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WO2007015350A1 - Method for manufacturing thin film transistor - Google Patents

Method for manufacturing thin film transistor Download PDF

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Publication number
WO2007015350A1
WO2007015350A1 PCT/JP2006/313648 JP2006313648W WO2007015350A1 WO 2007015350 A1 WO2007015350 A1 WO 2007015350A1 JP 2006313648 W JP2006313648 W JP 2006313648W WO 2007015350 A1 WO2007015350 A1 WO 2007015350A1
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WO
WIPO (PCT)
Prior art keywords
group
electrode
thin film
film transistor
layer
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2006/313648
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French (fr)
Japanese (ja)
Inventor
Katsura Hirai
Yasuo Nishi
Hironobu Iwashita
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Konica Minolta Inc
Original Assignee
Konica Minolta Inc
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Filing date
Publication date
Application filed by Konica Minolta Inc filed Critical Konica Minolta Inc
Priority to JP2007529197A priority Critical patent/JPWO2007015350A1/en
Publication of WO2007015350A1 publication Critical patent/WO2007015350A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1603—Process or apparatus coating on selected surface areas
    • C23C18/1607—Process or apparatus coating on selected surface areas by direct patterning
    • C23C18/1608—Process or apparatus coating on selected surface areas by direct patterning from pretreatment step, i.e. selective pre-treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
    • C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
    • C23C18/1886—Multistep pretreatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D30/00—Field-effect transistors [FET]
    • H10D30/01—Manufacture or treatment
    • H10D30/021—Manufacture or treatment of FETs having insulated gates [IGFET]
    • H10D30/031—Manufacture or treatment of FETs having insulated gates [IGFET] of thin-film transistors [TFT]
    • H10D30/0312—Manufacture or treatment of FETs having insulated gates [IGFET] of thin-film transistors [TFT] characterised by the gate electrodes
    • H10D30/0314—Manufacture or treatment of FETs having insulated gates [IGFET] of thin-film transistors [TFT] characterised by the gate electrodes of lateral top-gate TFTs comprising only a single gate
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D30/00—Field-effect transistors [FET]
    • H10D30/01—Manufacture or treatment
    • H10D30/021—Manufacture or treatment of FETs having insulated gates [IGFET]
    • H10D30/031—Manufacture or treatment of FETs having insulated gates [IGFET] of thin-film transistors [TFT]
    • H10D30/0321—Manufacture or treatment of FETs having insulated gates [IGFET] of thin-film transistors [TFT] comprising silicon, e.g. amorphous silicon or polysilicon
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D30/00—Field-effect transistors [FET]
    • H10D30/60—Insulated-gate field-effect transistors [IGFET]
    • H10D30/67—Thin-film transistors [TFT]
    • H10D30/6729—Thin-film transistors [TFT] characterised by the electrodes
    • H10D30/6737—Thin-film transistors [TFT] characterised by the electrodes characterised by the electrode materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D30/00—Field-effect transistors [FET]
    • H10D30/60—Insulated-gate field-effect transistors [IGFET]
    • H10D30/67—Thin-film transistors [TFT]
    • H10D30/6729—Thin-film transistors [TFT] characterised by the electrodes
    • H10D30/6737—Thin-film transistors [TFT] characterised by the electrodes characterised by the electrode materials
    • H10D30/6739—Conductor-insulator-semiconductor electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D30/00—Field-effect transistors [FET]
    • H10D30/60—Insulated-gate field-effect transistors [IGFET]
    • H10D30/67—Thin-film transistors [TFT]
    • H10D30/674—Thin-film transistors [TFT] characterised by the active materials
    • H10D30/6741—Group IV materials, e.g. germanium or silicon carbide
    • H10D30/6743—Silicon
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/80—Constructional details
    • H10K10/82—Electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/60—Forming conductive regions or layers, e.g. electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • 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
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
    • H01L21/76841—Barrier, adhesion or liner layers
    • H01L21/76871—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers
    • H01L21/76874—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers for electroless plating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D86/00—Integrated devices formed in or on insulating or conducting substrates, e.g. formed in silicon-on-insulator [SOI] substrates or on stainless steel or glass substrates
    • H10D86/01—Manufacture or treatment
    • H10D86/021—Manufacture or treatment of multiple TFTs
    • H10D86/0241—Manufacture or treatment of multiple TFTs using liquid deposition, e.g. printing
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/464—Lateral top-gate IGFETs comprising only a single gate
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/466—Lateral bottom-gate IGFETs comprising only a single gate

Definitions

  • the present invention relates to a method for manufacturing an organic semiconductor element, particularly an organic thin film transistor, and particularly, a low-resistance electrode is easily formed with high pattern accuracy by means of electrode pattern forming means having good resolution and pattern accuracy.
  • the present invention relates to a method for manufacturing an organic thin film transistor.
  • Devices using organic semiconductors have milder film-forming conditions than conventional inorganic semiconductor devices, and semiconductor thin films can be formed on various substrates or formed at room temperature. Expected to be low cost and flexible by forming a thin film on polymer film.
  • polyacene compounds such as anthracene, tetracene, and pentacene have been studied as well as conjugated polymers and oligomers such as polyphenylene vinylene, polypyrrole, polythiophene, and oligogophene.
  • a method of forming an electrode a method of forming an electrode pattern by etching or lift-off of a uniformly formed metal thin film, or a metal filler is included. And a method of forming an electrode pattern by printing a conductive polymer solution or a conductive polymer solution.
  • Patent Document 1 describes that an electroless plating is used to easily form a low-resistance electrode.
  • an electrode pattern is easily formed by combining a catalyst that generates electroless plating, a plating agent, and patterning using a printing method thereof. Thereby, an electrode pattern can be formed without going through complicated steps.
  • patterning by screen printing, letterpress, intaglio, lithographic printing, etc., or patterning by ordinary ink jet printing, etc. has a pattern accuracy higher than that by the above-mentioned method of forming a resist layer. There are problems such as becoming low. The present invention improves this.
  • Patent Document 1 Japanese Unexamined Patent Application Publication No. 2004-158805
  • An object of the present invention is to obtain a thin film transistor manufacturing method with high production efficiency that can form a low resistance electrode with high pattern accuracy by a simple electrode pattern forming method with good resolution and pattern accuracy.
  • an electrode with high patterning accuracy can be formed using an electroless plating, and a low-resistance electrode can be easily obtained with high accuracy.
  • FIG. 1 is a diagram showing a configuration example of an organic thin film transistor element of the present invention.
  • FIG. 2 is a schematic equivalent circuit diagram of an example of the organic thin film transistor element sheet of the present invention.
  • FIG. 3 is a schematic configuration diagram of an electrostatic suction ink jet apparatus.
  • FIG. 4 is a diagram for explaining the meniscus behavior of the ink in the ink jet apparatus shown in FIG.
  • FIG. 5 is a diagram for explaining a method of manufacturing the organic thin film transistor element (top contour outer type) of the present invention.
  • FIG. 6 is a diagram showing an example of the configuration of an organic thin film transistor element (bottom contour outer type) using the manufacturing method of the present invention.
  • FIG. 7 is a view for explaining an example of another method for producing the organic thin film transistor element (top contact type) of the present invention.
  • the thin film transistor element of the present invention includes a top gate type having a source electrode and a drain electrode in contact with an organic semiconductor layer on a support, and a gate electrode on the support via a gate insulating layer.
  • a top gate type having a source electrode and a drain electrode in contact with an organic semiconductor layer on a support
  • a gate electrode on the support via a gate insulating layer is roughly divided into a bottom gate type having a gate electrode and having a source electrode and a drain electrode connected by an organic semiconductor layer via a gate insulating layer.
  • Specific examples of the layer structure of the element are as shown in FIG. Become.
  • FIG. 1 is a diagram showing a configuration example of an organic thin film transistor element of the present invention.
  • A in the figure shows that a source electrode 52 and a drain electrode 53 are formed on a support 56 by a metal foil, etc.
  • An organic semiconductor layer 51 made of the organic semiconductor material of the invention is formed, an insulating layer 55 is formed thereon, and a gate electrode 54 is further formed thereon to form an organic thin film transistor element.
  • FIG. 4B shows the organic semiconductor layer 51 formed between the electrodes in FIG. 5A so as to cover the entire surface of the electrode and the support using a coating method or the like.
  • C shows that the organic semiconductor layer 51 is first formed on the support 56 using a coating method or the like, and then the source electrode 52, the drain electrode 53, the insulating layer 55, and the gate electrode 54 are formed.
  • FIG. 4D after forming a gate electrode 54 on a support 56 with a metal foil or the like, an insulating layer 55 is formed, and a source electrode 52 and a drain electrode 53 are formed thereon with a metal foil or the like. Then, an organic semiconductor layer 51 formed of the organic semiconductor material of the present invention is formed between the electrodes. In addition, it is possible to adopt a configuration as shown in FIGS.
  • FIG. 2 is a schematic equivalent circuit diagram of an example of a thin film transistor element sheet 10 in which a plurality of thin film transistor elements of the present invention are arranged.
  • the thin film transistor sheet 10 has a large number of thin film transistor elements 14 arranged in a matrix.
  • 11 is a gate bus line of the gate electrode of each thin film transistor element 14, and 12 is a source nos line of the source electrode of each thin film transistor element 14.
  • An output element 16 is connected to the drain electrode of each thin film transistor element 14, and this output element 16 is, for example, a liquid crystal or an electrophoretic element, and constitutes a pixel in the display device.
  • a liquid crystal is shown as the output element 16 in an equivalent circuit having both resistance and capacitor power.
  • 15 is a storage capacitor
  • 17 is a vertical drive circuit
  • 18 is a horizontal drive circuit.
  • the method of the present invention can be used for producing such a thin film transistor sheet in which organic TFT elements are two-dimensionally arranged on a support.
  • the source, drain, or gate electrode, and the gate or source bus line, etc. are not etched with a metal thin film using a photosensitive resin such as etching or lift-off.
  • a method using an electroless plating method is known.
  • the method for forming an electrode by an electroless plating method causes an electroless plating to occur at a portion where the electrode is provided by acting with a plating agent.
  • a liquid containing a plating catalyst for example, by a printing method (including inkjet printing), After patterning, the plating agent is brought into contact with the portion where the electrode is provided. Then, an electroless plating is performed on the portion by contact between the catalyst and the plating agent, and an electrode pattern is formed.
  • Either the electroless catalyst or the application of the plating agent may be reversed, or the pattern formation may be performed, but a method of forming a plating catalyst pattern and applying the plating agent to this is preferred. Good.
  • a printing method for example, screen printing, planographic printing, relief printing, intaglio printing, ink jet printing, or the like is used. Patterning of a plating catalyst or a plating agent by these printings is a highly precise circuit. When the pattern is required, the accuracy is not enough.
  • the catalyst that acts on the plating agent to generate electroless plating is composed of at least one compound selected from Pd, Rh, Pt, Ru, Os, Ir force, and their ions, or metal fine particles.
  • halides such as chlorides, bromides, and fluorides of the above elements
  • inorganic salts or composite salts such as sulfates, nitrates, phosphates, borates, and cyanides
  • carboxylic acids Salts organic sulfonates, organic phosphates, alkyl complexes, alkane complexes, alkene complexes, cyclopentagen complexes, porphyrins, phthalocyanines, and other organic complex salt powers selected or mixtures of these, ions of these elements, these Metal fine particles of these elements are applicable.
  • the plating agent for example, a solution in which metal ions deposited as an electrode are uniformly dissolved is used, and the reducing agent is contained together with the metal salt.
  • the force used for the solution is not limited to this as long as it causes electroless plating, and gaseous or powdered plating agents are used. It is also possible to apply.
  • metal salt metal halides, nitrates, sulfates, phosphates, borates, acetates, tartrate, kenates, and the like are applicable.
  • reducing agent hydrazine, hydrazine salt, borohalide salt, hypophosphite, hyposulfite, alcohol, aldehyde, carboxylic acid, carboxylate and the like are applicable.
  • elements such as boron, phosphorus, and nitrogen contained in these reducing agents may be contained in the deposited electrode.
  • a mixture of the metal salt and the reducing agent may be applied, or the metal salt and the reducing agent may be applied separately.
  • the metal salt and the reducing agent may be applied separately.
  • a more stable electrode pattern can be formed by first arranging the metal salt in the portion where the electrode is provided and then arranging the reducing agent.
  • the plating agent coconut can contain additives such as a buffer for adjusting pH and a surfactant.
  • additives such as a buffer for adjusting pH and a surfactant.
  • organic solvents such as alcohols, ketones and esters can be added as the solvent used in the solution.
  • the composition of the plating agent is composed of a metal salt of the metal to be deposited, a reducing agent, and, if necessary, an additive and an organic solvent, but the concentration and composition may be varied depending on the deposition rate. Can be adjusted. It is also possible to adjust the deposition rate by adjusting the temperature of the plating agent. Examples of the temperature adjusting method include a method of adjusting the temperature of the plating agent and a method of adjusting the temperature by heating and cooling the substrate before immersion. Furthermore, it is possible to adjust the thickness of the metal thin film that is deposited in the time it is immersed in the plating agent.
  • a method for printing a liquid containing the electroless plating catalyst a conventional screen printing method, a printing method such as a relief printing plate, a planographic printing plate, an intaglio printing method, or a printing method using a normal inkjet method is used. It is characterized by the use of an electrostatic bow I type liquid discharge device V. Electrostatic bow I-type liquid discharge device is used to form an electroless plating catalyst pattern, and then contact the plating agent to apply the electroless plating. As a result, an electrode pattern made of a metal thin film formed by electroless plating is obtained. [0038] The contact of the plating agent can be performed by coating, spraying, dipping or the like.
  • the plating agent may be printed by a pattern printing in a region including the region where the plating catalyst pattern is formed, such as ink jet printing, screen printing, intaglio printing, lithographic printing, letterpress printing, and the like.
  • a suction-type liquid ejection device may be used.
  • the electrode pattern is deposited by electroless plating, if the solute contained in the plating agent adheres to the substrate surface, it can be cleaned if necessary.
  • the application of the plating agent and the plating catalyst may be reversed! /.
  • puttering may be performed with a mastic agent.
  • the electrode provided by applying the electroless plating is composed of at least one metal selected from Au, Ag, Cu, Ni, Co, and Fe, or an alloy force thereof.
  • the metal includes an intermetallic compound.
  • Examples of the electrostatic suction type liquid ejection device include, for example, Japanese Patent Laid-Open No. 8-238774.
  • the electrostatic attraction method is a method capable of ejecting minute droplets, and the ejected droplets receive electrostatic force during flight separately from the ejection energy, and thus the ejection energy per unit volume. Can be reduced, and can be applied to the discharge of minute droplets, and a high-precision printed pattern can be obtained.
  • FIG. 3 is a schematic cross-sectional view of an electrostatic suction type ink jet device.
  • 101 is an ink ejection chamber
  • 102 is ink
  • 103 is an ink chamber
  • 104 is a nozzle hole
  • 105 is an ink tank
  • 106 is an ink supply path
  • 107 is a rotating roller
  • 108 is a recording medium
  • 110 is A control element unit 111 indicates a process control unit.
  • 114 is an electrostatic field applying electrode portion disposed on the ink chamber 103 side of the ink ejecting chamber 101
  • 115 is a counter electrode portion that is a metal drum installed on the rotating roller 107
  • 116 is a counter electrode portion.
  • This is a bias power supply that applies a negative voltage of several thousand volts to 115.
  • 117 is a high-voltage power supply section that supplies a high voltage of several hundred volts to the electrostatic field applying electrode section 114, and 118 is a grounding section. [0047]
  • the electrostatic field applying electrode part 114 and the counter electrode part 115 it is applied to the counter electrode part 115!
  • a bias power supply part 116 having a negative voltage of several thousand V and several hundred V The high voltage of the high voltage power supply unit 117 is superimposed to form a superimposed electric field, and ejection of the ink 102 from the nozzle hole 104 is controlled by this superimposed electric field.
  • 119 is a convex meniscus formed in the nozzle hole 104 by a bias voltage of several thousand V applied to the counter electrode 115.
  • the ink 102 is transferred to the nozzle hole 104 for discharging the ink 102 through the ink supply path 106 by capillary action.
  • the counter electrode portion 115 on which the recording medium 108 is mounted is disposed so as to face the nozzle hole 104.
  • the ink 102 that has reached the nozzle hole 104 is formed with a convex ink meniscus 119 by a bias voltage of several thousand V applied to the counter electrode 115. .
  • the voltage from the bias power source 116 applied to the counter electrode 115 by applying a signal voltage from the high voltage power source 117 of several hundred volts to the electrostatic field applying electrode 114 disposed in the ink chamber 103.
  • the ink 102 is ejected onto the recording medium 108 by the superimposed electric field, and a printed image is formed.
  • the charge generated on the liquid surface is further concentrated at the center, thereby forming a meniscus meniscus 119c called a tailor cone.
  • the electrostatic force due to the amount of charge concentrated on the top of the tailor cone is the surface of the ink.
  • the surface tension is exceeded, the droplets are separated and discharged.
  • the electrostatic suction type ink jet method is characterized in that it generates fine droplets compared to the nozzle diameter by electrostatic force, and uses a liquid containing a catalyst catalyst as ink. Pattern printing is performed on the electrode forming part to form a plating catalyst pattern.
  • the electroless plating catalyst solution can be used by adjusting the surface tension (for example, 10 to: LOOmNZm) applicable as an ink.
  • a soluble palladium salt (palladium chloride (Pd 2+ concentration 1. Og / L)
  • solvent isopropyl alcohol 12 wt%
  • glycerin 20 mass 0/0
  • 2-methyl-2 It is possible to use powerful catalyst solutions such as 4-pentanediol, 5% by mass, ion-exchanged water, and 40% by mass.
  • the method by electrostatic attraction is not limited to the above method, and any electrostatic attraction method including variations such as the structure (line head) of the above-mentioned Japanese Patent Application Laid-Open No. 2000-127410 and the method of applying an electric field.
  • a liquid ejection device may be used.
  • an electrode (pattern) is formed by contacting with a plating agent. ) Formation can be performed with high accuracy.
  • At least one of the gate, source, and drain electrodes is formed by an electroless plating method using the method of the present invention. That is, the formation of the plating catalyst pattern corresponding to the electrode pattern is performed and formed by using a liquid containing the plating catalyst as ink and discharging it with an electrostatic suction type liquid discharge device. By bringing a plating agent into contact with the plating catalyst pattern, a metal thin film by electroless plating is formed according to the plating catalyst pattern.
  • the amount of ink ejected can be controlled by the electrostatic field application time.
  • the electrostatic field applying electrode 114 is connected to the process control unit 111, and the process control unit 111 drives the control element unit 110 from the high-voltage power supply unit 117 to apply a signal voltage (a drive circuit is illustrated). do not do).
  • the process control unit 111 controls the electric field strength to form the tip of the nozzle 104.
  • the electric field strength at the meniscus 119a (see FIG. 4) can be controlled, and the ejection amount of the ink 102 from the nozzle 104 force is adjusted.
  • the driving voltage is set to several hundred volts (approximately 1000 volts or less)
  • the upper limit of the nozzle diameter when the electrostatic force exceeds the surface tension due to the local electric field strength is preferably 25 m, with a force of approximately 25 / zm. In particular, 1 is more preferable.
  • the nozzle diameter is desirably in the range of 0.01 to 8 / ⁇ ⁇ .
  • the evaporation rate of the solvent is relatively high, and therefore, the pattern formation of the plating catalyst component is also accelerated.
  • the ejected droplets tend to repel, which tends to hinder the formation of a pattern of the catalyst catalyst component. Refinement becomes possible.
  • the lower limit of the nozzle hole diameter (hereinafter referred to as nozzle diameter) is preferably 0.01 ⁇ m for production reasons.
  • the patterning is performed without using a resist or the like.
  • the pattern printing may be performed directly on the substrate on which the layer 2 is formed, for example, by discharging an electroless plating catalyst solution as an ink from an electrostatic suction ink jet apparatus.
  • an electroless plating catalyst pattern with high accuracy, so that an electrode pattern can be obtained with high precision by contacting a plating agent and forming a metal thin film by electroless plating.
  • the gate electrode in the top-gate thin film transistor in FIG. 1 can be formed with high accuracy by the same method.
  • the source or drain electrode is formed by the electroless plating method.
  • the source, drain electrode, source bus line, etc. are formed at a time. Preferred to be used when.
  • the method of the present invention is suitable for manufacturing a thin film transistor having a bottom-gate structure.
  • a source, a gate, a gate bus line, a gate insulating layer, a semiconductor layer, and the like are mounted on a substrate. It is preferable that the patterning of the source bus line, the drain electrode, etc. can be performed with high accuracy while avoiding complicated processes such as resist formation.
  • the method for producing a thin film transistor of the present invention is particularly advantageously used for producing an organic thin film transistor.
  • patterning can be performed easily and accurately without using a method such as forming a resist, and photosensitive resin is used for electrode patterning.
  • the photosensitive resin itself, and the process of forming and removing the resist from the photosensitive resin are limited to those that do not affect the organic semiconductor layer.
  • the method of invention is preferred.
  • the organic semiconductor when an electrode is formed on the organic semiconductor layer by electroless plating, the organic semiconductor is used in a region other than the electrode formation region (for example, a region that becomes a semiconductor channel in the thin film transistor element). It is preferable that the layer should not be in direct contact with these catalytic agents, which may have an impact on organic semiconductor materials. Therefore, in the manufacture of a thin film transistor having a top contact type structure, it is preferable to provide an organic semiconductor layer protective film in a required region other than the electrode formation region.
  • the protective film is preferably patterned so as to protect a protective region other than the electrode forming region (for example, a region for forming a semiconductor channel).
  • a plating catalyst pattern is formed, and electroless plating can be performed by contacting the plating agent with the plating catalyst pattern.
  • the method for bringing the plating agent into contact is not particularly limited, but for example, a method of spraying by dipping in the plating agent or printing such as an ink jet method, screen printing, intaglio, planographic printing, letterpress or the like is applicable.
  • the solute contained in the plating agent or the like adheres to the substrate surface. If necessary, the substrate can be cleaned if necessary.
  • the protective film formed on the organic semiconductor layer seals the action of the plating catalyst, the metal salt in the plating agent, the reducing agent, etc. If it is an inert material that does not significantly affect the organic semiconductor material, and if a photosensitive composition such as a photosensitive resin layer is formed on the organic semiconductor protective layer, the coating is applied. The material is preferred because it is not affected by the process and is not affected by the patterning of the photosensitive resin layer.
  • Examples of such materials include the following polymer materials, particularly materials containing a hydrophilic polymer, and more preferred are aqueous solutions or aqueous dispersions of hydrophilic polymers.
  • the hydrophilic polymer is a polymer that is soluble or dispersible in water or an acidic aqueous solution, an alkaline aqueous solution, an alcohol aqueous solution, or an aqueous solution of various surfactants.
  • polybulal alcohol, homopolymers and copolymers having component power such as HEMA, acrylic acid, and acrylamide can be suitably used.
  • materials containing inorganic oxides and inorganic nitrides are also preferable because they do not affect the organic semiconductor and do not affect other coating processes.
  • the material of the gate insulating layer described later can also be used.
  • the organic semiconductor protective layer containing an inorganic oxide or inorganic nitride as the gate insulating layer material is preferably formed by an atmospheric pressure plasma method.
  • a method for forming a thin film by a plasma method under atmospheric pressure is a process in which a thin film is formed on a substrate by discharging under atmospheric pressure or a pressure near atmospheric pressure, exciting a reactive gas into plasma, and
  • the method is as follows: JP 11-61406, 11-133205, 2000-121804, 2000-147209, 2000-185362, etc. (hereinafter referred to as atmospheric pressure plus) , Also called ma method).
  • atmospheric pressure plus also called ma method
  • the photoresist layer it is preferable to use a force-receptor photosensitive material that can use a known positive or negative material.
  • a force-receptor photosensitive material that can use a known positive or negative material.
  • a photoresist material (1) JP-A-11-271969, column 2001-117219, JP-A-11-311859, JP-A-1 1-352691, a dye-sensitized photopolymerization photosensitive material, (2) JP-A-9-179292, US Pat. No.
  • Negative photosensitive materials having sensitivity to infrared lasers such as 20 01-154374, (3) JP-A-9-171254, 5-115144, 10-87733, 9-43847, 10 -26 8512, 11-194504, 11-223936, 11-84657, 11-174 681, 7-285275, JP 2000-56452, W097Z39894, 98,42507
  • a positive photosensitive material having photosensitivity to an infrared laser (2) and (3) are preferable in that the process is not limited to a dark place, and when removing the photoresist layer, the positive type (3) is most preferable.
  • Solvents for forming the coating solution of the photosensitive resin include propylene glycol monomethylenoatenore, propyleneglycolenomonoethylenoatenore, methinorecellosonoleb, methinorecerosonoleb acetate, ethinorecerozolev, Examples include ethyl acetate sorb acetate, dimethylformamide, dimethyl sulfoxide, dioxane, acetone, cyclohexanone, trichloroethylene, and methyl ethyl ketone. These solvents are used alone or in combination of two or more.
  • Methods for forming the photosensitive resin layer include spray coating, spin coating, blade coating, dip coating, casting, roll coating, bar coating, die coating, and other coating methods. Etc., as described in the patterning of the protective film.
  • patterning exposure is performed by an Ar laser, a semiconductor laser, a He-Ne laser, a YAG laser, a carbon dioxide gas laser, or the like.
  • a semiconductor laser having an oscillation wavelength in the infrared is preferable.
  • the output is suitably 50mW or more, preferably lOOmW or more.
  • a water-based alkaline developer is suitable as the developer used for developing the photosensitive resin layer.
  • the aqueous alkaline developer include alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium metasilicate, potassium metasilicate, dibasic sodium phosphate, and tribasic sodium phosphate.
  • An aqueous solution in which an alkaline compound such as yuum hydroxide, piperidine, 1,8-diazabicyclo [5, 4, 0] -7-undecene is dissolved can be mentioned.
  • concentration of the alkaline compound in the present invention in the alkali developer is usually 1 to 10% by mass, preferably 2 to 5% by mass.
  • an organic solvent such as an ionic surfactant, an amphoteric surfactant, and alcohol can be added as necessary.
  • an organic solvent propylene glycol, ethylene glycol monophenyl ether, benzyl alcohol, n -propyl alcohol, and the like are useful.
  • an abrasion layer which is another photosensitive resin layer, may also be used for forming a protective catalyst pattern of the protective film, that is, for forming an electrode pattern.
  • the abrasion layer used in the present invention can also constitute an energy light absorber, a binder resin, and various additive powers added as necessary.
  • the energy light absorber various organic and inorganic materials that absorb the energy light to be irradiated can be used.
  • the laser light source is an infrared laser
  • Use ferromagnetic metal powder such as metal magnetic powder mainly composed of oxide, metal nitride, metal carbide, metal boride, graphite, carbon black, titanium black, Al, Fe, Ni, Co, etc. Among these, carbon black, cyanine-based pigments, and Fe-based ferromagnetic metal powders are preferred.
  • the content of the energy light absorber is about 30 to 95% by mass, preferably 40 to 80% by mass of the abrasion layer forming component.
  • the nodding resin of the abrasion layer can be used without particular limitation as long as it can sufficiently retain the colorant fine particles, and it can be used as a polyurethane resin, a polyester resin, or a salt vinyl.
  • examples thereof include a system resin, a polyvinylacetal resin, a cellulose resin, an acrylic resin, a phenoxy resin, a polycarbonate, a polyamide resin, a phenol resin, and an epoxy resin.
  • the content of Noinda rosin is about 5 to 70% by mass, preferably 20 to 60% by mass, of the abrasion layer forming component.
  • the ablation layer referred to in this specification refers to a layer that is ablated by irradiation with high-density energy light.
  • the ablation referred to herein is ablation caused by physical or chemical changes. This includes the phenomenon that the Yon layer is completely scattered, part of it is broken or scattered, and the physical or chemical change occurs only in the vicinity of the interface with the adjacent layer. Using this ablation, a resist image is formed and electrodes are formed.
  • the high-density energy light can be used without particular limitation as long as it is active light that generates ablation.
  • flash exposure using a xenon lamp, a halogen lamp, a mercury lamp, or the like may be performed through a photomask, or scanning exposure may be performed by converging laser light or the like.
  • the energy density is preferably 50 to 500 miZcm 2 , more preferably 100 to 300 mj / cm 2 .
  • an electrode material repellent layer having a thickness of about 0.5 ⁇ m on the photosensitive resin layer (ablation layer) by solvent coating.
  • the electrode material repellent layer uses a silicone rubber layer, a silane coupling agent, a titanate coupling agent, or the like to form an electrode material on the surface of the photosensitive layer, and in the present invention, against the plating catalyst solution or the plating agent solution. It is a layer that imparts repellent properties.
  • an electrode material repellent layer By coating an electrode material repellent layer on the photosensitive layer and exposing or developing the photosensitive layer, buttering can be performed in combination with the photosensitive layer.
  • an abrasion layer or a photopolymerizable photosensitive material is preferred.
  • the formed photosensitive layer and electrode material repellent layer are exposed to a pattern such as a source electrode and a source bus line with a semiconductor laser or the like, and then the exposed electrode material repellent layer (silicone rubber layer) is brushed. Remove. Since the adhesiveness between the photosensitive layer and the silicone rubber layer changes with exposure, the silicone rubber layer can be easily removed by brush treatment.
  • the effect of the protective layer can be enhanced, and only the portion where the electrode is formed can be accurately patterned, and the electrode material can be patterned by a simple process.
  • the resist image may be removed.
  • organic solvents used as photoresist coating solvents such as alcohols, ethers, esters, ketones, and glycol ethers. Solvents are preferred when the organic semiconductor layer is not eroded.
  • the patterning of the protective film itself can be performed using the electrostatic suction type liquid ejection apparatus according to the present invention.
  • the protective film material solution as ink By discharging the protective film material solution as ink using the electrostatic attraction type ink jet device, the protective film can be directly patterned without performing a resist formation method.
  • an electrostatic suction type ink jet device it is possible to easily perform patterning with high accuracy equivalent to resist formation by photosensitive resin.
  • the protective film may be removed after the electrode is formed.
  • the substrate surface is cleaned, but is preferably removed at that time. However, if the performance as a thin film transistor is not affected, it may be left as it is.
  • various condensed polycyclic aromatic compounds and conjugated compounds are applicable.
  • Examples of the condensed polycyclic aromatic compound include anthracene, tetracene, pentacene, hexacene, heptacene, taricene, picene, fluorene, pyrene, peropyrene, perylene, terylene, kuterite terylene, coronene, talillen. And compounds such as musantracene, bisanthene, zeslen, heptazelene, pyranslen, violanthene, isoviolanthene, sacobiphenyl, phthalocyanine, porphyrin, and derivatives thereof.
  • conjugated compound examples include polythiophene and its oligomer, polypyrrole and its oligomer, polyaniline, polyphenylene and its oligomer, polyphenylene vinylene and its oligomer, polyphenylene vinylene and its oligomer, polyacetylene, Polydiacetylene, tetrathiafulvalene compound, quinone compound, tetracyanoxy
  • conjugated compound include polythiophene and its oligomer, polypyrrole and its oligomer, polyaniline, polyphenylene and its oligomer, polyphenylene vinylene and its oligomer, polyphenylene vinylene and its oligomer, polyacetylene, Polydiacetylene, tetrathiafulvalene compound, quinone compound, tetracyanoxy
  • cyan compounds such as nodimethane, fullerenes and derivatives or mixtures thereof.
  • thiophene hexamer ⁇ -secthiophene e, ⁇ -dihexinore a-secciothiophene, e, ⁇ -dihexinore a-quinketiophene, ⁇ , ⁇ Oligomers such as —bis (3-butoxypropyl) -a-secciothiophene can be preferably used.
  • copper phthalocyanine is a metal phthalocyanine such as fluorine-substituted copper phthalocyanine described in JP-A-11-251601, naphthalene 1,4,5,8-tetracarboxylic acid diimide, N, N'-bis (4 Trifluoromethylbenzyl) naphthalene 1, 4, 5, 8-tetracarboxylic acid diimide, N, N'-bis (1H, 1H-perfluorooctyl), N, N'-bis (1H , 1H perfluorobutyl) and N, N'-dioctylnaphthalene 1,4,5,8-tetracarboxylic diimide derivatives, naphthalene 2, 3, 6, 7 naphthalene tetracarboxylic diimides such as tetracarboxylic diimide , And anthracene 2, 3, 6, 7-fused ring tetracarboxylic acid diimides such as
  • dyes such as notube, merocyanine dyes, and hemicyanine dyes.
  • At least one selected from the group consisting of condensed polycyclic aromatic compounds such as pentacene, fullerenes, condensed ring tetracarboxylic acid diimides, and metal phthalocyanines are Preferred.
  • examples of the organic semiconductor material according to the present invention include silylethyl-pentacene compounds described in Adv. Mater. 2003, 15, No. 23, December 3 (2009—2011), and J. Am. Chem. Soc., 2005, 127, 4986 to 4987 Compounds having acene and heteroacene as a mother nucleus are also preferred.
  • Silylethynylpentacene, trisalkylsilylpentacene, triisopropylpropylsilylethylpentacene, etc. Can be suitably used.
  • organic semiconductor materials include tetrathiafulvalene (TTF) -tetracyanoquinodimethane (TCNQ) complex, bisethylenetetrathiafulvalene (BEDTTTF) -perchloric acid complex, BEDTTTF iodine complex, TCNQ iodine complex, etc.
  • TTF tetrathiafulvalene
  • BEDTTTF bisethylenetetrathiafulvalene
  • TCNQ iodine complex etc.
  • Organic molecular complex Can also be used.
  • ⁇ -conjugated polymers such as polysilane and polygermane can also be used as organic'inorganic hybrid materials described in JP-A-2000-260999.
  • thiophene oligomer represented by the following general formula (1) is preferred.
  • R represents a substituent
  • the thiophene oligomer represented by the general formula (1) will be described.
  • examples of the substituent represented by R include an alkyl group (eg, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a hexyl group).
  • an alkyl group eg, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a hexyl group.
  • cycloalkyl group eg, cyclopentyl group, cyclohexyl group, etc.
  • alkenyl group eg, buyl group, aryl group, etc.
  • -Ruyl group for example, ethynyl group, propargyl group, etc.
  • aryl group for example, phenol group, p-chlorophenol group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, Azulenyl, acenaphthyl, fluorenyl, phenanthryl, indur, pyrenyl, biphenyl, etc.
  • aromatic heterocyclic groups eg, furyl, Group, pyridyl group, pyridazyl group, pyrimidyl group, birazyl group, triazyl group, imidazolyl group, pyrazolyl group, thiazolyl group, benzoimidazolyl group, benzoxazolyl group, quinazolyl group, phthalazyl group, etc.
  • heterocyclic group for example, pyrrolidyl group, imidazolidyl group
  • silyl group for example, trimethylsilyl group, triisopropylpropyl group, triphenylsilyl group, ferroethyl silyl group, etc.
  • a preferable substituent is an alkyl group, more preferably an alkyl group having 2 to 20 carbon atoms, and particularly preferably an alkyl group having 6 to 12 carbon atoms.
  • the terminal group of the thiophene oligomer used in the present invention will be described.
  • the terminal group of the thiophene oligomer used in the present invention does not have a chael group.
  • an aryl group for example, a phenyl group, p-Chlorofuryl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulyl group, acenaphthyl group, fluoro group, phenanthryl group, indenyl group, pyrenyl group, biphenyl group Etc.
  • alkyl group for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, etc.
  • the thiophene oligomer used in the present invention preferably has no head-to-head structure in the structure, and more preferably, the structure has a head-to-tail structure, or It preferably has a tail-to-tail structure.
  • Head-to-Head structure For example, " ⁇ -electron organic solid” (1998, published by the Japan Society for Publishing Press, Japan) This can be referred to on pages 27-32 and Adv. Mater. 1998, 10, No. 2, pages 93-116, etc.
  • specific structural features are shown below.
  • R has the same meaning as R in the general formula (1).
  • the organic semiconductor layer may be formed of, for example, a material having a functional group such as acrylic acid, acetamido, dimethylamino group, cyano group, carboxyl group, nitro group, benzoquinone derivative, tetracyanethylene.
  • a functional group such as acrylic acid, acetamido, dimethylamino group, cyano group, carboxyl group, nitro group, benzoquinone derivative, tetracyanethylene.
  • tetracyanoxydimethane and their Materials that accept electrons such as derivatives, materials having functional groups such as amino, triphenyl, alkyl, hydroxyl, alkoxy, and phenyl groups, substituted amines such as phenylenediamine , Anthracene, benzoanthracene, substituted benzoanthracene, pyrene, substituted pyrene, force rubazole and its derivatives, tetrathiofulvalene and its derivatives, etc. Processing may be performed.
  • the doping means introduction of an electron donating molecule (acceptor) or an electron donating molecule (donor) into the thin film as a dopant. Therefore, the doped thin film is a thin film containing the condensed polycyclic aromatic compound and the dopant.
  • a well-known thing can be employ
  • the organic semiconductor layer can be formed by a known method, for example, vacuum deposition, MBE (Molecular Beam Epitaxy), ion cluster beam method, low energy ion beam method, ion plate. Coating method, sputtering method, CVD (Chemical Vapor Deposition), laser deposition, electron beam deposition, electrodeposition, spin coating, dip coating, bar coating method, die coating method, spray coating method, LB method, etc., screen printing, Examples thereof include ink jet printing and blade coating.
  • the precursor film formed by coating is heat-treated. A thin film of the desired organic material may be formed.
  • the thickness of the organic semiconductor layer is not particularly limited, but the characteristics of the obtained transistor are largely influenced by the thickness of the organic semiconductor layer. Different forces depending on the conductor Generally 1 ⁇ m or less, particularly 10 to 300 nm is preferred.
  • At least one of the gate electrode and the source Z drain electrode is formed by the method for manufacturing an organic semiconductor element of the present invention, whereby a low-resistance electrode is formed. , Without causing deterioration of the characteristics of the organic semiconductor layer material layer It becomes possible to form.
  • the source electrode or the drain electrode is a force S formed by the electroless plating method, and one of the source electrode and the drain electrode is an electrode that does not depend on the electroless plating together with the gate electrode. It's okay.
  • the electrode is formed by a known method or a known electrode material.
  • the electrode material is not particularly limited as long as it is a conductive material.
  • conductive polymers whose conductivity has been improved by doping, for example, conductive polyarine, conductive polypyrrole, conductive polythiophene (polyethylenedithiophene and polystyrene sulfonic acid complex, etc.) are also suitable. Used.
  • materials having low electrical resistance at the contact surface with the semiconductor layer are preferred as materials for forming the source electrode or drain electrode.
  • ⁇ materials having low electrical resistance at the contact surface with the semiconductor layer are preferred.
  • the electrode is formed using a fluid electrode material such as a solution, paste, ink, or dispersion containing the above-described conductive material, in particular, a conductive polymer, Alternatively, a fluid electrode material containing fine metal particles containing platinum, gold, silver, and copper is preferable.
  • the solvent or dispersion medium is preferably a solvent or dispersion medium containing 60% or more, preferably 90% or more of water in order to suppress damage to the organic semiconductor.
  • a fluid electrode material containing fine metal particles for example, a known conductive paste may be used, but preferably a gold particle having a particle diameter of 1 to 50 nm, preferably 1 to: LOnm.
  • a gold particle having a particle diameter of 1 to 50 nm, preferably 1 to: LOnm This is a material in which metal fine particles are dispersed in water or an arbitrary organic solvent dispersion medium using a dispersion stabilizer as required.
  • the material of the metal fine particles is platinum, gold, silver, nickel, chromium, copper, iron, tin, antimony lead, tantalum, indium, palladium, tellurium, rhenium, iridium, aluminum, ruthenium, germanium, Molybdenum, tungsten, zinc, or the like can be used.
  • a metal phase in a liquid phase such as a physical production method such as a gas evaporation method, a sputtering method or a metal vapor synthesis method, a colloid method or a coprecipitation method is used.
  • the chemical production method include reducing metal ions to produce fine metal particles, but preferred are JP-A-11-76800, JP-A-11-80647, JP-A-11-319538, and JP-A-2000-239853. Colloidal method, JP 2001-254185, 2001-53028, 2001-352 55, 2000-124157, 2000-123634, etc. It is.
  • An electrode is formed using these metal fine particle dispersions, the solvent is dried, and then heated to a shape in the range of 100 to 300 ° C, preferably 150 to 200 ° C, as necessary. Fine particles are thermally fused to form an electrode pattern having a desired shape.
  • a method for forming an electrode a method for forming an electrode using a known photolithographic method or a lift-off method using a conductive thin film formed by a method such as vapor deposition or sputtering using the above as a raw material, aluminum, copper, or the like
  • a conductive polymer solution, a dispersion, a dispersion containing metal fine particles, or the like may be directly patterned by an ink jet method, or may be formed from a coating film by lithography, laser abrasion, or the like.
  • the source electrode and the drain electrode are particularly preferably formed using a photolithographic method.
  • a photo-sensitive resin solution is applied to the entire surface of the layer in contact with the organic semiconductor protective layer, and light is applied. Form a sensitive resin layer.
  • the photosensitive resin layer As the photosensitive resin layer, the positive type and the negative type used for the patterning of the protective layer are used. The same known photosensitive resin can be used.
  • the solvent for forming the photosensitive resin coating solution, the method for forming the photosensitive resin layer, and the like are as described in the patterning of the protective film.
  • an abrasion layer which is another photosensitive resin layer, may be used for electrode formation.
  • the abrasion layer the same ones as those used for patterning the protective layer can be mentioned.
  • Inorganic oxide films include silicon oxide, acid aluminum, acid tantalum, titanium oxide, tin oxide, vanadium oxide, barium strontium titanate, barium zirconate titanate, and zirconate zirconate titanate.
  • Inorganic nitrides such as silicon nitride and aluminum nitride can also be suitably used.
  • Examples of the film formation method include vacuum deposition, molecular beam epitaxy, ion cluster beam, low energy ion beam, ion plating, CVD, sputtering, and atmospheric pressure plasma. Dry process, spray coating method, spin coating method, blade coating method, dip coating method, casting method, roll coating method, bar coating method, die coating method and other coating methods, printing and ink jet patterning methods, etc. Can be used depending on the material.
  • the wet process is a method of applying and drying a liquid in which fine particles of inorganic oxide are dispersed in an arbitrary organic solvent or water using a dispersion aid such as a surfactant as necessary.
  • a so-called sol-gel method is used in which an oxide precursor, for example, an alkoxide solution is applied and dried.
  • the atmospheric pressure plasma method described above is preferable.
  • the gate insulating layer is composed of an anodized film or the anodized film and an insulating film.
  • the anodized film is preferably sealed.
  • the anodized film is formed by anodizing a metal that can be anodized by a known method.
  • Examples of the metal capable of anodizing treatment include aluminum and tantalum, and a known method with no particular limitation can be used for the method of anodizing treatment.
  • An oxide film is formed by anodizing.
  • an electrolytic solution used for anodizing treatment any electrolyte solution can be used as long as it can form a porous acid film, and generally, sulfuric acid, phosphoric acid, oxalic acid, chromic acid, boric acid.
  • sulfamic acid, benzene sulfonic acid, etc. are mixed acids in which two or more of these are combined, and salts thereof are used.
  • the treatment conditions for anodization vary depending on the electrolyte used, and therefore cannot be specified.
  • the electrolyte concentration is 1 to 80% by mass
  • the electrolyte temperature is 5 to 70 ° C
  • the current is Density 0.5-60AZdm 2
  • electrolysis time 10 seconds to 5 minutes are appropriate.
  • a preferred anodizing treatment is a method in which an aqueous solution of sulfuric acid, phosphoric acid or boric acid is used as the electrolytic solution and the treatment is performed with a direct current, but an alternating current can also be used.
  • the concentration of these acids is preferably 5 to 45% by weight.
  • Electrolytic treatment with an electrolyte temperature of 20 to 50 ° C and a current density of 0.5 to 20 AZdm 2 is preferred for 20 to 250 seconds! / ,.
  • organic compound film polyimide, polyamide, polyester, polyacrylate, photo-radical polymerization system, photopower thione polymerization system photocurable resin, or copolymer containing acrylonitrile component, polybule Phenolic alcohol, polybutyl alcohol, novolac resin, cyano ethyl pullulan and the like can also be used.
  • the wet process is preferred as the method for forming the organic compound film.
  • the inorganic oxide film and the organic oxide film can be laminated and used together.
  • the thickness of these insulating films is generally 50 nm to 3 ⁇ m, preferably 100 nm to 1 ⁇ m.
  • an organic semiconductor is formed on the gate insulating layer
  • an arbitrary surface treatment may be performed on the surface of the gate insulating layer.
  • Silane coupling agents such as octadecyl trichlorosilane, tri Self-organized alignment films such as chloromethylsilazane, alkane phosphoric acid, alkane sulfonic acid, and alkane carboxylic acid are preferably used.
  • the support material constituting the substrate can be used as ceramic substrates such as glass, quartz, aluminum oxide, sapphire, silicon nitride, and silicon carbide, silicon, germanium, and gallium arsenide.
  • a semiconductor substrate such as gallium phosphide or gallium nitrogen, paper, non-woven fabric or the like can be used.
  • the support is preferably made of a resin, for example, a plastic film sheet can be used.
  • plastic films examples include polyethylene terephthalate (PET), polyethylene naphthalate (PE N), polyether sulfone (PES), polyether imide, polyether ether ketone, poly-phenylene sulfide, polyarylate, polyimide, polycarbonate (PC ), Cellulose triacetate (TAC), cellulose acetate propionate (CAP), and other films.
  • PET polyethylene terephthalate
  • PE N polyethylene naphthalate
  • PES polyether sulfone
  • polyether imide polyether ether ketone
  • poly-phenylene sulfide polyarylate
  • polyimide polyimide
  • PC polycarbonate
  • TAC Cellulose triacetate
  • CAP cellulose acetate propionate
  • An element protective layer may be provided on the organic thin film transistor element of the present invention.
  • the protective layer include the inorganic oxides or inorganic nitrides described above, and it is preferable to form the protective layer by the atmospheric pressure plasma method described above. This improves the durability of the organic thin film transistor element.
  • the support is a plastic film
  • at least one of an undercoat layer containing a compound selected from an inorganic oxide and an inorganic nitride, and an undercoat layer containing a polymer is preferable to have.
  • the inorganic oxides contained in the undercoat layer include silicon oxide, aluminum oxide, titanium oxide, titanium oxide, tin oxide, vanadium oxide, barium strontium titanate, zirconium Barium titanate, lead zirconate titanate, lead lanthanum titanate, strontium titanate, barium titanate, magnesium barium fluoride, bismuth titanate, strontium bismuth titanate, strontium bismuth tantanoate, tantalate nitric acid Examples thereof include bismuth butyrate and trioxide yttrium.
  • an inorganic nitride examples thereof include silicon carbide and aluminum nitride.
  • silicon oxide aluminum oxide, tantalum oxide, titanium oxide, and silicon nitride.
  • the lower bow I layer containing a compound selected from inorganic oxides and inorganic nitride forces is formed by the atmospheric pressure plasma method described above.
  • Polymers used for the undercoat layer containing polymer include polyester resin, polycarbonate resin, cellulose resin, acrylic resin, polyurethane resin, polyethylene resin, polypropylene resin, polystyrene resin, Phenoxy resin, norbornene resin, epoxy resin, vinyl chloride-vinyl acetate copolymer, vinyl chloride resin, vinyl acetate resin, copolymer of vinyl acetate and vinyl alcohol, partially water-decomposed vinyl chloride -Ruacetate butyl copolymer, salt-bule monosalt-biurydene copolymer, salt butyl-acrylonitrile copolymer, ethylene vinyl alcohol copolymer, polybulu alcohol, chlorinated polysulphated butyl, ethylene Bile monochloride copolymer, ethylene-vinyl acetate copolymer and other vinyl polymers, polyamide resin, ethylene butadiene Down ⁇ , butadiene - Atari port - DOO drill ⁇ rubber such ⁇
  • Fig. 5 (6) is an example of a bottom gate type, top contact type organic thin film transistor element.
  • a bottom gate type, top contact type organic thin film transistor element is an example of a bottom gate type, top contact type organic thin film transistor element.
  • a polyethersulfone resin film 200 m was used, and first, a corona discharge treatment was performed on the condition of 50 WZm 2 Zmin. Thereafter, an undercoat layer was formed to improve adhesion as follows.
  • a coating solution having the following composition was applied to a dry film thickness of 2 m, dried at 90 ° C for 5 minutes, and then cured for 4 seconds from a distance of 10 cm under a 60 WZcm high-pressure mercury lamp.
  • an atmospheric pressure plasma treatment was performed on the layer under the following conditions to provide an oxide film having a thickness of 50 nm, and these layers were used as the undercoat layer 2 (FIG. 5 (1)).
  • Inert gas helium 98.25 volume 0/0
  • Reactive gas Oxygen gas 1.5% by volume
  • Reactive gas Tetraethoxysilane vapor (published with helium gas) 0.25 vol% (discharge conditions)
  • the electrode is coated with lmm of alumina by ceramic spraying on a stainless jacket roll base material having cooling means with cooling water, and then a solution obtained by diluting tetramethoxysilane with ethyl acetate is applied and dried, and then sealed by ultraviolet irradiation.
  • This is a roll electrode that has a dielectric (relative permittivity of 10) with a smooth surface and an Rmax of 5 ⁇ m.
  • the application electrode a hollow rectangular stainless steel pipe was covered with the same dielectric material under the same conditions.
  • the gate electrode 8 is formed.
  • the photosensitive resin composition 1 having the following composition is coated on the undercoat layer 2 and dried at 100 ° C for 1 minute, thereby obtaining a photosensitive film having a thickness of 2 m.
  • the gate line and gate electrode patterns were exposed to an energy density of 200 mjZcm 2 with a semiconductor laser having an oscillation wavelength of 830 nm and an output of lOOmW, and developed with an aqueous alkali solution to obtain a resist image. Further, a 300 nm thick aluminum film is formed on the entire surface by sputtering, and then the remaining part of the photosensitive resin layer is removed with MEK.
  • the in and gate electrodes 8 are fabricated (Fig. 5 (2)).
  • the pattern of the gate line and the gate electrode can be obtained by using the method of the present invention based on a combination of an electrostatic attraction type inkjet device and an electroless plating method, which is not the patterning by resist formation using photosensitive resin. It may be formed by an electrolytic plating method.
  • an anodic acid film was formed on the gate electrode as a negative insulating film for improving smoothness and insulation by the following anodic acid film forming process (not shown in the figure). .
  • the substrate is thoroughly cleaned, and the thickness of the anodic oxide film is reduced to 120 nm using direct current supplied from a 30 V low-voltage power supply in 30% by weight sulfuric acid aqueous solution for 2 minutes. Anodizing was performed until After washing well, steam sealing was performed in a steam chamber saturated at 1 atm and 100 ° C. In this way, a gate electrode having an anodized film was prepared on a polyethersulfone resin film which had been subjected to a subbing treatment.
  • a silicon oxide film having a thickness of 30 ⁇ m is provided by the above-described atmospheric pressure plasma method, and the above-described anodized aluminum layer is combined to form a gate insulating film having a thickness of 150nm.
  • Layer 7 was formed ((3) in FIG. 5).
  • an organic semiconductor layer was formed on the gate insulating layer using the following thiophene oligomer ⁇ 2> as a semiconductor material. That is, a cyclohexane solution (0.5% by mass) of thiophene oligomer ⁇ 2> was prepared and ejected to a region where a channel was to be formed using a piezo ink jet method. Drying was performed at ° C for 3 minutes to form an organic semiconductor layer 6 with a thickness of 20 nm on the substrate (Fig. 5 (4)).
  • the following electroless plating catalyst solution was used as ink, and a bias voltage of 2000V was applied to the rotating roll (support roll), Furthermore, ink was ejected according to the source and drain electrode patterns by superimposing a pulse voltage (400V).
  • the inner diameter of the nozzle outlet was 10 ⁇ m, and the gap between the nozzle outlet and the substrate was kept at 500 m.
  • the following formulation was used as the ink containing the catalyst catalyst.
  • the substrate surface on which the uniform solution gold thin film in which the solution was dissolved was sufficiently washed with pure water and dried to form the thin film transistor shown in FIG. 5 (6).
  • the size of the source and drain electrodes formed by the above method is 10 ⁇ m wide, 50 m long (channel width W), 150 nm thick, and the distance between the source and drain electrodes (channel length L) is 5 mm. It was ⁇ m, and a high-definition electrode pattern was formed. This thin film transistor operated well, and the mobility estimated from the saturation region was 0.07 cm 2 ZVs.
  • Example 1 instead of using an electrostatic suction type ink jet device, the electroless catalyst solution used in Example 1 was used as ink from a piezo-type ink jet head, and ink was ejected according to the source and drain electrode patterns. did. Further, an electroless plating process was performed in the same manner as in Example 1 to produce a source electrode and a drain electrode. As a result, the electroless catalyst solution was repelled, and the pattern of the source electrode and drain electrode was not formed.
  • the order of forming the organic semiconductor layer and the source and drain may be reversed. That is, after the gate insulating film 7 is formed, a plating catalyst pattern is formed by an electrostatic attraction ink jet method, contacted with a plating agent, and source and drain electrodes are formed (Ml, M2). Using a piezo ink jet method, the channel is discharged to the region where the channel is to be formed and dried in nitrogen gas at 50 ° C. for 3 minutes to form the organic semiconductor layer 6.
  • the bottom-contact type thin film transistor was manufactured by changing the process sequence of Example 1.
  • the size of the source and drain electrodes is 10 ⁇ m wide, 50 ⁇ (channel width W) long, 150 nm thick, and the distance between the source and drain electrodes (channel length L) is 5 ⁇ m.
  • a high-definition electrode pattern was formed.
  • This thin film transistor is good
  • the mobility that worked and the saturation region force was estimated was 0.05 cm 2 ZVs.
  • Figure 6 shows the configuration of this bottom contact thin film transistor.
  • the organic semiconductor layer is preferable because it is not exposed to a plating agent or the like.
  • Example 2 instead of using an electrostatic suction type ink jet device, the electroless plating catalyst solution used in Example 2 was used as ink from a piezo-type ink jet head, and ink was ejected according to the source and drain electrode patterns. did. Further, an electroless plating process was performed in the same manner as in Example 2 to produce a source electrode and a drain electrode. As a result, the electroless catalyst solution was repelled, and the pattern of the source electrode and drain electrode was not formed.
  • Fig. 7 (1) shows a PES (polyethersulfone) resin film (200 ⁇ m) as the substrate, and the gate electrode made of aluminum with the undercoat layer 2 and the anodized film 9 on the substrate 1 8 and the gate insulating film 7 and the organic semiconductor layer 6 are sequentially formed by the method shown in FIG.
  • PES polyethersulfone
  • an electrostatic field applying electrode part, a counter electrode part, A protective film is formed using an aqueous solution obtained by dissolving polyvinyl alcohol, which has been sufficiently purified by ultrapure manufacturing equipment, as ink, by appropriately adjusting conditions such as bias voltage and pulse voltage applied during The pattern was printed.
  • a protective film material was selectively ejected to a portion constituting the semiconductor channel between the source and drain electrodes of the organic semiconductor layer.
  • the film was thoroughly dried at 100 ° C in a nitrogen gas atmosphere to form an organic semiconductor protective layer 3 of polyvinyl alcohol having a thickness of 1 ⁇ m ((2) in Fig. 7).
  • the protective film is patterned by a method of forming a resist with a photosensitive resin! It doesn't matter.
  • the same electrostatic suction type ink jet apparatus as that used for printing the electroless plating catalyst pattern in the above embodiment is used, and the source electrode and drain electrode patterns are formed under the same conditions. Therefore, the following catalyst catalyst solution was discharged, dried and fixed to form a catalyst catalyst pattern Ml (Fig. 7 (3), (4)).
  • the catalyst solution can be ejected and arranged accurately according to the electrode pattern.
  • the catalyst was dried to fix the catalyst pattern.
  • the substrate on which the catalyst pattern is formed is placed on an electroless gold plating bath (disiano gold power 0.1 mol Z liter, sodium oxalate 0.1 mol Z liter, sodium potassium tartrate 0.
  • a metal thin film M2 having a thickness of lOnm was formed by immersing in 1 mol Z liter of a uniform solution), and source and drain electrodes were formed. After forming the electrode, it was thoroughly washed and dried to form a thin film transistor (Fig. 7 (5)).
  • the size of the formed source and drain electrodes is 10 ⁇ m wide, 50 ⁇ m long (channel width W), and the distance between the source and drain electrodes (channel length L) is 5 ⁇ m.
  • a high-definition electrode pattern was formed. This thin film transistor operated well, and the mobility estimated from the saturation region was 0.1 lcm 2 ZVs.
  • Example 3 instead of using an electrostatic suction ink jet apparatus, the electroless catalyst solution used in Example 3 was used as ink from a piezo-type ink jet head, and ink was ejected according to the source and drain electrode patterns. did. Further, an electroless plating process was performed in the same manner as in Example 3 to produce a source electrode and a drain electrode.
  • the size of the formed source and drain electrodes is approximately 70 ⁇ m wide, approximately 80 ⁇ m long, and the distance between the source and drain electrodes (channel length L) is 5 ⁇ m. As a result, the electrode thickness was significantly uneven. The thickness of the electrode was found to vary between 5 and 250 nm.
  • the mobility estimated for the saturation region force of this thin film transistor was 0.002 cm Vs.
  • the example of manufacturing the TFT sheet by the method for manufacturing the organic semiconductor element of the present invention has been described above, at least one of the electrodes of the organic thin film transistor element is formed by electroless plating according to the present invention.
  • electroless plating by using an electrostatic suction ink jet method to perform electrode patterning, it is possible to perform patterning with high accuracy and to form an electrode that is free from unevenness and repellency.
  • the organic semiconductor layer can be prevented from deteriorating due to electroless plating, and a high-performance organic thin film transistor element having a low resistance electrode (sheet) Can be formed.

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Abstract

Disclosed is a method for manufacturing a thin film transistor with high production efficiency which enables to form a low-resistance electrode with high pattern accuracy by a simple electrode-pattern-forming process with high resolution and high pattern accuracy. Specifically disclosed is a method for manufacturing a thin film transistor wherein at least one of gate, source and drain electrodes is formed by electroless plating wherein a plating catalyst pattern is formed and then a plating agent is brought into contact with the pattern. This method is characterized in that the formation of the plating catalyst pattern is performed by discharging a liquid containing a plating catalyst by using an electrostatic attraction type liquid discharging device.

Description

明 細 書  Specification

薄膜トランジスタの製造方法  Thin film transistor manufacturing method

技術分野  Technical field

[0001] 本発明は、有機半導体素子、特に有機薄膜トランジスタの製造方法に関するもの であり、特に、解像度、パターン精度の良好な電極パターン形成手段により、低抵抗 の電極を簡便に、パターン精度よく形成することの出来る有機薄膜トランジスタの製 造方法に関するものである。  The present invention relates to a method for manufacturing an organic semiconductor element, particularly an organic thin film transistor, and particularly, a low-resistance electrode is easily formed with high pattern accuracy by means of electrode pattern forming means having good resolution and pattern accuracy. The present invention relates to a method for manufacturing an organic thin film transistor.

背景技術  Background art

[0002] 有機半導体を用いたデバイスは、従来の無機半導体デバイスに比べて製膜条件が マイルドであり、各種基板上に半導体薄膜を形成したり、常温で製膜することが可能 であるため、低コスト化や、ポリマーフィルム等に薄膜を形成することによるフレキシブ ル化が期待されている。  [0002] Devices using organic semiconductors have milder film-forming conditions than conventional inorganic semiconductor devices, and semiconductor thin films can be formed on various substrates or formed at room temperature. Expected to be low cost and flexible by forming a thin film on polymer film.

[0003] 有機半導体材料としては、ポリフエ-レンビ-レン，ポリピロール，ポリチォフェン，ォ リゴチォフェンなどの共役系高分子、オリゴマーとともに、アントラセン，テトラセン，ぺ ンタセン等のポリアセンィ匕合物が研究されて 、る。  [0003] As organic semiconductor materials, polyacene compounds such as anthracene, tetracene, and pentacene have been studied as well as conjugated polymers and oligomers such as polyphenylene vinylene, polypyrrole, polythiophene, and oligogophene.

[0004] ところで、上述した有機半導体を用いたデバイスにお ヽて、電極を形成する方法と しては、均一形成した金属薄膜をエッチング又はリフトオフによって電極パターンを 形成する方法や、金属フィラーを含有する塗料、また導電性ポリマー溶液を印刷して 電極パターンを形成する方法などが用いられて 、る。  By the way, in the above-described device using an organic semiconductor, as a method of forming an electrode, a method of forming an electrode pattern by etching or lift-off of a uniformly formed metal thin film, or a metal filler is included. And a method of forming an electrode pattern by printing a conductive polymer solution or a conductive polymer solution.

[0005] しかしながら、電極パターンを形成するためのレジスト層の形成やこのレジスト層の 除去を行う必要があるため、パターン形成工程が煩雑であり、また、印刷による方法 では、含有されるバインダーの影響で電極の抵抗が増加してしまうという問題があつ た。  [0005] However, since it is necessary to form a resist layer for forming an electrode pattern and to remove the resist layer, the pattern forming process is complicated, and in the printing method, the effect of the contained binder As a result, the resistance of the electrode increases.

[0006] 特許文献 1には、無電解メツキを利用し低抵抗の電極を簡便に形成することが記載 されている。これは、無電解メツキを生じさせる触媒と、メツキ剤およびこれらの印刷法 等によるパターユングを組み合わせ電極パターンを簡単に形成するというものである 。これにより、煩雑な工程を経ることなぐ電極パターン形成が可能である。 [0007] し力しながら、スクリーン印刷、凸版、凹版、平版等の印刷法や、通常のインクジエツ ト印刷等によるパターユングは、前記のレジスト層の形成による方法等に比べ、パタ ーン精度が低くなつてしまうなどの問題がある。本発明はこれを改善するものである。 特許文献 1 :特開 2004— 158805号公報 [0006] Patent Document 1 describes that an electroless plating is used to easily form a low-resistance electrode. In this method, an electrode pattern is easily formed by combining a catalyst that generates electroless plating, a plating agent, and patterning using a printing method thereof. Thereby, an electrode pattern can be formed without going through complicated steps. [0007] However, patterning by screen printing, letterpress, intaglio, lithographic printing, etc., or patterning by ordinary ink jet printing, etc. has a pattern accuracy higher than that by the above-mentioned method of forming a resist layer. There are problems such as becoming low. The present invention improves this. Patent Document 1: Japanese Unexamined Patent Application Publication No. 2004-158805

発明の開示  Disclosure of the invention

発明が解決しょうとする課題  Problems to be solved by the invention

[0008] 簡便で、かつ、解像度、パターン精度の良好な電極パターン形成方法により、低抵 抗の電極をパターン精度よく形成することの出来る生産効率の高い薄膜トランジスタ の製造方法を得ることにある。 [0008] An object of the present invention is to obtain a thin film transistor manufacturing method with high production efficiency that can form a low resistance electrode with high pattern accuracy by a simple electrode pattern forming method with good resolution and pattern accuracy.

課題を解決するための手段  Means for solving the problem

[0009] (1)ゲート、ソース、ドレインの少なくとも一つの電極力 メツキ触媒パターンを形成し た後メツキ剤を接触させる、無電解メツキ法により形成される薄膜トランジスタの製造 方法において、前記メツキ触媒パターンの形成が、メツキ触媒を含有する液体を静電 吸引方式の液体吐出装置を用いて吐出することで行われることを特徴とする薄膜トラ ンジスタの製造方法。 [0009] (1) In a method of manufacturing a thin film transistor formed by an electroless plating method in which at least one electrode force of a gate, a source, and a drain is contacted with a plating agent after forming a plating catalyst pattern, A method of manufacturing a thin film transistor, wherein the formation is performed by discharging a liquid containing a catalyst catalyst using an electrostatic suction type liquid discharge device.

[0010] (2)前記静電吸引方式の液体吐出装置に備えられた液体を吐出するノズルの内径 力 S15 m以下であることを特徴とする前記（1)記載の薄膜トランジスタの製造方法。  [0010] (2) The method for producing a thin film transistor according to (1) above, wherein an inner diameter force S15 m or less of a nozzle for discharging a liquid provided in the electrostatic suction type liquid discharging apparatus is set.

[0011] (3)ソースまたはドレイン電極が前記無電解メツキ法により形成されることを特徴とす る前記（1)または（2)記載の薄膜トランジスタの製造方法。 [0011] (3) The method for producing a thin film transistor according to (1) or (2), wherein the source or drain electrode is formed by the electroless plating method.

[0012] (4)少なくとも 1種の有機半導体を用いることを特徴とする前記（1)〜（3)の 、ずれ 力 1項記載の薄膜トランジスタの製造方法。 [0012] (4) The method for producing a thin film transistor according to (1) above, wherein at least one organic semiconductor is used.

[0013] (5)ボトムゲート型構造を形成することを特徴とする前記（1)〜 (4)の ヽずれか 1項 記載の薄膜トランジスタの製造方法。 [0013] (5) The method of manufacturing a thin film transistor according to any one of (1) to (4), wherein a bottom gate structure is formed.

発明の効果  The invention's effect

[0014] 本発明により、無電解メツキを用いて、パターユング精度のよい電極形成を行うこと ができ、低抵抗の電極を精度よく簡便に得ることが出来る。  [0014] According to the present invention, an electrode with high patterning accuracy can be formed using an electroless plating, and a low-resistance electrode can be easily obtained with high accuracy.

図面の簡単な説明 [0015] [図 1]本発明の有機薄膜トランジスタ素子の構成例を示す図である。 Brief Description of Drawings FIG. 1 is a diagram showing a configuration example of an organic thin film transistor element of the present invention.

[図 2]本発明の有機薄膜トランジスタ素子シートの一例の概略の等価回路図である。  FIG. 2 is a schematic equivalent circuit diagram of an example of the organic thin film transistor element sheet of the present invention.

[図 3]静電吸引型インクジェット装置の概略構成図である。  FIG. 3 is a schematic configuration diagram of an electrostatic suction ink jet apparatus.

[図 4]図 3に示すインクジェット装置におけるインクのメニスカス挙動を説明する図であ る。  FIG. 4 is a diagram for explaining the meniscus behavior of the ink in the ink jet apparatus shown in FIG.

[図 5]本発明の有機薄膜トランジスタ素子 (トップコンタ外型)の製造方法を説明する ための図である。  FIG. 5 is a diagram for explaining a method of manufacturing the organic thin film transistor element (top contour outer type) of the present invention.

[図 6]本発明の製造方法を用いた有機薄膜トランジスタ素子 (ボトムコンタ外型)の構 成の一例を示す図である。  FIG. 6 is a diagram showing an example of the configuration of an organic thin film transistor element (bottom contour outer type) using the manufacturing method of the present invention.

[図 7]本発明の有機薄膜トランジスタ素子（トップコンタクト型)の別の製造方法の一例 を説明するための図である。  FIG. 7 is a view for explaining an example of another method for producing the organic thin film transistor element (top contact type) of the present invention.

符号の説明  Explanation of symbols

[0016] 1、 56 支持体 [0016] 1, 56 Support

2 下引き層  2 Underlayer

3 有機半導体保護層  3 Organic semiconductor protective layer

6、 51 有機半導体層  6, 51 Organic semiconductor layer

7 ゲート絶縁層  7 Gate insulation layer

8、 54 ゲート電極  8, 54 Gate electrode

9 陽極酸化皮膜  9 Anodized film

10 有機薄膜トランジスタシート  10 Organic thin film transistor sheet

11 ゲートバスライン  11 Gate bus line

12 ソースノ スライン  12 Sourceno Sline

14 有機薄膜トランジスタ素子  14 Organic thin-film transistor elements

15 蓄積コンデンサ  15 Storage capacitor

16 出力素子  16 output elements

17 垂直駆動回路  17 Vertical drive circuit

18 水平駆動回路  18 Horizontal drive circuit

52 ソース電極 53 ドレイン電極 52 Source electrode 53 Drain electrode

55 絶縁層  55 Insulation layer

101 インク噴射室  101 Ink ejection chamber

102 インク  102 ink

103 インク室  103 Ink chamber

104 ノズル孑し  104 Nozzle tanning

105 インクタンク  105 Ink tank

106 インク供給路  106 Ink supply path

107 回転ローラー  107 Rotating roller

108 被記録媒体  108 Recording medium

110 制御素子部  110 Control element

111 プロセス制御部  111 Process control section

114 静電界印加用電極部  114 Electrostatic field application electrode

115 対向電極部  115 Counter electrode

116 バイアス電源部  116 Bias power supply

117 高圧電源部  117 High voltage power supply

118 接地部  118 Grounding part

119、 119a, 119b, 119c メ-スカス  119, 119a, 119b, 119c

発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION

[0017] 以下、本発明を実施するための最良の形態について説明するが、本発明はこれに より限定されるものではない。 Hereinafter, the best mode for carrying out the present invention will be described, but the present invention is not limited thereto.

[0018] 本発明の薄膜トランジスタ素子は、支持体上に有機半導体層に接したソース電極と ドレイン電極を有し、その上にゲート絶縁層を介してゲート電極を有するトップゲート 型と、支持体上にまずゲート電極を有し、ゲート絶縁層を介して有機半導体層で連結 されたソース電極とドレイン電極を有するボトムゲート型に大別され、具体的な素子の 層構成例は図 1に示す如くなる。 [0018] The thin film transistor element of the present invention includes a top gate type having a source electrode and a drain electrode in contact with an organic semiconductor layer on a support, and a gate electrode on the support via a gate insulating layer. First, it is roughly divided into a bottom gate type having a gate electrode and having a source electrode and a drain electrode connected by an organic semiconductor layer via a gate insulating layer. Specific examples of the layer structure of the element are as shown in FIG. Become.

[0019] 図 1は本発明の有機薄膜トランジスタ素子の構成例を示す図である。同図（a)は支 持体 56上に金属箔等によりソース電極 52、ドレイン電極 53を形成し、両電極間に本 発明の有機半導体材料からなる有機半導体層 51を形成し、その上に絶縁層 55を形 成し、更にその上にゲート電極 54を形成して有機薄膜トランジスタ素子を形成したも のである。同図（b)は有機半導体層 51を、（a)では電極間に形成したものを、コート 法等を用いて電極及び支持体表面全体を覆うように形成したものを表す。（c)は支持 体 56上に先ずコート法等を用いて、有機半導体層 51を形成し、その後ソース電極 5 2、ドレイン電極 53、絶縁層 55、ゲート電極 54を形成したものを表す。 FIG. 1 is a diagram showing a configuration example of an organic thin film transistor element of the present invention. (A) in the figure shows that a source electrode 52 and a drain electrode 53 are formed on a support 56 by a metal foil, etc. An organic semiconductor layer 51 made of the organic semiconductor material of the invention is formed, an insulating layer 55 is formed thereon, and a gate electrode 54 is further formed thereon to form an organic thin film transistor element. FIG. 4B shows the organic semiconductor layer 51 formed between the electrodes in FIG. 5A so as to cover the entire surface of the electrode and the support using a coating method or the like. (C) shows that the organic semiconductor layer 51 is first formed on the support 56 using a coating method or the like, and then the source electrode 52, the drain electrode 53, the insulating layer 55, and the gate electrode 54 are formed.

[0020] 同図（d)は支持体 56上にゲート電極 54を金属箔等で形成した後、絶縁層 55を形 成し、その上に金属箔等で、ソース電極 52及びドレイン電極 53を形成し、該電極間 に本発明の有機半導体材料により形成された有機半導体層 51を形成する。その他 、同図 (e)、 （f)に示すような構成をとることもできる。  In FIG. 4D, after forming a gate electrode 54 on a support 56 with a metal foil or the like, an insulating layer 55 is formed, and a source electrode 52 and a drain electrode 53 are formed thereon with a metal foil or the like. Then, an organic semiconductor layer 51 formed of the organic semiconductor material of the present invention is formed between the electrodes. In addition, it is possible to adopt a configuration as shown in FIGS.

[0021] 図 2は、本発明の薄膜トランジスタ素子が複数配置される薄膜トランジスタ素子シー ト 10の 1例の概略の等価回路図である。  FIG. 2 is a schematic equivalent circuit diagram of an example of a thin film transistor element sheet 10 in which a plurality of thin film transistor elements of the present invention are arranged.

[0022] 薄膜トランジスタシート 10はマトリクス配置された多数の薄膜トランジスタ素子 14を 有する。 11は各薄膜トランジスタ素子 14のゲート電極のゲートバスラインであり、 12 は各薄膜トランジスタ素子 14のソース電極のソースノ スラインである。各薄膜トランジ スタ素子 14のドレイン電極には、出力素子 16が接続され、この出力素子 16は例えば 液晶、電気泳動素子等であり、表示装置における画素を構成する。図示の例では、 出力素子 16として液晶が、抵抗とコンデンサ力もなる等価回路で示されている。 15 は蓄積コンデンサ、 17は垂直駆動回路、 18は水平駆動回路である。  The thin film transistor sheet 10 has a large number of thin film transistor elements 14 arranged in a matrix. 11 is a gate bus line of the gate electrode of each thin film transistor element 14, and 12 is a source nos line of the source electrode of each thin film transistor element 14. An output element 16 is connected to the drain electrode of each thin film transistor element 14, and this output element 16 is, for example, a liquid crystal or an electrophoretic element, and constitutes a pixel in the display device. In the illustrated example, a liquid crystal is shown as the output element 16 in an equivalent circuit having both resistance and capacitor power. 15 is a storage capacitor, 17 is a vertical drive circuit, and 18 is a horizontal drive circuit.

[0023] この様な、支持体上に有機 TFT素子を 2次元的に配列した薄膜トランジスタシート の作製に本発明の方法を用いることができる。  [0023] The method of the present invention can be used for producing such a thin film transistor sheet in which organic TFT elements are two-dimensionally arranged on a support.

[0024] これら薄膜トランジスタ（素子シート）における、ソース、ドレイン、或いはゲート電極 等の電極、またゲート、或いはソースバスライン等を、エッチング又はリフトオフ等感光 性榭脂等を用いた金属薄膜のノターユングなしに形成する方法として、無電解メツキ 法による方法が知られて 、る。  [0024] In these thin film transistors (element sheets), the source, drain, or gate electrode, and the gate or source bus line, etc., are not etched with a metal thin film using a photosensitive resin such as etching or lift-off. As a forming method, a method using an electroless plating method is known.

[0025] 無電解メツキ法による電極の形成方法に関しては、特開 2004— 158805 (旭化成） にも記載されたように、電極を設ける部分に、メツキ剤と作用して無電解メツキを生じさ せるメツキ触媒を含有する液体を、例えば印刷法 (インクジェット印刷含む）によって、 パターニングした後に、メツキ剤を電極を設ける部分に接触させる。そうすると、前記 触媒とメツキ剤との接触により前記部分に無電解メツキが施されて、電極パターンが 形成されるというものである。 [0025] As described in JP-A-2004-158805 (Asahi Kasei), the method for forming an electrode by an electroless plating method causes an electroless plating to occur at a portion where the electrode is provided by acting with a plating agent. A liquid containing a plating catalyst, for example, by a printing method (including inkjet printing), After patterning, the plating agent is brought into contact with the portion where the electrode is provided. Then, an electroless plating is performed on the portion by contact between the catalyst and the plating agent, and an electrode pattern is formed.

[0026] 無電解メツキの触媒と、メツキ剤の適用を逆にしてもよぐまたパターン形成をどちら で行ってもよいが、メツキ触媒パターンを形成し、これにメツキ剤を適用する方法が好 ましい。  [0026] Either the electroless catalyst or the application of the plating agent may be reversed, or the pattern formation may be performed, but a method of forming a plating catalyst pattern and applying the plating agent to this is preferred. Good.

[0027] し力 ながら、印刷法としては、例えば、スクリーン印刷、平版、凸版、凹版又インク ジェット法による印刷などが用いられる力 これらの印刷によるメツキ触媒又はメツキ剤 のパターニングは高細精な回路パターンが要求される場合、精度が充分ではな 、。  [0027] However, as a printing method, for example, screen printing, planographic printing, relief printing, intaglio printing, ink jet printing, or the like is used. Patterning of a plating catalyst or a plating agent by these printings is a highly precise circuit. When the pattern is required, the accuracy is not enough.

[0028] 本発明者等は、鋭意検討の結果、印刷或いは通常のインクジェット法ではなぐメッ キ触媒を含有する液体を静電吸引方式の液体吐出装置を用い印刷する方法が、高 細精の印刷に適しており、無電解メツキによる電極パターン形成を精度高く行える方 法であることを見 、だした。これにより低抵抗で高細精な電極パターンが簡便に得ら れる。  [0028] As a result of intensive studies, the present inventors have found that a method of printing a liquid containing a catalyst that is not printed or using a normal ink jet method using an electrostatic suction type liquid discharge device is a highly precise printing. It was found to be a method that can be used to accurately form electrode patterns by electroless plating. As a result, a highly precise electrode pattern with low resistance can be easily obtained.

[0029] 以下無電解メツキ法について説明する。  [0029] The electroless plating method will be described below.

[0030] メツキ剤に作用して無電解メツキを生じさせる触媒としては、 Pd、 Rh、 Pt、 Ru、 Os、 Ir力 選択される少なくとも一種の化合物及びこれらのイオン、或いは金属微粒子か ら構成される。  [0030] The catalyst that acts on the plating agent to generate electroless plating is composed of at least one compound selected from Pd, Rh, Pt, Ru, Os, Ir force, and their ions, or metal fine particles. The

[0031] 具体的には、上記元素の塩化物、臭化物、フッ化物などのハロゲン化物や、硫酸 塩、硝酸塩、燐酸塩、ホウ酸塩、シアンィ匕物などの無機塩或いは複合塩や、カルボン 酸塩、有機スルホン酸塩、有機燐酸塩、アルキル錯体、アルカン錯体、アルケン錯体 、シクロペンタジェン錯体、ポルフィリン、フタロシアニンなどの有機錯体塩力 選択さ れる単体或いはこれらの混合物、これらの元素のイオン、これらの元素の金属微粒子 が適用可能である。なお、有機錯体塩からなる触媒に、界面活性剤ゃ榭脂バインダ 一を含有させた溶液或いは分散体を適用することも可能である。  [0031] Specifically, halides such as chlorides, bromides, and fluorides of the above elements, inorganic salts or composite salts such as sulfates, nitrates, phosphates, borates, and cyanides, and carboxylic acids Salts, organic sulfonates, organic phosphates, alkyl complexes, alkane complexes, alkene complexes, cyclopentagen complexes, porphyrins, phthalocyanines, and other organic complex salt powers selected or mixtures of these, ions of these elements, these Metal fine particles of these elements are applicable. It is also possible to apply a solution or dispersion containing a surfactant or a resin binder to a catalyst made of an organic complex salt.

[0032] また、メツキ剤は、例えば、電極として析出させる金属イオンが均一溶解された溶液 が用いられ、金属塩とともに還元剤が含有される。ここで、通常は溶液が用いられる 力 無電解メツキを生じさせるものであればこれに限らず、ガス状や粉体のメツキ剤を 適用することも可能である。 [0032] In addition, as the plating agent, for example, a solution in which metal ions deposited as an electrode are uniformly dissolved is used, and the reducing agent is contained together with the metal salt. Here, the force used for the solution is not limited to this as long as it causes electroless plating, and gaseous or powdered plating agents are used. It is also possible to apply.

[0033] 具体的に、この金属塩としては、金属のハロゲン化物、硝酸塩、硫酸塩、燐酸塩、 ホウ酸塩、酢酸塩、酒石酸塩、クェン酸塩などが適用可能である。還元剤としては、ヒ ドラジン、ヒドラジン塩、ボロハライド塩、次亜燐酸塩、次亜硫酸塩、アルコール、アル デヒド、カルボン酸、カルボン酸塩などが適用可能である。なお、これらの還元剤に含 有されるボロン、燐、窒素などの元素が、析出する電極に含有されていても構わない  Specifically, as the metal salt, metal halides, nitrates, sulfates, phosphates, borates, acetates, tartrate, kenates, and the like are applicable. As the reducing agent, hydrazine, hydrazine salt, borohalide salt, hypophosphite, hyposulfite, alcohol, aldehyde, carboxylic acid, carboxylate and the like are applicable. In addition, elements such as boron, phosphorus, and nitrogen contained in these reducing agents may be contained in the deposited electrode.

[0034] このメツキ剤は、上記金属塩と還元剤とが混合されたものを適用するようにしてもよ いし、或いは金属塩と還元剤とを別個に適用するようにしてもよい。ここで、電極パタ ーンをより鮮明に形成するためには、金属塩と還元剤とが混合されたものを適用する ことが好ましい。また、金属塩と還元剤とを別個に適用する場合には、電極を設ける 部分にまず金属塩を配した後、還元剤を配することで、より安定した電極パターンを 形成することができる。 [0034] As the plating agent, a mixture of the metal salt and the reducing agent may be applied, or the metal salt and the reducing agent may be applied separately. Here, in order to form the electrode pattern more clearly, it is preferable to apply a mixture of a metal salt and a reducing agent. In addition, when the metal salt and the reducing agent are applied separately, a more stable electrode pattern can be formed by first arranging the metal salt in the portion where the electrode is provided and then arranging the reducing agent.

[0035] また、メツキ剤〖こは、必要があれば、 pH調整のための緩衝剤、界面活性剤などの 添加物を含有させることができる。また、溶液に用いる溶媒としては、水以外にアルコ ール、ケトン、エステルなどの有機溶剤を添加するようにしても力まわない。  [0035] Further, if necessary, the plating agent coconut can contain additives such as a buffer for adjusting pH and a surfactant. In addition to water, organic solvents such as alcohols, ketones and esters can be added as the solvent used in the solution.

[0036] さらに、メツキ剤の組成は、析出させる金属の金属塩、還元剤、および必要に応じて 添加物、有機溶媒を添加した組成で構成されるが、析出速度に応じて濃度や組成を 調整することができる。また、メツキ剤の温度を調節して析出速度を調整することもで きる。この温度調整の方法としては、メツキ剤の温度を調整する方法、浸漬前に基板 を加熱、冷却して温度調節する方法などが挙げられる。さらに、メツキ剤に浸漬する 時間で析出する金属薄膜の膜厚を調整することもできる。  [0036] Further, the composition of the plating agent is composed of a metal salt of the metal to be deposited, a reducing agent, and, if necessary, an additive and an organic solvent, but the concentration and composition may be varied depending on the deposition rate. Can be adjusted. It is also possible to adjust the deposition rate by adjusting the temperature of the plating agent. Examples of the temperature adjusting method include a method of adjusting the temperature of the plating agent and a method of adjusting the temperature by heating and cooling the substrate before immersion. Furthermore, it is possible to adjust the thickness of the metal thin film that is deposited in the time it is immersed in the plating agent.

[0037] 本発明にお ヽては、前記無電解メツキ触媒を含有する液体の印刷法として、従来 のスクリーン印刷、凸版、平版、凹版等の印刷法、また、通常のインクジェット法による 印刷にかえて静電吸弓 I方式の液体吐出装置を用 V、ることに特徴がある。静電吸弓 I方 式の液体吐出装置によって、無電解メツキの触媒のパターンを形成して、その後、メ ツキ剤を、接触させ、無電解メツキを施す。これにより無電解メツキによって形成された 金属薄膜からなる電極パターンが得られる。 [0038] メツキ剤の接触は、塗布、或 、はスプレー等、また、浸漬等によって行うことができる 。また、メツキ剤をメツキ触媒と同様に、メツキ触媒パターンを形成した領域を含む領 域にパターン印刷する方法でもよい、インクジヱット法、スクリーン印刷、凹版、平版、 凸版などの印刷、又これも静電吸引方式の液体吐出装置を用いてもよい。また、電 極パターンを無電解メツキにより析出させた後、基板表面にメツキ剤に含有された溶 質が付着して 、る場合、必要があれば洗浄することができる。 [0037] In the present invention, as a method for printing a liquid containing the electroless plating catalyst, a conventional screen printing method, a printing method such as a relief printing plate, a planographic printing plate, an intaglio printing method, or a printing method using a normal inkjet method is used. It is characterized by the use of an electrostatic bow I type liquid discharge device V. Electrostatic bow I-type liquid discharge device is used to form an electroless plating catalyst pattern, and then contact the plating agent to apply the electroless plating. As a result, an electrode pattern made of a metal thin film formed by electroless plating is obtained. [0038] The contact of the plating agent can be performed by coating, spraying, dipping or the like. In addition, like the plating catalyst, the plating agent may be printed by a pattern printing in a region including the region where the plating catalyst pattern is formed, such as ink jet printing, screen printing, intaglio printing, lithographic printing, letterpress printing, and the like. A suction-type liquid ejection device may be used. In addition, after the electrode pattern is deposited by electroless plating, if the solute contained in the plating agent adheres to the substrate surface, it can be cleaned if necessary.

[0039] また、メツキ剤、また、メツキ触媒は、適用を逆にしてもよ!/、。またパターユングをメッ キ剤で行ってもよい。 [0039] Further, the application of the plating agent and the plating catalyst may be reversed! /. Alternatively, puttering may be performed with a mastic agent.

[0040] 前記無電解メツキを施すことで設ける電極は、 Au、 Ag、 Cu、 Ni、 Co、 Feから選択 される少なくとも 1種の金属或いはこれらの合金力 構成される。ここで、上記金属に は、金属間化合物も含まれる。  [0040] The electrode provided by applying the electroless plating is composed of at least one metal selected from Au, Ag, Cu, Ni, Co, and Fe, or an alloy force thereof. Here, the metal includes an intermetallic compound.

[0041] 前記静電吸引方式の液体吐出装置の例としては、例えば、特開平 8— 238774号[0041] Examples of the electrostatic suction type liquid ejection device include, for example, Japanese Patent Laid-Open No. 8-238774.

、また特開 2000— 127410号等に記載されており、これらに準じた装置を有利に用 いることがでさる。 Further, it is described in JP-A No. 2000-127410 and the like, and an apparatus according to these can be advantageously used.

[0042] 静電吸引方式は、微小液滴を吐出できる方法であり、吐出された液滴は、吐出エネ ルギ一とは別に、飛翔中にも静電力を受けるため、単位体積当たりの吐出エネルギ 一を軽減でき、微小液滴の吐出への適用が可能となり、高精度の印刷パターンを得 ることが出来る。  [0042] The electrostatic attraction method is a method capable of ejecting minute droplets, and the ejected droplets receive electrostatic force during flight separately from the ejection energy, and thus the ejection energy per unit volume. Can be reduced, and can be applied to the discharge of minute droplets, and a high-precision printed pattern can be obtained.

[0043] 例えば、特開平 8— 238774号に開示されたインクジェット装置をもちいて静電吸引 方式の液体吐出装置について説明する。  For example, an electrostatic suction type liquid discharge apparatus will be described using an ink jet apparatus disclosed in JP-A-8-238774.

[0044] 図 3は、静電吸引型インクジェット装置の断面模式図である。  FIG. 3 is a schematic cross-sectional view of an electrostatic suction type ink jet device.

[0045] 図において、 101はインク噴射室、 102はインク、 103はインク室、 104はノズル孔、 105はインクタンク、 106はインク供給路、 107は回転ローラー、 108は被記録媒体、 110は制御素子部、 111はプロセス制御部を示して 、る。  In the figure, 101 is an ink ejection chamber, 102 is ink, 103 is an ink chamber, 104 is a nozzle hole, 105 is an ink tank, 106 is an ink supply path, 107 is a rotating roller, 108 is a recording medium, and 110 is A control element unit 111 indicates a process control unit.

[0046] さらに、 114はインク噴射室 101のインク室 103側に配設された静電界印加用電極 部、 115は回転ローラー 107に設置された金属ドラムである対向電極部、 116は対向 電極部 115に数千 Vの負電圧を印加するバイアス電源部である。 117は静電界印加 用電極部 114に数百 Vの高電圧を供給する高圧電源部、 118は接地部である。 [0047] ここで、静電界印加用電極部 114と対向電極部 115との間において、対向電極部 1 15に印加されて!、る数千 Vの負電圧のバイアス電源部 116と数百 Vの高圧電源部 1 17の高圧電圧とが重畳されて、重畳電界が形成されており、この重畳電界によって インク 102のノズル孔 104からの吐出が制御されている。 Further, 114 is an electrostatic field applying electrode portion disposed on the ink chamber 103 side of the ink ejecting chamber 101, 115 is a counter electrode portion that is a metal drum installed on the rotating roller 107, and 116 is a counter electrode portion. This is a bias power supply that applies a negative voltage of several thousand volts to 115. 117 is a high-voltage power supply section that supplies a high voltage of several hundred volts to the electrostatic field applying electrode section 114, and 118 is a grounding section. [0047] Here, between the electrostatic field applying electrode part 114 and the counter electrode part 115, it is applied to the counter electrode part 115! A bias power supply part 116 having a negative voltage of several thousand V and several hundred V The high voltage of the high voltage power supply unit 117 is superimposed to form a superimposed electric field, and ejection of the ink 102 from the nozzle hole 104 is controlled by this superimposed electric field.

[0048] また、 119は対向電極部 115に印加された数千 Vのバイアス電圧によってノズル孔 104に形成される凸状のメニスカスである。  Further, 119 is a convex meniscus formed in the nozzle hole 104 by a bias voltage of several thousand V applied to the counter electrode 115.

[0049] 以上のように構成された静電吸引方式のインクジェット装置の動作について、以下 に説明する。  [0049] The operation of the electrostatic suction ink jet apparatus configured as described above will be described below.

[0050] まず、インク 102は、毛細管現象により、インク供給路 106を伝わって、インク 102を 吐出するノズル孔 104まで移送される。このとき、ノズル孔 104に対向して、被記録媒 体 108を装着した対向電極部 115が配置されている。  First, the ink 102 is transferred to the nozzle hole 104 for discharging the ink 102 through the ink supply path 106 by capillary action. At this time, the counter electrode portion 115 on which the recording medium 108 is mounted is disposed so as to face the nozzle hole 104.

[0051] ノズル孔 104まで達したインク 102は、対向電極部 115に印加された数千 Vのバイ ァス電圧によってノズル孔 104〖こお!/、て凸状のインクメニスカス 119が形成される。ィ ンク室 103内に配設された静電界印加用電極部 114に数百 Vの高圧電源部 117か ら信号電圧を印加することで対向電極部 115に印加されたバイアス電源部 116から の電圧とが重畳され、重畳電界によってインク 102は被記録媒体 108に吐出され、印 字画像が形成される。  [0051] The ink 102 that has reached the nozzle hole 104 is formed with a convex ink meniscus 119 by a bias voltage of several thousand V applied to the counter electrode 115. . The voltage from the bias power source 116 applied to the counter electrode 115 by applying a signal voltage from the high voltage power source 117 of several hundred volts to the electrostatic field applying electrode 114 disposed in the ink chamber 103. And the ink 102 is ejected onto the recording medium 108 by the superimposed electric field, and a printed image is formed.

[0052] 上記インクジェット装置における液滴の飛翔までのメニスカスの挙動を、図 4 (a)〜 図 5 (c)を参照しながら以下に説明する。  [0052] The behavior of the meniscus until the droplets fly in the ink jet apparatus will be described below with reference to FIGS. 4 (a) to 5 (c).

[0053] 駆動電圧を印加する前は、図 4 (a)に示すように、インクに加えられて!/、るバイアス 電圧による静電力とインクの表面張力の釣り合いにより、インク表面に盛り上がったメ ニスカス 119aが形成された状態となって!/、る。 [0053] Before applying the drive voltage, as shown in FIG. 4 (a), the ink that is raised on the ink surface due to the balance between the electrostatic force due to the bias voltage applied to the ink and the surface tension of the ink is applied. Niscus 119a is formed!

[0054] 上記の状態で駆動電圧を印加すると、図 4 (b)に示すように、メニスカス 119bは、液 表面に発生した電荷が液面の盛り上がりの中心に寄り初め、それにより液面の盛り上 力 Sりの中心が高くなつたメニスカス 119bが形成される。 When a drive voltage is applied in the above state, as shown in FIG. 4 (b), the meniscus 119b starts to move toward the center of the rise of the liquid surface, thereby causing the liquid surface to rise. A meniscus 119b having a high center of upper force S is formed.

[0055] その後、駆動電圧を印加し続けると、図 4 (c)に示すように、液表面に発生した電荷 が更に中心に集中することによりテーラーコーンとよばれる半月状のメニスカス 119c が形成され、該テーラーコーンの頂部に集中した電荷量による静電力がインクの表 面張力を超えた段階で液滴の分離が行われ吐出される。 Thereafter, when the drive voltage is continuously applied, as shown in FIG. 4 (c), the charge generated on the liquid surface is further concentrated at the center, thereby forming a meniscus meniscus 119c called a tailor cone. The electrostatic force due to the amount of charge concentrated on the top of the tailor cone is the surface of the ink. When the surface tension is exceeded, the droplets are separated and discharged.

[0056] 以上のように、静電吸引型インクジェット方式は、静電力によって、ノズル径に比べ 、微少な液滴を発生させる点に特徴があり、メツキ触媒を含有する液体をインクとして 用いて、電極形成部分に、これをパターン印刷してメツキ触媒パターンを形成させる  [0056] As described above, the electrostatic suction type ink jet method is characterized in that it generates fine droplets compared to the nozzle diameter by electrostatic force, and uses a liquid containing a catalyst catalyst as ink. Pattern printing is performed on the electrode forming part to form a plating catalyst pattern.

[0057] メツキ触媒を含有するインクの例としては、前記無電解メツキ触媒液を、インクとして 適用可能な、表面張力（例えば、 10〜： LOOmNZm)に調整し用いることができる。 [0057] As an example of an ink containing a plating catalyst, the electroless plating catalyst solution can be used by adjusting the surface tension (for example, 10 to: LOOmNZm) applicable as an ink.

[0058] 例えば、一例としては、可溶性パラジウム塩 (塩化パラジウム (Pd2+濃度 1. Og/L) ) 、溶剤はイソプロピルアルコール、 12質量％、グリセリン、 20質量0 /0、 2—メチルー 2, 4—ペンタンジオール、 5質量％、イオン交換水、 40質量％など力 なる触媒液を用 いることがでさる。 [0058] For example, as an example, a soluble palladium salt (palladium chloride (Pd 2+ concentration 1. Og / L)), solvent isopropyl alcohol, 12 wt%, glycerin, 20 mass 0/0, 2-methyl-2, It is possible to use powerful catalyst solutions such as 4-pentanediol, 5% by mass, ion-exchanged water, and 40% by mass.

[0059] 静電吸引による方法としては上記の方法に限らず、例えば前記特開 2000— 1274 10号等の構造 (ラインヘッド）、又電界の適用方法等のバリエーションを含むいかなる 静電吸引方式の液体吐出装置を用いてもよい。  [0059] The method by electrostatic attraction is not limited to the above method, and any electrostatic attraction method including variations such as the structure (line head) of the above-mentioned Japanese Patent Application Laid-Open No. 2000-127410 and the method of applying an electric field. A liquid ejection device may be used.

[0060] このような静電吸引方式の液体吐出装置を用いたインクジェット印刷により、無電解 メツキの触媒を電極パターンに従って形成した後、次いで、メツキ剤と接触させること で無電解メツキによる電極 (パターン)形成が精度よく行える。  [0060] After forming an electroless plating catalyst in accordance with an electrode pattern by ink jet printing using such an electrostatic suction type liquid discharge device, an electrode (pattern) is formed by contacting with a plating agent. ) Formation can be performed with high accuracy.

[0061] 本発明においては、ゲート、ソース、ドレインの少なくとも一つの電極は、本発明の 方法を用いた無電解メツキ法により形成される。即ち、前記電極パターンに対応する メツキ触媒パターンの形成が、メツキ触媒を含有する液体をインクとして用い、静電吸 引方式の液体吐出装置によって、これを吐出することで行われ、また、形成されたメッ キ触媒パターンにメツキ剤を接触させることで無電解メツキによる金属薄膜がメツキ触 媒パターンに従って形成される。  In the present invention, at least one of the gate, source, and drain electrodes is formed by an electroless plating method using the method of the present invention. That is, the formation of the plating catalyst pattern corresponding to the electrode pattern is performed and formed by using a liquid containing the plating catalyst as ink and discharging it with an electrostatic suction type liquid discharge device. By bringing a plating agent into contact with the plating catalyst pattern, a metal thin film by electroless plating is formed according to the plating catalyst pattern.

[0062] 静電吸引方式の液体吐出装置 (静電吸引型インクジェット装置）については、飛び 出すインク量を静電界印加時間によって制御できる。静電界印加用電極 114は、プ ロセス制御部 111に接続され、このプロセス制御部 111によって、高圧電源部 117か ら、制御素子部 110を駆動して、信号電圧を印加する (駆動回路は図示しない)。プ ロセス制御部 111がこの電界強度を制御することで、ノズル 104の先端部に形成され るメニスカス 119a (図 4参照）における電界強度を制御することができ、ノズル 104力 らのインク 102の吐出量が調整される。 For the electrostatic suction type liquid ejection device (electrostatic suction type ink jet device), the amount of ink ejected can be controlled by the electrostatic field application time. The electrostatic field applying electrode 114 is connected to the process control unit 111, and the process control unit 111 drives the control element unit 110 from the high-voltage power supply unit 117 to apply a signal voltage (a drive circuit is illustrated). do not do). The process control unit 111 controls the electric field strength to form the tip of the nozzle 104. The electric field strength at the meniscus 119a (see FIG. 4) can be controlled, and the ejection amount of the ink 102 from the nozzle 104 force is adjusted.

[0063] 微少な液滴を得るためには、大きな径のノズルでは、 1000V以下の駆動電圧にす ることは困難であり、数百 Vの駆動電圧で制御するには、大凡 25 m以下である必 要があり、また、前記の駆動電圧を数百 V (大凡 1000V以下）としたとき、局所的な電 界強度によって、静電的な力が表面張力を上回る時のノズル直径の上限が大凡 25 /z mであること力もも、ノズル直径の上限値は、 25 mであることが好ましい。特に、 1 がより好ましい。特に、局所的な電界集中効果をより効果的に利用するには、ノ ズル直径は 0. 01〜8 /ζ πιの範囲が望ましい。  [0063] In order to obtain minute droplets, it is difficult to achieve a driving voltage of 1000 V or less with a large-diameter nozzle. To control with a driving voltage of several hundred V, it is about 25 m or less. In addition, when the driving voltage is set to several hundred volts (approximately 1000 volts or less), the upper limit of the nozzle diameter when the electrostatic force exceeds the surface tension due to the local electric field strength. The upper limit of the nozzle diameter is preferably 25 m, with a force of approximately 25 / zm. In particular, 1 is more preferable. In particular, in order to more effectively use the local electric field concentration effect, the nozzle diameter is desirably in the range of 0.01 to 8 / ζ πι.

[0064] この範囲にすることで、微小量の液滴の吐出、あるいは微小量の連続噴射が可能と なり、高細精パターン印刷が可能となる。  [0064] By setting this range, it is possible to discharge a minute amount of liquid droplets or to continuously eject a minute amount, and to print a highly fine pattern.

[0065] また、微小液滴を用いるため、溶媒の蒸発速度が相対的に速くなり、従ってメツキ触 媒成分のパターン形成も早くなる。蒸発速度が遅 、従来のピエゾ方式のインクジエツ トでは、吐出された液滴がはじく現象が発生し、メツキ触媒成分のパターン形成の障 害となる傾向があるが、この点でも、本発明では高精細化が可能になる。  [0065] Further, since fine droplets are used, the evaporation rate of the solvent is relatively high, and therefore, the pattern formation of the plating catalyst component is also accelerated. In the conventional piezo ink jet, which has a low evaporation rate, the ejected droplets tend to repel, which tends to hinder the formation of a pattern of the catalyst catalyst component. Refinement becomes possible.

[0066] ノズル孔の直径（以下、ノズル直径）の下限値は、制作上の都合から 0. 01 μ mが好 ましい。  [0066] The lower limit of the nozzle hole diameter (hereinafter referred to as nozzle diameter) is preferably 0.01 μm for production reasons.

[0067] 従って、前記図 1で示されるボトムゲート型薄膜トランジスタに例をとれば、ゲート電 極 8を基板上に形成する際には、パターユングをレジスト等を用いて行わずに、下引 き層 2を形成した基板上に直接、例えば、無電解メツキの触媒液をインクとして、静電 吸引型インクジェット装置から吐出してパターン印刷すればよい。これにより高精度で 無電解メツキの触媒パターンを形成することが出来るので、これにメツキ剤を接触させ 、無電解メツキにより金属薄膜を形成して、電極パターンを精度よく得ることが出来る  Therefore, taking the bottom gate type thin film transistor shown in FIG. 1 as an example, when forming the gate electrode 8 on the substrate, the patterning is performed without using a resist or the like. The pattern printing may be performed directly on the substrate on which the layer 2 is formed, for example, by discharging an electroless plating catalyst solution as an ink from an electrostatic suction ink jet apparatus. As a result, it is possible to form an electroless plating catalyst pattern with high accuracy, so that an electrode pattern can be obtained with high precision by contacting a plating agent and forming a metal thin film by electroless plating.

[0068] また、図 1のトップゲート型薄膜トランジスタにおけるゲート電極も同様の方法で精 度よく形成することが出来る。 [0068] In addition, the gate electrode in the top-gate thin film transistor in FIG. 1 can be formed with high accuracy by the same method.

[0069] 本発明においては、ソースまたはドレイン電極が前記無電解メツキ法により形成され ることが好ましぐ特に、ソース、ドレイン電極、ソースバスライン等を一度に形成する 際に用いられることが好ま 、。 In the present invention, it is preferable that the source or drain electrode is formed by the electroless plating method. In particular, the source, drain electrode, source bus line, etc. are formed at a time. Preferred to be used when.

[0070] また、本発明の方法は、ボトムゲート型構造を有する薄膜トランジスタの製造に適し ており、ゲート電極、ゲートバスライン、ゲート絶縁層、また半導体層等が実装された 基板上に、ソース、ソースバスライン、ドレイン電極等のパターユングを、レジスト形成 等による複雑工程を回避して、精度よく行えることは好ましい。  [0070] Further, the method of the present invention is suitable for manufacturing a thin film transistor having a bottom-gate structure. A source, a gate, a gate bus line, a gate insulating layer, a semiconductor layer, and the like are mounted on a substrate. It is preferable that the patterning of the source bus line, the drain electrode, etc. can be performed with high accuracy while avoiding complicated processes such as resist formation.

[0071] また、従って、本発明の薄膜トランジスタの製造方法は有機薄膜トランジスタの製造 に特に有利に用いられる。有機半導体層上にソース、ドレイン電極を形成する際に、 レジスト等を形成する方法を用いずに簡便に精度のょ 、パター-ングが行えるほか、 電極のパター-ングに感光性榭脂を用いる場合には、感光性榭脂そのものが、また 感光性榭脂からのレジストの形成プロセスやまたその除去プロセスが有機半導体層 に対する影響がないものに限定されるため、有機半導体材料を用いる場合特に本発 明の方法は好ましい。  [0071] Therefore, the method for producing a thin film transistor of the present invention is particularly advantageously used for producing an organic thin film transistor. When forming the source and drain electrodes on the organic semiconductor layer, patterning can be performed easily and accurately without using a method such as forming a resist, and photosensitive resin is used for electrode patterning. In some cases, the photosensitive resin itself, and the process of forming and removing the resist from the photosensitive resin are limited to those that do not affect the organic semiconductor layer. The method of invention is preferred.

[0072] 本発明に係わる薄膜トランジスタにおいて、無電解メツキによって有機半導体層上 に、電極を形成する場合、電極形成領域以外の領域 (例えば、薄膜トランジスタ素子 において半導体チャネルとなる領域等）においては、有機半導体層は、有機半導体 材料に対し影響が考えられるこれら触媒ゃメツキ剤と直接接触しな ヽことが好ま 、。 そのためには、トップコンタクト型の構成をとる薄膜トランジスタの製造においては、有 機半導体層保護膜を電極形成領域以外の必要とされる領域に設けることが好ましい  [0072] In the thin film transistor according to the present invention, when an electrode is formed on the organic semiconductor layer by electroless plating, the organic semiconductor is used in a region other than the electrode formation region (for example, a region that becomes a semiconductor channel in the thin film transistor element). It is preferable that the layer should not be in direct contact with these catalytic agents, which may have an impact on organic semiconductor materials. Therefore, in the manufacture of a thin film transistor having a top contact type structure, it is preferable to provide an organic semiconductor layer protective film in a required region other than the electrode formation region.

[0073] 保護膜は、従って、電極形成領域以外の保護領域 (例えば半導体チャネルを形成 する領域)を保護するようにパターユングされて!/ヽることが好ま ヽ。保護膜を形成し た後、メツキ触媒パターンを形成し、これに、メツキ剤を接触させる方法で、無電解メッ キを行うことができる。メツキ剤を接触させる方法は特に限定されないが、例えば、メッ キ剤への浸漬ゃスプレー吹き付け、或いはインクジェット法、スクリーン印刷、凹版、 平版、凸版などの印刷による方法が適用可能である。 [0073] Accordingly, the protective film is preferably patterned so as to protect a protective region other than the electrode forming region (for example, a region for forming a semiconductor channel). After forming the protective film, a plating catalyst pattern is formed, and electroless plating can be performed by contacting the plating agent with the plating catalyst pattern. The method for bringing the plating agent into contact is not particularly limited, but for example, a method of spraying by dipping in the plating agent or printing such as an ink jet method, screen printing, intaglio, planographic printing, letterpress or the like is applicable.

[0074] また、無電解メツキにより金属薄膜パターンを形成した後、基板表面にメツキ剤等に 含有された溶質が付着して 、る場合、必要があれば洗浄することができる。  [0074] In addition, after the metal thin film pattern is formed by electroless plating, the solute contained in the plating agent or the like adheres to the substrate surface. If necessary, the substrate can be cleaned if necessary.

[0075] 〔保護膜について〕 本発明において、上記無電解メツキにより電極が設けられる前に、有機半導体層上 に形成される保護膜としては、前記、メツキ触媒、またメツキ剤中の金属塩また還元剤 等の作用を封じる、有機半導体材料にたいし影響を与えない不活性な材料であれば よぐまた有機半導体保護層の上に光感応性榭脂層等の感光性組成物を形成する ような場合には、その塗布工程で影響を受けないことと、さらに光感応性榭脂層のパ ターニング時にも影響を受けな 、材料であるが好まし 、。 [Protective film] In the present invention, before the electrode is provided by the electroless plating, the protective film formed on the organic semiconductor layer seals the action of the plating catalyst, the metal salt in the plating agent, the reducing agent, etc. If it is an inert material that does not significantly affect the organic semiconductor material, and if a photosensitive composition such as a photosensitive resin layer is formed on the organic semiconductor protective layer, the coating is applied. The material is preferred because it is not affected by the process and is not affected by the patterning of the photosensitive resin layer.

[0076] そのような材料として、以下に挙げる高分子材料、特に親水性ポリマーを含有する 材料が挙げられ、さらに好ましくは、親水性ポリマーの水溶液又は水分散液が挙げら れる。 [0076] Examples of such materials include the following polymer materials, particularly materials containing a hydrophilic polymer, and more preferred are aqueous solutions or aqueous dispersions of hydrophilic polymers.

[0077] 親水性ポリマーとしては、水、または酸性水溶液、アルカリ性水溶液、アルコール水 溶液、各種の界面活性剤の水溶液に対して、溶解性または分散性を有するポリマー である。たとえばポリビュルアルコールや、 HEMA、アクリル酸、アクリルアミドなどの 成分力もなるホモポリマー、コポリマーを好適に用いることができる。またその他の材 料として、無機酸化物、無機窒化物を含有する材料も、有機半導体への影響を与え ず、その他塗布工程での影響を与えないので好ましい。さらに後述するゲート絶縁層 の材料も用いることができる。  [0077] The hydrophilic polymer is a polymer that is soluble or dispersible in water or an acidic aqueous solution, an alkaline aqueous solution, an alcohol aqueous solution, or an aqueous solution of various surfactants. For example, polybulal alcohol, homopolymers and copolymers having component power such as HEMA, acrylic acid, and acrylamide can be suitably used. As other materials, materials containing inorganic oxides and inorganic nitrides are also preferable because they do not affect the organic semiconductor and do not affect other coating processes. Furthermore, the material of the gate insulating layer described later can also be used.

[0078] ゲート絶縁層材料である無機酸ィ匕物又は無機窒化物を含有する有機半導体保護 層は、大気圧プラズマ法で形成されるのが好ま 、。  [0078] The organic semiconductor protective layer containing an inorganic oxide or inorganic nitride as the gate insulating layer material is preferably formed by an atmospheric pressure plasma method.

[0079] 大気圧下でのプラズマ法による薄膜の形成方法は、大気圧または大気圧近傍の圧 力下で放電し、反応性ガスをプラズマ励起し、基材上に薄膜を形成する処理で、そ の方法【こつ ヽて ίま特開平 11— 61406、同 11— 133205、特開 2000— 121804、 同 2000— 147209、同 2000— 185362等【こ記載されて!ヽる（以下、大気圧プラス、 マ法とも称する)。これによつて高機能性の薄膜を、生産性高く形成することができる  [0079] A method for forming a thin film by a plasma method under atmospheric pressure is a process in which a thin film is formed on a substrate by discharging under atmospheric pressure or a pressure near atmospheric pressure, exciting a reactive gas into plasma, and The method is as follows: JP 11-61406, 11-133205, 2000-121804, 2000-147209, 2000-185362, etc. (hereinafter referred to as atmospheric pressure plus) , Also called ma method). As a result, a highly functional thin film can be formed with high productivity.

[0080] また、保護膜のパターユングを行う時にフォトレジストを用いることが好ましい。 [0080] Further, it is preferable to use a photoresist when patterning the protective film.

[0081] フォトレジスト層としては、ポジ型、ネガ型の公知の材料を用いることができる力 レ 一ザ感光性の材料を用いることが好ましい。このようなフォトレジスト材料として、（1) 特開平 11— 271969号、欄 2001— 117219、特開平 11— 311859号、特開平 1 1— 352691号のような色素増感型の光重合感光材料、（2)特開平 9— 179292号、 米国特許第 5, 340, 699号、特開平 10— 90885号、特開 2000— 321780、同 20 01— 154374のような赤外線レーザに感光性を有するネガ型感光材料、 (3)特開平 9— 171254号、同 5— 115144号、同 10— 87733号、同 9— 43847号、同 10— 26 8512号、同 11— 194504号、同 11— 223936号、同 11— 84657号、同 11— 174 681号、同 7— 285275号、特開 2000— 56452、 W097Z39894、同 98,42507 のような赤外線レーザに感光性を有するポジ型感光材料が挙げられる。工程が暗所 に限定されない点で、好ましいのは（2)と（3)であり、フォトレジスト層を除去する場合 には、ポジ型である（3)が最も好ましい。 As the photoresist layer, it is preferable to use a force-receptor photosensitive material that can use a known positive or negative material. As such a photoresist material, (1) JP-A-11-271969, column 2001-117219, JP-A-11-311859, JP-A-1 1-352691, a dye-sensitized photopolymerization photosensitive material, (2) JP-A-9-179292, US Pat. No. 5,340,699, JP-A-10-90885, JP-A-2000-321780, Negative photosensitive materials having sensitivity to infrared lasers such as 20 01-154374, (3) JP-A-9-171254, 5-115144, 10-87733, 9-43847, 10 -26 8512, 11-194504, 11-223936, 11-84657, 11-174 681, 7-285275, JP 2000-56452, W097Z39894, 98,42507 And a positive photosensitive material having photosensitivity to an infrared laser. (2) and (3) are preferable in that the process is not limited to a dark place, and when removing the photoresist layer, the positive type (3) is most preferable.

[0082] 光感応性榭脂の塗布溶液を形成する溶媒としては、プロピレングリコールモノメチ ノレエーテノレ、プロピレングリコーノレモノエチノレエーテノレ、メチノレセロソノレブ、メチノレセ ロソノレブアセテート、ェチノレセロソノレブ、ェチルセ口ソルブアセテート、ジメチルホルム アミド、ジメチルスルホキシド、ジォキサン、アセトン、シクロへキサノン、トリクロロェチ レン、メチルェチルケトン等が挙げられる。これら溶媒は、単独であるいは 2種以上混 合して使用する。 [0082] Solvents for forming the coating solution of the photosensitive resin include propylene glycol monomethylenoatenore, propyleneglycolenomonoethylenoatenore, methinorecellosonoleb, methinorecerosonoleb acetate, ethinorecerozolev, Examples include ethyl acetate sorb acetate, dimethylformamide, dimethyl sulfoxide, dioxane, acetone, cyclohexanone, trichloroethylene, and methyl ethyl ketone. These solvents are used alone or in combination of two or more.

[0083] 光感応性榭脂層を形成する方法としては、スプレーコート法、スピンコート法、ブレ ードコート法、ディップコート法、キャスト法、ロールコート法、バーコート法、ダイコート 法などの塗布による方法等、前記保護膜のパターユングに述べたとおりである。  [0083] Methods for forming the photosensitive resin layer include spray coating, spin coating, blade coating, dip coating, casting, roll coating, bar coating, die coating, and other coating methods. Etc., as described in the patterning of the protective film.

[0084] 光感応性榭脂層が形成後、パターニング露光を、 Arレーザ、半導体レーザ、 He— Neレーザ、 YAGレーザ、炭酸ガスレーザ等により行う。赤外に発振波長がある半導 体レーザが好ましい。出力は 50mW以上が適当であり、好ましくは lOOmW以上であ る。 [0084] After the photosensitive resin layer is formed, patterning exposure is performed by an Ar laser, a semiconductor laser, a He-Ne laser, a YAG laser, a carbon dioxide gas laser, or the like. A semiconductor laser having an oscillation wavelength in the infrared is preferable. The output is suitably 50mW or more, preferably lOOmW or more.

[0085] 光感応性榭脂層の現像に用いられる現像液としては、水系アルカリ現像液が好適 である。水系アルカリ現像液としては、例えば、水酸化ナトリウム、水酸ィ匕カリウム、炭 酸ナトリウム、炭酸カリウム、メタケイ酸ナトリウム、メタケイ酸カリウム、第二リン酸ナトリ ゥム、第三リン酸ナトリウム等のアルカリ金属塩の水溶液や、アンモニア、ェチルァミン 、 n—プロピルァミン、ジェチルァミン、ジ—n—プロピルァミン、トリェチルァミン、メチ ルジェチルァミン、ジメチルエタノールァミン、トリエタノールァミン、テトラメチルアンモ ユウムヒドロキシド、ピぺリジン、 1, 8—ジァザビシクロー [5, 4, 0]—7—ゥンデセン 等のアルカリ性ィ匕合物を溶解した水溶液水を挙げることが出来る。本発明におけるァ ルカリ性ィ匕合物のアルカリ現像液中における濃度は、通常 1〜10質量％、好ましくは 2〜5質量％である。 [0085] A water-based alkaline developer is suitable as the developer used for developing the photosensitive resin layer. Examples of the aqueous alkaline developer include alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium metasilicate, potassium metasilicate, dibasic sodium phosphate, and tribasic sodium phosphate. Aqueous solutions of metal salts, ammonia, ethylamine, n-propylamine, jetylamine, di-n-propylamine, triethylamine, methyljetylamine, dimethylethanolamine, triethanolamine, tetramethylammonium An aqueous solution in which an alkaline compound such as yuum hydroxide, piperidine, 1,8-diazabicyclo [5, 4, 0] -7-undecene is dissolved can be mentioned. The concentration of the alkaline compound in the present invention in the alkali developer is usually 1 to 10% by mass, preferably 2 to 5% by mass.

[0086] 現像液には、必要に応じァ-オン性界面活性剤、両性界面活性剤やアルコール等 の有機溶剤をカ卩えることができる。有機溶剤としては、プロピレングリコール、エチレン グリコールモノフエ-ルエーテル、ベンジルアルコール、 n—プロピルアルコール等が 有用である。 [0086] In the developer, an organic solvent such as an ionic surfactant, an amphoteric surfactant, and alcohol can be added as necessary. As the organic solvent, propylene glycol, ethylene glycol monophenyl ether, benzyl alcohol, n -propyl alcohol, and the like are useful.

[0087] 本発明においては、また、保護膜のメツキ触媒パターン形成、即ち、電極パターン 形成には、他の光感応性榭脂層であるアブレーシヨン層をもちいてもよい。  In the present invention, an abrasion layer, which is another photosensitive resin layer, may also be used for forming a protective catalyst pattern of the protective film, that is, for forming an electrode pattern.

[0088] 本発明に用いられるアブレーシヨン層は、エネルギー光吸収剤、ノ インダー榭脂お よび必要に応じて添加される各種添加剤力も構成することができる。  [0088] The abrasion layer used in the present invention can also constitute an energy light absorber, a binder resin, and various additive powers added as necessary.

[0089] エネルギー光吸収剤は、照射するエネルギー光を吸収する各種の有機および無機 材料が使用可能であり、たとえばレーザ光源を赤外線レーザとした場合、赤外線を吸 収する顔料、色素、金属、金属酸化物、金属窒化物、金属炭化物、金属ホウ化物、 グラフアイト、カーボンブラック、チタンブラック、 Al、 Fe、 Ni、 Co等を主成分とするメタ ル磁性粉末等の強磁性金属粉末などを用いることができ、中でも、カーボンブラック、 シァニン系などの色素、 Fe系強磁性金属粉末が好ましい。エネルギー光吸収剤の 含有量は、アブレーシヨン層形成成分の 30〜95質量％程度、好ましくは 40〜80質 量％である。  [0089] As the energy light absorber, various organic and inorganic materials that absorb the energy light to be irradiated can be used. For example, when the laser light source is an infrared laser, a pigment, a dye, a metal, or a metal that absorbs infrared light. Use ferromagnetic metal powder such as metal magnetic powder mainly composed of oxide, metal nitride, metal carbide, metal boride, graphite, carbon black, titanium black, Al, Fe, Ni, Co, etc. Among these, carbon black, cyanine-based pigments, and Fe-based ferromagnetic metal powders are preferred. The content of the energy light absorber is about 30 to 95% by mass, preferably 40 to 80% by mass of the abrasion layer forming component.

[0090] アブレーシヨン層のノ インダー榭脂は、前記色材微粒子を十分に保持できるもので あれば、特に制限無く用いることができ、ポリウレタン系榭脂、ポリエステル系榭脂、 塩ィ匕ビ二ル系榭脂、ポリビニルァセタール系榭脂、セルロース系榭脂、アクリル系榭 脂、フエノキシ榭脂、ポリカーボネート、ポリアミド系榭脂、フエノール榭脂、エポキシ 榭脂などを挙げることができる。ノインダー榭脂の含有量は、アブレーシヨン層形成 成分 5〜70質量％程度、好ましくは 20〜60質量％である。  [0090] The nodding resin of the abrasion layer can be used without particular limitation as long as it can sufficiently retain the colorant fine particles, and it can be used as a polyurethane resin, a polyester resin, or a salt vinyl. Examples thereof include a system resin, a polyvinylacetal resin, a cellulose resin, an acrylic resin, a phenoxy resin, a polycarbonate, a polyamide resin, a phenol resin, and an epoxy resin. The content of Noinda rosin is about 5 to 70% by mass, preferably 20 to 60% by mass, of the abrasion layer forming component.

[0091] 本明細書でいうアブレーシヨン層とは、高密度エネルギー光の照射によりアブレート する層を指し、ここで言うアブレートとは、物理的或いは化学的変化によりアブレーシ ヨン層が完全に飛散する、一部が破壊される或いは飛散する、隣接する層との界面 近傍のみに物理的或いは化学的変化が起こるという現象を含む。このアブレートを利 用してレジスト像を形成し、電極を形成させる。 [0091] The ablation layer referred to in this specification refers to a layer that is ablated by irradiation with high-density energy light. The ablation referred to herein is ablation caused by physical or chemical changes. This includes the phenomenon that the Yon layer is completely scattered, part of it is broken or scattered, and the physical or chemical change occurs only in the vicinity of the interface with the adjacent layer. Using this ablation, a resist image is formed and electrodes are formed.

[0092] 高密度エネルギー光は、アブレートを発生させる活性光であれば特に制限はなく 用いることができる。露光方法としては、キセノンランプ、ハロゲンランプ、水銀ランプ などによるフラッシュ露光を、フォトマスクを介して行ってもよいし、レーザ光等を収束 させ走査露光を行っても良い。レーザ 1ビーム当たりの出力は 20〜200mWである赤 外線レーザ、特に半導体レーザが最も好ましく用いられる。エネルギー密度としては 、好ましくは 50〜500miZcm2、更に好ましくは 100〜300mj/cm2である。 [0092] The high-density energy light can be used without particular limitation as long as it is active light that generates ablation. As an exposure method, flash exposure using a xenon lamp, a halogen lamp, a mercury lamp, or the like may be performed through a photomask, or scanning exposure may be performed by converging laser light or the like. An infrared laser having an output per laser beam of 20 to 200 mW, particularly a semiconductor laser, is most preferably used. The energy density is preferably 50 to 500 miZcm 2 , more preferably 100 to 300 mj / cm 2 .

[0093] また、前記光感応性榭脂層（アブレーシヨン層）上に、溶剤塗布によって、厚さ 0. 5 μ m程度の電極材料反撥層を形成することが好ましい。  In addition, it is preferable to form an electrode material repellent layer having a thickness of about 0.5 μm on the photosensitive resin layer (ablation layer) by solvent coating.

[0094] 電極材料反撥層は、シリコーンゴム層、またはシランカップリング剤、チタネートカツ プリング剤などを用いて、感光層表面に電極材料、本発明においては、メツキ触媒液 、または、メツキ剤液に対する反撥性を付与する層であり、感光層上に電極材料反撥 層を塗設し、感光層に露光または現像を行うことにより、感光層と組み合わせてバタ 一ユングを行える。感光層としてはアブレーシヨン層、また光重合性感光材料等が好 ましい。  [0094] The electrode material repellent layer uses a silicone rubber layer, a silane coupling agent, a titanate coupling agent, or the like to form an electrode material on the surface of the photosensitive layer, and in the present invention, against the plating catalyst solution or the plating agent solution. It is a layer that imparts repellent properties. By coating an electrode material repellent layer on the photosensitive layer and exposing or developing the photosensitive layer, buttering can be performed in combination with the photosensitive layer. As the photosensitive layer, an abrasion layer or a photopolymerizable photosensitive material is preferred.

[0095] 形成した感光層及び電極材料反撥層に、半導体レーザ等で例えば、ソース電極、 ソースバスライン等のパターンを露光し、次いで露光部の電極材料反撥層（シリコー ンゴム層）をブラシ処理で除去する。感光層とシリコーンゴム層との接着性が露光によ り変化するので、ブラシ処理で簡単にシリコーンゴム層を除去することが出来る。  The formed photosensitive layer and electrode material repellent layer are exposed to a pattern such as a source electrode and a source bus line with a semiconductor laser or the like, and then the exposed electrode material repellent layer (silicone rubber layer) is brushed. Remove. Since the adhesiveness between the photosensitive layer and the silicone rubber layer changes with exposure, the silicone rubber layer can be easily removed by brush treatment.

[0096] さらにこれを水でよく洗浄し露光部の感光層また例えば、ポリビュルアルコール等 の保護層も溶解して除去することで、保護層が除去され、無電解メツキを施す領域に おいて有機半導体薄層を露出させる。  [0096] Further, this is thoroughly washed with water, and the photosensitive layer in the exposed portion or the protective layer such as polybutyl alcohol is dissolved and removed, so that the protective layer is removed and in the region where electroless plating is applied. The thin organic semiconductor layer is exposed.

[0097] この電極材料反撥層と無電解メツキ材料を組み合わせることで、保護層の効果を高 め、電極形成させる部分のみ精度よくパターユングでき、簡単なプロセスで電極材料 のパター-ングが行える。  [0097] By combining the electrode material repellent layer and the electroless plating material, the effect of the protective layer can be enhanced, and only the portion where the electrode is formed can be accurately patterned, and the electrode material can be patterned by a simple process.

[0098] 電極薄膜の形成後は、上記のレジスト像を除去してもよい。レジスト像をするには、 アルコール系、エーテル系、エステル系、ケトン系、グリコールエーテル系などフォト レジストの塗布溶媒に利用される広範囲の有機溶媒から、適宜選択し用いる。有機 半導体層が浸食されな 、溶媒が好まし ヽ。 [0098] After the formation of the electrode thin film, the resist image may be removed. To make a resist image, It is appropriately selected from a wide range of organic solvents used as photoresist coating solvents such as alcohols, ethers, esters, ketones, and glycol ethers. Solvents are preferred when the organic semiconductor layer is not eroded.

[0099] また、保護膜のパターユング自体を、本発明に係わる、静電吸引方式の液体吐出 装置を用いて行うことができる。前記静電吸引型インクジェット装置を用いて、保護膜 材料溶液をインクとして吐出することで、レジストの形成による方法を行うことなしに、 保護膜のパターユングを直接行うことができる。特に、静電吸引型インクジェット装置 を用いることで、感光性榭脂によるレジスト形成同等の精度のよいパターユングが簡 便に行える。 [0099] Further, the patterning of the protective film itself can be performed using the electrostatic suction type liquid ejection apparatus according to the present invention. By discharging the protective film material solution as ink using the electrostatic attraction type ink jet device, the protective film can be directly patterned without performing a resist formation method. In particular, by using an electrostatic suction type ink jet device, it is possible to easily perform patterning with high accuracy equivalent to resist formation by photosensitive resin.

[0100] 保護膜については、電極形成後に、除去してもよぐ例えばトップコンタクト型薄膜ト ランジスタの場合、ソース、ドレイン電極を形成した後、基板表面に付着したメツキ剤 液を洗い落とすために、基板表面を洗浄するが、その際に除去されるのが好ましい。 しかしながら、薄膜トランジスタとしての性能に影響を与えない場合にはそのまま残し ても構わない。  [0100] The protective film may be removed after the electrode is formed. For example, in the case of a top contact type thin film transistor, after forming the source and drain electrodes, in order to wash off the plating solution adhering to the substrate surface, The substrate surface is cleaned, but is preferably removed at that time. However, if the performance as a thin film transistor is not affected, it may be left as it is.

[0101] 次いで、本発明を構成する有機薄膜トランジスタのその他の構成要素について説 明する。  [0101] Next, other components of the organic thin film transistor constituting the present invention will be described.

[0102] 〔有機半導体層について〕  [0102] [Organic semiconductor layer]

有機半導体層を構成する材料としては、種々の縮合多環芳香族化合物や共役系 化合物が適用可能である。  As a material constituting the organic semiconductor layer, various condensed polycyclic aromatic compounds and conjugated compounds are applicable.

[0103] 縮合多環芳香族化合物としては、例えば、アントラセン、テトラセン、ペンタセン、へ キサセン、ヘプタセン、タリセン、ピセン、フルミネン、ピレン、ぺロピレン、ペリレン、テ リレン、ク才テリレン、コロネン、才ノ レン、サ一力ムアントラセン、ビスアンテン、ゼスレ ン、ヘプタゼスレン、ピランスレン、ビオランテン、イソビオランテン、サーコビフエニル 、フタロシアニン、ポルフィリンなどの化合物及びこれらの誘導体が挙げられる。  [0103] Examples of the condensed polycyclic aromatic compound include anthracene, tetracene, pentacene, hexacene, heptacene, taricene, picene, fluorene, pyrene, peropyrene, perylene, terylene, kuterite terylene, coronene, talillen. And compounds such as musantracene, bisanthene, zeslen, heptazelene, pyranslen, violanthene, isoviolanthene, sacobiphenyl, phthalocyanine, porphyrin, and derivatives thereof.

[0104] 共役系化合物としては、例えば、ポリチォフェン及びそのオリゴマー、ポリピロール 及びそのオリゴマー、ポリア二リン、ポリフエ二レン及びそのオリゴマー、ポリフエ二レン ビニレン及びそのオリゴマー、ポリチェ二レンビニレン及びそのオリゴマー、ポリアセ チレン、ポリジアセチレン、テトラチアフルバレンィ匕合物、キノンィ匕合物、テトラシァノキ ノジメタンなどのシァノ化合物、フラーレン及びこれらの誘導体或いは混合物を挙げ ることがでさる。 [0104] Examples of the conjugated compound include polythiophene and its oligomer, polypyrrole and its oligomer, polyaniline, polyphenylene and its oligomer, polyphenylene vinylene and its oligomer, polyphenylene vinylene and its oligomer, polyacetylene, Polydiacetylene, tetrathiafulvalene compound, quinone compound, tetracyanoxy Examples include cyan compounds such as nodimethane, fullerenes and derivatives or mixtures thereof.

[0105] また、特にポリチォフェン及びそのオリゴマーのうち、チォフェン 6量体である α—セ クシチォフェン e , ω—ジへキシノレ aーセクシチォフェン、 e , ω—ジへキシノレ a—キンケチォフェン、 α , ω—ビス（3—ブトキシプロピル） - a—セクシチォフェン 、などのオリゴマーが好適に用いることができる。  [0105] Furthermore, among polythiophene and oligomers thereof, thiophene hexamer α-secthiophene e, ω-dihexinore a-secciothiophene, e, ω-dihexinore a-quinketiophene, α, ω Oligomers such as —bis (3-butoxypropyl) -a-secciothiophene can be preferably used.

[0106] さらに銅フタロシア-ンゃ特開平 1 1— 251601に記載のフッ素置換銅フタロシア- ンなどの金属フタロシアニン類、ナフタレン 1 , 4, 5, 8—テトラカルボン酸ジイミド、 N , N' —ビス（4 トリフルォロメチルベンジル）ナフタレン 1 , 4, 5, 8—テトラカルボン 酸ジイミドとともに、 N, N' —ビス（1H, 1H—ペルフルォロォクチル）、 N, N' —ビ ス（1H, 1H ペルフルォロブチル）及び N, N' —ジォクチルナフタレン 1 , 4, 5, 8 ーテトラカルボン酸ジイミド誘導体、ナフタレン 2, 3, 6, 7テトラカルボン酸ジイミドな どのナフタレンテトラカルボン酸ジイミド類、及びアントラセン 2, 3, 6, 7—テトラカル ボン酸ジイミドなどのアントラセンテトラカルボン酸ジイミド類などの縮合環テトラカル ボン酸ジイミド類、 C 、C 、C 、C 、C 等フラーレン類、 SWNTなどのカーボンナ  Further, copper phthalocyanine is a metal phthalocyanine such as fluorine-substituted copper phthalocyanine described in JP-A-11-251601, naphthalene 1,4,5,8-tetracarboxylic acid diimide, N, N'-bis (4 Trifluoromethylbenzyl) naphthalene 1, 4, 5, 8-tetracarboxylic acid diimide, N, N'-bis (1H, 1H-perfluorooctyl), N, N'-bis (1H , 1H perfluorobutyl) and N, N'-dioctylnaphthalene 1,4,5,8-tetracarboxylic diimide derivatives, naphthalene 2, 3, 6, 7 naphthalene tetracarboxylic diimides such as tetracarboxylic diimide , And anthracene 2, 3, 6, 7-fused ring tetracarboxylic acid diimides such as anthracene tetracarboxylic acid diimides such as tetracarboxylic acid diimide, fullerenes such as C, C, C, C, C Bonna

60 70 76 78 84  60 70 76 78 84

ノチューブ、メロシアニン色素類、へミシァニン色素類などの色素などがあげられる。  And dyes such as notube, merocyanine dyes, and hemicyanine dyes.

[0107] これらの π共役系材料のうちでも、ペンタセンなどの縮合多環芳香族化合物、フラ 一レン類、縮合環テトラカルボン酸ジイミド類、金属フタロシアニンよりなる群カゝら選ば れた少なくとも 1種が好ま 、。  [0107] Among these π-conjugated materials, at least one selected from the group consisting of condensed polycyclic aromatic compounds such as pentacene, fullerenes, condensed ring tetracarboxylic acid diimides, and metal phthalocyanines. Preferred.

[0108] また、本発明に係る有機半導体材料としては、 Adv. Mater. 2003, 15、 No . 23 , December 3 (2009— 201 1)に記載のシリルェチ-ルペンタセン化合物、また、 J . Am. Chem. Soc. , 2005、 127, 4986〜4987に記載のァセン、ヘテロァセンを 母核として有する化合物等も好ましぐシリルェチニルペンタセン、トリスアルキルシリ ルェチ-ルペンタセン、トリイソプロビルシリルェチ-ルペンタセンなどを好適に用い ることがでさる。  [0108] Further, examples of the organic semiconductor material according to the present invention include silylethyl-pentacene compounds described in Adv. Mater. 2003, 15, No. 23, December 3 (2009—2011), and J. Am. Chem. Soc., 2005, 127, 4986 to 4987 Compounds having acene and heteroacene as a mother nucleus are also preferred. Silylethynylpentacene, trisalkylsilylpentacene, triisopropylpropylsilylethylpentacene, etc. Can be suitably used.

[0109] また、その他の有機半導体材料としては、テトラチアフルバレン (TTF)—テトラシァ ノキノジメタン (TCNQ)錯体、ビスエチレンテトラチアフルバレン（BEDTTTF)—過 塩素酸錯体、 BEDTTTF ヨウ素錯体、 TCNQ ヨウ素錯体、などの有機分子錯体 も用いることができる。さらにポリシラン、ポリゲルマンなどの σ共役系ポリマーゃ特開 2000— 260999に記載の有機'無機混成材料も用いることができる。 [0109] Other organic semiconductor materials include tetrathiafulvalene (TTF) -tetracyanoquinodimethane (TCNQ) complex, bisethylenetetrathiafulvalene (BEDTTTF) -perchloric acid complex, BEDTTTF iodine complex, TCNQ iodine complex, etc. Organic molecular complex Can also be used. Furthermore, σ-conjugated polymers such as polysilane and polygermane can also be used as organic'inorganic hybrid materials described in JP-A-2000-260999.

[0110] また、前記ポリチォフェン及びそのオリゴマーのうち、下記一般式（1)で表されるチ ォフェンオリゴマーが好まし 、。  [0110] Of the polythiophene and oligomers thereof, a thiophene oligomer represented by the following general formula (1) is preferred.

[0111] [化 1]  [0111] [Chemical 1]

—般式 (1 )

Figure imgf000021_0001
—General formula (1)
Figure imgf000021_0001

[0112] 式中、 Rは置換基を表す。 [0112] In the formula, R represents a substituent.

[0113] 《一般式（1)で表されるチォフェンオリゴマー》  [0113] Thiophene oligomer represented by the general formula (1)

前記一般式（1)で表されるチオフ ンオリゴマーについて説明する。  The thiophene oligomer represented by the general formula (1) will be described.

[0114] 一般式（1)において、 Rで表される置換基としては、例えば、アルキル基 (例えば、 メチル基、ェチル基、プロピル基、イソプロピル基、 tert—ブチル基、ペンチル基、へ キシル基、ォクチル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基 等）、シクロアルキル基 (例えば、シクロペンチル基、シクロへキシル基等）、ァルケ- ル基 (例えば、ビュル基、ァリル基等）、アルキ-ル基 (例えば、ェチニル基、プロパル ギル基等）、ァリール基（例えば、フエ-ル基、 p—クロ口フエ-ル基、メシチル基、トリ ル基、キシリル基、ナフチル基、アントリル基、ァズレニル基、ァセナフテュル基、フル ォレニル基、フエナントリル基、インデュル基、ピレニル基、ビフエ-リル基等）、芳香 族複素環基 (例えば、フリル基、チェニル基、ピリジル基、ピリダジル基、ピリミジル基 、ビラジル基、トリアジル基、イミダゾリル基、ピラゾリル基、チアゾリル基、ベンゾイミダ ゾリル基、ベンゾォキサゾリル基、キナゾリル基、フタラジル基等）、複素環基 (例えば 、ピロリジル基、イミダゾリジル基、モルホリル基、ォキサゾリジル基等）、アルコキシル 基 (例えば、メトキシ基、エトキシ基、プロピルォキシ基、ペンチルォキシ基、へキシル ォキシ基、ォクチルォキシ基、ドデシルォキシ基等）、シクロアルコキシル基 (例えば、 シクロペンチルォキシ基、シクロへキシルォキシ基等）、ァリールォキシ基 (例えば、フ エノキシ基、ナフチルォキシ基等）、アルキルチオ基 (例えば、メチルチオ基、ェチル チォ基、プロピルチオ基、ペンチルチオ基、へキシルチオ基、ォクチルチオ基、ドデ シルチオ基等）、シクロアルキルチオ基 (例えば、シクロペンチルチオ基、シクロへキ シルチオ基等）、ァリールチオ基 (例えば、フエ二ルチオ基、ナフチルチオ基等）、ァ ルコキシカルボ-ル基（例えば、メチルォキシカルボ-ル基、ェチルォキシカルボ- ル基、ブチルォキシカルボ-ル基、ォクチルォキシカルボ-ル基、ドデシルォキシ力 ルポ-ル基等）、ァリールォキシカルボ-ル基（例えば、フエ-ルォキシカルボ-ル基 、ナフチルォキシカルボ-ル基等）、スルファモイル基（例えば、アミノスルホ -ル基、 メチルアミノスルホ -ル基、ジメチルアミノスルホ -ル基、ブチルアミノスルホ -ル基、 へキシルアミノスルホ -ル基、シクロへキシルアミノスルホ -ル基、ォクチルアミノスル ホ-ル基、ドデシルアミノスルホ-ル基、フエ-ルアミノスルホ -ル基、ナフチルァミノ スルホ-ル基、 2—ピリジルアミノスルホ -ル基等）、ァシル基 (例えば、ァセチル基、 ェチルカルボ-ル基、プロピルカルボ-ル基、ペンチルカルボ-ル基、シクロへキシ ルカルボニル基、ォクチルカルポ-ル基、 2—ェチルへキシルカルボ-ル基、ドデシ ルカルボニル基、フヱ-ルカルボ-ル基、ナフチルカルボ-ル基、ピリジルカルボ- ル基等）、ァシルォキシ基 (例えば、ァセチルォキシ基、ェチルカルボ-ルォキシ基、 ブチルカルボ-ルォキシ基、ォクチルカルボ-ルォキシ基、ドデシルカルボ-ルォキ シ基、フエ-ルカルポニルォキシ基等）、アミド基 (例えば、メチルカルボニルァミノ基 、ェチルカルボ-ルァミノ基、ジメチルカルボ-ルァミノ基、プロピルカルボ-ルァミノ 基、ペンチルカルボ-ルァミノ基、シクロへキシルカルボ-ルァミノ基、 2—ェチルへ キシルカルボ-ルァミノ基、ォクチルカルボ-ルァミノ基、ドデシルカルボ-ルァミノ基 、フエ-ルカルポ-ルァミノ基、ナフチルカルボ-ルァミノ基等）、力ルバモイル基（例 えば、ァミノカルボ-ル基、メチルァミノカルボ-ル基、ジメチルァミノカルボ-ル基、 プロピルアミノカルボ-ル基、ペンチルァミノカルボ-ル基、シクロへキシルァミノカル ボ-ル基、ォクチルァミノカルボ-ル基、 2—ェチルへキシルァミノカルボ-ル基、ド デシルァミノカルボ-ル基、フエ-ルァミノカルボ-ル基、ナフチルァミノカルボ-ル 基、 2—ピリジルァミノカルボニル基等）、ウレイド基 (例えば、メチルウレイド基、ェチ ルゥレイド基、ペンチルゥレイド基、シクロへキシルウレイド基、ォクチルゥレイド基、ド デシルゥレイド基、フエニルゥレイド基、ナフチルウレイド基、 2—ピリジルアミノウレイド 基等）、スルフィエル基（例えば、メチルスルフィ-ル基、ェチルスルフィ-ル基、プチ ルスルフィ-ル基、シクロへキシルスルフィエル基、 2—ェチルへキシルスルフィエル 基、ドデシルスルフィエル基、フヱニルスルフィ-ル基、ナフチルスルフィ-ル基、 2— ピリジルスルフィ -ル基等）、アルキルスルホ -ル基（例えば、メチルスルホ -ル基、ェ チルスルホ-ル基、ブチルスルホ -ル基、シクロへキシルスルホ -ル基、 2—ェチル へキシルスルホ -ル基、ドデシルスルホ -ル基等）、ァリールスルホ -ル基（例えば、 フエ-ルスルホ-ル基、ナフチルスルホ-ル基、 2—ピリジルスルホ -ル基等）、ァミノ 基 (例えば、アミノ基、ェチルァミノ基、ジメチルァミノ基、プチルァミノ基、シクロペン チルァミノ基、 2—ェチルへキシルァミノ基、ドデシルァミノ基、ァ-リノ基、ナフチルァ ミノ基、 2—ピリジルァミノ基等）、ハロゲン原子 (例えば、フッ素原子、塩素原子、臭素 原子等）、フッ化炭化水素基 (例えば、フルォロメチル基、トリフルォロメチル基、ペン タフルォロェチル基、ペンタフルォロフエ-ル基等）、シァノ基、シリル基 (例えば、トリ メチルシリル基、トリイソプロビルシリル基、トリフエ-ルシリル基、フエ-ルジェチルシリ ル基等)等が挙げられる。 In the general formula (1), examples of the substituent represented by R include an alkyl group (eg, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a hexyl group). Octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (eg, buyl group, aryl group, etc.), alkyl, etc. -Ruyl group (for example, ethynyl group, propargyl group, etc.), aryl group (for example, phenol group, p-chlorophenol group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, Azulenyl, acenaphthyl, fluorenyl, phenanthryl, indur, pyrenyl, biphenyl, etc.), aromatic heterocyclic groups (eg, furyl, Group, pyridyl group, pyridazyl group, pyrimidyl group, birazyl group, triazyl group, imidazolyl group, pyrazolyl group, thiazolyl group, benzoimidazolyl group, benzoxazolyl group, quinazolyl group, phthalazyl group, etc.), heterocyclic group ( For example, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxyl group (for example, methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group, etc.), cycloalkoxyl group ( For example, cyclopentyloxy group, cyclohexyloxy group, etc.), aryloxy group (eg, phenoxy group, naphthyloxy group, etc.), alkylthio group (eg, methylthio group, ethyl group, etc.) Thio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio group (eg, cyclopentylthio group, cyclohexylthio group, etc.), arylthio group (eg, phenylthio group, etc.) , Naphthylthio groups, etc.), alkoxy carboxylic groups (for example, methyloxy carbo yl groups, eth oxy carboxy groups, butyl oxy carbo ol groups, oct oxy carboxy groups, dodecyl oxy groups) Group), aryloxycarbonyl group (eg, phenylcarbol group, naphthyloxycarbonyl group, etc.), sulfamoyl group (eg, aminosulfol group, methylaminosulfol group) Group, dimethylaminosulfol group, butylaminosulfol group, hexylaminosulfol group, cyclohexylaminosulfol group Group, octylaminosulfol group, dodecylaminosulfol group, phenylaminosulfol group, naphthylaminosulfol group, 2-pyridylaminosulfol group, etc.), acyl group (for example, acetyl group, ethylcarbo group) -Propyl group, propyl carboxylic group, pentyl carbo yl group, cyclohexyl carbonyl group, octyl carbo yl group, 2-ethyl hexyl carbo yl group, dodecyl carbonyl group, chloro carbo yl group, Naphthyl carboyl group, pyridyl carbo ol group, etc.), acyloxy group (for example, acetyloxy group, ethyl carbo oxy group, butyl carbo oxy group, octyl carbo oxy group, dodecyl carbo oxy group, phenyl carbonyl group) Group), amide group (for example, methylcarbonylamino group, ethylcarbolumino group, dimethylcarbola group) Mino group, propyl carbolumino group, pentyl carbolumino group, cyclohexyl carbolumino group, 2-ethyl hexyl carbolumino group, octyl carbolumino group, dodecyl carbolumino group, phenol carbolumino group, naphthyl Carboamino groups, etc.), strong rubamoyl groups (for example, amino carbo group, methyl amino carbo group, dimethyl amino carbo ol group, propyl amino carbo ol group, pentyl amino carbo ol group, Cyclohexylaminocarbol, Octylaminocarbol, 2-Ethylhexylaminocarbol, Dodecylaminocarbol, Phenylaminocarbol, Naphtylaminocarbo Group, 2-pyridylaminocarbonyl group, etc.), ureido group (eg methylureido group, ethylureido group, pentyl) Raid group, Kishiruureido group cyclohexylene, Okuchiruureido group, de Deshiruureido group, Fueniruureido group, Nafuchiruureido group, 2-pyridyl-amino ureido Groups), sulfier groups (for example, methyl sulfyl group, ethyl sulfyl group, propyl sulfyl group, cyclohexyl sulfiel group, 2-ethyl sulfyl group, dodecyl sulfiel group, phenyl sulfyl group) , Naphthylsulfyl group, 2-pyridylsulfyl group, etc.), alkylsulfol group (for example, methylsulfol group, ethylsulfol group, butylsulfol group, cyclohexylsulfol group, 2-ethylhexylsulfol group, dodecylsulfol group, etc.), arylsulfol group (eg, phenylsulfol group, naphthylsulfol group, 2-pyridylsulfol group, etc.), amino group ( For example, amino group, ethylamino group, dimethylamino group, ptylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecyl group. Amino group, amino-group, naphthylamino group, 2-pyridylamino group, etc.), halogen atom (eg, fluorine atom, chlorine atom, bromine atom), fluorinated hydrocarbon group (eg, fluoromethyl group, trifluoromethyl group) Group, pentafluoroethyl group, pentafluorophenyl group, etc.), cyan group, silyl group (for example, trimethylsilyl group, triisopropylpropyl group, triphenylsilyl group, ferroethyl silyl group, etc.) It is done.

[0115] これらの置換基は上記の置換基によって更に置換されていても、複数が互いに結 合して環を形成して 、てもよ 、。  [0115] These substituents may be further substituted with the above substituents, or a plurality thereof may be bonded to each other to form a ring.

[0116] 中でも好ましい置換基は、アルキル基であり、更に好ましくは、炭素原子数が 2〜2 0のアルキル基であり、特に好ましくは、炭素原子数 6〜 12のアルキル基である。  Among them, a preferable substituent is an alkyl group, more preferably an alkyl group having 2 to 20 carbon atoms, and particularly preferably an alkyl group having 6 to 12 carbon atoms.

[0117] 《チォフェンオリゴマーの末端基》  [0117] <End group of thiophene oligomer>

本発明に用いられるチォフェンオリゴマーの末端基にっ 、て説明する。  The terminal group of the thiophene oligomer used in the present invention will be described.

[0118] 本発明に用いられるチォフェンオリゴマーの末端基は、チェ-ル基をもたないこと が好ましぐまた、前記末端基として好ましい基としては、ァリール基 (例えば、フエ二 ル基、 p—クロロフヱ-ル基、メシチル基、トリル基、キシリル基、ナフチル基、アントリ ル基、ァズレ-ル基、ァセナフテュル基、フルォレ -ル基、フエナントリル基、インデニ ル基、ピレニル基、ビフヱ-リル基等）、アルキル基 (例えば、メチル基、ェチル基、プ 口ピル基、イソプロピル基、 tert—ブチル基、ペンチル基、へキシル基、ォクチル基、 ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基等）、ハロゲン原子 (例え ば、フッ素原子、塩素原子、臭素原子等)等が挙げられる。 [0119] 《チォフェンオリゴマーの繰り返し単位の立体構造的特性》 [0118] It is preferable that the terminal group of the thiophene oligomer used in the present invention does not have a chael group. Further, as the preferable group as the terminal group, an aryl group (for example, a phenyl group, p-Chlorofuryl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulyl group, acenaphthyl group, fluoro group, phenanthryl group, indenyl group, pyrenyl group, biphenyl group Etc.), alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, etc.) And halogen atoms (for example, fluorine atom, chlorine atom, bromine atom, etc.). [0119] <Stereostructural characteristics of repeating unit of thiophene oligomer>

本発明に用いられるチォフェンオリゴマーは、構造中に、 Head— to— Head構造 を持たないことが好ましぐそれに加えて、更に好ましくは、前記構造中に、 Head-t o— Tail構造、または、 Tail— to— Tail構造を有することが好ましい。  The thiophene oligomer used in the present invention preferably has no head-to-head structure in the structure, and more preferably, the structure has a head-to-tail structure, or It preferably has a tail-to-tail structure.

[0120] 本発明に係る Head— to— Head構造、 Head— to— Tail構造、 Tail— to— Tail構 造については、例えば、『π電子系有機固体』（1998年、学会出版センター発行、日 本ィ匕学界編） 27〜32頁、 Adv. Mater. 1998, 10, No. 2, 93〜116頁等により参 照出来るが、ここで、具体的に各々の構造的特徴を下記に示す。  [0120] Regarding the Head-to-Head structure, Head-to-Tail structure, and Tail-to-Tail structure according to the present invention, for example, "π-electron organic solid" (1998, published by the Japan Society for Publishing Press, Japan) This can be referred to on pages 27-32 and Adv. Mater. 1998, 10, No. 2, pages 93-116, etc. Here, specific structural features are shown below.

[0121] 尚、ここにおいて Rは前記一般式（1)における Rと同義である。  [0121] Here, R has the same meaning as R in the general formula (1).

[0122] [化 2]  [0122] [Chemical 2]

Head—to— Head構造

Figure imgf000024_0001
Head—to—Head structure
Figure imgf000024_0001

[0123] [化 3] [0123] [Chemical 3]

Head— to— Tai I構造

Figure imgf000024_0002
Head— to— Tai I structure
Figure imgf000024_0002

[0124] [化 4] [0124] [Chemical 4]

Tail— to— Tail構造

Figure imgf000024_0003
Tail— to— Tail structure
Figure imgf000024_0003

[0125] 以下、本発明に用いられるこれらチオフ ンオリゴマーの具体例を示すが、本発明 はこれらに限定されない。 [0125] Specific examples of these thiophene oligomers used in the present invention are shown below, but the present invention is not limited thereto.

Figure imgf000025_0001
Figure imgf000025_0001

[0127] [化 6]

Figure imgf000026_0001
[0127] [Chemical 6]
Figure imgf000026_0001

置¾012 置 ¾012

Figure imgf000027_0001
Figure imgf000027_0001

Figure imgf000028_0001
Figure imgf000028_0001

[0130] これらのチォフェンオリゴマーの製造法は、本発明者等による特願 2004— 17231 7号（2004年 6月 10日出願）に記載されている。 [0130] The method for producing these thiophene oligomers is described in Japanese Patent Application No. 2004-172317 (filed on June 10, 2004) by the present inventors.

[0131] また、本発明においては、有機半導体層に、たとえば、アクリル酸、ァセトアミド、ジ メチルァミノ基、シァノ基、カルボキシル基、ニトロ基などの官能基を有する材料や、 ベンゾキノン誘導体、テトラシァノエチレンおよびテトラシァノキノジメタンやそれらの 誘導体などのように電子を受容するァクセプターとなる材料や、たとえばアミノ基、トリ フエニル基、アルキル基、水酸基、アルコキシ基、フエ-ル基などの官能基を有する 材料、フエ-レンジァミンなどの置換アミン類、アントラセン、ベンゾアントラセン、置換 ベンゾアントラセン類、ピレン、置換ピレン、力ルバゾールおよびその誘導体、テトラチ ァフルバレンとその誘導体などのように電子の供与体であるドナーとなるような材料を 含有させ、いわゆるドーピング処理を施してもよい。 [0131] In the present invention, the organic semiconductor layer may be formed of, for example, a material having a functional group such as acrylic acid, acetamido, dimethylamino group, cyano group, carboxyl group, nitro group, benzoquinone derivative, tetracyanethylene. And tetracyanoxydimethane and their Materials that accept electrons, such as derivatives, materials having functional groups such as amino, triphenyl, alkyl, hydroxyl, alkoxy, and phenyl groups, substituted amines such as phenylenediamine , Anthracene, benzoanthracene, substituted benzoanthracene, pyrene, substituted pyrene, force rubazole and its derivatives, tetrathiofulvalene and its derivatives, etc. Processing may be performed.

[0132] 前記ドーピングとは電子授与性分子 (ァクセプター)または電子供与性分子 (ドナー )をドーパントとして該薄膜に導入することを意味する。従って，ドーピングが施された 薄膜は、前記の縮合多環芳香族化合物とドーパントを含有する薄膜である。本発明 に用いるドーパントとしては公知のものを採用することができる。  [0132] The doping means introduction of an electron donating molecule (acceptor) or an electron donating molecule (donor) into the thin film as a dopant. Therefore, the doped thin film is a thin film containing the condensed polycyclic aromatic compound and the dopant. A well-known thing can be employ | adopted as a dopant used for this invention.

[0133] これらの有機半導体層を形成する方法としては、公知の方法で形成することができ 、例えば、真空蒸着、 MBE (Molecular Beam Epitaxy)、イオンクラスタービーム 法、低エネルギーイオンビーム法、イオンプレーティング法、スパッター法、 CVD (Ch emical Vapor Deposition)、レーザ蒸着、電子ビーム蒸着、電着、スピンコート、 ディップコート、バーコート法、ダイコート法、スプレーコート法、および LB法等、また スクリーン印刷、インクジェット印刷、ブレード塗布などの方法を挙げることができる。  [0133] The organic semiconductor layer can be formed by a known method, for example, vacuum deposition, MBE (Molecular Beam Epitaxy), ion cluster beam method, low energy ion beam method, ion plate. Coating method, sputtering method, CVD (Chemical Vapor Deposition), laser deposition, electron beam deposition, electrodeposition, spin coating, dip coating, bar coating method, die coating method, spray coating method, LB method, etc., screen printing, Examples thereof include ink jet printing and blade coating.

[0134] この中で生産性の点で、有機半導体の溶液を用いて簡単かつ精密に薄膜が形成 できるスピンコート法、ブレードコート法、ディップコート法、ロールコート法、バーコ一 ト法、ダイコート法等が好まれる。 [0134] Among these, in terms of productivity, spin coating, blade coating, dip coating, roll coating, bar coating, and die coating, which can easily and precisely form a thin film using an organic semiconductor solution. Etc. are preferred.

[0135] なお Advanced Material誌 1999年 第 6号、 p480〜483に記載の様に、ペン タセン等前駆体が溶媒に可溶であるものは、塗布により形成した前駆体の膜を熱処 理して目的とする有機材料の薄膜を形成しても良い。 [0135] As described in Advanced Material 1999 No. 6, p480-483, if the precursor such as pentacene is soluble in the solvent, the precursor film formed by coating is heat-treated. A thin film of the desired organic material may be formed.

[0136] これら有機半導体層の膜厚としては、特に制限はないが、得られたトランジスタの特 性は、有機半導体層の膜厚に大きく左右される場合が多ぐその膜厚は、有機半導 体により異なる力 一般に 1 μ m以下、特に 10〜300nmが好ましい。 [0136] The thickness of the organic semiconductor layer is not particularly limited, but the characteristics of the obtained transistor are largely influenced by the thickness of the organic semiconductor layer. Different forces depending on the conductor Generally 1 μm or less, particularly 10 to 300 nm is preferred.

[0137] さらに、本発明の有機半導体素子によれば、そのゲート電極、ソース Zドレイン電極 のうち少なくとも一つを本発明の有機半導体素子の製造方法によって形成することに よって、低抵抗の電極を、有機半導体層材料層の特性劣化を引き起こすことなし〖こ 形成することが可能となる。 [0137] Furthermore, according to the organic semiconductor element of the present invention, at least one of the gate electrode and the source Z drain electrode is formed by the method for manufacturing an organic semiconductor element of the present invention, whereby a low-resistance electrode is formed. , Without causing deterioration of the characteristics of the organic semiconductor layer material layer It becomes possible to form.

[0138] 本発明の薄膜トランジスタ素子において、ソース電極またはドレイン電極は、前記無 電解メツキ法により形成される力 S、ソース電極およびドレイン電極のひとつはゲート電 極と共に無電解メツキによらない電極であってよい。その場合、電極は公知の方法、 公知の電極材料にて形成される。電極材料としては導電性材料であれば特に限定さ れず、白金、金、銀、ニッケル、クロム、銅、鉄、錫、アンチモン鉛、タンタル、インジゥ ム、パラジウム、テルル、レニウム、イリジウム、アルミニウム、ルテニウム、ゲルマニウム 、モリブデン、タングステン、酸化スズ 'アンチモン、酸化インジウム'スズ (ITO)、フッ 素ドープ酸ィ匕亜鉛、亜鉛、炭素、グラフアイト、グラッシ一カーボン、銀ペーストおよび カーボンペースト、リチウム、ベリリウム、ナトリウム、マグネシウム、カリウム、カノレシゥム 、スカンジウム、チタン、マンガン、ジルコニウム、ガリウム、ニオブ、ナトリウム、ナトリウ ムーカリウム合金、マグネシウム、リチウム、アルミニウム、マグネシウム Z銅混合物、 マグネシウム Z銀混合物、マグネシウム Zアルミニウム混合物、マグネシウム Zインジ ゥム混合物、アルミニウム Z酸ィ匕アルミニウム混合物、リチウム Zアルミニウム混合物 等が用いられる。あるいはドーピング等で導電率を向上させた公知の導電性ポリマー 、例えば導電性ポリア-リン、導電性ポリピロール、導電性ポリチォフェン (ポリエチレ ンジォキシチオフヱンとポリスチレンスルホン酸の錯体など）も好適に用いられる。  [0138] In the thin film transistor element of the present invention, the source electrode or the drain electrode is a force S formed by the electroless plating method, and one of the source electrode and the drain electrode is an electrode that does not depend on the electroless plating together with the gate electrode. It's okay. In that case, the electrode is formed by a known method or a known electrode material. The electrode material is not particularly limited as long as it is a conductive material. Platinum, gold, silver, nickel, chromium, copper, iron, tin, antimony lead, tantalum, indium, palladium, tellurium, rhenium, iridium, aluminum, ruthenium , Germanium, molybdenum, tungsten, tin oxide 'antimony, indium oxide' tin (ITO), fluorine-doped zinc oxide, zinc, carbon, graphite, glassy carbon, silver paste and carbon paste, lithium, beryllium, sodium , Magnesium, potassium, canoleum, scandium, titanium, manganese, zirconium, gallium, niobium, sodium, sodium potassium alloy, magnesium, lithium, aluminum, magnesium Z copper mixture, magnesium Z silver mixture, magnesium Z Aluminum mixture, magnesium Z indicator © beam mixtures, aluminum Z Sani匕 aluminum mixture, lithium Z aluminum mixture, or the like is used. Alternatively, known conductive polymers whose conductivity has been improved by doping, for example, conductive polyarine, conductive polypyrrole, conductive polythiophene (polyethylenedithiophene and polystyrene sulfonic acid complex, etc.) are also suitable. Used.

[0139] ソース電極またドレイン電極を形成する材料としては、上に挙げた中でも半導体層 との接触面において電気抵抗が少ないものが好ましぐ P型半導体の場合は特に、白 金、金、銀、 ιτο、導電性ポリマーおよび炭素が好ましい。  [0139] Of the materials listed above, materials having low electrical resistance at the contact surface with the semiconductor layer are preferred as materials for forming the source electrode or drain electrode. , Ιτο, conductive polymers and carbon are preferred.

[0140] ソース電極またドレイン電極とする場合は、上記の導電性材料を含む、溶液、ぺー スト、インク、分散液などの流動性電極材料を用いて形成したもの、特に、導電性ポリ マー、または白金、金、銀、銅を含有する金属微粒子を含む流動性電極材料が好ま しい。また、溶媒や分散媒体としては、有機半導体へのダメージを抑制するため、水 を 60%以上、好ましくは 90%以上含有する溶媒または分散媒体であることが好まし い。 [0140] When the source electrode or the drain electrode is used, the electrode is formed using a fluid electrode material such as a solution, paste, ink, or dispersion containing the above-described conductive material, in particular, a conductive polymer, Alternatively, a fluid electrode material containing fine metal particles containing platinum, gold, silver, and copper is preferable. The solvent or dispersion medium is preferably a solvent or dispersion medium containing 60% or more, preferably 90% or more of water in order to suppress damage to the organic semiconductor.

[0141] 金属微粒子を含有する流動性電極材料としては、たとえば公知の導電性ペースト などを用いても良いが、好ましくは、粒子径が l〜50nm、好ましくは 1〜： LOnmの金 属微粒子を、必要に応じて分散安定剤を用いて、水や任意の有機溶剤である分散 媒中に分散した材料である。 [0141] As a fluid electrode material containing fine metal particles, for example, a known conductive paste may be used, but preferably a gold particle having a particle diameter of 1 to 50 nm, preferably 1 to: LOnm. This is a material in which metal fine particles are dispersed in water or an arbitrary organic solvent dispersion medium using a dispersion stabilizer as required.

[0142] 金属微粒子の材料としては白金、金、銀、ニッケル、クロム、銅、鉄、錫、アンチモン 鉛、タンタル、インジウム、パラジウム、テルル、レニウム、イリジウム、アルミニウム、ル テ-ゥム、ゲルマニウム、モリブデン、タングステン、亜鉛等を用いることができる。  [0142] The material of the metal fine particles is platinum, gold, silver, nickel, chromium, copper, iron, tin, antimony lead, tantalum, indium, palladium, tellurium, rhenium, iridium, aluminum, ruthenium, germanium, Molybdenum, tungsten, zinc, or the like can be used.

[0143] このような金属微粒子の分散物の製造方法として、ガス中蒸発法、スパッタリング法 、金属蒸気合成法などの物理的生成法や、コロイド法、共沈法などの、液相で金属ィ オンを還元して金属微粒子を生成する化学的生成法が挙げられるが、好ましくは、特 開平 11— 76800号、同 11— 80647号、同 11— 319538号、特開 2000— 239853 等に示されたコロイド法、特開 2001— 254185、同 2001— 53028、同 2001— 352 55、同 2000— 124157、同 2000— 123634など【こ記載されたガス中蒸発法【こより 製造された金属微粒子の分散物である。これらの金属微粒子分散物を用いて電極を 成形し、溶媒を乾燥させた後、必要に応じて 100〜300°C、好ましくは 150〜200°C の範囲で形状様に加熱することにより、金属微粒子を熱融着させ、目的の形状を有 する電極パターンを形成するものである。  [0143] As a method for producing such a dispersion of metal fine particles, a metal phase in a liquid phase such as a physical production method such as a gas evaporation method, a sputtering method or a metal vapor synthesis method, a colloid method or a coprecipitation method is used. Examples of the chemical production method include reducing metal ions to produce fine metal particles, but preferred are JP-A-11-76800, JP-A-11-80647, JP-A-11-319538, and JP-A-2000-239853. Colloidal method, JP 2001-254185, 2001-53028, 2001-352 55, 2000-124157, 2000-123634, etc. It is. An electrode is formed using these metal fine particle dispersions, the solvent is dried, and then heated to a shape in the range of 100 to 300 ° C, preferably 150 to 200 ° C, as necessary. Fine particles are thermally fused to form an electrode pattern having a desired shape.

[0144] 電極の形成方法としては、上記を原料として蒸着やスパッタリング等の方法を用い て形成した導電性薄膜を、公知のフォトリソグラフ法やリフトオフ法を用いて電極形成 する方法、アルミニウムや銅などの金属箔上に熱転写、インクジェット等により、レジス トを形成しエッチングする方法がある。また導電性ポリマーの溶液ある 、は分散液、 金属微粒子を含有する分散液等を直接インクジェット法によりパターユングしてもよい し、塗工膜からリソグラフやレーザアブレーシヨンなどにより形成してもよい。さらに導 電性ポリマーや金属微粒子を含有する導電性インク、導電性ペーストなどを凸版、凹 版、平版、スクリーン印刷などの印刷法でパターユングする方法も用いることができる  [0144] As a method for forming an electrode, a method for forming an electrode using a known photolithographic method or a lift-off method using a conductive thin film formed by a method such as vapor deposition or sputtering using the above as a raw material, aluminum, copper, or the like There is a method in which a resist is formed on a metal foil by thermal transfer, ink jet or the like and etched. In addition, a conductive polymer solution, a dispersion, a dispersion containing metal fine particles, or the like may be directly patterned by an ink jet method, or may be formed from a coating film by lithography, laser abrasion, or the like. . Furthermore, it is possible to use a method of patterning a conductive ink or conductive paste containing a conductive polymer or metal fine particles by a printing method such as relief printing, intaglio printing, planographic printing or screen printing.

[0145] ソース電極及びドレイン電極は、特にフォトリソグラフ法を用いて形成することが好ま しぐこの場合、有機半導体保護層に接して層の全面に光感応性榭脂の溶液を塗布 し、光感応性榭脂層を形成する。 [0145] The source electrode and the drain electrode are particularly preferably formed using a photolithographic method. In this case, a photo-sensitive resin solution is applied to the entire surface of the layer in contact with the organic semiconductor protective layer, and light is applied. Form a sensitive resin layer.

[0146] 光感応性榭脂層としては、前記、保護層のパターニングに用いるポジ型、ネガ型の 公知の感光性榭脂と同じものが使用できる。 [0146] As the photosensitive resin layer, the positive type and the negative type used for the patterning of the protective layer are used. The same known photosensitive resin can be used.

[0147] フォトリソグラフ法では、この後にソース電極及びドレイン電極の材料として金属微 粒子含有分散体又は導電性ポリマーを用いてパターユングし、必要に応じて熱融着 し作製する。  [0147] In the photolithographic method, after that, patterning is performed using a metal fine particle-containing dispersion or conductive polymer as a material for the source electrode and the drain electrode, and heat fusion is performed as necessary.

[0148] 光感応性榭脂の塗布溶液を形成する溶媒、光感応性榭脂層を形成する方法等、 前記保護膜のパターニングに述べたとおりである。  [0148] The solvent for forming the photosensitive resin coating solution, the method for forming the photosensitive resin layer, and the like are as described in the patterning of the protective film.

[0149] 光感応性榭脂層を形成後、パターユング露光に用いる光源、光感応性榭脂層の現 像に用いられる現像液についても同様である。また、電極形成には他の光感応性榭 脂層であるアブレーシヨン層をもちいてもよい。アブレーシヨン層についても、前記、 保護層のパターユングに用いるものと同様のものが挙げられる。  The same applies to the light source used for patterning exposure and the developer used for the present image of the photosensitive resin layer after the formation of the photosensitive resin layer. In addition, an abrasion layer, which is another photosensitive resin layer, may be used for electrode formation. As the abrasion layer, the same ones as those used for patterning the protective layer can be mentioned.

[0150] 本発明の有機薄膜トランジスタ素子のゲート絶縁層としては種々の絶縁膜を用いる ことができるが、特に、比誘電率の高い無機酸ィ匕物皮膜が好ましい。無機酸化物とし ては、酸化ケィ素、酸ィ匕アルミニウム、酸ィ匕タンタル、酸化チタン、酸化スズ、酸化バ ナジゥム、チタン酸バリウムストロンチウム、ジルコニウム酸チタン酸バリウム、ジルコ- ゥム酸チタン酸鈴、チタン酸鈴ランタン、チタン酸ストロンチウム、チタン酸バリウム、フ ツイ匕ノ リウムマグネシウム、チタン酸ビスマス、チタン酸ストロンチウムビスマス、タンタ ル酸ストロンチウムビスマス、タンタル酸-ォブ酸ビスマス、トリオキサイドイットリウムな どが挙げられる。それらのうち好ましいのは、酸化ケィ素、酸ィ匕アルミニウム、酸ィ匕タン タル、酸ィ匕チタンである。窒化ケィ素、窒化アルミニウム等の無機窒化物も好適に用 いることがでさる。  [0150] As the gate insulating layer of the organic thin film transistor element of the present invention, various insulating films can be used. In particular, an inorganic oxide film having a high relative dielectric constant is preferable. Inorganic oxides include silicon oxide, acid aluminum, acid tantalum, titanium oxide, tin oxide, vanadium oxide, barium strontium titanate, barium zirconate titanate, and zirconate zirconate titanate. Lanthanum, lanthanum titanate, strontium titanate, barium titanate, magnesium magnesium titanate, bismuth titanate, strontium bismuth titanate, strontium bismuth tantalite, bismuth tantalate-obobate, trioxide yttrium, etc. Can be mentioned. Among them, preferred are silicon oxide, acid aluminum, acid tantalum, and acid titanium. Inorganic nitrides such as silicon nitride and aluminum nitride can also be suitably used.

[0151] 上記皮膜の形成方法としては、真空蒸着法、分子線ェピタキシャル成長法、イオン クラスタービーム法、低エネルギーイオンビーム法、イオンプレーティング法、 CVD法 、スパッタリング法、大気圧プラズマ法などのドライプロセスや、スプレーコート法、スピ ンコート法、ブレードコート法、ディップコート法、キャスト法、ロールコート法、バーコ ート法、ダイコート法などの塗布による方法、印刷やインクジェットなどのパターユング による方法などのウエットプロセスが挙げられ、材料に応じて使用できる。  [0151] Examples of the film formation method include vacuum deposition, molecular beam epitaxy, ion cluster beam, low energy ion beam, ion plating, CVD, sputtering, and atmospheric pressure plasma. Dry process, spray coating method, spin coating method, blade coating method, dip coating method, casting method, roll coating method, bar coating method, die coating method and other coating methods, printing and ink jet patterning methods, etc. Can be used depending on the material.

[0152] ウエットプロセスは、無機酸化物の微粒子を、任意の有機溶剤あるいは水に必要に 応じて界面活性剤などの分散補助剤を用いて分散した液を塗布、乾燥する方法や、 酸化物前駆体、例えばアルコキシド体の溶液を塗布、乾燥する、いわゆるゾルゲル 法が用いられる。 [0152] The wet process is a method of applying and drying a liquid in which fine particles of inorganic oxide are dispersed in an arbitrary organic solvent or water using a dispersion aid such as a surfactant as necessary. A so-called sol-gel method is used in which an oxide precursor, for example, an alkoxide solution is applied and dried.

[0153] これらのうち好ましいのは、上述した大気圧プラズマ法である。  Of these, the atmospheric pressure plasma method described above is preferable.

[0154] ゲート絶縁層が陽極酸ィ匕膜又は該陽極酸ィ匕膜と絶縁膜とで構成されることも好まし い。陽極酸ィ匕膜は封孔処理されることが望ましい。陽極酸ィ匕膜は、陽極酸化が可能 な金属を公知の方法により陽極酸化することにより形成される。  [0154] It is also preferable that the gate insulating layer is composed of an anodized film or the anodized film and an insulating film. The anodized film is preferably sealed. The anodized film is formed by anodizing a metal that can be anodized by a known method.

[0155] 陽極酸ィ匕処理可能な金属としては、アルミニウム又はタンタルを挙げることができ、 陽極酸化処理の方法には特に制限はなぐ公知の方法を用いることができる。陽極 酸化処理を行なうことにより、酸化被膜が形成される。陽極酸化処理に用いられる電 解液としては、多孔質酸ィ匕皮膜を形成することができるものならば 、かなるものでも使 用でき、一般には、硫酸、燐酸、蓚酸、クロム酸、ホウ酸、スルファミン酸、ベンゼンス ルホン酸等ある 、はこれらを 2種類以上組み合わせた混酸ある 、それらの塩が用い られる。陽極酸化の処理条件は使用する電解液により種々変化するので一概に特定 し得ないが、一般的には、電解液の濃度が 1〜80質量％、電解液の温度 5〜70°C、 電流密度 0. 5〜60AZdm2、電圧 1〜： LOOボルト、電解時間 10秒〜 5分の範囲が適 当である。好ましい陽極酸化処理は、電解液として硫酸、リン酸又はホウ酸の水溶液 を用い、直流電流で処理する方法であるが、交流電流を用いることもできる。これらの 酸の濃度は 5〜45質量％であることが好ましぐ電解液の温度 20〜50°C、電流密度 0. 5〜20AZdm2で 20〜250秒間電解処理するのが好まし!/、。 [0155] Examples of the metal capable of anodizing treatment include aluminum and tantalum, and a known method with no particular limitation can be used for the method of anodizing treatment. An oxide film is formed by anodizing. As an electrolytic solution used for anodizing treatment, any electrolyte solution can be used as long as it can form a porous acid film, and generally, sulfuric acid, phosphoric acid, oxalic acid, chromic acid, boric acid. In addition, sulfamic acid, benzene sulfonic acid, etc. are mixed acids in which two or more of these are combined, and salts thereof are used. The treatment conditions for anodization vary depending on the electrolyte used, and therefore cannot be specified. However, in general, the electrolyte concentration is 1 to 80% by mass, the electrolyte temperature is 5 to 70 ° C, the current is Density 0.5-60AZdm 2 , voltage 1-: LOO volts, electrolysis time 10 seconds to 5 minutes are appropriate. A preferred anodizing treatment is a method in which an aqueous solution of sulfuric acid, phosphoric acid or boric acid is used as the electrolytic solution and the treatment is performed with a direct current, but an alternating current can also be used. The concentration of these acids is preferably 5 to 45% by weight. Electrolytic treatment with an electrolyte temperature of 20 to 50 ° C and a current density of 0.5 to 20 AZdm 2 is preferred for 20 to 250 seconds! / ,.

[0156] また有機化合物皮膜としては、ポリイミド、ポリアミド、ポリエステル、ポリアタリレート、 光ラジカル重合系、光力チオン重合系の光硬化性榭脂、あるいはアクリロニトリル成 分を含有する共重合体、ポリビュルフエノール、ポリビュルアルコール、ノボラック榭 脂、およびシァノエチルプルラン等を用いることもできる。  [0156] In addition, as the organic compound film, polyimide, polyamide, polyester, polyacrylate, photo-radical polymerization system, photopower thione polymerization system photocurable resin, or copolymer containing acrylonitrile component, polybule Phenolic alcohol, polybutyl alcohol, novolac resin, cyano ethyl pullulan and the like can also be used.

[0157] 有機化合物皮膜の形成法としては、前記ウエットプロセスが好ましい。  [0157] The wet process is preferred as the method for forming the organic compound film.

[0158] 無機酸ィ匕物皮膜と有機酸ィ匕物皮膜は積層して併用することができる。またこれら絶 縁膜の膜厚としては、一般に 50nm〜3 μ m、好ましくは、 100nm〜l μ mである。  [0158] The inorganic oxide film and the organic oxide film can be laminated and used together. The thickness of these insulating films is generally 50 nm to 3 μm, preferably 100 nm to 1 μm.

[0159] ゲート絶縁層上に有機半導体を形成する場合、ゲート絶縁層表面に、任意の表面 処理を施してもよい。シランカップリング剤、たとえばォクタデシルトリクロロシラン、トリ クロロメチルシラザンや、アルカン燐酸、アルカンスルホン酸、アルカンカルボン酸な どの自己組織ィ匕配向膜が好適に用いられる。 [0159] When an organic semiconductor is formed on the gate insulating layer, an arbitrary surface treatment may be performed on the surface of the gate insulating layer. Silane coupling agents such as octadecyl trichlorosilane, tri Self-organized alignment films such as chloromethylsilazane, alkane phosphoric acid, alkane sulfonic acid, and alkane carboxylic acid are preferably used.

[0160] 〔基板について〕  [Substrate]

基板を構成する支持体材料としては、種々の材料が利用可能であり、例えば、ガラ ス、石英、酸ィ匕アルミニウム、サファイア、チッ化珪素、炭化珪素などのセラミック基板 、シリコン、ゲルマニウム、ガリウム砒素、ガリウム燐、ガリウム窒素など半導体基板、紙 、不織布などを用いることができるが、本発明において支持体は榭脂からなることが 好ましぐ例えばプラスチックフィルムシートを用いることができる。プラスチックフィル ムとしては、例えばポリエチレンテレフタレート（PET)、ポリエチレンナフタレート（PE N)、ポリエーテルスルホン（PES)、ポリエーテルイミド、ポリエーテルエーテルケトン、 ポリフエ-レンスルフイド、ポリアリレート、ポリイミド、ボリカーボネート（PC)、セルロー ストリアセテート (TAC)、セルロースアセテートプロピオネート（CAP)等カゝらなるフィ ルム等が挙げられる。プラスチックフィルムを用いることで、ガラス基板を用いる場合 に比べて軽量ィ匕を図ることができ、可搬性を高めることができるとともに、衝撃に対す る耐性を向上できる。  Various materials can be used as the support material constituting the substrate, such as ceramic substrates such as glass, quartz, aluminum oxide, sapphire, silicon nitride, and silicon carbide, silicon, germanium, and gallium arsenide. A semiconductor substrate such as gallium phosphide or gallium nitrogen, paper, non-woven fabric or the like can be used. In the present invention, the support is preferably made of a resin, for example, a plastic film sheet can be used. Examples of plastic films include polyethylene terephthalate (PET), polyethylene naphthalate (PE N), polyether sulfone (PES), polyether imide, polyether ether ketone, poly-phenylene sulfide, polyarylate, polyimide, polycarbonate (PC ), Cellulose triacetate (TAC), cellulose acetate propionate (CAP), and other films. By using a plastic film, the weight can be reduced compared to the case of using a glass substrate, the portability can be improved, and the resistance to impact can be improved.

[0161] また本発明の有機薄膜トランジスタ素子上には素子保護層を設けることも可能であ る。保護層としては前述した無機酸ィ匕物又は無機窒化物等が挙げられ、上述した大 気圧プラズマ法で形成するのが好ましい。これにより、有機薄膜トランジスタ素子の耐 久性が向上する。  [0161] An element protective layer may be provided on the organic thin film transistor element of the present invention. Examples of the protective layer include the inorganic oxides or inorganic nitrides described above, and it is preferable to form the protective layer by the atmospheric pressure plasma method described above. This improves the durability of the organic thin film transistor element.

[0162] 本発明の薄膜トランジスタ素子においては、支持体がプラスチックフィルムの場合、 無機酸ィ匕物及び無機窒化物から選ばれる化合物を含有する下引き層、及びポリマ 一を含む下引き層の少なくとも一方を有することが好ましい。  [0162] In the thin film transistor element of the present invention, when the support is a plastic film, at least one of an undercoat layer containing a compound selected from an inorganic oxide and an inorganic nitride, and an undercoat layer containing a polymer. It is preferable to have.

[0163] 下引き層に含有される無機酸ィ匕物としては、酸化ケィ素、酸ィ匕アルミニウム、酸ィ匕タ ンタル、酸化チタン、酸化スズ、酸化バナジウム、チタン酸バリウムストロンチウム、ジ ルコ-ゥム酸チタン酸バリウム、ジルコニウム酸チタン酸鉛、チタン酸鉛ランタン、チタ ン酸ストロンチウム、チタン酸バリウム、フッ化バリウムマグネシウム，チタン酸ビスマス 、チタン酸ストロンチウムビスマス、タンタノレ酸ストロンチウムビスマス、タンタノレ酸ニ才 ブ酸ビスマス、トリオキサイドイットリウム等が挙げられる。また無機窒化物としては窒 化ケィ素、窒化アルミニウム等が挙げられる。 [0163] The inorganic oxides contained in the undercoat layer include silicon oxide, aluminum oxide, titanium oxide, titanium oxide, tin oxide, vanadium oxide, barium strontium titanate, zirconium Barium titanate, lead zirconate titanate, lead lanthanum titanate, strontium titanate, barium titanate, magnesium barium fluoride, bismuth titanate, strontium bismuth titanate, strontium bismuth tantanoate, tantalate nitric acid Examples thereof include bismuth butyrate and trioxide yttrium. In addition, as an inorganic nitride, Examples thereof include silicon carbide and aluminum nitride.

[0164] それらのうち好ましいのは、酸化ケィ素、酸化アルミニウム、酸化タンタル、酸化チタ ン、窒化ケィ素である。  Of these, preferable are silicon oxide, aluminum oxide, tantalum oxide, titanium oxide, and silicon nitride.

[0165] 本発明において、無機酸ィ匕物及び無機窒化物力 選ばれる化合物を含有する下 弓 Iき層は上述した大気圧プラズマ法で形成されるのが好ま Uヽ。  [0165] In the present invention, it is preferable that the lower bow I layer containing a compound selected from inorganic oxides and inorganic nitride forces is formed by the atmospheric pressure plasma method described above.

[0166] ポリマーを含む下引き層に用いるポリマーとしては、ポリエステル榭脂、ポリカーボ ネート榭脂、セルロース榭脂、アクリル榭脂、ポリウレタン榭脂、ポリエチレン榭脂、ポ リプロピレン榭脂、ポリスチレン榭脂、フエノキシ榭脂、ノルボルネン榭脂、エポキシ榭 脂、塩化ビニルー酢酸ビニル共重合体、塩化ビニル榭脂、酢酸ビニル榭脂、酢酸ビ -ルとビニルアルコールの共重合体、部分カ卩水分解した塩化ビ-ルー酢酸ビュル共 重合体、塩ィ匕ビュル一塩ィ匕ビユリデン共重合体、塩ィ匕ビュル—アクリロニトリル共重 合体、エチレン ビニルアルコール共重合体、ポリビュルアルコール、塩素化ポリ塩 化ビュル、エチレン一塩化ビュル共重合体、エチレン 酢酸ビニル共重合体等のビ -ル系重合体、ポリアミド榭脂、エチレン ブタジエン榭脂、ブタジエン—アタリ口-ト リル榭脂等のゴム系榭脂、シリコーン榭脂、フッ素系榭脂等を挙げることができる。  [0166] Polymers used for the undercoat layer containing polymer include polyester resin, polycarbonate resin, cellulose resin, acrylic resin, polyurethane resin, polyethylene resin, polypropylene resin, polystyrene resin, Phenoxy resin, norbornene resin, epoxy resin, vinyl chloride-vinyl acetate copolymer, vinyl chloride resin, vinyl acetate resin, copolymer of vinyl acetate and vinyl alcohol, partially water-decomposed vinyl chloride -Ruacetate butyl copolymer, salt-bule monosalt-biurydene copolymer, salt butyl-acrylonitrile copolymer, ethylene vinyl alcohol copolymer, polybulu alcohol, chlorinated polysulphated butyl, ethylene Bile monochloride copolymer, ethylene-vinyl acetate copolymer and other vinyl polymers, polyamide resin, ethylene butadiene Down 榭脂, butadiene - Atari port - DOO drill 榭脂 rubber such 榭脂, silicone 榭脂, a fluorine-based 榭脂 like.

[0167] 以下、本発明の薄膜トランジスタの製造方法の好ましい実施形態について詳細に 説明する力 本発明はこれにより限定されるものではない。  [0167] Hereinafter, the power to explain in detail a preferred embodiment of the method for producing a thin film transistor of the present invention. The present invention is not limited thereby.

[0168] 図 5 (6)はボトムゲート型、トップコンタクト型の有機薄膜トランジスタ素子の一例であ る。以下、本発明の製造方法を用いた作製の一例を挙げる。  [0168] Fig. 5 (6) is an example of a bottom gate type, top contact type organic thin film transistor element. Hereinafter, an example of production using the production method of the present invention will be given.

実施例  Example

[0169] 実施例 1  [0169] Example 1

榭脂支持体 1として、ポリエーテルスルホン榭脂フィルム（200 m)を用い、この上 に、先ず、 50WZm2Zminの条件でコロナ放電処理を施した。その後以下のように 接着性向上のため下引き層を形成した。 As the resin support 1, a polyethersulfone resin film (200 m) was used, and first, a corona discharge treatment was performed on the condition of 50 WZm 2 Zmin. Thereafter, an undercoat layer was formed to improve adhesion as follows.

[0170] (下引き層の形成） [0170] (Formation of undercoat layer)

下記組成の塗布液を乾燥膜厚 2 mになるように塗布し、 90°Cで 5分間乾燥した後 、 60WZcmの高圧水銀灯下 10cmの距離から 4秒間硬化させた。  A coating solution having the following composition was applied to a dry film thickness of 2 m, dried at 90 ° C for 5 minutes, and then cured for 4 seconds from a distance of 10 cm under a 60 WZcm high-pressure mercury lamp.

[0171] ジペンタエリスリトールへキサアタリレート単量体 60g ジペンタエリスリトールへキサアタリレ [0171] Dipentaerythritol hexaatalylate monomer 60g Dipentaerythritol Hexaataire

ジペンタエリスリトールへキサアタリレ  Dipentaerythritol Hexaataire

ジエトキシベンゾフエノン UV開始剤  Diethoxybenzophenone UV initiator

シリコーン系界面活性剤  Silicone surfactant

メチルェチルケトン  Methyl ethyl ketone

メチルプロピレングリコ一ノレ  Methylpropylene glycol

さらにその層の上に下記条件で連続的に大気圧プラズマ処理して厚さ 50nmの酸 化ケィ素膜を設け、これらの層を下引き層 2とした（図 5 (1) )。  Further, an atmospheric pressure plasma treatment was performed on the layer under the following conditions to provide an oxide film having a thickness of 50 nm, and these layers were used as the undercoat layer 2 (FIG. 5 (1)).

[0172] (使用ガス） [0172] (Used gas)

不活性ガス:ヘリウム 98. 25体積0 /0 Inert gas: helium 98.25 volume 0/0

反応性ガス：酸素ガス 1. 5体積％  Reactive gas: Oxygen gas 1.5% by volume

反応性ガス:テトラエトキシシラン蒸気 (ヘリウムガスにてパブリング) 0. 25体積％ (放電条件）  Reactive gas: Tetraethoxysilane vapor (published with helium gas) 0.25 vol% (discharge conditions)

放電出力： lOWZcm2 Discharge output: lOWZcm 2

(電極条件）  (Electrode condition)

電極は、冷却水による冷却手段を有するステンレス製ジャケットロール母材に対し て、セラミック溶射によるアルミナを lmm被覆し、その後、テトラメトキシシランを酢酸 ェチルで希釈した溶液を塗布乾燥後、紫外線照射により封孔処理を行い、表面を平 滑にして Rmax5 μ mとした誘電体（比誘電率 10)を有するロール電極であり、アース されている。一方、印加電極としては、中空の角型のステンレスパイプに対し、上記同 様の誘電体を同条件にて被覆した。  The electrode is coated with lmm of alumina by ceramic spraying on a stainless jacket roll base material having cooling means with cooling water, and then a solution obtained by diluting tetramethoxysilane with ethyl acetate is applied and dried, and then sealed by ultraviolet irradiation. This is a roll electrode that has a dielectric (relative permittivity of 10) with a smooth surface and an Rmax of 5 μm. On the other hand, as the application electrode, a hollow rectangular stainless steel pipe was covered with the same dielectric material under the same conditions.

[0173] 次いで、ゲート電極 8を形成する。 [0173] Next, the gate electrode 8 is formed.

[0174] 即ち、上記の下引き層 2上に、下記組成の光感応性榭脂組成液 1を塗布し、 100°C にて 1分間乾燥させることで、厚さ 2 mの光感応性榭脂層を形成したのち、発振波 長 830nm、出力 lOOmWの半導体レーザで 200mjZcm2のエネルギー密度でゲー トラインおよびゲート電極のパターンを露光し、アルカリ水溶液で現像してレジスト像 を得た。さらにその上に、スパッタ法により、厚さ 300nmのアルミニウム皮膜を一面に 成膜した後、 MEKで上記光感応性榭脂層の残存部を除去することで、ゲートバスラ インおよびゲート電極 8を作製する（図 5 (2) )。 [0174] That is, the photosensitive resin composition 1 having the following composition is coated on the undercoat layer 2 and dried at 100 ° C for 1 minute, thereby obtaining a photosensitive film having a thickness of 2 m. After forming the oil layer, the gate line and gate electrode patterns were exposed to an energy density of 200 mjZcm 2 with a semiconductor laser having an oscillation wavelength of 830 nm and an output of lOOmW, and developed with an aqueous alkali solution to obtain a resist image. Further, a 300 nm thick aluminum film is formed on the entire surface by sputtering, and then the remaining part of the photosensitive resin layer is removed with MEK. The in and gate electrodes 8 are fabricated (Fig. 5 (2)).

[0175] (光感応性榭脂組成液 1) [0175] (Photosensitive resin composition 1)

色素 A 7部  Dye A 7 parts

ノボラック榭脂（フエノールと m―、 p 混合クレゾールとホルムアルデヒドを共縮合さ せたノボラック榭脂（Mw=4000、フエノール Zm クレゾ一ノレ Zp―クレゾ一ノレのモ ル比がそれぞれ 5Z57Z38) ) 90部  Novolac resin (novolak resin obtained by co-condensation of phenol and m-, p-mixed cresol and formaldehyde (Mw = 4000, phenol Zm Cresol Monore Zp-Cresol Monore molar ratio 5Z57Z38, respectively)) 90 parts

クリスタルバイオレット 3部  Crystal violet 3 parts

プロピレングリコーノレモノメチノレエーテノレ 1000咅  Propylene Glycole Monomethino Rete Tenor 1000 咅

[0176] [化 9] 色素 A [0176] [Chemical 9] Dye A

Figure imgf000037_0001
Figure imgf000037_0001

[0177] また感光性榭脂を用いたレジスト形成によるパターユングではなぐ静電吸引型イン クジェット装置と無電解メツキ法との組み合わせによる本発明の方法を用い、ゲートラ インおよびゲート電極のパターンを無電解メツキ法により形成してもよい。 [0177] Further, the pattern of the gate line and the gate electrode can be obtained by using the method of the present invention based on a combination of an electrostatic attraction type inkjet device and an electroless plating method, which is not the patterning by resist formation using photosensitive resin. It may be formed by an electrolytic plating method.

[0178] 次いで、以下の陽極酸ィ匕皮膜形成工程により、平滑化、絶縁'性向上のためのネ ΐ助 的絶縁膜として、ゲート電極に陽極酸ィ匕被膜を形成した (図では省略)。  [0178] Next, an anodic acid film was formed on the gate electrode as a negative insulating film for improving smoothness and insulation by the following anodic acid film forming process (not shown in the figure). .

[0179] (陽極酸化被膜形成工程）  [0179] (Anodized film forming process)

ゲート電極を形成したのち基板をよく洗浄し、 30質量％硫酸水溶液中で、 2分間、 30Vの低電圧電源カゝら供給される直流を用いて、陽極酸ィ匕皮膜の厚さが 120nmに なるまで陽極酸ィ匕をおこなった。よく洗浄した後に、 1気圧、 100°Cの飽和した蒸気チ ヤンバーの中で、蒸気封孔処理を施した。この様にして陽極酸化被膜を有するゲート 電極を下引き処理したポリエーテルスルホン榭脂フィルム上に作製した。  After forming the gate electrode, the substrate is thoroughly cleaned, and the thickness of the anodic oxide film is reduced to 120 nm using direct current supplied from a 30 V low-voltage power supply in 30% by weight sulfuric acid aqueous solution for 2 minutes. Anodizing was performed until After washing well, steam sealing was performed in a steam chamber saturated at 1 atm and 100 ° C. In this way, a gate electrode having an anodized film was prepared on a polyethersulfone resin film which had been subjected to a subbing treatment.

[0180] 次いで、さらにフィルム温度 200°Cにて、上述した大気圧プラズマ法により厚さ 30η mの酸化珪素膜を設け、前記した陽極酸ィ匕アルミニウム層を併せて、厚さ 150nmの ゲート絶縁層 7を形成した（図 5の（3) )。 [0181] 次に、半導体材料として、下記チォフェンオリゴマー〈2〉を用いて、ゲート絶縁層上 に有機半導体層を形成した。即ち、チォフェンオリゴマー〈2〉のシクロへキサン溶液 ( 0. 5質量％)を調製し、ピエゾ方式のインクジェット法を用いて、チャネルを形成すベ き領域に吐出し、窒素ガス中で、 50°Cで 3分乾燥し、基板上に膜厚 20nmの有機半 導体層 6を形成した (図 5 (4) )。 [0180] Next, at a film temperature of 200 ° C, a silicon oxide film having a thickness of 30ηm is provided by the above-described atmospheric pressure plasma method, and the above-described anodized aluminum layer is combined to form a gate insulating film having a thickness of 150nm. Layer 7 was formed ((3) in FIG. 5). [0181] Next, an organic semiconductor layer was formed on the gate insulating layer using the following thiophene oligomer <2> as a semiconductor material. That is, a cyclohexane solution (0.5% by mass) of thiophene oligomer <2> was prepared and ejected to a region where a channel was to be formed using a piezo ink jet method. Drying was performed at ° C for 3 minutes to form an organic semiconductor layer 6 with a thickness of 20 nm on the substrate (Fig. 5 (4)).

[0182] [化 10]  [0182] [Chemical 10]

Figure imgf000038_0001
Figure imgf000038_0001

[0183] 次いで、前記図 3で表される静電吸引型インクジェット装置にて、下記無電解メツキ 触媒液をインクとして用い、回転ロール（支持ロール）にはバイアス電圧 2000Vの電 圧を印加し、更にパルス電圧（400V)を重畳させてソース、ドレイン電極パターンに 従ってインクを吐出した。ノズル吐出口の内径は 10 μ mとし、ノズル吐出口と基材と のギャップは 500 mに保持した。メツキ触媒含有インクとして下記処方のものを用い た。 [0183] Next, in the electrostatic attraction type ink jet apparatus shown in Fig. 3, the following electroless plating catalyst solution was used as ink, and a bias voltage of 2000V was applied to the rotating roll (support roll), Furthermore, ink was ejected according to the source and drain electrode patterns by superimposing a pulse voltage (400V). The inner diameter of the nozzle outlet was 10 μm, and the gap between the nozzle outlet and the substrate was kept at 500 m. The following formulation was used as the ink containing the catalyst catalyst.

[0184] (無電解メツキ触媒液）  [0184] (Electroless plating catalyst solution)

可溶性パラジウム塩 (塩化パラジウム） 20質量％ (Pd2+濃度 1. Og/1) イソプロピルアルコール 12質量％ Soluble palladium salt (palladium chloride) 20% by mass (Pd 2+ concentration 1. Og / 1) Isopropyl alcohol 12% by mass

グリセリン 20質量％  Glycerin 20% by mass

2—メチル ペンタンチオール 5質量％  2-Methyl pentanethiol 5% by mass

1, 3 ブタンジオール 3質量％  1, 3 Butanediol 3% by mass

イオン交換水 40質量％  Ion exchange water 40% by mass

更に、乾燥定着させて、触媒パターン Mlを形成した (図 5 (5) )。  Furthermore, drying and fixing were performed to form a catalyst pattern Ml (Fig. 5 (5)).

[0185] 次いで、スクリーン印刷法により、下記無電解金メッキ液をインクとして用いてメツキ 触媒パターンが形成された領域を含む領域に印刷をおこなった。メツキ剤力 Sメツキ触 媒と接触することでメツキ触媒のパターン上に無電解メツキが施され、金薄膜 M2が形 成された。 [0186] (無電解金メッキ液） [0185] Next, printing was performed on a region including a region where a plating catalyst pattern was formed using the following electroless gold plating solution as an ink by a screen printing method. Electrolytic plating was applied to the plating catalyst pattern by contact with S plating catalyst, and gold thin film M2 was formed. [0186] (Electroless gold plating solution)

ジシァノ金カリウム 0. 1モル ZL  Disiano gold potassium 0.1 mol ZL

蓚酸ナトリウム 0. 1モル ZL  Sodium oxalate 0.1 mol ZL

酒石酸ナトリウムカリウム 0. 1モル ZL  Sodium potassium tartrate 0.1 mol ZL

を溶解した均一溶液金薄膜が形成された基板表面を、純水で、充分に洗浄、乾燥し て、図 5 (6)に示される薄膜トランジスタが形成された。以上の方法により形成したソ ース電極およびドレイン電極のサイズは、幅 10 μ m、長さ 50 m (チャネル幅 W)、厚 さ 150nm、ソース電極、ドレイン電極の距離（チャネル長 L)は 5 μ mであり、高精細な 電極パターンが形成されていた。この薄膜トランジスタは良好に動作し、飽和領域か ら見積もられた移動度は、 0. 07cm2ZVsであった。 The substrate surface on which the uniform solution gold thin film in which the solution was dissolved was sufficiently washed with pure water and dried to form the thin film transistor shown in FIG. 5 (6). The size of the source and drain electrodes formed by the above method is 10 μm wide, 50 m long (channel width W), 150 nm thick, and the distance between the source and drain electrodes (channel length L) is 5 mm. It was μm, and a high-definition electrode pattern was formed. This thin film transistor operated well, and the mobility estimated from the saturation region was 0.07 cm 2 ZVs.

[0187] 比較例 1  [0187] Comparative Example 1

実施例 1にて、静電吸引型インクジェット装置を用いる代わりに、ピエゾ方式のインク ジェットヘッドから、実施例 1で用いた無電解メツキ触媒液をインクとして用い、ソース 、ドレイン電極パターンに従ってインクを吐出した。さらに実施例 1と同様に無電解め つき処理を行い、ソース電極およびドレイン電極の作製を行った。し力し、無電解メッ キ触媒液がはじ 、てしま ヅース電極、ドレイン電極のパターンが形成されなかった。  In Example 1, instead of using an electrostatic suction type ink jet device, the electroless catalyst solution used in Example 1 was used as ink from a piezo-type ink jet head, and ink was ejected according to the source and drain electrode patterns. did. Further, an electroless plating process was performed in the same manner as in Example 1 to produce a source electrode and a drain electrode. As a result, the electroless catalyst solution was repelled, and the pattern of the source electrode and drain electrode was not formed.

[0188] 以上、トップコンタクト型の薄膜トランジスタの作製例を示した。  [0188] The example of manufacturing the top contact thin film transistor has been described above.

[0189] 実施例 2  [0189] Example 2

ボトムコンタクト型の実施態様については、前記の有機半導体層とソース、ドレインの 形成順序を逆にすればよい。即ち、ゲート絶縁膜 7形成後、静電吸引型インクジェッ ト法によりメツキ触媒パターンを形成し、メツキ剤と接触させ、ソース、ドレイン電極を形 成した後（Ml、 M2)、有機半導体材料を、ピエゾ方式のインクジェット法を用いて、 チャネルを形成すべき領域に吐出し、窒素ガス中で、 50°Cで 3分乾燥し有機半導体 層 6を形成する。  In the bottom contact type embodiment, the order of forming the organic semiconductor layer and the source and drain may be reversed. That is, after the gate insulating film 7 is formed, a plating catalyst pattern is formed by an electrostatic attraction ink jet method, contacted with a plating agent, and source and drain electrodes are formed (Ml, M2). Using a piezo ink jet method, the channel is discharged to the region where the channel is to be formed and dried in nitrogen gas at 50 ° C. for 3 minutes to form the organic semiconductor layer 6.

このように実施例 1の工程順序を変えて、ボトムコンタクト型の薄膜トランジスタを作製 した。このとき、ソース電極およびドレイン電極のサイズは、幅 10 μ m、長さ 50 μ ΐη { チャネル幅 W)、厚さ 150nm、ソース電極、ドレイン電極の距離（チャネル長 L)は 5 μ mであり、高精細な電極パターンが形成されていた。この薄膜トランジスタは良好に 動作し、飽和領域力も見積もられた移動度は、 0. 05cm2ZVsであった。 図 6にこのボトムコンタクト型薄膜トランジスタの構成を示した。この場合には、有機半 導体層がメツキ剤等に晒されることがなく好ましい。 In this way, the bottom-contact type thin film transistor was manufactured by changing the process sequence of Example 1. At this time, the size of the source and drain electrodes is 10 μm wide, 50 μΐη (channel width W) long, 150 nm thick, and the distance between the source and drain electrodes (channel length L) is 5 μm. A high-definition electrode pattern was formed. This thin film transistor is good The mobility that worked and the saturation region force was estimated was 0.05 cm 2 ZVs. Figure 6 shows the configuration of this bottom contact thin film transistor. In this case, the organic semiconductor layer is preferable because it is not exposed to a plating agent or the like.

[0190] 比較例 2  [0190] Comparative Example 2

実施例 2にて、静電吸引型インクジェット装置を用いる代わりに、ピエゾ方式のインク ジェットヘッドから、実施例 2で用いた無電解メツキ触媒液をインクとして用い、ソース 、ドレイン電極パターンに従ってインクを吐出した。さらに実施例 2と同様に無電解め つき処理を行い、ソース電極およびドレイン電極の作製を行った。し力し、無電解メッ キ触媒液がはじ 、てしま ヅース電極、ドレイン電極のパターンが形成されなかった。  In Example 2, instead of using an electrostatic suction type ink jet device, the electroless plating catalyst solution used in Example 2 was used as ink from a piezo-type ink jet head, and ink was ejected according to the source and drain electrode patterns. did. Further, an electroless plating process was performed in the same manner as in Example 2 to produce a source electrode and a drain electrode. As a result, the electroless catalyst solution was repelled, and the pattern of the source electrode and drain electrode was not formed.

[0191] 次いで、トップコンタクト型の薄膜トランジスタを用いた TFTシート (有機薄膜トランジ スタ素子シート)の製造のより具体的な実施態様について図 7を用いて説明する。  Next, a more specific embodiment of manufacturing a TFT sheet (organic thin film transistor element sheet) using a top contact type thin film transistor will be described with reference to FIG.

[0192] 実施例 3  [0192] Example 3

〈ゲートバスラインおよびゲート電極の形成〉  <Formation of gate bus line and gate electrode>

図 7の（1)は、 PES (ポリエーテルスルホン)榭脂フィルム（200 μ m)を基板として、 基板 1上に、前記下引き層 2および陽極酸ィ匕被膜 9付きのアルミニウムによるゲート電 極 8、そして、ゲート絶縁膜 7、有機半導体層 6が、前記図 5において示した方法によ り順次形成されたところを示す。  Fig. 7 (1) shows a PES (polyethersulfone) resin film (200 µm) as the substrate, and the gate electrode made of aluminum with the undercoat layer 2 and the anodized film 9 on the substrate 1 8 and the gate insulating film 7 and the organic semiconductor layer 6 are sequentially formed by the method shown in FIG.

[0193] (有機半導体保護層形成工程）  [0193] (Organic semiconductor protective layer formation process)

この有機半導体層 6の上に、前記実施態様において無電解メツキの触媒のパター ンを印刷するのに用いたものと同じ静電吸引型インクジェット装置で、静電界印加用 電極部と対向電極部との間に印加されるバイアス電圧およびパルス電圧等の条件を 適宜調整し、十分に精製を行ったポリビニルアルコールを超純粋製造装置で精製さ れた水に溶解した水溶液をインクとして用いて、保護膜パターンの印刷をおこなった 。印刷は、有機半導体層の、ソース、ドレイン電極間において、半導体チャネルを構 成する部分に選択的に保護膜材料を吐出した。印刷後、窒素ガス雰囲気中 100°C にて、よく乾燥させ、厚さ 1 μ mのポリビニルアルコールの有機半導体保護層 3を形成 した（図 7の（2) )。  On this organic semiconductor layer 6, the same electrostatic attraction type ink jet apparatus used for printing the electroless plating catalyst pattern in the above embodiment, an electrostatic field applying electrode part, a counter electrode part, A protective film is formed using an aqueous solution obtained by dissolving polyvinyl alcohol, which has been sufficiently purified by ultrapure manufacturing equipment, as ink, by appropriately adjusting conditions such as bias voltage and pulse voltage applied during The pattern was printed. In the printing, a protective film material was selectively ejected to a portion constituting the semiconductor channel between the source and drain electrodes of the organic semiconductor layer. After printing, the film was thoroughly dried at 100 ° C in a nitrogen gas atmosphere to form an organic semiconductor protective layer 3 of polyvinyl alcohol having a thickness of 1 µm ((2) in Fig. 7).

[0194] 保護膜のパターニングは、感光性榭脂をもち!/、てレジストを形成させる方法によつ ても構わない。 [0194] The protective film is patterned by a method of forming a resist with a photosensitive resin! It doesn't matter.

[0195] (電極形成工程）  [0195] (Electrode formation process)

(メツキ触媒パターン形成）  (Metsuki catalyst pattern formation)

次いで、電極形成領域に、前記実施態様において無電解メツキの触媒のパターン を印刷するのに用いたものと同じ静電吸引型インクジェット装置を用いて、同条件に てソース電極、ドレイン電極のパターンにしたがって下記メツキ触媒液を吐出し、これ を乾燥、定着しメツキ触媒パターン Mlを形成した (図 7 (3)、 （4) )。  Next, in the electrode forming region, the same electrostatic suction type ink jet apparatus as that used for printing the electroless plating catalyst pattern in the above embodiment is used, and the source electrode and drain electrode patterns are formed under the same conditions. Therefore, the following catalyst catalyst solution was discharged, dried and fixed to form a catalyst catalyst pattern Ml (Fig. 7 (3), (4)).

[0196] (メツキ触媒液） [0196] (Metsuki catalyst solution)

可溶性パラジウム塩 (塩化パラジウム） 20質量％ (Pd2+濃度 1. Og/1) イソプロピルアルコール 12質量％ Soluble palladium salt (palladium chloride) 20% by mass (Pd 2+ concentration 1. Og / 1) Isopropyl alcohol 12% by mass

グリセリン 20質量％  Glycerin 20% by mass

2—メチル ペンタンチオール 5質量％  2-Methyl pentanethiol 5% by mass

1, 3 ブタンジオール 3質量％  1, 3 Butanediol 3% by mass

イオン交換水 40質量％  Ion exchange water 40% by mass

レジストの形成によるソース電極、ソースバスライン、又ドレイン電極の正確なパター ユングを用いることなぐ静電吸引型インクジェット装置による印刷を用い、メツキ触媒 液を正確に電極パターンに従って吐出、配置できる。次いで、メツキ触媒を乾燥して 、触媒パターンを定着した。  Using the printing by the electrostatic suction type ink jet device without using the accurate pattern of the source electrode, the source bus line, and the drain electrode by forming the resist, the catalyst solution can be ejected and arranged accurately according to the electrode pattern. Next, the catalyst was dried to fix the catalyst pattern.

[0197] (メツキ剤の供給） [0197] (Supplying of a remedy)

次に、上記の触媒パターンが形成された基板を無電解金メッキ浴 (ジシァノ金力リウ ム 0. 1モル Zリットル、蓚酸ナトリウム 0. 1モル Zリットル、酒石酸ナトリウムカリウム 0. Next, the substrate on which the catalyst pattern is formed is placed on an electroless gold plating bath (disiano gold power 0.1 mol Z liter, sodium oxalate 0.1 mol Z liter, sodium potassium tartrate 0.

1モル Zリットルを溶解した均一溶液）に浸漬して、厚み l lOnmの金力ゝらなる金属薄 膜 M2を形成させ、ソース、ドレイン電極を形成した。電極形成後充分に洗浄、乾燥し 、薄膜トランジスタを形成した（図 7 (5) )。 A metal thin film M2 having a thickness of lOnm was formed by immersing in 1 mol Z liter of a uniform solution), and source and drain electrodes were formed. After forming the electrode, it was thoroughly washed and dried to form a thin film transistor (Fig. 7 (5)).

[0198] 形成したソース電極およびドレイン電極のサイズは、幅 10 μ m、長さ 50 μ m (チヤネ ル幅 W)、ソース電極、ドレイン電極の距離（チャネル長 L)は 5 μ mであり、高精細な 電極パターンが形成されていた。この薄膜トランジスタは良好に動作し、飽和領域か ら見積もられた移動度は、 0. l lcm2ZVsであった。 [0199] 比較例 3 [0198] The size of the formed source and drain electrodes is 10 μm wide, 50 μm long (channel width W), and the distance between the source and drain electrodes (channel length L) is 5 μm. A high-definition electrode pattern was formed. This thin film transistor operated well, and the mobility estimated from the saturation region was 0.1 lcm 2 ZVs. [0199] Comparative Example 3

実施例 3にて、静電吸引型インクジェット装置を用いる代わりに、ピエゾ方式のインク ジェットヘッドから、実施例 3で用いた無電解メツキ触媒液をインクとして用い、ソース 、ドレイン電極パターンに従ってインクを吐出した。さらに実施例 3と同様に無電解め つき処理を行い、ソース電極およびドレイン電極の作製を行った。形成したソース電 極およびドレイン電極のサイズは、幅約 70 μ m、長さ約 80 μ m、ソース電極、ドレイン 電極の距離（チャネル長 L)は 5 μ mであり、電極のパターンにやや乱れが生じ、電極 の厚さにも著しいムラが発生していた。電極の厚さは 5〜250nmの間で変動が確認 された。この薄膜トランジスタの飽和領域力も見積もられた移動度は、 0. 002cm Vsであった。  In Example 3, instead of using an electrostatic suction ink jet apparatus, the electroless catalyst solution used in Example 3 was used as ink from a piezo-type ink jet head, and ink was ejected according to the source and drain electrode patterns. did. Further, an electroless plating process was performed in the same manner as in Example 3 to produce a source electrode and a drain electrode. The size of the formed source and drain electrodes is approximately 70 μm wide, approximately 80 μm long, and the distance between the source and drain electrodes (channel length L) is 5 μm. As a result, the electrode thickness was significantly uneven. The thickness of the electrode was found to vary between 5 and 250 nm. The mobility estimated for the saturation region force of this thin film transistor was 0.002 cm Vs.

[0200] 以上、本発明の有機半導体素子の製造方法による TFTシートの製造例を示したが 、この様に、本発明により、無電解メツキによって、有機薄膜トランジスタ素子の電極 の少なくとも一つを形成する際に、静電吸引型インクジエツト方式を用 ヽ電極のバタ 一ユングをおこなうことで、精度のよいパターユングが可能となり、ムラやハジキのな い電極の形成が可能となる。また電極の形成に関してはレジスト等による複雑な工程 を経るパターユングを回避できる。また、有機半導体層の電極形成領域以外は有機 半導体保護層で保護することで、無電解メツキによる有機半導体層の劣化を防止で き、低抵抗な電極を有する高性能の有機薄膜トランジスタ素子 (シート)を形成するこ とが可能である。  [0200] Although the example of manufacturing the TFT sheet by the method for manufacturing the organic semiconductor element of the present invention has been described above, at least one of the electrodes of the organic thin film transistor element is formed by electroless plating according to the present invention. At the same time, by using an electrostatic suction ink jet method to perform electrode patterning, it is possible to perform patterning with high accuracy and to form an electrode that is free from unevenness and repellency. In addition, with respect to the formation of the electrodes, it is possible to avoid patterning that involves complicated processes such as resist. In addition, by protecting the organic semiconductor layer other than the electrode formation region with an organic semiconductor protective layer, the organic semiconductor layer can be prevented from deteriorating due to electroless plating, and a high-performance organic thin film transistor element having a low resistance electrode (sheet) Can be formed.

Claims

請求の範囲 The scope of the claims [1] ゲート、ソース、ドレインの少なくとも一つの電極力 メツキ触媒パターンを形成した後 メツキ剤を接触させる、無電解メツキ法により形成される薄膜トランジスタの製造方法 において、前記メツキ触媒パターンの形成力 メツキ触媒を含有する液体を静電吸引 方式の液体吐出装置を用いて吐出することで行われることを特徴とする薄膜トランジ スタの製造方法。  [1] At least one electrode force of a gate, a source, and a drain. After forming a plating catalyst pattern, a plating agent is brought into contact with the thin film transistor formed by an electroless plating method. A method for producing a thin film transistor, comprising: discharging a liquid containing a liquid using an electrostatic suction type liquid discharge device. [2] 前記静電吸弓 I方式の液体吐出装置に備えられた液体を吐出するノズルの内径が 15 m以下であることを特徴とする請求の範囲第 1項に記載の薄膜トランジスタの製造 方法。  [2] The method for producing a thin film transistor according to [1], wherein an inner diameter of a nozzle for discharging a liquid provided in the liquid discharging device of the electrostatic arch I type is 15 m or less. [3] ソースまたはドレイン電極が前記無電解メツキ法により形成されることを特徴とする請 求の範囲第 1項または第 2項に記載の薄膜トランジスタの製造方法。  [3] The method for manufacturing a thin film transistor according to item 1 or 2, wherein the source or drain electrode is formed by the electroless plating method. [4] 少なくとも 1種の有機半導体を用いることを特徴とする請求の範囲第 1項〜第 3項の いずれか 1項に記載の薄膜トランジスタの製造方法。  [4] The method for producing a thin film transistor according to any one of [1] to [3], wherein at least one organic semiconductor is used. [5] ボトムゲート型構造を形成することを特徴とする請求の範囲第 1項〜第 4項のいずれ 力 1項に記載の薄膜トランジスタの製造方法。  [5] The method for producing a thin film transistor according to any one of [1] to [4], wherein a bottom gate structure is formed.
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WO2004028815A1 (en) * 2002-09-24 2004-04-08 Konica Minolta Holdings, Inc. Method for manufacturing electrostatic attraction type liquid discharge head, method for manufacturing nozzle plate, method for driving electrostatic attraction type liquid discharge head, electrostatic attraction type liquid discharging apparatus, and liquid discharging apparatus
JP2004158805A (en) * 2002-11-08 2004-06-03 Asahi Kasei Corp Method of manufacturing organic semiconductor device and organic semiconductor device
JP2004289044A (en) * 2003-03-25 2004-10-14 Konica Minolta Holdings Inc Thin film transistor element sheet and method of manufacturing thin film transistor element sheet
WO2005014289A1 (en) * 2003-08-08 2005-02-17 Konica Minolta Holdings, Inc. Liquid jetting device, liquid jetting method, and method of forming wiring pattern on circuit board

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JP2009239169A (en) * 2008-03-28 2009-10-15 Konica Minolta Holdings Inc Method of manufacturing organic thin-film transistor
JP2016157711A (en) * 2015-02-23 2016-09-01 国立大学法人 東京大学 Contact electrode and method for forming the same

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