WO2018168004A1 - Dispersion de particules fines de métal, encre conductrice et dispositif électronique - Google Patents

Dispersion de particules fines de métal, encre conductrice et dispositif électronique Download PDF

Info

Publication number
WO2018168004A1
WO2018168004A1 PCT/JP2017/030889 JP2017030889W WO2018168004A1 WO 2018168004 A1 WO2018168004 A1 WO 2018168004A1 JP 2017030889 W JP2017030889 W JP 2017030889W WO 2018168004 A1 WO2018168004 A1 WO 2018168004A1
Authority
WO
WIPO (PCT)
Prior art keywords
metal fine
fine particle
particle dispersion
ink
electrode
Prior art date
Application number
PCT/JP2017/030889
Other languages
English (en)
Japanese (ja)
Inventor
亮太 山口
香 河村
矢次　健一
敦久 宮脇
小澤　徹
佑介 狩野
Original Assignee
Dic株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dic株式会社 filed Critical Dic株式会社
Publication of WO2018168004A1 publication Critical patent/WO2018168004A1/fr

Links

Images

Classifications

    • 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
    • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
    • 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
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • 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
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
    • H01L21/288—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • H01L29/76—Unipolar devices, e.g. field effect transistors
    • H01L29/772—Field effect transistors
    • H01L29/78—Field effect transistors with field effect produced by an insulated gate
    • H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns

Definitions

  • the present invention relates to an organic electroluminescent element, an organic thin film transistor, an organic thin film solar cell, etc., in an organic electronic device, a conductive material used for wiring, electrode, etc. formed by printing, in particular, metal fine particles used for an electrode in contact with an organic semiconductor, and TECHNICAL FIELD
  • the present invention relates to a metal fine particle dispersion in which it is dispersed, a conductive ink prepared from the metal fine particle dispersion, a thin film transistor electrode formed by applying the conductive ink to form a conductive film, a thin film transistor having the electrode, and an electronic device It is an invention.
  • Nano-sized and micro-sized fine metal particles are used for the formation of wiring parts and electrode parts by printed electronics technology. By forming these metal fine particles into ink, wiring parts and electrode parts can be easily formed by printing. Is possible.
  • the source electrode and the drain electrode of the thin film transistor electrode greatly affect the charge mobility, which is one of the transistor characteristics, of the smoothness of the electrode surface. Therefore, it is necessary that the metal fine particles are nano-sized or a mixture of nano-sized particles.
  • Nano-sized metal fine particles cannot exist stably as a dispersion unless they are protected with organic matter because of their high surface activity.
  • the organic matter remaining on the surface after forming the electrode serves as an insulator, which obstructs the electron path at the interface between the electrode and the organic semiconductor, and deteriorates the transistor characteristics. It is difficult to develop high conductivity and high transistor characteristics while ensuring this dispersion stability.
  • a letterpress reverse printing method As a method for producing high-definition wiring portions and electrode portions by printing, a letterpress reverse printing method is known.
  • the letterpress reverse printing method printing is generally performed via a transfer member having a releasability made of silicone rubber. Therefore, when the metal fine particle dispersion, which is a nonpolar solvent, is used as an ink, the nonpolar solvent, which is a dispersion medium, swells the silicone rubber that is a transfer member having releasability, so that it can be reproduced continuously. An electrode image cannot be produced with good properties.
  • the metal fine particle dispersion In order to produce an electrode image by the letterpress reverse printing method, the metal fine particle dispersion must be dispersed in a low polarity or high polarity solvent.
  • Patent Document 1 A method to be used is disclosed (Patent Document 1, Patent Document 2). This is because the low molecular weight protective agent is detached from the electrode surface during coating film sintering, and thus organic substances remaining on the electrode surface can be reduced.
  • Patent Document 2 A method to be used is disclosed (Patent Document 1, Patent Document 2). This is because the low molecular weight protective agent is detached from the electrode surface during coating film sintering, and thus organic substances remaining on the electrode surface can be reduced.
  • any of these publications is a dispersion of metal fine particles using a low molecular weight protective agent in a nonpolar solvent, and cannot be suitably used as an ink for letterpress reverse printing.
  • Patent Document 3 a method of dispersing metal fine particles in a polar solvent by using a high molecular weight dispersant in combination with metal fine particles using a low molecular weight substance as a protective agent is disclosed.
  • Patent Document 4 Since the high molecular weight dispersant adheres firmly to the surface of the metal fine particles, a stable metal fine particle dispersion can be obtained even in a polar solvent.
  • the dispersant that adheres firmly to the metal surface does not desorb during low-temperature firing at 120 ° C., and prevents fusion between the metal fine particles, making it difficult to develop high conductivity.
  • This high sintering temperature makes it difficult to adapt to the transistor electrode corresponding to the flexible base material and its peripheral circuit.
  • the dispersant remaining on the electrode surface becomes an insulator at the interface with the semiconductor, and the transistor characteristics are remarkably deteriorated. Therefore, a metal fine particle dispersion consisting only of a low molecular weight protective agent that does not use a high molecular weight dispersant is required.
  • the problems to be solved by the present invention include metal fine particles that exhibit sufficient conductivity and transistor characteristics at a firing temperature of about 120 ° C., metal fine particle dispersions containing the metal fine particles, and metal fine particles using the metal fine particle dispersions It is an object of the present invention to provide a thin film transistor electrode, a thin film transistor, and an electronic device using an ink and a metal fine particle ink using the metal fine particle dispersion.
  • the present inventors use a high molecular weight dispersant by using a primary amine compound containing at least one hetero element in addition to an amino group as a protective agent.
  • the inventors have completed the invention of fine metal particles that can be stably dispersed in a polar solvent or a low-polar solvent. It has been found that the metal fine particle dispersion according to the present invention exhibits excellent conductivity when fired at a low temperature of about 120 ° C. and excellent transistor characteristics when fired at a low temperature of about 120 ° C. Further, it was found that the fine particle dispersion can be stably dispersed even at 23 ° C. in addition to exhibiting the above properties.
  • An electronic circuit including a conductive film or a conductive pattern according to (9) or an electronic device according to (11) in its configuration.
  • the present invention uses metal fine particles that exhibit sufficient conductivity and transistor characteristics at a baking temperature of about 120 ° C., metal fine particle ink using the metal fine particle dispersion, and metal fine particle ink using the metal fine particle dispersion. Thin film transistor electrodes, thin film transistors, and electronic devices.
  • FIG. 3 is a TG-DTA measurement result of a silver fine particle dispersion produced based on Example 1.
  • FIG. 4 is a TG-DTA measurement result of a silver fine particle dispersion produced based on Example 2.
  • FIG. 4 is a transmission electron microscope image of a silver fine particle dispersion produced based on Example 1.
  • FIG. 7 is a transmission electron microscope image of a silver fine particle dispersion produced based on Example 2.
  • the method for producing fine metal particles according to the present embodiment produces a complex compound by mixing an amine mixed solution containing a primary amine compound having a hetero element other than nitrogen of a primary amino group and a metal compound. Step (first step), step of heating and decomposing the complex compound to produce metal fine particles (second step), and purification step of removing unnecessary substances from the reaction product containing metal fine particles (third step) ) And.
  • boiling point means a boiling point at 1 atm.
  • an amine compound that can completely complex the metal compound. If it is a compound containing a primary amino group selected from one or more primary amine compounds containing 3 or more carbon atoms containing a hetero element in addition to nitrogen of the primary amino group, two or more types may be used alone. These compounds may be used as a mixture. From the viewpoint of reactivity, an amine compound having a high amine concentration per volume is preferable, and an amine compound having 8 or less carbon atoms is preferably included.
  • the surface of the generated metal fine particles is effectively coated from the viewpoint of stabilizing the dispersion by preventing collisions between the metal colloid particles.
  • an amine compound that can be used. If it is a compound containing a primary amino group selected from one or more primary amine compounds containing 4 or more carbon atoms containing a hetero element in addition to nitrogen of the primary amino group, it may be used alone or in combination of two or more. These compounds may be used as a mixture. In order to reduce the formation of aggregates due to contact between particles, an amine compound having a long chain structure or a branched structure having 6 or more carbon atoms is preferably contained.
  • the complex compound produced in the first step needs to have a useful amine compound in the second step. Even when the first step is started with only the useful amine compound in the first step, the useful amine compound in the second step can be added before the second step is started. Moreover, when starting a 1st process, the amine compound useful in a 1st process and the amine compound useful in a 2nd process can also be used together. When the same kind of compound can be used as the amine compound useful in the first step and the amine compound useful in the second step, only one kind may be used as the amine compound.
  • the amine compound which can be utilized for the 1st process and the 2nd process is illustrated below, it is not limited to this.
  • a branched structure may exist, and the element at the branched portion is a hetero element such as nitrogen or phosphorus other than carbon. There may be.
  • alkoxyalkylamines having 3 or more carbon atoms having an alkoxy group in addition to the primary amino group can be used.
  • an alkanolamine having 4 or more carbon atoms having a hydroxyl group in addition to the primary amino group can be used.
  • amine compound containing nitrogen as a hetero element other than nitrogen of the primary amino group a diamine having 4 or more carbon atoms having a secondary or tertiary amino group or the like in addition to the primary amine can be used.
  • amine compound containing nitrogen as a hetero element other than nitrogen of the primary amino group a polyamine having 4 or more carbon atoms having a secondary or tertiary amino group or the like in addition to the primary amine can also be used.
  • alkylthioalkylamines having 3 or more carbon atoms having an alkylthio group in addition to the primary amino group can be used.
  • an amine compound containing no hetero element other than nitrogen of the primary amino group can be used in combination as amines.
  • an alkylamine can be used as the primary amine, specifically, 1-octylamine, 2-ethylhexylamine, 1-nonylamine, 1-decylamine, isodecylamine, 1-undecylamine, Examples include 1-dodecylamine, 1-tridecylamine, 1-tetradecylamine, 1-pentadecylamine, 1-hexadecylamine, 1-heptadecylamine, stearylamine, oleylamine and the like.
  • dialkylamine can be used, and specifically, di-n-ethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-n-hexylamine, di-1-octylamine Bis (2-ethylhexyl) amine, di-1-nonylamine, di-1-decylamine, diisodecylamine, di-1-undecylamine, di-1-dodecylamine, dioleylamine and the like.
  • a tertiary amine compound can be used in combination as amines as long as the effects of the present invention are not impaired.
  • a trialkylamine can be used, and specifically, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, heptacosafluorotributylamine, tri-n-amylamine, perfluorotria Myramine, tri-n-hexylamine, N, Nn-octylamine, tri-n-octylamine, tri-n-octylamine, tris (2-ethylhexyl) amine, tri-n-nonylamine, tri-n -Decylamine, triisodecylamine, tri-n-undecylamine, tri-n-dodecylamine, trioleylamine, 1- [N, N-bis (2-ethylhexyl)
  • alkanolamines having 4 or more carbon atoms having a hydroxyl group can be used as the tertiary amine compound.
  • amidines can be used in combination as long as the effects of the present invention are not impaired.
  • 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.4.0] -7-undecene and the like can be exemplified.
  • Carboxylic acids can be added as long as the effects of the present invention are not impaired.
  • Carboxylic acids include fatty acids having 1 to 22 carbon atoms, oleic acid, linoleic acid, linolenic acid, ricinoleic acid, 15-hydroxypentadecanoic acid, 12-hydroxystearic acid, cholic acid, deoxycholic acid, dehydrocol Acid, chenooxycholic acid, 12-oxochenodeoxycholic acid, glycocholic acid, colanic acid, lithocholic acid, hyodeoxycholic acid, ursodeoxycholic acid, apocholic acid, taurocholic acid, abietic acid, dehydroabietic acid, glycyrrhizic acid, glycyrrhizin Acid, lauroyl sarcosine, stearoyl sarcosine, oleoyl sarcosine acid, 6-aminohexanoic
  • thiols can be added as long as the effects of the present invention are not impaired.
  • thiols octanethiol, decanethiol, dodecanethiol, perfluorooctanethiol, perfluorodecanethiol, perfluorododecanethiol, benzenethiol, 3-methylbenzenethiol, 4-methylbenzenethiol, 3-fluorobenzenethiol, 4 -Fluorobenzenethiol, 3-chlorobenzenethiol, 4-chlorobenzenethiol, pentachlorobenzenethiol, 3-bromobenzenethiol, 4-bromobenzenethiol, 3-methoxybenzenethiol, 4-methoxybenzenethiol, 3-methylthiobenzenethiol, 4 -Methylthiobenzenethiol, 3-trifluorometh
  • phosphines can be added as long as the effects of the present invention are not impaired. Examples thereof include tri-1-butylphosphine, tri-1-octylphosphine, tricyclohexylphosphine, and triphenylphosphine.
  • the metal species of the metal fine particles of the present invention are limited as long as the metal can be chemically bonded to a nitrogen-containing functional group selected from a primary amino group, a secondary amino group, a tertiary amino group, and an amidino group.
  • a nitrogen-containing functional group selected from a primary amino group, a secondary amino group, a tertiary amino group, and an amidino group.
  • gold, silver, copper, nickel, zinc, aluminum, platinum, palladium, tin, chromium, lead, tungsten, or the like can be used.
  • the metal species may be one type, a mixture of two or more types, or an alloy.
  • carboxylate a chloride, an oxide, carbonate, nitrate etc. are mentioned, for example.
  • oxalate and formate are particularly preferable. Oxalates and formates are because the carboxylate ions are decomposed by heating to reduce silver ions and volatilize as carbon dioxide at the same time, so that impurities hardly remain.
  • (First step) In the first step of producing a complex compound, an amine compound and a silver compound are mixed to produce a complex compound therebetween.
  • the total amount of amine contained in the amine mixture is preferably equal to or greater than the stoichiometric amount of the metal in the metal compound. This is because if a metal compound that does not become a complex compound remains, uniform and stable dispersion of metal nanoparticles may be hindered.
  • the formation reaction of the complex compound between the amine mixture and the metal compound needs to be adjusted because the reactivity changes depending on the amine compound and the metal compound to be used, but the mixture containing the amine mixture and the metal compound can be adjusted from 30 ° C. It can be carried out by stirring at about 50 ° C. for about 5 minutes to 3 hours. Although the reaction time can be shortened by increasing the reaction temperature, the reaction temperature is preferably 50 ° C. or less from the viewpoint of avoiding an unexpected decomposition reaction by providing a sufficient temperature difference from the thermal decomposition start temperature in the second step. . In order to avoid chemical changes and ignition of the reaction system, particularly amine compounds, it is preferable to avoid mixing of carbon dioxide and moisture, and the reaction can be performed in an inert gas such as nitrogen or argon, or in a dry air atmosphere.
  • an inert gas such as nitrogen or argon
  • step metal complexes are formed by heating and decomposing the complex compound produced in the previous step.
  • the temperature at which the complex compound is decomposed by heating varies depending on the amine compound and the metal compound to be used, so adjustment is necessary, but the metal compound is decomposed to generate a metal, and the amine compound from the generated metal fine particles From the viewpoint of preventing desorption, it is preferable to react in the range of 70 ° C. to 150 ° C. for about 5 minutes to 2 hours.
  • the reaction temperature in this step should not exceed the boiling point of the amine compound due to the heat generated by the progress of the thermal decomposition reaction. It is preferable from the viewpoint of avoiding bumping.
  • in order to prevent ignition of the vaporized amine compound it is preferable to make it react on low oxygen concentration conditions.
  • the reaction heat due to thermal decomposition of the metal oxalate metal salt amine complex occurs, and therefore it is possible that the reaction heat cannot be controlled when the reaction scale is expanded. Therefore, when the ratio of the molar amount m2 of the amine to the molar amount m1 of the metal (m2 / m1) is, for example, in the range of 5-20, the amine solution is added excessively to generate oxalate during thermal decomposition. The reaction heat to be absorbed can be absorbed by the amine solution, and bumping can be prevented.
  • the reaction liquid after the thermal decomposition of the complex compound becomes, for example, a brown suspension when the metal species is silver. From this suspension, target metal fine particles can be obtained by a separation operation such as decantation.
  • Metal fine particle dispersion It is considered that the metal fine particles whose surface is coated with a protective agent by decantation reflects the chemical properties of the protective agent and is well dispersed in a solvent that gives an interaction within a specific range.
  • an amine compound containing a hetero element in addition to nitrogen of the primary amino group By selecting and using an amine compound containing a hetero element in addition to nitrogen of the primary amino group, the polarity of the surface of the fine particles coated with the amine compound can be increased and uniformly and stably in a polar solvent. Metal fine particles that can be dispersed are obtained.
  • the polar solvent in the present invention has at least one hydroxyl group, carboxyl group, amino group, ether group, carbonyl group, amide group, nitrile group, or ester group as a polar functional group, and has a solubility parameter (SP value). It refers to a solvent of 20 [MPa 1/2 ] or more.
  • the polar solvent used here may be used independently, but can also be mixed and used. If the SP value as a mixture is 20 [MPa 1/2 ] or more, a low polarity solvent having an SP value of less than 20 [MPa 1/2 ] can be used in combination.
  • the selection criterion is not limited to the SP value, and another parameter may be used as long as the polarity of the solvent can be evaluated based on an appropriate criterion.
  • the solubility parameter is a parameter related to mutual solubility of substances proposed by Hildebrand et al., And is determined by measuring the energy required for vaporization of a single component per average molar volume, as shown in Equation (1).
  • solubility parameter [MPa 1/2 ] E heat of vaporization T; Temperature R; gas constant V m; molar volume [Delta] H; vaporization enthalpy Delta] E; vaporization energy
  • the organic fine particle dispersion of the present invention is selected by selecting an organic solvent having a solubility parameter (SP value) of 20 [MPa 1/2 ] or more as a polar solvent, adding the metal nanoparticles obtained in the second step, and stirring. Can be obtained.
  • organic solvents having an SP value of 20 [MPa 1/2 ] or more are described in, for example, Polymer Handbook 4th Edition, John Wiley & Sons, Inc. And can be selected based on the value.
  • Examples of the organic solvent having an SP value of 20 [MPa 1/2 ] or more include the following hydroxyl group-containing solvents.
  • the value in () is the SP value of the solvent.
  • organic solvents having an SP value of 20 [MPa 1/2 ] or more include acetone (20.3), cyclopentanone (21.3), cyclohexanone (20.3), acetophenone (21.7), acrylonitrile. (24.3), propionitrile (22.1), n-butyronitrile (21.5), isobutyronitrile (20.1), ⁇ -butyrolactone (25.8), ⁇ -caprolactone (20.7) ), Propiolactone (27.2), 2,3-butylene carbonate (24.8), ethylene carbonate (30.1), 1,2-ethylene carbonate (27.2), dimethyl carbonate (20.3) ), Ethylene carbonate (30.1), dimethyl malonate (22.5), ethyl lactate (20.5), methyl benzoate (21.5), methyl salicylate (21.7), ethylene glycol diacetate Cole (20.5), ⁇ -caprolactam (26.0), dimethyl sulfoxide (29.7), N, N-dimethylformamide (24.8), N, N-di
  • solvents that can be used in combination include water, isoamyl alcohol, 3-methoxy-1-butanol, 2-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 1- Hexanol, 2-hexanol, 2-ethylhexanol, 1-octanol, isooctyl alcohol, 2-butyl-1-octanol, 1-nonanol, 1-decanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, Alcohols such as 2- (2-ethoxyethoxy) ethanol, 2- (2-butoxyethoxy) ethanol, furfuryl alcohol, terpineol, phenol, 2-phenoxyethanol, 1-phenoxy-2-propanol, ethylene glycol , Propylene glycol, diethylene glycol, 1,2-butanediol, 1,3-butanediol, 1,
  • Hydrocarbon ethyl acetate, propyl acetate, isopropyl acetate, 1-methoxy-2-propyl acetate, 3-methoxybutyl acetate, ethylene glycol monomethyl ether acetate, 2- (2-ethoxyethoxy) ethyl acetate Cetates, 2- (2-butoxyethoxy) ethyl acetate, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, ⁇ -butyrolactone, esters such as ethyl lactate, methyl ethyl ketone, methyl isobutyl ketone, 2 -Ketones such as pentanone, 2-heptanone, cyclohexanone, ethers such as diethyl ether, 1,2-dimethoxyethane, ethylene glycol diethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, N, N
  • amines, alkanolamines, amidines, carboxylic acids, thiols, and phosphines exemplified above may be added.
  • a fatty acid and a hydroxy fatty acid dispersibility in a nonpolar solvent is improved, and dispersion at a metal concentration of 50% or more becomes possible. Also, the dispersion stability at room temperature is improved.
  • Metal fine particle ink The metal fine particle dispersion of the present invention is converted into an ink by pad printing, screen printing, screen offset printing, ink jet printing, flexographic printing, letterpress printing, planographic offset printing, waterless planographic offset printing, gravure printing, gravure offset printing,
  • the image can be formed using a printing method selected from the group consisting of letterpress reversal printing, laser printing, xerographic printing, pad printing, and combinations thereof.
  • a low viscosity solvent of 50 mPa ⁇ s or less at 20 ° C.
  • a solvent include water, methanol, ethanol, 1-propanol, isopropanol, 1-butanol, sec-butanol, tert-butanol, isoamyl alcohol, 3-methoxy-1-butanol, 1-pentanol, 2 -Pentanol, 4-methyl-2-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 1-hexanol, 2-hexanol, 2-ethylhexanol, 1-octanol, isooctyl Alcohol, 2-butyl-1-octanol, 1-nonanol, 1-decanol, oleyl alcohol, 2- (2-ethoxyethoxy) ethanol, 2- (2-
  • the metal fine particle ink includes a binder component such as a resin, an antifoaming agent, an adhesion imparting agent to the base material, an antioxidant, and various catalysts for promoting film formation.
  • a binder component such as a resin, an antifoaming agent, an adhesion imparting agent to the base material, an antioxidant, and various catalysts for promoting film formation.
  • Various surfactants such as silicone surfactants and fluorine surfactants, leveling agents, mold release accelerators, and the like can be added as printing aids.
  • the metal fine particle ink of the present invention is excellent in dispersion stability, it can be suitably used for forming an image such as a thin film electrode. Furthermore, since firing at a low temperature is possible, the metal fine particle ink of this embodiment can be applied or printed on a substrate having low heat resistance such as a resin substrate or a paper substrate to form a wiring.
  • a thin film transistor having such a source electrode and a drain electrode is a thin film transistor with less variation in mobility and threshold voltage when driven.
  • the electrodes have the same thickness, both of which are made of extremely uniform conductors of 50 nm or more, preferably 100 to 200 nm, and can be easily formed into electrodes having an appropriate electrode shape with no abnormalities such as concave and convex shapes. Is obtained.
  • an electrode is optimal for obtaining a transistor array including a thin film transistor, an integrated circuit, and the like.
  • the thin film transistor since a stable channel shape can be obtained in the thin film transistor electrode, the thin film transistor has less variation in mobility and threshold voltage when driven.
  • Such excellent features are the features of transfer printing described above, which cannot be achieved by conventional printing methods such as screen printing and ink jet printing.
  • a letterpress on which a convex portion corresponding to an image reversal pattern is formed and a transferred member (blanket) having releasability are used. Applying metal fine particle ink to the entire surface of the member to be transferred and pressing the relief plate onto the coated surface on the member to be transferred, and transferring and removing the portion corresponding to the reversal pattern of the image on the relief plate And a step of transferring and printing an image on a support such as a substrate using a member to be transferred on which an image portion corresponding to the image pattern is formed by removing the reverse pattern pressed by the relief printing plate.
  • the printing method provided with.
  • the viscosity of the ink is excessive because the high-boiling solvent remains in the ink coating until the image formed on the transferred member by the letterpress is transferred to the printing substrate. Can be prevented, and can maintain appropriate adhesiveness and cohesive force necessary for transfer, and printing becomes possible.
  • the high boiling point solvent solvent added to the fine metal particle ink used for letterpress reverse printing one or more of ester solvents, alcohol solvents, ether solvents and hydrocarbon solvents are used.
  • the total ink composition contains 5 to 90% by mass, preferably 30 to 70% by mass, and more preferably 40 to 60% by mass.
  • the blending amount is adjusted in the range of 5 to 90% by mass depending on the printing speed and printing order of the letterpress reverse printing method.
  • the high boiling point solvent used in the ink is selected in consideration of the dispersion stability of the metal fine particles, and the following can be used, but is not limited thereto.
  • n-nonane (boiling point 150 ° C.), n-decane (boiling point 174 ° C.), n-undecane (boiling point 195 ° C.), n-dodecane (boiling point 216 ° C.), n-tridecane (boiling point 235 ° C.), n-tetradecane (Boiling point 253 ° C), n-hexanol (boiling point 157 ° C), n-heptanol (boiling point 177 ° C), n-octanol (boiling point 194 ° C), n-nonanol (boiling point 214 ° C), n-decanol (boiling
  • the metal fine particles of the present invention are excellent in low-temperature sinterability, and can exhibit excellent conductivity by sintering at a temperature of 120 ° C. or lower. Therefore, the metal fine particles of the present invention can be used for materials having low heat resistance such as resin films.
  • the firing method for sintering the metal fine particles is not limited to sintering by heat, and the metal fine particles may be fused.
  • the metal fine particles can be sintered by using visible light, infrared light or laser light irradiation, or plasma treatment including hydrogen gas.
  • visible light when visible light is used for sintering of the metal fine particles, it can be performed by light irradiation using a flash lamp.
  • the metal fine particles of this embodiment are used, wiring, electrodes, etc. having sufficiently low resistivity (6 ⁇ 10E-6 ⁇ ⁇ cm or less by baking at 120 ° C. when silver is used for the metal).
  • a conductive structure can be formed. Therefore, the metal fine particles of the present embodiment can be suitably used for manufacturing various electronic components such as a thin film transistor, an integrated circuit including a thin film transistor, a touch panel, an RFID, a flexible display, an organic EL, a circuit board, and a sensor device.
  • a thin film transistor is a transistor in which at least a gate electrode, an insulator layer, a source electrode and a drain electrode, and a semiconductor layer are stacked over a substrate.
  • the thin film transistor usually has a thickness of 0.1 to 3 ⁇ m excluding the substrate serving as a support.
  • a thin film transistor is formed by laminating a source electrode, a drain electrode, a gate electrode, a semiconductor layer, and an insulator layer made of a conductor in any order on a substrate so that the function of the transistor is exhibited. It can be manufactured easily.
  • the thin film transistor of the present invention can have horizontal and vertical transistor structures.
  • a bottom-gate (BG) or top-gate (TG) transistor defined by the positional relationship of the gate electrode with the transistor component can be used.
  • a transistor structure such as a bottom contact type, a top contact type, and a bottom top contact type can be adopted.
  • the thin film transistor of the present invention is characterized in that at least one electrode is formed using the metal fine particles of the present invention.
  • the electrode for the thin film organic transistor includes the metal fine particles of the present invention and other conductive materials (for example, gold, silver, copper, nickel, zinc, aluminum, calcium, magnesium, iron, platinum, palladium, tin, chromium).
  • Metal particles such as silver, palladium, and alloys of these metals such as silver / palladium; thermally decomposable metal compounds that give a conductive metal by thermal differentiation at a relatively low temperature, such as silver oxide, organic silver, and organic gold; zinc oxide (ZnO), conductive metal oxide particles such as indium tin oxide (ITO), etc.) can also be used as a mixture.
  • the electrode for a thin film organic transistor of the present invention is an ink jet printing method, a screen printing method, a screen offset printing method, a spin coating method, a bar coating method, a pad printing method, a slit coating method, a dip coating method, a spray coating method, a gravure printing method.
  • a printing method selected from the group consisting of a flexographic printing method, a lithographic offset printing method, a gravure offset printing method, a relief printing method, a relief printing method, a relief printing method, a relief printing method, and combinations thereof. it can.
  • a letterpress reverse printing method because an electrode image portion can be formed with a finer and smoother thin film.
  • the electrode width in the laminated section of the thin film transistor is not different in the thickness direction, and an electrode having no transfer abnormality is obtained.
  • a thin film transistor having such an electrode is a thin film transistor with less variation in mobility and threshold voltage when driven.
  • the method of forming transistor electrodes by letterpress reversal printing does not require an expensive vacuum device and can drastically reduce production costs including capital investment, compared to methods for obtaining the electrodes by vapor deposition or other dry methods. It becomes.
  • the process can be reduced in temperature, and a resin film can be used as the substrate, which is preferable for realizing flexibility and low cost.
  • the source and drain electrodes of the thin film transistor of the present invention By subjecting the source and drain electrodes of the thin film transistor of the present invention to surface treatment as necessary, the charge injection efficiency into the semiconductor layer can be improved.
  • the surface treatment material of the electrode for the thin film organic transistor can be arbitrarily selected according to the energy level of the semiconductor.
  • the electrode for a thin film organic transistor it can be formed by any known and commonly used dry or wet process.
  • the wet method include spin coating, bar coating, slit coating, dip coating, spray coating, dispenser, and ink jet.
  • the surface treatment amount of the thin film organic transistor electrode can be determined by measuring the work function of the electrode before and after the surface treatment using an atmospheric photoelectron spectrometer.
  • substrate for thin film organic transistor there are no limitations on the substrate applicable to the thin film transistor of the present invention.
  • silicon a thermal oxide film silicon whose surface is oxidized to be an insulating layer, glass, a thin metal plate such as stainless steel on which an insulating layer is formed; polycarbonate (PC)
  • Plastic films such as polyethylene terephthalate (PET), polyimide (PI), polyethersulfone (PES), polyethylene naphthalate (PEN), liquid crystal polymer (LCP), polyparaxylylene, polyphenylene sulfide (PPS), cellulose;
  • a composite film obtained by adding a gas barrier layer, a hard coat layer, etc. to a plastic film can be used.
  • a resin film can be suitably used as the substrate.
  • the insulator material used for the insulator layer of the thin film transistor of the present invention is not limited as long as it includes an insulating material, and a publicly known material can be used.
  • a publicly known material can be used.
  • oxides such as zirconia, silicon dioxide, aluminum oxide, titanium oxide, and tantalum oxide, ferroelectric oxides such as SrTiO 3 and BaTiO 3 , Dielectric fine particles such as nitrides such as silicon nitride and aluminum nitride, sulfides and fluorides can be dispersed.
  • the insulator layer and the gate electrode layer can be formed by any known and commonly used dry or wet processes.
  • the surface of the insulator layer may be formed by, for example, hexamethyldisilazane (HMDS), octyltrichlorosilane (OTS-8), octadecyltrichlorosilane, (OTS-18), dodecyltrichlorosilane (DTS), SAM (self-assembled film) treatment can be performed with various silane coupling agents such as fluorine-substituted octatrichlorosilane (PFOTS) and ⁇ -phenethyltrichlorosilane.
  • HMDS hexamethyldisilazane
  • OTS-8 octyltrichlorosilane
  • OTS-18 octadecyltrichlorosilane
  • DTS dodecyltrichlorosilane
  • SAM self-assembled film
  • a fluorine-based material is used.
  • a surfactant or the like can be used.
  • the thickness of the insulating layer and the gate electrode of the thin film transistor of the present invention is not particularly limited, but the thickness of the insulating layer is preferably 5 to 1000 nm from the viewpoint of suppressing variations in ON / OFF values.
  • the thickness of the gate electrode is preferably 20 to 1000 nm from the viewpoint of good followability to a flexible substrate.
  • organic semiconductor material As a semiconductor material used for the semiconductor layer of the thin film transistor, an organic or inorganic semiconductor material can be applied.
  • organic semiconductor materials include low-molecular organic semiconductors such as phthalocyanine derivatives, porphyrin derivatives, naphthalene tetracarboxylic acid diimide derivatives, fullerene derivatives, pentacene and pentacentriisopropylsilyl (TIPS) pentacene, and various pentacene precursors.
  • Body anthracene, perylene, pyrene, phenanthrene, coronene and other polycyclic aromatic compounds and derivatives thereof, oligothiophene and derivatives thereof, thiazole derivatives, fullerene derivatives, dinaphthothiophene compounds, carbon nanotubes and other carbon compounds, etc.
  • thiophene such as benzothienobenzothiophene, phenylene, vinylene, and the like, and copolymers thereof can be suitably used.
  • polythiophene poly(2-hexylthiophene) (P3HT)
  • P3HT polythiophene polymers
  • PQT-12 polythiophene-thienothiophene copolymers
  • B10TTT thiophene-thienothiophene copolymers
  • fluorenes such as F8T2 Polymers
  • phenylene vinylene polymers such as paraphenylene vinylene
  • arylamine polymers such as polytriarylamine, and the like
  • solution-soluble Si semiconductor precursors that can be modified into inorganic semiconductors by energy treatment such as heat treatment, EB, and Xe flash lamps, and oxide semiconductors such as IGZO, YGZO, and ZnO A precursor of the above can be applied.
  • an organic semiconductor is preferable to an inorganic semiconductor because the semiconductor layer can be easily formed at a lower temperature and is easy to handle.
  • organic semiconductors those having a high self-aggregation property and easy to take a crystal structure are preferable because more excellent transistor characteristics can be exhibited.
  • Solvents that can be applied to inks of organic and inorganic semiconductor materials only need to be able to dissolve the semiconductor materials at room temperature or slightly heated, have appropriate volatility, and form an organic semiconductor thin film after volatilization of the solvent.
  • An organic solvent such as can be used.
  • the method for forming the semiconductor layer of the thin film transistor is not particularly limited, and the thin film transistor can be formed by any known and commonly used dry or wet process.
  • a protective film layer can be formed on the uppermost layer if necessary.
  • the protective film layer By providing the protective film layer, the influence of outside air can be minimized, and the electrical characteristics of the thin film transistor can be stabilized.
  • the thin film transistor of the present invention can be manufactured by any of the manufacturing methods exemplified above. Further, the thin film transistor thus obtained can be a transistor array or an integrated circuit by integrating a plurality of elements.
  • the metal fine particle dispersion is subjected to dynamic light scattering measurement using a particle size distribution measuring device (UPA-EX manufactured by MicrotracBEL), the particle size distribution is calculated from the frequency of the obtained scattered light, and the volume average particle size value is a reference value. Used as.
  • thermogravimetric analysis 2-25 mg of fine metal particle dispersion is precisely weighed on an aluminum pan for thermogravimetric analysis and placed on an EXSTAR TG / DTA6300 differential thermogravimetric analyzer (made by SII NanoTechnology Co., Ltd.). The temperature was increased at a rate of 10 ° C. per minute until a weight reduction rate of 100 ° C. to 600 ° C. was measured.
  • a coating film was prepared by spin-coating a metal fine particle dispersion on a non-alkali glass substrate (40 mm ⁇ 50 mm) having a thickness of 0.7 mm.
  • the obtained coating film was sintered at 120 ° C. for 30 minutes with a constant temperature / dryer (clean oven DE411 made by Yamato Kagaku) to obtain a sintered film.
  • the number of rotations during spin coating was adjusted so that the thickness of the sintered film was 100 nm.
  • the volume resistivity was measured with a low resistivity meter Lorester EP (manufactured by Mitsubishi Chemical Corporation) using a four-terminal measurement method.
  • the volume resistivity was determined from the film thickness of the conductive film (sintered film) of the test piece. For example, the volume resistivity is shown by a method in which 8.8 ⁇ 10 ⁇ 6 ⁇ ⁇ cm is described as “8.8E-6 ⁇ ⁇ cm”.
  • a silver fine particle ink in which silver fine particles having an average particle size of nanometer order are uniformly dispersed in a liquid medium is uniformly applied to a silicone rubber surface of a transparent blanket in which a silicone rubber layer is formed on a film by a slit coater. It was dried to such an extent that the tack remained.
  • a glass relief plate on which a negative pattern of a desired source and drain electrode pattern was formed was pressed against the silver fine particle ink uniform coating surface to remove unnecessary portions.
  • the glass relief printing plate is obtained by wet etching of glass excellent in accuracy of convex acute angle portions (edges).
  • the pattern remaining on the blanket was further dried and the solvent in the silver fine particle ink was sufficiently volatilized, it was pressed onto the substrate at a pressure of 150 kPa to transfer the desired source and drain electrode patterns onto the substrate.
  • the average value was 0.8 nm.
  • the electrode pattern produced by letterpress reverse printing was produced with a channel length (L) of 20 ⁇ m and a channel width (W) of 100 ⁇ m.
  • the electrode film thickness was made to be 100 nm after sintering.
  • the fabricated device was subjected to a heat treatment in the atmosphere at 50 ° C. for about 10 minutes, and the Id-Vg and Id-Vd characteristics were measured with a semiconductor parameter measuring device (Keithley 4200CSC). The / OFF ratio was determined by a known method.
  • the unit of field effect mobility is cm 2 / Vs.
  • Example 1 Synthesis of silver fine particle dispersion
  • N, N-dimethylethylenediamine manufactured by Tokyo Chemical Industry Co., Ltd.
  • 3- (2-ethylhexyloxy) propyl After adding 325.6 g (1.738 mmol) of amine (manufactured by Tokyo Chemical Industry Co., Ltd.), the mixture was heated and stirred with an oil bath until the internal temperature of the amine solution reached 30 ° C.
  • the prepared metal fine particle dispersion was spin coated on a glass substrate to prepare a coating film.
  • the obtained coating film was sintered at 120 ° C. for 30 minutes with a constant temperature dryer to obtain a sintered film.
  • the volume resistivity estimated from the resistance value obtained by measurement and the sintered film thickness was 8.1E-6 ⁇ ⁇ cm.
  • a thin film transistor having a bottom gate bottom contact (BGBC) structure having a source electrode or a drain electrode formed by patterning a silver fine particle ink produced using the silver fine particle dispersion of the present invention by a letterpress reverse printing method was produced and evaluated by the following procedure. .
  • gate electrode A Cr film having a film thickness of 100 nm is formed on a non-alkali glass having a thickness of 0.7 mm by sputtering, then a photoresist is applied, exposed and developed, and the Cr film is formed by wet etching. A gate electrode was formed by patterning.
  • Source electrode and drain electrode by letterpress reverse printing method
  • Silver fine particle ink comprising the silver fine particle dispersion of the present invention containing 1-butanol or 1-propanol (manufactured by Kanto Chemical Co., Inc.) as a solvent on the insulating layer.
  • a source electrode and a drain electrode were produced by using a letterpress reverse printing method.
  • the channel length of the transistor was 20 ⁇ m and the channel width was 100 ⁇ m.
  • sintering was performed at 120 ° C. for 30 minutes in a clean oven.
  • the electrode thickness after sintering was 100 nm.
  • the fabricated device had a field effect mobility of 0.6 and an ON / OFF ratio of 3.8E + 6.
  • Example 2 Synthesis of silver fine particle dispersion
  • the prepared metal fine particle dispersion was spin coated on a glass substrate to prepare a coating film.
  • the obtained coating film was sintered at 120 ° C. for 30 minutes with a constant temperature / dryer to obtain a sintered film.
  • the volume resistivity estimated from the resistance value obtained by measurement and the sintered film thickness was 6.2E-6 ⁇ ⁇ cm.
  • a source electrode and a drain electrode were prepared by a letterpress reverse printing method using a silver fine particle ink produced using the silver fine particle dispersion of the present invention. Otherwise, a thin film transistor having a bottom gate bottom contact (BGBC) structure was produced in the same manner as in the method described in Example 1.
  • BGBC bottom gate bottom contact
  • the fabricated device had a field effect mobility of 0.8 and an ON / OFF ratio of 1.2E + 5.
  • Comparative Example 1 Synthesis of silver fine particle dispersion
  • the silver fine particle dispersion used in Comparative Example 1 was prepared by the method described in [Sample 1] of the examples described in WO2015 / 075929.
  • n-octylamine manufactured by Tokyo Chemical Industry Co., Ltd.
  • 7.6 mmol of N, N-dibutylethylenediamine manufactured by Tokyo Chemical Industry Co., Ltd.
  • 1 mmol of oleylamine manufactured by Tokyo Chemical Industry Co., Ltd.
  • Oleic acid 47.7 ⁇ L
  • n-dodecane manufactured by Tokyo Chemical Industry Co., Ltd.
  • n-nonanol manufactured by Tokyo Chemical Industry Co., Ltd.
  • the prepared metal fine particle dispersion was spin coated on a glass substrate to prepare a coating film.
  • the obtained coating film was sintered at 120 ° C. for 30 minutes with a constant temperature / dryer to obtain a sintered film.
  • the volume resistivity estimated from the resistance value obtained by measurement and the sintered film thickness was 6.0E + 1 ⁇ ⁇ cm.
  • a source electrode and a drain electrode were prepared by a letterpress reverse printing method using a silver fine particle ink prepared by adjusting the silver fine particle dispersion prepared in this Comparative Example. Otherwise, a thin film transistor having a bottom gate bottom contact (BGBC) structure was produced in the same manner as in the method described in Example 1.
  • BGBC bottom gate bottom contact
  • the fabricated device had a field effect mobility of 0.9 and an ON / OFF ratio of 5.7E + 5.
  • Comparative Example 2 Synthesis of silver fine particles
  • the conductive paste used in Comparative Example 2 was produced by the method described in Example 1 described in WO2007 / 120756.
  • Toluene was removed from the solution using a rotor evaporator to obtain a highly viscous silver fine particle dispersion.
  • To the resulting silver fine particle dispersion 125 ml of methanol and 125 ml of acetone were added to precipitate silver fine particles.
  • the solution containing silver particulates was filtered through a fine sintered glass funnel and the solid product was collected and dried in vacuo at room temperature. 2.3 g of a dark blue solid product as silver fine particles was obtained.
  • Cyclohexane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the dark blue solid product obtained by synthesis so that the silver concentration was 50 wt%, and the mixture was stirred overnight to obtain a silver fine particle dispersion.
  • the prepared metal fine particle dispersion was spin coated on a glass substrate to prepare a coating film.
  • the obtained coating film was sintered at 120 ° C. for 30 minutes with a constant temperature / dryer to obtain a sintered film.
  • the volume resistivity estimated from the resistance value obtained by measurement and the sintered film thickness was 6.7E-6 ⁇ ⁇ cm.
  • a mixed solvent of 200 ml of isopropyl alcohol and 200 ml of hexane was added to the dispersion obtained after completion of the reaction and stirred for 2 minutes, followed by centrifugal concentration at 3000 rpm for 5 minutes. After removing the supernatant, 20 g of water was further added to the precipitate, followed by stirring for 2 minutes, and the organic solvent was removed under reduced pressure to obtain a silver fine particle dispersion.
  • the prepared metal fine particle dispersion was spin coated on a glass substrate to prepare a coating film.
  • the obtained coating film was sintered at 120 ° C. for 30 minutes with a constant temperature / dryer to obtain a sintered film.
  • the volume resistivity estimated from the resistance value obtained by the measurement and the sintered film thickness was 2.5E + 1 ⁇ ⁇ cm.
  • a source electrode and a drain electrode were prepared by a letterpress reverse printing method using a silver fine particle ink produced using the silver fine particle dispersion of the present invention. Otherwise, a thin film transistor having a bottom gate bottom contact (BGBC) structure was produced in the same manner as in the method described in Example 1.
  • BGBC bottom gate bottom contact
  • the fabricated device had a field effect mobility of 0.07 and an ON / OFF ratio of 6.5E + 5.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Organic Chemistry (AREA)
  • Computer Hardware Design (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Ceramic Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Thin Film Transistor (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)

Abstract

La présente invention concerne : des particules fines de métal qui présentent une conductivité électrique et des caractéristiques de transistor suffisantes avec une température de cuisson d'environ 120 °C ; une dispersion de particules fines de métal qui contient les particules fines de métal ; une encre de particules fines de métal qui utilise la dispersion de particules fines de métal ; et une électrode de transistor à couche mince, un transistor à couche mince et un dispositif électronique, dont chacun utilise l'encre de particules fines de métal qui utilise la dispersion de particules fines de métal. Selon la présente invention, des particules fines de métal qui peuvent être dispersées de manière stable dans un solvant polaire ou un solvant à faible polarité sans utiliser de dispersant qui a un poids moléculaire élevé sont produites au moyen, en tant qu'agent protecteur, d'une amine primaire qui contient au moins un hétéroélément autre qu'un groupe amino. On a découvert qu'une dispersion de particules fines de métal selon la présente invention présente une excellente conductivité électrique par cuisson à une basse température d'environ 120 °C, tout en présentant d'excellentes caractéristiques de transistor par cuisson à une basse température d'environ 120 °C. On a également découvert que la dispersion de particules peut être dispersée de manière stable à 23 °C, tout en présentant les caractéristiques décrites ci-dessus.
PCT/JP2017/030889 2017-03-15 2017-08-29 Dispersion de particules fines de métal, encre conductrice et dispositif électronique WO2018168004A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017049820 2017-03-15
JP2017-049820 2017-03-15

Publications (1)

Publication Number Publication Date
WO2018168004A1 true WO2018168004A1 (fr) 2018-09-20

Family

ID=63523455

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/030889 WO2018168004A1 (fr) 2017-03-15 2017-08-29 Dispersion de particules fines de métal, encre conductrice et dispositif électronique

Country Status (1)

Country Link
WO (1) WO2018168004A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020071198A1 (fr) * 2018-10-02 2020-04-09 ヤスハラケミカル株式会社 Composition de solvant pour pâte conductrice, véhicule, et pâte conductrice

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013036057A (ja) * 2011-08-03 2013-02-21 Dai Ichi Kogyo Seiyaku Co Ltd 銀粒子分散体組成物、これを用いた導電性回路および導電性回路の形成方法
JP2015161008A (ja) * 2014-02-28 2015-09-07 ハリマ化成株式会社 銀微粒子の調製方法
WO2016204105A1 (fr) * 2015-06-15 2016-12-22 株式会社大阪ソーダ Composition pour la fabrication de nanoparticules métalliques

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013036057A (ja) * 2011-08-03 2013-02-21 Dai Ichi Kogyo Seiyaku Co Ltd 銀粒子分散体組成物、これを用いた導電性回路および導電性回路の形成方法
JP2015161008A (ja) * 2014-02-28 2015-09-07 ハリマ化成株式会社 銀微粒子の調製方法
WO2016204105A1 (fr) * 2015-06-15 2016-12-22 株式会社大阪ソーダ Composition pour la fabrication de nanoparticules métalliques

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020071198A1 (fr) * 2018-10-02 2020-04-09 ヤスハラケミカル株式会社 Composition de solvant pour pâte conductrice, véhicule, et pâte conductrice
JP2020057691A (ja) * 2018-10-02 2020-04-09 ヤスハラケミカル株式会社 導電性ペースト用溶剤組成物、ビヒクル、および導電性ペースト
CN112640002A (zh) * 2018-10-02 2021-04-09 安原化学股份有限公司 导电性糊用溶剂组合物、载体和导电性糊
KR20210068395A (ko) * 2018-10-02 2021-06-09 야스하라 케미카루 가부시키가이샤 도전성 페이스트용 용제 조성물, 비히클, 및 도전성 페이스트
CN112640002B (zh) * 2018-10-02 2022-09-23 安原化学股份有限公司 导电性糊用溶剂组合物、载体和导电性糊
JP7198031B2 (ja) 2018-10-02 2022-12-28 ヤスハラケミカル株式会社 導電性ペースト用溶剤組成物、ビヒクル、および導電性ペースト
KR102707721B1 (ko) 2018-10-02 2024-09-19 야스하라 케미카루 가부시키가이샤 도전성 페이스트용 용제 조성물, 비히클, 및 도전성 페이스트

Similar Documents

Publication Publication Date Title
US7847397B2 (en) Nanoparticles with covalently bonded stabilizer
Liu et al. Self‐Assembled Monolayers of Phosphonic Acids with Enhanced Surface Energy for High‐Performance Solution‐Processed N‐Channel Organic Thin‐Film Transistors
US8274084B2 (en) Method and structure for establishing contacts in thin film transistor devices
JP5428104B2 (ja) 有機半導体組成物
EP2423264B1 (fr) Nanofils de phtalocyanine, composition d'encre et élément électronique contenant ceux-ci et procédé de fabrication de nanofils de phtalocyanine
EP2304821B1 (fr) Systèmes de solvants mixtes pour le dépôt de semi-conducteurs organiques
KR102027362B1 (ko) 반도체 조성물
JP5470763B2 (ja) カーボンナノチューブ分散溶液、有機半導体コンポジット溶液、有機半導体薄膜ならびに有機電界効果型トランジスタ
US8319206B2 (en) Thin film transistors comprising surface modified carbon nanotubes
US20120187379A1 (en) Electronic device
US20090004771A1 (en) Methods for making electronic devices with a solution deposited gate dielectric
WO2006137233A1 (fr) Procédé de formation de film mince à matériau semi-conducteur organique et processus de fabrication de transistor à film mince organique
JP2018154806A (ja) 金属微粒子分散体、導電性インク、および電子デバイス
JP6393936B2 (ja) 薄膜トランジスタ、トランジスタアレイ、薄膜トランジスタの製造方法及びトランジスタアレイの製造方法
US20090001356A1 (en) Electronic devices having a solution deposited gate dielectric
WO2018168004A1 (fr) Dispersion de particules fines de métal, encre conductrice et dispositif électronique
JP5715664B2 (ja) 有機半導体組成物
JP2007173472A (ja) 有機半導体層の形成方法及びそれを用いた有機半導体素子の製造方法
JP2007188923A (ja) 電界効果型トランジスタおよびそれを用いた画像表示装置
US20100093129A1 (en) Semiconducting ink formulation
Shin et al. The effect of thermal annealing on pentacene thin film transistor with micro contact printing
JP2010123952A (ja) 薄膜トランジスタおよび半導体組成物
JP2018059137A (ja) 金属微粒子、金属微粒子分散体、導電性インク、および電子デバイス
JP5103982B2 (ja) 有機半導体素子の製造方法
JP2006093539A (ja) 半導体組成物、半導体組成物の分散液および該半導体組成物を用いた薄膜トランジスタ

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17901050

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17901050

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP