swelling properties, and are more excellent as rubbers for release surfaces of blankets.
  • PDMS polydimethylsilicone
  • the ink for letterpress reversal printing of the present invention is a conductive ink containing no binder component, and the conductive particles having a volume average particle diameter (Mv) of 2 to 250 nm are composed of a fluorine-based surface energy adjusting agent and / or a silicon-based ink.
  • a low-temperature firing characterized by containing a surface energy adjusting agent and being dispersed in a liquid medium composed of an organic solvent containing 0.5 to 40% by weight of water as an essential component with respect to the total liquid medium. It is an ink for letterpress reversal printing that exhibits excellent electrical conductivity substantially by melt bonding between particles.
  • the relief printing ink of the present invention may be included in the relief printing ink of the present invention.
  • the relief printing ink may be simply abbreviated as conductive ink.
  • conductive ink In general conductive ink, a large amount of binder component mainly composed of resin is included in order to develop transfer printability, film-forming property and a certain degree of conductivity. In order to promote the binding, it is preferable not to include a binder component that inhibits the binding. Since the preferred conductive ink of the present invention does not substantially contain a binder component, the conductive particles are melt-bonded even in a lower temperature heat treatment, and the conductivity is significantly higher than that of a system containing the binder component. be able to.
  • the conductive ink as described above of the present invention exhibits excellent conductivity comparable to bulk silver when baked at a heat treatment temperature of 80 ° C. or higher and lower than 180 ° C., preferably 100 ° C. or higher and 150 ° C. or lower. I can do it.
  • binder component used in general conductive ink include, for example, natural rubber, olefin resin, polyether such as polyethylene oxide, polypropylene oxide, unsaturated polyester resin, acrylic resin, phenol resin, melamine Resins, benzoguanamine resins, epoxy resins, urethane resins, vinyl polyester resins, petroleum resins, rosin resins, silicone resins, polyvinyl alcohol, vinyl chloride, vinyl acetate, vinyl chloride vinyl acetate copolymers, cellulose Resin, natural polysaccharides and the like, and the preferred conductive ink of the present invention does not contain any of these resins.
  • natural rubber olefin resin
  • polyether such as polyethylene oxide, polypropylene oxide
  • unsaturated polyester resin acrylic resin, phenol resin, melamine Resins, benzoguanamine resins, epoxy resins, urethane resins, vinyl polyester resins, petroleum resins, rosin resins, silicone resins, polyvinyl alcohol, vinyl chloride, vinyl
  • the amount of the resin component different from these binder components is also 10% or less, more preferably 5% or less, still more preferably based on the total mass of the conductive particles contained in the conductive ink. Is preferably 3% or less.
  • An ink containing more than 10% of a resin component is not preferable because it may inhibit the expression of conductivity due to heat treatment at a low temperature.
  • the present inventors dispersed conductive particles having a specific particle diameter in a liquid medium composed of an organic solvent containing a fluorine-based surface energy adjusting agent and / or a silicon-based surface energy adjusting agent and a specific ratio of water. It was found that by using a conductive ink, an excellent letterpress reverse printing characteristic was exhibited without including a binder component.
  • Mv Mean Volume Diameter
  • the conductive particles include gold (Au), silver (Ag), copper (Cu), nickel (Ni), zinc (Zn), aluminum (Al), iron (Fe), platinum (Pt), palladium ( Metal particles such as Pd), tin (Sn), chromium (Cr), lead (Pb), and alloys of these metals such as palladium alloys (Ag / Pd) and core-shell particles; zinc oxide (ZnO), indium tin oxide (ITO) ), In addition to conductive metal oxide particles such as indium zinc oxide (IZO), if necessary; metal complexes such as carboxylic acid silver salts and silver aminocarboxylic acid salts, 180 such as silver oxide (Ag 2 O) A thermally decomposable compound that thermally decomposes at a temperature of 0 ° C. or lower to give a conductive metal; conductive polymer particles such as polyethylenedioxythiophene / polystyrene sulfonic acid (PEDOT / PSS
  • silver and / or copper particles that is, nano-silver particles, nano-copper particles, silver-copper alloy nanoparticles, and core-shell particles having silver and / or copper as a core are better conductive. It is preferable because it is possible to obtain properties.
  • any known and commonly used dispersion stabilizer can be used.
  • alkylamines polyvinylpyrrolidone, polyethyleneimine, polyethylene glycol, polyvinylpyrrolidone, alkyl A thiol, alkyl thioether, a phthalocyanine compound whose terminal is substituted with an alkylamino group, and a mixture or copolymer thereof can be used.
  • preferred dispersion stabilizers are organic compounds containing substantially basic nitrogen atoms.
  • organic compound containing a basic nitrogen atom a low molecular organic compound such as a monoalkylamine or polyoxyalkyleneamine having a primary amino group such as dodecylamine can be used. From the viewpoint of protecting the conductive particles, it is preferable to use a polymer organic compound.
  • Examples of such a polymer compound include polyvinyl pyrrolidone, a polyvinyl pyrrolidone polymer which is a copolymer of vinyl pyrrolidone and other monomers, a polyethylene imine, a copolymer of ethylene imine and other monomers.
  • the polyethyleneimine type polymer etc. which are can be mentioned.
  • These high molecular compounds containing a basic nitrogen atom may be a binary copolymer or a ternary copolymer from the viewpoint of the number of constituent monomers, and may be a straight chain from the viewpoint of the molecular structure. From the viewpoint of localization in the copolymer of individual monomers, a random copolymer, a block copolymer, or a graft copolymer may be used.
  • the silver ions When combined with silver nanoparticles in the presence of these polymer compounds, the silver ions are easily reduced at room temperature or under heating in the presence of an appropriate reducing agent after coordination with the nitrogen atom of the polymer compound. Particularly preferred.
  • the polymer compound containing a basic nitrogen atom preferably has an average molecular weight of 5,000 to 30,000.
  • Examples of such a polymer organic compound containing a basic nitrogen atom include, for example, Polyvinylpyrrolidone K series (registered trademark) manufactured by Nippon Shokubai Co., Ltd., Epomin (registered trademark) series which is polyethyleneimine manufactured by the same company, WO2008 / A polymer compound having a polyethyleneimine chain and a nonionic hydrophilic segment as described in Japanese Patent No. 143061 can be used.
  • the conductive particles protected with an organic compound containing a basic nitrogen atom are added with a metal oxide or a metal ion solution in a medium in which the polymer compound is dispersed. It can be easily obtained by reducing oxides or ions and stabilizing them as metal nanoparticles.
  • the metal nanoparticle dispersion produced in this way is excellent in dispersion stability and storage characteristics, and potentially has the electrical function of conductive particles.
  • a fluorine-based surface energy adjusting agent and / or a silicon-based surface energy adjusting agent can be used as the surface energy adjusting agent.
  • fluorine-based surface energy adjusting agent examples include well-known and commonly used low-molecular or high-molecular fluorine-based surface energy adjusting agents.
  • DIC Corporation's Megafax series and 3M's Novec series Is applicable.
  • a fluorine-based film composed of a fluorinated (meth) acrylic polymer that can provide a coating film with excellent smoothness when applied with ink and can provide an excellent conductive film by interparticle fusion bonding of conductive particles.
  • a surface energy adjusting agent can be suitably applied.
  • silicon-based surface energy adjusting agent any known and commonly used silicon-based surface energy adjusting agent can be used.
  • a water-soluble surface energy adjusting agent of BYK series of Big Chemie Japan can be suitably used.
  • These surface energy adjusting agents are added in an amount of 0.05 to 5.0% by mass, preferably 0.1 to 0.5% by mass, based on 100% by mass of all components of the conductive ink. The amount added. If it is in the above range, ink repelling does not occur on a highly liquid-repellent blanket, and a uniform ink thin film can be easily obtained, and a substantial decrease in the conductivity of the ink coating after firing is also suppressed. it can.
  • Fluorine-based surface energy modifiers and silicon-based surface energy modifiers may be used alone, but in particular, by using both together, the release surface of the blanket can be used with a smaller amount of addition to the ink. This is particularly preferable because fine ink repellency can be suppressed.
  • Fluorine-type surface energy regulator / silicon-type surface energy regulator 1 / 1-1 in conversion of the non volatile matter mass. /0.1 is preferable in that the above effective effect can be obtained.
  • the liquid medium in which the conductive particles are dispersed contains a fluorine-based surface energy adjusting agent and / or a silicon-based surface energy adjusting agent, and contains water as an essential component.
  • a liquid medium made of a solvent is used.
  • any solvent can be used as long as it is compatible with water alone or in a mixture and the applied conductive particles can be dispersed stably alone or in a mixture. it can.
  • organic solvents examples include alcohols such as methanol, ethanol, butyl alcohol, methoxybutanol, and tertiary butanol; polyhydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, and glycerin; ethyl acetate, methyl acetate, and isobutyl acetate.
  • Esters such as ethyl lactate and carbonates such as propylene carbonate; ethers such as isopropyl ether, methyl tertiary butyl ether and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclohexanone and diacetone alcohol Class: methyl cellosolve, cellosolve, butyl cellosolve, diethylene glycol monomethyl ether, dipropylene glyco Glycol ethers such as ethylene monomethyl ether, propylene glycol monomethyl ether, glycol acetates such as ethylene glycol monomethyl ether acetate; glycol diethers such as methyl triglyme and ethyl monoglyme; cyclohexanone, methylcyclohexanone, Alicyclic hydrocarbons such as cyclohexanol and methylcyclohex
  • the conductive ink of the present invention preferably contains an organic solvent (sometimes referred to as a blanket swellable liquid) that can swell the blanket release surface, other than the organic solvent described above.
  • an organic solvent sometimes referred to as a blanket swellable liquid
  • it is first required to form a uniform ink thin film having no defects on the smooth surface and the liquid repellent release surface of the blanket. At this time, if a fine repellency is generated, a pattern defect occurs.
  • an organic solvent that can swell the blanket release surface in the liquid medium of the present invention in which conductive particles are dispersed the present inventors can easily form a uniform ink film that is free from defects and has no defects. I found that it can be formed.
  • the organic solvent has a rubber weight increase rate of 10% or more, more preferably 20% or more when the PDMS rubber is immersed in a solvent for 15 minutes. Can be suitably applied.
  • the content of the blanket-swellable liquid in the conductive particle dispersion medium including water is preferably 5 to 70%, more preferably 20 to 50%, based on mass.
  • blanket swellable liquid examples include dimethyl carbonate, diethyl carbonate, isopropyl acetate, npropyl acetate, butyl acetate, methoxybutyl acetate, dioxane, isopropyl alcohol, butanol, methyl monoglyme, ethyl monoglyme, and methyldiglyme.
  • Ethyl diglyme ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether, propylene glycol n butyl ether, propylene glycol n propyl ether, dipropylene glycol n butyl ether, di Propylene glycol n propyl ether, propi Glycol monomethyl ether acetate, octanol, etc. can be suitably used.
  • the present inventors By incorporating water in the scope of the present invention into the conventional conductive ink, the present inventors have transferred patterns from a blanket, that is, removal of unnecessary patterns by punching plates, and image lines formed on the blanket. In addition to improving the transferability of the pattern to the transfer target, it does not substantially increase the time required to dry the ink film (standby time) in order to form an appropriate pattern by punching and has a wide allowable range. I discovered that the transferable time (range) was realized.
  • an unnecessary pattern is formed by punching from the viewpoint of shortening the printing tact time. It is necessary for the standby time to be completely removed from the blanket release surface and to form a sharp image line to be reasonably short.
  • the image line pattern formed on the blanket is completely transferred to the transferred object side. A long time range (range), that is, a wide process window is required.
  • the liquid medium is composed of water and an organic solvent, and contains 0.5 to 40% of water with respect to the total liquid medium (total of water and organic solvent) on a mass basis. Characterized by the application of a liquid medium.
  • the water content is preferably 0.5 to 30%, more preferably 0.5 to 20%.
  • the amount of water added is less than 0.5%, it is not preferable because the effect described above becomes small. That is, the effect of improving the releasability of the pattern from the blanket is not sufficient, and it is difficult to sufficiently widen the allowable time width (range) in which the pattern formed on the blanket by the punching plate can be completely transferred onto the transfer target.
  • it exceeds 40% the drying property of the ink film is extremely lowered, and a long standby time is required, so that it is difficult to shorten the printing tact time. Furthermore, it becomes difficult to suppress fine repellency on the release surface of the liquid repellent blanket.
  • the conductive ink of the present invention containing not only an organic solvent but also water as an essential component is used, it can be removed by a printing plate at a normal atmosphere of about 25 ° C. and a relative humidity of about 50%, with a waiting time of 1 minute or less.
  • a sharp fine line having a line width of 5 ⁇ m or less can be formed, and a longer transfer permissible time (range) can be realized as compared with a conventional relief printing ink containing only an organic solvent.
  • the conductive ink of the present invention can easily realize a transfer allowable time range (range) of 10 minutes or more to a transfer target.
  • the printing tact can be further shortened by forcibly drying the ink surface applied on the blanket with a gentle breeze such as dry air.
  • the conductive ink of the present invention has sufficient pattern formability and transferability even in such forced drying.
  • the surface energy at 25 ° C. of the conductive ink is preferably adjusted to 27 mN / m or less by adding the above-described surface energy adjusting agent.
  • the surface energy of the ink is more preferably 21 mN / m or less.
  • the release surface may be subjected to ozone UV or ozone plasma treatment for the purpose of suppressing fine repellency of ink on the release surface of the blanket.
  • these surface treatments for suppressing ink repellency and pattern transferability (separation) from the blanket release surface are in a trade-off relationship.
  • the conductive ink of the present invention is used, these surface treatments are performed. Even from the blanket liquid repellent surface, it is possible to easily transfer completely onto the transfer target without any pattern residue.
  • a release agent can be further added to the conductive ink of the present invention as necessary for the purpose of improving the image line pattern formability and pattern transferability.
  • the mold release agent include silicone oils such as KF96 series manufactured by Shin-Etsu Chemical Co., Ltd. and SH28 manufactured by Toray Dow Corning Co., Ltd. (both are trade names).
  • a low molecular weight silicone molecular weight of about 148 to 2000 which is a dimer to 30 mer of silicone is preferable because it has little influence on the conductivity of the coating film after ink patterning and baking.
  • silicone oil include silicones having a dynamic viscosity at 25 ° C. of 20 mm 2 / s or less of KF96 series manufactured by Shin-Etsu Chemical.
  • the content of the release agent is 0.05 to 5.0% by mass, preferably 0.1 to 1.0% by mass, when all the components of the conductive ink are 100% by mass.
  • the conductive ink of the present invention for example, alkylamines such as diethylamine, triethylamine, diisopropylamine, monoethanolamine, diethanolamine is used as necessary.
  • alkylamines such as diethylamine, triethylamine, diisopropylamine, monoethanolamine, diethanolamine is used as necessary.
  • Ethanolamines such as triethanolamine, various ammonium carbonates, various ammonium carbamates, amine compounds such as formic acid, acetic acid, propionic acid, nitric acid, phosphoric acid, hydrogen peroxide, amine nitrate, inorganic acids, organic acids, etc. It may be added.
  • the pattern transfer method of the relief printing method of the present invention for example, a method of contacting a blanket, which is a relief printing plate having a negative pattern in a parallel lithographic method, or a blanket wound around a roll is removed from a flat plate.
  • a method of rolling and contacting the plate a method of forming a blank plate on the roll side and rolling and contacting a flat blanket, a method of forming a blanket and a blank plate on a roll and bringing them into contact with each other can be applied.
  • a fine transistor capable of realizing high-definition thin film transistor printing can be easily formed by the letterpress reverse printing method.
  • a thin film transistor can be manufactured, and a thin film transistor containing a conductive pattern obtained by an insulating film, a semiconductor film, and a relief printing method can be formed using the conductive ink of the present invention.
  • the thin film transistor may be referred to as a TFT.
  • the basic steps for forming various conductive patterns of a thin film transistor by the letterpress reverse printing method of the present invention will be described below with reference to FIG.
  • Fig. 1 (a) The conductive ink of the present invention is applied on the liquid repellent release surface of the blanket (Fig. 1-2) to form a uniform ink film (Fig. 1-1), and the pattern can be formed by relief printing. Dry moderately. In this case, it is preferable to control the drying conditions by controlling the atmospheric temperature and humidity. Furthermore, a fine breeze of dry air may be used to shorten the drying time.
  • an ink film having a predetermined thickness can be formed by, for example, slit coating, bar coating, or spin coating.
  • the wet film thickness of the ink to be applied is adjusted to 0.1 ⁇ m to 5 ⁇ m, more preferably 0.15 ⁇ m to 1.5 ⁇ m, from the viewpoint of subsequent fine pattern formability, drying property, and conductivity obtained by ink modification To preferred.
  • a uniform ink thin film having no pinholes can be easily formed on the liquid repellent surface.
  • Pattern forming process by punching plate FIG. 1 (b) A relief plate 3 corresponding to the punched plate is prepared. Next, lightly press the release plate with the negative pattern of the required TFT electrode pattern on the relief plate (Fig. 2-3) against the ink film, and then release it to remove the conductive ink in the portion that comes into contact with the relief portion of the release plate. Remove the coating pattern. As a result, a conductive ink pattern to be a conductive pattern of the TFT is formed on the blanket release surface. It is important to make the contact with the ink film surface on the blanket of the punching plate as light as possible.
  • the material of the stencil used here there are no particular limitations on the material of the stencil used here as long as it can remove ink from the blanket release surface of the ink film.
  • various metals such as glass, silicon, and stainless steel, and various resins can be used.
  • the processing method for these relief plates there is no limitation on the processing method for these relief plates, and an optimum method for the material, pattern accuracy, relief plate depth, etc. can be selected.
  • a processing method such as wet etching or dry etching can be applied.
  • metal wet etching, electroforming, sandblasting, etc.
  • a resin such as a material, a processing method such as photolithography etching, laser, or focused ion beam can be suitably applied.
  • Transfer process Fig. 1 (c) The conductive ink pattern formed on the blanket release surface is lightly pressed against the transfer target (FIGS. 1-4) to completely transfer the pattern.
  • a coating film pattern corresponding to the conductive pattern serving as the basis of the bottom gate bottom contact type TFT is formed on the substrate to be transferred.
  • the formed conductive pattern imparts conductivity using a known conductive ink modification method.
  • these conductive ink modification methods for example, hot air oven firing, infrared radiation firing, light firing with a xenon lamp, plasma firing, electromagnetic wave firing, and the like can be applied.
  • These reforming methods may be applied alone or in combination of two or more reforming methods. Specifically, by heating and drying the above-mentioned coating pattern, the conductive pattern in the coating pattern obtained above can be melt-bonded between the particles to form a conductive pattern. it can.
  • the most common baking method is hot-air oven heating baking, but if the preferred ink for letterpress reversal printing of the present invention using nano silver is used, the baking time is 80 ° C. or higher and 180 ° C. or lower and within 5 minutes. A conductive film having a specific resistance on the order of ⁇ cm can be easily formed.
  • the transfer target of the gate array pattern is generally a substrate made of various films, glass, silicon or the like. After forming a gate insulating film on the gate array pattern formed on these substrates, the gate array pattern is aligned with the pattern through the insulating film, and then the source / drain array pattern is formed in the same manner as the gate array pattern is formed.
  • a basic BGBC TFT can be formed by laminating semiconductor layers. The source / drain may be referred to as S / D.
  • the pattern transfer method of the relief printing method of the present invention for example, a method of bringing a blanket and a blanket into contact with each other by a parallel lithographic method, a method of rolling a blanket wound around a roll and bringing it into contact with a plate on a flat plate, A method of forming a punching plate on the roll side and rolling and bringing it into contact with a flat blanket, a method of forming a blanket and a punching plate on a roll and bringing them into contact with each other can be applied.
  • FIG. 2 shows a model diagram of a bottom gate bottom contact (BGBC) transistor element as an example of a transistor that can be formed according to the present invention.
  • a gate insulating film (FIG. 2-7) is formed on the gate array pattern (FIG. 2-8) formed on the substrate (FIG. 2-9) by the method of the present invention, and then aligned with the gate pattern through the insulating film.
  • an S / D array pattern (FIGS. 2-5) is formed by letterpress reverse printing.
  • a semiconductor layer (FIGS. 2-6) is formed on the S / D electrode and the gate insulating film to form a transistor basic structure.
  • the structure of the transistor that can be formed is not limited, and besides BGBC, various transistors having a horizontal transistor and a vertical structure including a top gate bottom contact can be formed.
  • each electric component constituting the transistor such as a gate electrode, a data line, a signal line, an S / D pattern, and a pixel electrode is formed by a letterpress inversion printing method.
  • the material and forming method of the gate insulating film applicable in the present invention there are no particular limitations on the material and forming method of the gate insulating film applicable in the present invention, and known materials and forming methods can be used.
  • applicable materials include inorganic materials such as silicon nitride and silicon oxide, and inorganic materials such as parylene, polyimide, polyvinylphenol, polystyrene, epoxy resin, polymethyl methacrylate, polyamide resin, fluorine resin, melamine resin, and silsesquioxane resin.
  • Thermoplastic resins such as organic hybrid resins, silicone resins, and urethane resins, thermal crosslinking, and energy beam crosslinking resins can be applied.
  • film forming methods include known methods such as spin coating, slit die coating, letterpress reverse printing, screen printing, gravure printing, flexographic printing, ink jet, vacuum deposition, and CVD.
  • the semiconductor material applicable in the present invention and the formation method thereof are not limited.
  • the semiconductor material include inorganic semiconductors such as silicon, IGZOx, and ZnO; phthalocyanine derivatives, porphyrin derivatives, naphthalene tetracarboxylic acid diimide derivatives, fullerene derivatives, pentacene, pentacene.
  • Polycyclic aromatic compounds such as triisopropylsilyl (TIPS) pentacene, fluorinated pentacene, fluorinated tetracene, perylene, tetracene, pyrene, phenanthrene, coronene and derivatives thereof, thiophenes such as benzothienothiophene, dinaphthothienothiophene, oligothiophene Derivatives, thiazole derivatives, fullerene derivatives, other low molecular semiconductors that combine thiophene, phenylene, vinylene, etc., and organic semiconductors that become organic semiconductors by heating, etc.
  • TIPS triisopropylsilyl
  • Precursor polythiophene, poly (3-hexylthiophene), polythiophene polymer such as PQT-12, thiophene-thienothiophene copolymer such as B10TTT, PB12TTT, PB14TTT, fluorene polymer such as F8T2, etc., paraphenylene
  • polymer semiconductors such as phenylene vinylene polymers such as vinylene, arylamine polymers such as polytriarylamine, and other carbon compounds such as carbon nanotubes and fullerenes can be applied.
  • a known method can be applied to the method for forming the semiconductor layer. For example, known methods such as percoat, slit die coat, spin coat, ink jet, flexographic printing, gravure printing, letterpress reverse printing, and vacuum deposition can be applied.
  • the printing of the conductive pattern on the transfer medium using the conductive ink of the present invention is performed by a letterpress reverse printing method.
  • the transfer target includes plastic, silicon, paper, glass, ceramics, and metal.
  • the transfer body includes a stacked body in which the gate electrode and the gate insulating film are stacked in this order on the transfer body before the S / D electrode in FIG. 2 is provided.
  • a conductive pattern corresponding to the S / D electrode can be provided on the gate insulating film of the laminate with the conductive ink of the present invention.
  • the conductivity of the conductive pattern is reduced when a binder component is added.
  • the ink is adjusted without adding the binder component, the cohesiveness of the ink is reduced, and a relief printing plate or transferred image is obtained. There was a portion that was not transferred as intended (transfer residue), and it was difficult to form a fine pattern with high definition.
  • the conductive ink of the present invention by having the above-described ink composition, the ink is easily released from the release surface of the blanket by the kiss touch of the release plate, so that complete transfer is easily realized. And a fine pattern with a line width of 5 ⁇ m or less can be easily formed.
  • a conductive layer (conductive pattern) can be formed by drying the conductive pattern printed on the transfer medium as necessary and then baking it at a temperature lower than conventional temperatures, such as 80 ° C. or higher and 180 ° C. or lower. it can.
  • the conductive layer thus formed can be used for flexible substrate wiring, electromagnetic wave shields, transparent electrodes (touch panels), etc., in addition to the formation of various conductive parts of organic semiconductors.
  • the thin film transistor of the present invention is manufactured using the conductive ink of the present invention, a part having conductivity required, specifically, a transistor such as a gate electrode, a data line, a signal line, an S / D electrode, and a pixel electrode It is only necessary that at least some of the electrode constituent elements constituting the above are formed by the letterpress reverse printing method as described above.
  • a conductive pattern made of a conductive film can be formed by a letterpress reverse printing method to form a TFT.
  • a ink for forming an insulating film or a semiconductor film a heat-drying type or a heat-curing type ink is used, and each coating film is formed on a transferred body by wet-on-wet coating.
  • the insulating film and the semiconductor film can be heated at once to form a TFT.
  • Finesphere SVE102 Nano silver dispersion manufactured by Nippon Paint Co., Ltd. (Mv: about 20 nm, solid content: about 30%, ethanol dispersion, containing about 2% or less nanoparticle dispersant)
  • Finesphere SVW102 Nano silver dispersion manufactured by Nippon Paint Co., Ltd.
  • NASH-010 Nano silver dispersion manufactured by DIC Corporation (Mv: about 15 nm, solid content: about 70%, aqueous dispersion, including dispersant containing 3% or less polyethyleneimine polymer)
  • CU387E2 Core shell nano copper (core Ag, shell Cu) manufactured by DIC Corporation, solid content of about 45%, ethanol dispersion, particle size of about 35 nm
  • F-555 Fluoro-based surface energy regulator Megafac manufactured by DIC Corporation, comprising a fluorinated (meth) acrylic polymer.
  • BYK-333 Silicone surface energy regulator manufactured by Big Chemie, Inc.
  • PC Propylene carbonate
  • IPAC Isopropyl acetate
  • IPA Isopropyl alcohol
  • KF96-1cs Silicone oil manufactured by Shin-Etsu Chemical Co., Ltd.
  • PVA Polyvinyl alcohol
  • a relief printing ink having a water / total liquid medium ratio of about 7.5% was prepared.
  • the ink surface energy was 21 mN / m or less.
  • the content of the blanket swellable liquid in the liquid medium including water was in the range of 20 to 50% on a mass basis.
  • a grid-like conductive pattern with a line width of about 15 ⁇ m is produced on a PC (polycarbonate) film by the letterpress reverse printing method using a glass punch having a grid-like recess with a line width of about 15 ⁇ m. did. In an atmosphere at an ambient temperature of 25 ° C.
  • the ink is uniformly applied to the PDMS smooth surface, which is the release surface of the blanket, with a bar coater so that the wet film thickness is about 0.3 ⁇ m, and left for about 1 minute Waiting time)
  • the bar coater so that the wet film thickness is about 0.3 ⁇ m, and left for about 1 minute Waiting time
  • the ink was cut off by the punching plate, and an image line having a sharp edge was formed.
  • the time width (range) of the standing was changed immediately after removing the pattern, 30 seconds, 1 minute, 3 minutes, 5 minutes, 10 minutes, and the ink pattern formed on the blanket was transferred to the transfer object.
  • the PC film was lightly pressed to completely transfer the pattern.
  • the pattern was completely transferred to the PC film 10 minutes after the pattern was formed on the blanket, and no residue was observed on the blanket.
  • the ink thin film formed by solid transfer on the PC film was baked at 150 ° C. for 5 minutes to melt-bond between particles, and the specific resistance was measured to be 5.3 ⁇ 10 ⁇ 6 ⁇ ⁇ cm. .
  • an ink for letterpress reverse printing having a water / total liquid medium ratio of about 16% was prepared.
  • the ink surface energy was 21 mN / m or less.
  • the content of the blanket swellable liquid in the liquid medium including water was in the range of 20 to 50% on a mass basis.
  • Ink is applied to the smooth surface of the PDMS rubber, which is the release surface of the blanket that has been subjected to UV ozone treatment for about 30 seconds, so that the wet film thickness is about 0.3 ⁇ m with a bar coater in an atmosphere of 25 ° C. and 48% relative humidity It was applied evenly.
  • a grid pattern having a line width of about 15 ⁇ m was formed in the same manner as in Example 1 except that a fine breeze of dry air was blown onto the ink-coated surface for about 30 seconds and dried.
  • the ink was cut off by the punching plate, and an image line having a sharp edge was formed.
  • the time width (range) of the standing was changed immediately after removing the pattern, 30 seconds, 1 minute, 3 minutes, 5 minutes, 10 minutes, and the ink pattern formed on the blanket was transferred to the transfer object.
  • the PC film was lightly pressed to completely transfer the pattern.
  • the pattern was completely transferred to the PC film in all 10 minutes immediately after that, and no residue was observed on the blanket.
  • IPA 10% dimethyl carbonate (blanket swellable liquid) 30%
  • methyl monoglyme 10% bladenket swellable liquid
  • Example 2 Using this ink, a grid pattern having a line width of about 15 ⁇ m was formed on the blanket in the same manner as in Example 1. The ink was cut off by the punching plate, and an image line having a sharp edge was formed. Next, the time width (range) of the standing was changed immediately after removing the pattern, 30 seconds, 1 minute, 3 minutes, 5 minutes, 10 minutes, and the ink pattern formed on the blanket was transferred to the transfer object. The PC film was lightly pressed to completely transfer the pattern. The pattern was completely transferred to the PC film 10 minutes after the pattern was formed on the blanket, and no residue was observed on the blanket. Order to intergranular fusion bonding, separately ink film was transferred to form a solid and fired 5 minutes at 0.99 ° C. on a PC film was measured for specific resistance was 8.3 ⁇ 10 -6 ⁇ ⁇ cm.
  • the ink for letterpress reversal printing of Comparative Example 1 containing a larger amount of water than specified in the present invention has a drastic decrease in the drying property of the ink film.
  • Example 1 in which forced drying was performed has a wide allowable time range (range) in which all transfer is possible, as in Example 1 in which forced drying is not performed. It can be seen that the printing tact time can be shortened. Furthermore, as can be seen from the comparison between Example 1 and Example 3, compared with Example 3 using only the fluorine-based surface energy adjusting agent, the combined use of the fluorine-based surface energy adjusting agent and the silicone-based surface energy adjusting agent. It can be seen that Example 1 can suppress fine ink repellency on the release surface of the blanket and can further increase the conductivity with a smaller amount of the surface energy adjusting agent added.
  • the ink is applied to the smooth surface of the PDMS rubber, which is the release surface of the blanket that has been subjected to UV ozone treatment for about 30 seconds, so that the wet film thickness is about 0.3 ⁇ m by a bar coater in an atmosphere of 25 ° C. and 48% relative humidity Was applied uniformly, and a lattice pattern having a line width of about 15 ⁇ m was formed on the blanket in the same manner as in Example 1.
  • the ink was completely cut by the punching plate, and an image line having a sharp edge was obtained.
  • the time width (range) of the standing was changed immediately after pattern formation, 30 seconds later, 1 minute later, 3 minutes later, 5 minutes later, and 10 minutes later, and the ink pattern formed on the blanket was transferred to the object to be transferred.
  • the PC film was pressed lightly to transfer the pattern.
  • the pattern was completely transferred to the PC film 10 minutes after the pattern was formed on the blanket, and no residue was observed on the blanket.
  • the ink thin film formed by transferring the ink onto a PC film was baked at 170 ° C. for 30 minutes, and then the specific resistance was measured. As a result, it was 7.9 ⁇ 10 ⁇ 6 ⁇ ⁇ cm. there were.
  • Comparative Example 2 48% Finesphere SVE102, 1.2% F-555, 30.1% ethanol, 20% IPAC, 0.5% PC, 0.2% KF96-1cs as a release agent Thus, a conductive ink containing no water was prepared.
  • a lattice pattern having a line width of about 15 ⁇ m was formed on the blanket in the same manner as in Example 1.
  • the ink was completely cut by the punching plate, and an image line having a sharp edge was obtained.
  • the time width (range) of the standing was changed immediately after removing the pattern, 30 seconds, 1 minute, 3 minutes, 5 minutes, 10 minutes, and the ink pattern formed on the blanket was transferred to the transfer object.
  • the PC film was lightly pressed to try to transfer the pattern. Immediately after that, the pattern was almost completely transferred onto the PC film until 1 minute, but after 3 minutes, part of the pattern remained on the blanket, and after 5 minutes, it was not transferred at all.
  • the ink film with the ink is formed by transferring a solid onto the PC film was baked for 30 minutes at 180 ° C., was measured resistivity was 9.6 ⁇ 10 -6 ⁇ ⁇ cm.
  • Comparative Example 3 48% fine sphere SVE102 (solid content approx. 30%), 1.1% megafac F-555 (solid content approx. 30%), 20.2% ethanol, 25% IPAC (blanket) Swellable liquid), 0.5% PC, 0.2% KF96-1cs as a release agent, and 5% PVA as a binder resin with respect to the total amount of ink, thereby adding water according to Comparative Example 3 A conductive ink not containing was produced.
  • a grid pattern having a line width of about 15 ⁇ m was formed on the blanket in the same manner as in Example 1.
  • the ink breakage due to the punching plate was slightly worse, and many fine burrs were observed at the edge of the image line.
  • the time width (range) of the standing was changed immediately after removing the pattern, 30 seconds, 1 minute, 3 minutes, 5 minutes, 10 minutes, and the ink pattern formed on the blanket was changed to the substrate to be transferred.
  • the resulting glass plate was pressed and transferred. Immediately after that, the pattern was transferred almost completely onto the PC film to be transferred, but after 5 minutes, part of the pattern remained on the blanket and was not transferred at all after 10 minutes.
  • the conductivity was 2.6 ⁇ 10 ⁇ 2 ⁇ ⁇ cm when the ink thin film formed by solidly transferring the ink on a PC film was baked at 190 ° C. for 30 minutes and the specific resistance was measured.
  • the conductive ink of Comparative Example 2 which does not substantially contain water, has not only a narrow allowable time range (range) that can be completely transferred, but also has high conductivity. In order to obtain a pattern, baking at a high temperature for a long time is necessary. Further, it can be seen from the comparison between Comparative Example 2 and Comparative Example 3 that the conductive ink of Comparative Example 3 containing no water and containing a binder component has a narrow allowable time range (range) in which the entire transfer can be performed.
  • a relief printing ink having a water / liquid medium ratio of about 3.7% was prepared.
  • the ink surface energy prepared was 21 mN / m or less.
  • a grid-like conductive pattern having a line width of about 15 ⁇ m was formed on the release surface made of blanket PDMS rubber by the same method as in Example 1.
  • the ink was completely cut by the punching plate, and a grid pattern having sharp edges was obtained.
  • the range after pattern formation on the blanket is changed immediately after pattern removal, 30 seconds, 1 minute, 3 minutes, 5 minutes, 10 minutes, and the ink pattern formed on the blanket to be transferred
  • the PC film to be transferred was lightly pressed and transferred. The pattern was completely transferred to the transfer medium 10 minutes after the start, and no residue was observed on the blanket.
  • the formed pattern was pre-fired in an air atmosphere at 150 ° C. for 5 minutes, and then fired in air using a xenon flash lamp manufactured by USHIO INC. With a pulse width of 0.6 ms, a voltage of 650 V, and an estimated irradiation energy of 10 J / m 2 . To obtain a copper fired film having a thickness of about 170 nm. The conductivity of the film obtained by fusion bonding between particles was about 7 ⁇ 10 ⁇ 6 ⁇ cm.
  • a TFT array having the bottom gate bottom contact (BGBC) structure shown in FIG. 3 was prepared by the following procedure.
  • a UV-curable ink for a gate insulating film mainly composed of a silsesquioxane compound having an acryloyl group, a bismaleimide, a polyfunctional acrylate, and an organic solvent for viscosity adjustment
  • the gate insulation is applied on the gate electrode array pattern created in step 1 and then cured with a UV curing device using a high-pressure mercury lamp as the light source with an illuminance of 200 mW / cm 2 and an integrated light amount of about 1800 mJ / cm 2.
  • a film was formed.
  • a PC substrate on which a gate insulating film on the gate electrode array was formed was prepared.
  • Example 3 Formation of Source / Drain Electrode
  • the conductive ink prepared in Example 1 was used with a slit coater on a film substrate transparent blanket on which a PDMS rubber smooth surface having a thickness of about 0.1 mm as a pattern release surface was formed on a transparent film. A uniform ink film was formed. After moderate drying, the source / drain electrode array pattern is formed on the blanket in the same manner as the formation of the gate electrode array using a glass blank plate with the negative pattern of the TFT source / drain electrode array pattern as a convex portion. Formed.
  • the aligner uses the aligner to adjust the position so that the gate electrode array pattern of the PC film substrate formed in the previous two steps and the corresponding part of the source / drain electrode array pattern overlap each other through the gate insulating film, and lightly press the two together
  • the entire region was transferred onto the PC film substrate on which the gate electrode array and the gate insulating film were formed so that the corresponding portion of the source / drain electrode array pattern overlapped the corresponding portion of the gate electrode pattern through the insulating film.
  • the substrate is then baked in an oven at 150 ° C.
  • TFT electrode pattern arrays each having a drain electrode array were prepared.
  • FIG. 3 shows a 200 ppi BGBC type organic transistor array having a channel length of about 5 ⁇ m and a wiring width of about 5 ⁇ m formed by this manufacturing method.
  • the elements prepared in the above 1 to 4 were subjected to heat treatment at 150 ° C. for about 5 minutes in a glove box, and then used in a glow box using a semiconductor parameter measuring apparatus (Keithley 4200).
  • the field-effect mobility at a drain voltage load of ⁇ 40 V was about 0.04 cm 2 / Vs, and the ON / OFF (maximum drain current value / minimum value) was about 1 ⁇ 10 8.
  • the threshold voltage (Vth) was ⁇ 5V.
  • the thin film transistor in which the transistor structure including the insulating film and the semiconductor film including the conductive film formed using the conductive ink for reversal printing of the present invention was manufactured by the printing method effectively functions as a transistor.
  • the conductive ink of the present invention is optimal for forming a fine and precise printed pattern on a substrate to be printed by a letterpress reverse printing method, and includes an organic semiconductor electrode, wiring, flexible substrate wiring, electromagnetic wave shield, transparent electrode ( It can be used for manufacturing a touch panel).

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Abstract

La présente invention concerne une encre conductrice qui est destinée à être utilisée en impression typographique en transparence et qui présente un intervalle de temps admissible plus large pour transférer sur un substrat un motif entier formé sur un blanchet. L'invention concerne plus particulièrement une encre conductrice qui est destinée à être utilisée en impression typographique en transparence et qui peut former un motif conducteur par liaison-fusion de particules conductrices, ladite encre conductrice étant caractérisée en ce qu'elle comprend : des particules conductrices ayant un diamètre de particule moyen en volume (Mv) situé dans la plage allant de 2 à 250 nm; et un milieu liquide comprenant un solvant organique contenant de l'eau et contenant un régulateur d'énergie de surface à base de fluor et/ou un régulateur d'énergie de surface à base de silicone et dans lequel sont dispersées les particules conductrices. L'invention concerne également : un procédé de production d'un transistor à film mince, caractérisé en ce qu'il comprend une étape de formation d'un revêtement de l'encre conductrice suivant un motif sur un substrat par le biais d'un procédé d'impression typographique en transparence, et ensuite une étape de fusion-liaison des particules conductrices contenues dans le revêtement de la forme d'un motif afin de former un motif conducteur; et un transistor à film mince.
PCT/JP2013/069184 2012-07-26 2013-07-12 Encre conductrice pour impression en transparence, procédé de production de transistor à film mince, et transistor à film mince produit par ledit procédé WO2014017323A1 (fr)

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US11104813B2 (en) 2015-06-02 2021-08-31 Asahi Kasei Kabushiki Kaisha Dispersion
JP2023027058A (ja) * 2017-03-16 2023-03-01 旭化成株式会社 分散体並びにこれを用いた導電性パターン付構造体の製造方法及び導電性パターン付構造体
US11760895B2 (en) 2017-07-27 2023-09-19 Asahi Kasei Kabushiki Kaisha Copper oxide ink and method for producing conductive substrate using same, product containing coating film and method for producing product using same, method for producing product with conductive pattern, and product with conductive pattern
JP7420762B2 (ja) 2020-05-27 2024-01-23 三ツ星ベルト株式会社 インク組成物

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WO2010113931A1 (fr) * 2009-03-31 2010-10-07 Dic株式会社 Composition d'encre semi-conductrice organique et procédé de formation d'un motif semi-conducteur organique au moyen de celle-ci
JP2011178832A (ja) * 2010-02-26 2011-09-15 Dic Corp 紫外線硬化型インクジェット記録用インク、それから得られた絶縁膜、電子素子及び電子素子の製造方法

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JP4173051B2 (ja) * 2003-05-22 2008-10-29 シヤチハタ株式会社 水性ボールペン用インキ
JP5152631B2 (ja) * 2006-09-15 2013-02-27 株式会社リコー インクジェット記録用インク、インクジェット記録用インクセット、インクジェット記録用インク−メディアセット、インクカートリッジ、インクジェット記録方法、インクジェット記録装置。
JP2009102480A (ja) * 2007-10-22 2009-05-14 Dic Corp インクジェット記録用インク、インクセット及びインクジェット記録方法

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WO2008111484A1 (fr) * 2007-03-15 2008-09-18 Dic Corporation Encre conductrice pour une impression en transparence typographique
WO2010113931A1 (fr) * 2009-03-31 2010-10-07 Dic株式会社 Composition d'encre semi-conductrice organique et procédé de formation d'un motif semi-conducteur organique au moyen de celle-ci
JP2011178832A (ja) * 2010-02-26 2011-09-15 Dic Corp 紫外線硬化型インクジェット記録用インク、それから得られた絶縁膜、電子素子及び電子素子の製造方法

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11104813B2 (en) 2015-06-02 2021-08-31 Asahi Kasei Kabushiki Kaisha Dispersion
JP2023027058A (ja) * 2017-03-16 2023-03-01 旭化成株式会社 分散体並びにこれを用いた導電性パターン付構造体の製造方法及び導電性パターン付構造体
JP7477581B2 (ja) 2017-03-16 2024-05-01 旭化成株式会社 分散体並びにこれを用いた導電性パターン付構造体の製造方法及び導電性パターン付構造体
US11760895B2 (en) 2017-07-27 2023-09-19 Asahi Kasei Kabushiki Kaisha Copper oxide ink and method for producing conductive substrate using same, product containing coating film and method for producing product using same, method for producing product with conductive pattern, and product with conductive pattern
JP7420762B2 (ja) 2020-05-27 2024-01-23 三ツ星ベルト株式会社 インク組成物

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