JP2015142091A - Method for manufacturing organic thin film transistor, and organic thin film transistor manufactured thereby - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a method for manufacturing an organic thin film transistor superior in carrier mobility, migration resistance, and electrode adhesion; and an organic thin film transistor manufactured by such a method.SOLUTION: A method for manufacturing a bottom gate-bottom contact type or top gate-top contact type organic thin film transistor having a gate electrode, a gate insulative film layer including an organic insulative material, a source electrode, a drain electrode, and an organic semiconductor layer comprises: a process for forming at least one of a source electrode and a drain electrode by heating and sintering a coating film formed by use of a composition for conductive film formation which includes (A) copper oxide particles having an average primary particle diameter of 100 nm or less, (B) metal particles or salt including a predetermined metal element, and (C) an alcohol compound.

Description

  The present invention relates to an organic thin film transistor manufacturing method and an organic thin film transistor manufactured by the manufacturing method.

  Light weight, low cost, and flexibility are possible, so organic devices such as FETs (field effect transistors), RFIDs (RF tags), and memories that are used in liquid crystal displays and organic EL displays An organic thin film transistor (organic TFT) having a semiconductor film (organic semiconductor layer) is used.

  As a method for producing such an organic thin film transistor, for example, a metal fine particle layer (metal fine particles having an average particle size of 50 nm or less is obtained by patterning a metal fine particle dispersion such as gold, silver, copper, etc. by a printing method on a source electrode and a drain electrode. Patent Document 1 describes a method of forming an electrode by thermally fusing metal fine particles by forming a layer substantially consisting of a group) and then performing heat treatment.

JP 2004-031933 A

On the other hand, in recent years, with improvement in performance and generalization of each electronic device device and the like, the organic thin film transistor is required to further improve the operation speed and reliability.
When the inventor examined the method for producing an organic thin film transistor described in Patent Document 1, it was found that there was room for improvement in operating speed (carrier mobility) and reliability (migration resistance, electrode adhesion). It was done. The migration resistance is intended to prevent the occurrence of metal ion migration between the source electrode and the drain electrode, and the electrode adhesion is a gate insulating film layer adjacent to the electrode (source electrode and / or drain electrode). Intended to adhere to.

  Then, this invention makes it a subject to provide the organic thin-film transistor manufactured by the manufacturing method of the organic thin-film transistor and its manufacturing method for manufacturing the organic thin-film transistor excellent in carrier mobility, migration resistance, and electrode adhesiveness To do.

As a result of intensive studies to solve the above-mentioned problems, the present inventor can obtain a desired effect by forming a source electrode and / or a drain electrode using a predetermined composition for forming a conductive film. As a result, the present invention was completed.
That is, the present inventors have found that the above problem can be solved by the following configuration.

(1) A gate electrode, a gate insulating film layer containing an organic insulating material, a source electrode, a drain electrode, and an organic semiconductor layer are provided, the gate insulating film layer and the source electrode, and the gate insulating film layer and the drain electrode. Is a method for manufacturing a bottom gate-bottom contact type or top gate-top contact type organic thin film transistor, each having a structure in contact with each other,
Copper oxide particles (A) having an average primary particle size of 100 nm or less, and metal particles or salts (B) containing at least one metal element selected from the group consisting of Group 8 to 11 elements of the periodic table; A step of forming at least one of the source electrode and the drain electrode by subjecting the coating film formed using the composition for forming a conductive film containing the alcohol compound (C) to heat baking or photo baking. A method for producing an organic thin film transistor.
(2) The method for producing an organic thin film transistor according to (1), wherein the organic insulating material includes an organic insulating material having a siloxane group or a perfluoro group.
(3) The heating and baking in the step of forming at least one of the source electrode and the drain electrode is performed by heat treatment at a temperature equal to or higher than the glass transition temperature of the organic insulating material in the gate insulating film layer. ) For producing an organic thin film transistor.
(4) The method for producing an organic thin film transistor according to any one of (1) to (3), wherein the coating film is formed by a printing method.
(5) The metal particles or salt (B) includes metal particles or salts containing at least one metal element selected from the group consisting of Group 10 elements of the Periodic Table, (1) to (4) The manufacturing method of the organic thin-film transistor of any one.
(6) The method for producing an organic thin film transistor according to any one of (1) to (5), wherein the alcohol compound (C) contains a trivalent alcohol.
(7) The manufacturing method of the organic thin-film transistor of any one of (1)-(6) whose film thickness of a gate insulating-film layer is 200 nm-1 micrometer.
(8) The manufacturing method of the organic thin-film transistor of any one of (1)-(7) whose thickness of a source electrode and a drain electrode is 50-500 nm.
(9) An organic thin film transistor manufactured by the method for manufacturing an organic thin film transistor according to any one of (1) to (8).

  ADVANTAGE OF THE INVENTION According to this invention, the organic thin-film transistor manufactured by the manufacturing method of the organic thin-film transistor and its manufacturing method for manufacturing the organic thin-film transistor excellent in carrier mobility, migration resistance, and electrode adhesiveness can be provided.

FIG. 1 is a cross-sectional view of one embodiment of a bottom gate-bottom contact type organic thin film transistor. FIG. 2 is a cross-sectional view of another embodiment of a bottom gate-bottom contact type organic thin film transistor. FIG. 3 is a cross-sectional view of one embodiment of a top gate-top contact type organic thin film transistor. FIG. 4 is a cross-sectional view of another embodiment of a top gate-top contact type organic thin film transistor. FIG. 5 is a plan view of the metal mask used in the example.

Below, the manufacturing method of the organic thin-film transistor of this invention and the organic thin-film transistor obtained from the manufacturing method of an organic thin-film transistor are demonstrated.
In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
One of the features of the manufacturing method of the present invention is that, in the manufacture of a bottom gate-bottom contact type or top gate-top contact type organic thin film transistor, a source electrode is formed using a conductive film forming composition containing a predetermined component. And / or the point which produces the drain electrode is mentioned. As will be described later, in a bottom gate-bottom contact type or top gate-top contact type organic thin film transistor, a gate insulating film layer containing an organic insulating material is in contact with a source electrode and a drain electrode. Therefore, when a source electrode and / or a drain electrode are produced by performing heat baking or light baking using a conductive film forming composition described later, the organic insulating material of the gate insulating film layer and the conductive film forming composition are derived. By the interaction with this component, the adhesion of the formed electrode to the gate insulating film layer is improved. In addition, in the case of light baking, it is estimated that adhesiveness improves according to the heat | fever which the composition for electrically conductive film formation absorbed and generated light. Moreover, when this composition for electrically conductive film formation is used, while the migration between electrodes is suppressed, the fall of the mobility in an organic-semiconductor layer is also suppressed. In addition, it is estimated that the improvement of the adhesiveness of the said electrode contributes as one of the factors by which the fall of the mobility of an organic-semiconductor layer is suppressed.
Hereinafter, a manufacturing method of a bottom gate-bottom contact type organic thin film transistor will be described in detail as a first aspect, and a manufacturing method of a top gate-top contact type organic thin film transistor will be described in detail as a second aspect.

<< First Aspect >>
FIG. 1 shows a cross-sectional view of one embodiment of a bottom gate-bottom contact type organic thin film transistor.
As shown in FIG. 1, the organic thin film transistor 10 includes a support 12, a gate electrode 14 disposed on the support 12, a gate insulating film layer 16 in contact with the gate electrode 14, and a gate of the gate insulating film layer 16. The source electrode 18 and the drain electrode 20 disposed so as to be in contact with the surface opposite to the electrode 14 side, the source electrode 18, the drain electrode 20, and the gate in the region sandwiched between the source electrode 18 and the drain electrode 20. The organic semiconductor layer 22 is disposed so as to cover the insulating film layer 16. As will be described later, the gate insulating film layer 16 includes an organic insulating material.
The production method of the present invention is a step of forming at least one of the source electrode 18 and the drain electrode 20 by subjecting a coating film formed using the composition for forming a conductive film, which will be described later, to heat baking or light baking. (Hereinafter also referred to as source / drain formation step) at least, and the formation method of other members (gate electrode 14, gate insulating film layer 16, organic semiconductor layer 22) is not particularly limited, Step of forming gate electrode 14 (gate forming step), step of forming gate insulating film layer 16 (insulating film layer forming step), source / drain forming step, and step of forming organic semiconductor layer 22 (organic semiconductor) It is preferable to carry out the forming step in this order.
Below, the procedure which has the said process is explained in full detail as one of the suitable aspects of the manufacturing method of the organic thin-film transistor 10 shown in FIG.

<Gate formation process>
This step is a step of forming a gate electrode on the support. Below, the support body and gate electrode which are used are explained in full detail first.
The type of the support is not particularly limited, and is mainly composed of glass or a flexible resin sheet. For example, a plastic film can be used as the sheet. Examples of the plastic film include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyether ether ketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate (PC), cellulose triacetate (TAC), and cellulose acetate propionate. Examples thereof include a film made of (CAP) or the like. Thus, by using a plastic film, it is possible to reduce the weight as compared to the case of using a glass support, to improve portability, and to improve resistance to impact.

The material constituting the gate electrode is not particularly limited as long as it is a conductive material. For example, gold (Au), silver, aluminum (Al), copper, chromium, nickel, cobalt, titanium, platinum, magnesium, calcium, barium, Metals such as sodium; conductive oxides such as InO ₂ , SnO ₂ , ITO; conductive polymers such as polyaniline, polypyrrole, polythiophene, polyacetylene, polydiacetylene; semiconductors such as silicon, germanium, gallium arsenide; fullerene, carbon Examples thereof include carbon materials such as nanotubes and graphite. Especially, it is preferable that it is a metal, and it is more preferable that they are silver and aluminum.

The method for forming the gate electrode is not particularly limited. For example, a method for forming a conductive thin film formed using a method such as vapor deposition or sputtering using a known photolithography method or a lift-off method, aluminum, copper, or the like. There is a method of etching on a metal foil using a resist such as thermal transfer or ink jet.
Alternatively, a conductive polymer solution or dispersion, or a conductive fine particle dispersion may be directly patterned by ink jetting, or may be formed from a coating film by lithography or laser ablation. Furthermore, a method of patterning an ink containing a conductive polymer or conductive fine particles, a conductive paste, or the like by a printing method such as relief printing, intaglio printing, planographic printing, or screen printing can also be used. Moreover, you may form a gate electrode using the composition for electrically conductive film formation mentioned later.
The thickness of the gate electrode is not particularly limited, but is preferably 20 to 200 nm.

<Insulating film layer forming step>
This step is a step of forming a gate insulating film layer in contact with the gate electrode on the support. The gate insulating film layer is usually disposed so as to cover the gate electrode. Below, the material which comprises a gate insulating-film layer is explained in full detail first.

The gate insulating film layer includes an organic insulating material. By including an organic insulating material in the gate insulating film layer, excellent adhesion between the source electrode and / or the drain electrode is achieved at the time of heat baking or light baking in the source / drain formation process described later. .
The content of the organic insulating material in the gate insulating film layer is not particularly limited, but is preferably included as a main component. Here, the main component means that the content of the organic insulating material is 75% by mass or more with respect to the total mass of the gate insulating film layer, and the source electrode and / or drain electrode, the gate insulating film layer, 90 mass% or more is preferable at the point which is more excellent in adhesiveness, and 100 mass% is more preferable.

The organic insulating material is not particularly limited as long as it is an organic substance (organic compound) exhibiting insulating properties. For example, an insulating resin is preferable, and more specifically, polyimide, polyamide, polyester, polyacrylate, photo-curing resin of photo radical polymerization type or photo cationic polymerization type, copolymer containing acrylonitrile component, polyvinyl phenol, polyvinyl Alcohol, novolac resin, epoxy resin, cyanoethyl pullulan, silicon polymer, fluorine polymer, or the like can be used.
As the organic insulating material, an organic insulating material having a siloxane group or a perfluoro group in that the adhesion between the source electrode and / or drain electrode and the gate insulating film layer is more excellent, or the mobility of the organic thin film transistor is more excellent. Is preferred. As the organic insulating material having a siloxane group or a perfluoro group, a siloxane group-containing polymer or a perfluoro group-containing polymer is preferably used. Examples of the siloxane group-containing polymer include polydimethylsiloxane and polysilsesquioxane. Examples of the perfluoro group-containing polymer include Teflon ^(R) (Mitsui / DuPont Fluorochemicals), Cytop ^{(R )} (Manufactured by Asahi Glass Co., Ltd.), and amorphous fluororesins such as NEOFLON ^TM (manufactured by Daikin).
The siloxane group means a group represented by Si—O, and the perfluoro group means a group in which all hydrogen atoms are substituted with fluorine atoms.

A method for forming the gate insulating film layer is not particularly limited. For example, the gate insulating film layer is formed by applying a composition for forming a gate insulating film layer containing the organic insulating material onto a support on which a gate electrode is formed. And a method of forming a gate insulating film layer by vapor deposition or sputtering of the organic insulating material. Note that the composition for forming a gate insulating film layer may contain a solvent (water or an organic solvent) as necessary. The composition for forming a gate insulating film layer may contain a crosslinking component. For example, a crosslinked structure can be introduced into the gate insulating film layer by adding a crosslinking component such as melamine to an organic insulating material containing a hydroxy group.
The method for applying the gate insulating film layer forming composition is not particularly limited, and is applied by spray coating, spin coating, blade coating, dip coating, casting, roll coating, bar coating, die coating, or the like. A wet process such as a method using a patterning method or a method using a patterning method such as inkjet is preferable.
When a gate insulating film layer-forming composition is applied to form a gate insulating film layer, it may be heated (baked) after application for the purpose of solvent removal, crosslinking and the like.

  The film thickness of the gate insulating film layer is not particularly limited, and is preferably 50 nm to 3 μm, and more preferably 200 nm to 1 μm.

<Source / drain formation process>
This step is a step of forming at least one of a source electrode and a drain electrode by subjecting a coating film formed using a predetermined conductive film forming composition to heat baking or light baking. More specifically, the conductive film forming composition is applied onto the gate insulating film layer in the laminate including the support, the gate electrode, and the gate insulating film layer to form a coating film, Heat baking or light baking is performed. In the following, an embodiment in which both the source electrode and the drain electrode are formed using the conductive film forming composition will be described in detail, but only one of the source electrode and the drain electrode is used using the conductive film forming composition. May be formed.
Below, the composition for electrically conductive film formation used at this process is explained in full detail first.

<Composition for forming conductive film>
The composition for forming a conductive film (hereinafter also simply referred to as a composition) is selected from the group consisting of copper oxide particles (A) having an average primary particle size of 100 nm or less and Group 8 to 11 elements of the periodic table. It contains metal particles or salt (B) containing at least one metal element, and an alcohol compound (C). Hereinafter, the components contained in the composition will be described in detail.

<< Copper oxide particles (A) with an average primary particle diameter of 100 nm or less >>
The composition for forming an electrically conductive film includes copper oxide particles (A) having an average primary particle diameter of 100 nm or less (hereinafter sometimes simply referred to as “copper oxide particles (A)”). In the copper oxide particles (A), the copper oxide is reduced to metallic copper by a sintering process described later, and constitutes a metal conductor in the electrode film.
As the copper oxide, copper (I) oxide, copper (II) oxide or a mixture thereof is preferable, and copper (II) oxide is more preferable because it is available at low cost and is more stable in the air.

  The “copper oxide” in the present invention is a compound that does not substantially contain copper that has not been oxidized. Specifically, in crystal analysis by X-ray diffraction, a peak derived from copper oxide is detected, and metallic copper. It refers to a compound for which no peak is detected. The phrase “substantially free of copper” means that the copper content is 1% by mass or less based on the copper oxide particles.

Although the average primary particle diameter of copper oxide particle (A) will not be specifically limited if it is 100 nm or less, 1-80 nm is preferable and 10-50 nm is more preferable. As the average primary particle size is smaller, copper oxide is more easily reduced, and a conductive film having high conductivity can be produced even when sintered at a lower sintering temperature. When the average primary particle size is 10 nm or more, better dispersion stability can be obtained.
The average primary particle diameter of the copper oxide particles (A) is the horizontal ferret diameter and vertical ferret diameter of 100 particles randomly selected from a scanning electron microscope (hereinafter sometimes referred to as “SEM”) image. The diameter is measured, and the larger measured value among them is calculated as the primary particle diameter of the particles by arithmetic averaging. When the horizontal ferret diameter and the vertical ferret diameter are the same, any value may be used.

<< Metal particles or salt (B) containing at least one metal element selected from the group consisting of Group 8 to 11 elements in the periodic table >>
The conductive film forming composition is a metal particle or salt (B) containing at least one metal element selected from the group consisting of Group 8 to 11 elements of the periodic table (hereinafter simply referred to as “Group 8 to 11”). Elemental metal particles or salt (B) ”).

  In the present invention, the Group 8-11 elements are iron (Fe), ruthenium (Ru), osmium (Os), cobalt (Co) in which stable isotopes exist among Groups 8-11 of the IUPAC periodic table. ), Rhodium (Rh), iridium (Ir), nickel (Ni), palladium (Pd), platinum (Pt), copper (Cu), silver (Ag), and gold (Au). The Group 8-11 element is preferably palladium, rhodium, platinum or a combination of two or more of these, more preferably palladium, platinum or a combination thereof, and even more preferably palladium.

  In the heat treatment or light irradiation treatment in producing the source electrode and the drain electrode using the conductive film forming composition of the present invention, metal ions contained in the metal particles containing the metal element or the salt containing the metal element The simple substance of the metal produced by reduction of the copper promotes the reduction of the copper oxide particles (A) and promotes the fusion of the copper particles produced by reducing the copper oxide of the copper oxide particles (A). A conductive film (electrode) having conductivity can be manufactured.

(Metal particles)
Metal particles containing at least one metal element selected from the group consisting of Group 8 to 11 elements of the Periodic Table (hereinafter sometimes simply referred to as “Group 8 to 11 metal particles (B1)”). , Metal particles containing one or more elements selected from iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver and gold.
The Group 8-11 metal particles (B1) are metal particles containing a Group 8-11 element, preferably 85% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more.
The surface of the Group 8-11 metal particles (B1) may be coated with a coating agent such as sodium polyacrylate or a protective colloid in order to prevent oxidation, aggregation and the like.

Although the average primary particle diameter of a Group 8-11 metal particle (B1) is not specifically limited, 1-50 nm is preferable, 1-10 nm is more preferable, and 1-5 nm is further more preferable.
The average primary particle diameter of the Group 8-11 metal particles (B1) was measured by measuring the horizontal ferret diameter and the vertical ferret diameter of 100 particles randomly selected from the SEM image. One of the measured values was calculated as the primary particle diameter of the particles by arithmetic averaging. When the horizontal ferret diameter and the vertical ferret diameter are the same, any value may be used.

(salt)
The salt of at least one metal element selected from the group consisting of Group 8 to 11 elements of the periodic table (hereinafter sometimes referred to as “Group 8 to 11 metal salt (B2)”) is iron or ruthenium. , Osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, and a salt (including a complex) containing one or more elements selected from gold and gold. Group 8-11 metal salts (B2) include palladium (II) chloride, halide salts such as chloride such as potassium tetrachloroparadate; nitrates such as palladium nitrate; sulfates; carbonates; Carboxylates such as acetates such as II); ammine complexes; tetraammine nitrates such as tetraamminepalladium (II) nitrate and tetraammineplatinum (II) nitrate; metal carbonyls such as triruthenium dodecacarbonyl (dodecacarbonyltriruthenium) Complexes; acetylacetonate salts such as di (acetylacetonato) palladium; phosphines such as tetrakis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) platinum, dichloro [bis (1,2-diphenylphosphino) ethane] nickel Complex; bis (1,5-cyclooctane Diene complexes such as diene) platinum and bis (1,5-cyclooctadiene) nickel; π-allyl complexes such as chloro (π-allyl) palladium dimer; pentakis (trichlorostanato) paradate, pentakis (trichlorostanato) platinate And trichlorostanato complexes such as diethyl (2,2′-bipyridyl) palladium; and benzalacetone complexes such as di (benzalacetone) palladium and tri (benzalacetone) dipalladium.
Among them, metal particles containing at least one metal element selected from the group consisting of Group 10 elements of the Periodic Table in that the migration resistance between the electrodes is more excellent and the electrode adhesion is more excellent, or A salt is preferable, and a salt containing palladium (palladium salt) is more preferable.

<< Alcohol Compound (C) >>
The composition for electrically conductive film formation used for the manufacturing method of the organic thin-film transistor of this invention contains an alcohol compound (C). The alcohol compound (C) acts as a reducing agent for reducing the copper oxide of the copper oxide particles (A) during the heat treatment.

  The alcohol compound (C) is not particularly limited as long as it is a compound having one or more alcoholic hydroxy groups in one molecule.

  Specific examples of the alcohol compound (C) include methanol, ethanol, propanol, 2-propanol, allyl alcohol, butanol, 2-butanol, pentanol, 2-pentanol, 3-pentanol, and cyclopentanol. , Hexanol, 2-hexanol, 3-hexanol, cyclohexanol, heptanol, 2-heptanol, 3-heptanol, 4-heptanol, cycloheptanol, octanol, 2-octanol, 3-octanol, 4-octanol, cyclooctanol, nonanol 2-nonanol, 3,5,5-trimethyl-1-hexanol, 3-methyl-3-octanol, 3-ethyl-2,2-dimethyl-3-pentanol, 2,6-dimethyl-4-heptanol, Decanol, -Decanol, 3,7-dimethyl-1-octanol, 3,7-dimethyl-3-octanol, undecanol, dodecanol, 2-dodecanol, 2-butyl-1-octanol, tridecanol, tetradecanol, 2-tetradecanol , Monovalent alcohols such as pentadecanol, hexadecanol, 2-hexadecanol, heptadecanol, octadecanol, 1-phenethyl alcohol, 2-phenethyl alcohol; ethylene glycol, 1,3-propanediol, 1 , 2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,2-hexanediol, 1,5-hexanediol, 1, 6-hexanediol, 2,5-hexanediol, 1,7 Heptanediol, 1,2-octanediol, 1,8-octanediol, 1,3-nonanediol, 1,9-nonanediol, 1,2-decanediol, 1,10-decanediol, 2,7-dimethyl -3,6-octanediol, 2,2-dibutyl-1,3-propanediol, 1,2-dodecanediol, 1,12-dodecanediol, 1,2-tetradecanediol, 1,14-tetradecanediol, 2, , 2,4-Trimethyl-1,3-pentanediol, 2,4-pentanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1-hydroxymethyl-2- (2-hydroxyethyl) Cyclohexane, 1-hydroxy-2- (3-hydroxypropyl) cyclohexane, 1-hydroxy-2 -(2-hydroxyethyl) cyclohexane, 1-hydroxymethyl-2- (2-hydroxyethyl) benzene, 1-hydroxymethyl-2- (3-hydroxypropyl) benzene, 1-hydroxy-2- (2-hydroxyethyl) ) Divalent alcohols such as benzene, 1,2-benzyldimethylol, 1,3-benzyldimethylol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol; glycerin (propane- 1,2,3-triol), butane-1,2,4-triol, hexane-1,2,6-triol, 3-methylpentane-1,3,5-triol, trimethylolpropane (2-hydroxymethyl) Trivalent alcohols such as 2-ethylpropane-1,3-diol); Tan-1,3,5,7-tetraol, etc. tetravalent alcohols such as pentaerythritol (2,2-bis (hydroxymethyl) -1,3-propanediol) and the like.

  The alcohol compound (C) preferably contains a divalent or trivalent alcohol, and more preferably contains a trivalent alcohol in terms of better migration resistance between electrodes and electrode adhesion. As the divalent alcohol, trimethylolpropane is particularly preferable.

"solvent"
The composition for forming a conductive film may further contain a solvent (however, the alcohol compound (C) is not included). As the solvent, copper oxide particles (A), metal particles of Group 8 to 11 elements or salts (B) and alcohol compounds (C) can be dispersed or dissolved, and particularly those that do not react with them. Without limitation, alcohol is not included. Examples of the solvent include one selected from water, ethers, esters, hydrocarbons, and aromatic hydrocarbons, or a mixture of two or more compatible.

As the solvent, water, an alkyl ether derived from a water-soluble alcohol, an alkyl ester derived from a water-soluble alcohol, or a mixture thereof is preferably used because of excellent compatibility with the alcohol compound (C).
As water, what has the purity of the level more than ion-exchange water, for example, reverse osmosis filtered water (RO water), milli Q water, distilled water, etc. are preferable.
Among these solvents, it is particularly preferable to use water as the main solvent because the boiling point is not too high. The main solvent is a solvent having the highest content in the solvent.

《Other ingredients》
The conductive film-forming composition contains other components in addition to the copper oxide particles (A), the metal particles or salts (B) of Group 8 to 11 elements, the alcohol compound (C), and the solvent. Also good.
For example, the composition for forming a conductive film may contain a surfactant. The surfactant plays a role of improving the dispersibility of the copper oxide particles. The type of the surfactant is not particularly limited, and examples thereof include an anionic surfactant, a cationic surfactant, a nonionic surfactant, a fluorine surfactant, and an amphoteric surfactant. These surfactants can be used alone or in combination of two or more.

The composition for forming a conductive film comprises a mixture of copper oxide particles (A), group 8-11 metal particles or salts (B), an alcohol compound (C), and a solvent (D), if desired. Can be manufactured.
The mass ratio (B / A) of the copper oxide particles (A) and the metal particles or the salt (B) of the group 8 to 11 element in the conductive film forming composition is not particularly limited, but the source electrode and / or The adhesion between the drain electrode and the gate insulating film layer is more excellent, the migration resistance between the electrodes is excellent, or the mobility of the organic thin film transistor is more excellent (hereinafter simply referred to as “the effect of the present invention is more excellent”). 0.005-0.1 is preferable, and 0.01-0.05 is more preferable.
The mass ratio (C / A) between the copper oxide particles (A) and the alcohol compound (C) in the composition for forming a conductive film is not particularly limited, but is 0.1 to 0.1 in that the effect of the present invention is more excellent. 10 is preferable, and 0.3 to 6.0 is more preferable.
The mass ratio (D / A) between the copper oxide particles (A) and the solvent (D) in the composition for forming a conductive film is not particularly limited, but is 0.2 to 5 in that the effect of the present invention is more excellent. 0.0 is preferable, and 0.3 to 3.0 is more preferable.

(Production method of electrode)
The source electrode and the drain electrode can be formed by subjecting a coating film formed using the above-described conductive film forming composition to heat baking or light baking. More specifically, the composition for forming a conductive film described above is applied on the gate insulating film layer (applied in a pattern), and the obtained coating film is subjected to heat baking or light baking to obtain a source. An electrode and a drain electrode are formed.

The method for applying the conductive film forming composition is not particularly limited, and a known method is employed. For example, the composition for forming a conductive film can be patterned at a predetermined position by a printing method such as letterpress printing, screen printing, planographic printing, intaglio printing, stencil printing, or ink jet printing. In general, when the conductive film forming composition is applied, it is applied in a pattern so as to have a predetermined shape of the source electrode and the drain electrode. Moreover, the thickness of the coating film formed is adjusted so that it may become the suitable thickness of the source electrode and drain electrode which are mentioned later.
The ink jet method is a method of patterning by discharging a conductive film forming composition from an ink jet head. As a method of discharging from the ink jet head, an on-demand type such as a piezo method or a bubble jet ^(R) method, Patterning can be performed by a known method such as a continuous jet type ink jet method such as an electrostatic suction method.
In addition, after the said application | coating, you may give a drying process as needed. By applying the drying treatment, the solvent in the coating film can be removed.

  Next, a conductive film is formed by subjecting the obtained coating film (layer of the composition for forming a conductive film) to a sintering process such as heat baking or light baking, and the source electrode and the drain electrode are formed. .

There are no particular restrictions on the heat treatment conditions during the baking, but a conductive film (source electrode and drain electrode) that is more excellent in conductivity can be formed, and the electrode temperature is higher, and the heating temperature is the gate insulating film. The glass transition temperature (Tg) or higher of the organic insulating material in the layer is preferable.
As heat treatment conditions in the case of heat firing, first, the heating temperature is preferably 150 to 220 ° C, more preferably 160 to 200 ° C. The heating time is preferably 5 to 120 minutes and more preferably 5 to 30 minutes. The heating means is not particularly limited, and known heating means such as an oven and a hot plate can be used.

  Unlike the above-mentioned heat-firing, the light irradiation treatment at the time of photo-firing makes it possible to reduce and sinter to metallic copper by irradiating light on the part to which the coating film is applied at room temperature for a short time. The base material (gate insulating film layer) is not deteriorated by heating for a long time, and the adhesion of the conductive film to the base material becomes better.

The light source used in the light irradiation treatment is not particularly limited, and examples thereof include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, and a carbon arc lamp. Examples of radiation include electron beams, X-rays, ion beams, and far infrared rays. Further, g-line, i-line, deep-UV light, and high-density energy beam (laser beam) are also used.
Specific examples of preferred embodiments include scanning exposure with an infrared laser, high-illuminance flash exposure such as a xenon discharge lamp, and infrared lamp exposure.

  The light irradiation is preferably light irradiation with a flash lamp, and more preferably pulsed light irradiation with a flash lamp. Irradiation with high-energy pulsed light can concentrate and heat the surface of the portion to which the coating film has been applied in a very short time, so that the influence of heat on the substrate can be extremely reduced.

The irradiation energy of the pulse light is preferably 1~100J / cm ^2, more preferably 1~30J / cm ^2, preferably 1μ seconds ~100m sec as a pulse width, and more preferably 10μ sec ~10m seconds. The irradiation time of the pulsed light is preferably 1 to 100 milliseconds, more preferably 1 to 50 milliseconds, and further preferably 1 to 20 milliseconds.
Note that the light irradiation treatment can be performed in an air atmosphere, an inert gas atmosphere, or the like, but is preferably performed in an air atmosphere.

  The heat treatment and the light irradiation treatment may be performed alone or both may be performed simultaneously. Moreover, after performing one process, you may perform the other process further.

  Although the thickness of the source electrode and drain electrode to be formed is not particularly limited, 10 nm to 1 μm is preferable, and 50 to 500 nm is more preferable.

<Organic semiconductor formation process>
This step is a step of further forming an organic semiconductor layer on the gate insulating film layer on which the above-described source electrode and drain electrode are disposed. More specifically, in this step, the organic semiconductor layer is formed so as to cover the source electrode, the drain electrode, and the gate insulating film layer in a region sandwiched between the source electrode and the drain electrode. Note that this step is not limited to the mode shown in FIG. 1. For example, as shown in the organic thin film transistor 100 in FIG. 2, the gate insulating film layer 16 in a region sandwiched between the source electrode 18 and the drain electrode 20 is covered. It is sufficient that at least the organic semiconductor layer 22 is formed.
Below, the material which comprises an organic-semiconductor layer is explained in full detail.

  A π-conjugated material is used as the organic semiconductor material. Examples of the π-conjugated material include polypyrroles such as polypyrrole, poly (N-substituted pyrrole), poly (3-substituted pyrrole), and poly (3,4-disubstituted pyrrole); polythiophene and poly (3-substituted thiophene) ), Poly (3,4-disubstituted thiophene), polythiophenes such as polybenzothiophene; polyisothianaphthenes such as polyisothianaphthene; polychenylene vinylenes such as polychenylene vinylene; poly (p-phenylene) Poly (p-phenylene vinylenes) such as vinylene; polyanilines such as polyaniline, poly (N-substituted aniline), poly (3-substituted aniline), poly (2,3-substituted aniline); polyacetylenes such as polyacetylene Polydiacetylenes such as polydiacetylene; polyazulenes such as polyazulene; polypyrene Polypyrenes; polycarbazoles such as polycarbazole and poly (N-substituted carbazole); polyselenophenes such as polyselenophene; polyfurans such as polyfuran and polybenzofuran; poly (p-phenylene) such as poly (p-phenylene) -Phenylene) s; polyindoles such as polyindole; polypyridazines such as polypyridazine; naphthacene, pentacene, hexacene, heptacene, dibenzopentacene, tetrabenzopentacene, pyrene, dibenzopyrene, chrysene, perylene, coronene, terylene, ovalene , Derivatives of polyacenes such as quaterylene and circumanthracene, and polyacenes substituted with functional groups such as atoms such as N, S and O, and carbonyl groups (triphenodioxazine, triphenodithiazine, hexacene-6) , 15-quinone, etc.); polymers such as polyvinyl carbazole, polyphenylene sulfide, polyvinylene sulfide; polycyclic condensates described in JP-A No. 11-195790 can be used.

  In addition, these polymers have the same repeating unit, for example, α-sexual thiophene, α, ω-dihexyl-α-sexual thiophene, α, ω-dihexyl-α-quinkethiophene, α, ω, which are thiophene hexamers. Oligomers such as -bis (3-butoxypropyl) -α-sexithiophene and styrylbenzene derivatives can also be suitably used.

  Further, metal phthalocyanines such as copper phthalocyanine and fluorine-substituted copper phthalocyanine described in JP-A No. 11-251601, naphthalene 1,4,5,8-tetracarboxylic acid diimide, N, N′-bis (4-trifluoromethyl) Benzyl) naphthalene 1,4,5,8-tetracarboxylic acid diimide with N, N′-bis (1H, 1H-perfluorooctyl), N, N′-bis (1H, 1H-perfluorobutyl) and N, N '-Dioctylnaphthalene-1,4,5,8-tetracarboxylic acid diimide derivative, naphthalene tetracarboxylic acid diimides such as naphthalene-2,3,6,7-tetracarboxylic acid diimide, and anthracene-2,3,6 Condensed rings such as anthracene tetracarboxylic acid diimides such as 1,7-tetracarboxylic acid diimide Tetracarboxylic acid diimides, C60, C70, C76, C78, C84 etc. fullerenes, carbon nanotubes, merocyanine dyes such as SWNT, and the like dyes such as hemicyanine dyes.

  Among these π-conjugated materials, thiophene, vinylene, chelenylene vinylene, phenylene vinylene, p-phenylene, a substituent thereof, or two or more of these are used as a repeating unit, and the number n of the repeating units is 4 to 4 At least one selected from the group consisting of 10 oligomers or polymers having 20 or more repeating units, condensed polycyclic aromatic compounds such as pentacene, fullerenes, condensed ring tetracarboxylic diimides, and metal phthalocyanines. Is preferred.

  Other organic semiconductor materials include tetrathiafulvalene (TTF) -tetracyanoquinodimethane (TCNQ) complex, bisethylenetetrathiafulvalene (BEDTTTTF) -perchloric acid complex, BEDTTTTF-iodine complex, TCNQ-iodine complex. Organic molecular complexes such as can also be used. Furthermore, (sigma) conjugated polymers, such as polysilane and polygermane, and organic-inorganic hybrid material as described in Unexamined-Japanese-Patent No. 2000-260999 can also be used.

  Examples of the organic semiconductor material include DNTT (dinaphtho [2,3-b: 2 ′, 3′-f] thieno [3,2-b] thiophene), DPh-BTBT (2,7-diphenyl [1] benzothieno). [3,2-b] [1] benzothiophene), DT-BTT (2,6-ditolylbenzo [1,2-b: 4,5-b ′] dithiophene), DPh-BTT (2,6-diphenylbenzo) [1,2-b: 4,5-b ′] dithiophene), TIPS pentacene (6,13-bis (triisopropylsilylethynyl) pentacene), TES pentacene (6,13-bis ((triethylsilyl) ethynyl) pentacene ), ADT (anthra [2,3-b: 6,7-b ′] dithiophene), DFH-4T (5,5 ″ ″-bis (tridecafluorohexyl) -2,2 ′: 5 ′, 2 ´ ': 5 ″, 2 ″ ″-tetrathiophene), TES-ADT (5,11-bis (triethylsilylethynyl) anthradithiophene), 1,2,3,4,5,6,7,8- Octafluoro-9,10-bis (mesitylethynyl) anthracene, 1,2,3,4,5,6,7,8-octafluoro-9,10-bis [4- (trifluoromethyl) phenyl] anthracene , DH-FTTF (5,5'-bis (7-hexyl-9H-fluoren-2-yl) -2,2'-bithiophene), NSFAAP (13,6-N-sulfinylacetamidopentacene), pentacene-N- Examples also include sulfinyl-tert-butylcarbamic acid, 9,10-bis [(triisopropylsilyl) ethynyl] anthracene and the like.

  In the present invention, the organic semiconductor layer is made of, for example, a material having a functional group such as acrylic acid, acetamide, dimethylamino group, cyano group, carboxyl group, nitro group, benzoquinone derivative, tetracyanoethylene and tetracyanoquino Materials that accept electrons, such as dimethane and derivatives thereof, materials having functional groups such as amino group, triphenyl group, alkyl group, hydroxyl group, alkoxy group, phenyl group, phenylenediamine, etc. Including substituted amines, anthracene, benzoanthracene, substituted benzoanthracenes, pyrene, substituted pyrene, carbazole and derivatives thereof, tetrathiafulvalene and derivatives thereof, and the like materials that serve as donors of electrons, Even if a so-called doping treatment is applied There.

  Doping means introducing 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.

Either an acceptor or a donor can be used as the dopant used in the present invention. As this acceptor, Cl ₂ , Br ₂ , I ₂ , ICl, ICl ₃ , IBr ₃ , halogen such as IF, PF ₅ , AsF ₅ , SbF ₅ , BF ₃ , BC1 ₃ , Lewis acid such as BBr ₃ , SO ₃ , HF , HC1, HNO ₃ , H ₂ SO ₄ , HClO ₄ , FSO ₃ H, ClSO ₃ H, CF ₃ SO ₃ H and other protic acids, acetic acid, formic acid, amino acids and other organic acids, FeCl ₃ , FeOCl, TiCl ₄ , Transition metal compounds such as ZrCl ₄ , HfCl ₄ , NbF ₅ , NbCl ₅ , TaCl ₅ , MoCl ₅ , WF ₅ , WCl ₆ , UF ₆ , LnCl ₃ (Ln = La, Ce, Nd, Pr and other lanthanoids and Y) ^{, Cl -, Br -, I} -, ClO 4-, PF 6-, AsF 5-, SbF 6-, BF 4-, sulfonate anion And the like can be mentioned electrolyte anions.

As donors used in the present invention, alkali metals such as Li, Na, K, Rb and Cs, alkaline earth metals such as Ca, Sr and Ba, Y, La, Ce, Pr, Nd, Sm, Eu, Rd metals such as Gd, Tb, Dy, Ho, Er, Yb, ammonium ions, R ₄ P ⁺ , R ₄ As ⁺ , R ₃ S ⁺ (each R represents an alkyl group, an aryl group, etc.), acetylcholine, and the like. Can be mentioned.

  As a method for doping these dopants, either an organic semiconductor layer is prepared in advance and a dopant is introduced later, or a dopant is introduced when an organic semiconductor layer is produced can be used. As doping of the former method, gas phase doping using a dopant in a gas state, liquid phase doping in which a solution or liquid dopant is brought into contact with the organic semiconductor layer, and a dopant in a solid state brought into contact with the organic semiconductor layer A solid phase doping method for diffusion doping can be mentioned. In liquid phase doping, the efficiency of doping can be adjusted by applying electrolysis. In the latter method, a mixed solution or dispersion of an organic semiconductor compound and a dopant may be simultaneously applied and dried. For example, when using a vacuum evaporation method, a dopant can be introduce | transduced by co-evaporating a dopant with an organic-semiconductor compound. When an organic semiconductor layer is formed by a sputtering method, a dopant can be introduced into a thin film by sputtering using a binary target of an organic semiconductor compound and a dopant. Still other methods include chemical doping such as electrochemical doping, photoinitiated doping, and physics such as ion implantation shown in a publication (Industrial Materials, Vol. 34, No. 4, p. 55, 1986). Any of the chemical dopings can be used.

  The method for producing the organic semiconductor layer is not particularly limited, and for example, vacuum deposition, molecular beam epitaxial growth, ion cluster beam, low energy ion beam, ion plating, CVD, sputtering, plasma polymerization, electrolysis Examples include polymerization methods, chemical polymerization methods, spray coating methods, spin coating methods, blade coating methods, dip coating methods, cast methods, roll coating methods, bar coating methods, die coating methods, and LB methods, which can be used depending on the material. . However, in terms of productivity, spin coating method, blade coating method, dip coating method, roll coating method, bar coating method, die coating method, etc. that can form a thin film easily and precisely using an organic semiconductor solution. Liked. Alternatively, the organic semiconductor layer may be formed by discharging an organic semiconductor solution or dispersion with an ink jet and drying and removing the solvent.

  Although there is no restriction | limiting in particular as the film thickness of an organic-semiconductor layer, The characteristic of the obtained transistor is largely influenced by the film thickness of the active layer which consists of organic semiconductors, and the film thickness changes with organic semiconductors. However, 1 micrometer or less is preferable and 10-300 nm is more preferable.

<< Second Embodiment >>
FIG. 3 shows a schematic view of one embodiment of a top gate-top contact type organic thin film transistor.
As shown in FIG. 3, the organic thin film transistor 200 includes a support 12, an organic semiconductor layer 22 disposed on the support 12, and a source electrode 18 and a drain electrode 20 disposed so as to be in contact with the organic semiconductor layer 22. The gate insulating film layer 16 disposed on the organic semiconductor layer 22 so as to cover the source electrode 18 and the drain electrode 20 is in contact with the surface of the gate insulating film layer 16 opposite to the source electrode 18 and the drain electrode 20 side. And the gate electrode 14 arranged as described above.
The members constituting the organic thin film transistor 200 shown in FIG. 3 are the same as the members constituting the organic thin film transistor 10 shown in FIG. 1 described above, and the same members are denoted by the same reference numerals and description thereof is omitted. . The organic thin film transistor 200 shown in FIG. 3 and the organic thin film transistor 10 shown in FIG.
As in the first embodiment described above, at least one of the source electrode and the drain electrode in the organic thin film transistor 200 is heated or light-baked with respect to the coating film formed using the conductive film-forming composition. It is formed by applying. That is, the method for manufacturing the organic thin film transistor 200 includes at least the source / drain formation step.
The method for producing the organic thin film transistor 200 is not particularly limited, and it is sufficient that the organic thin film transistor 200 has the source / drain forming step. Usually, the step of forming the organic semiconductor layer 22 on the support 12 (organic semiconductor forming step), Step of forming source electrode 18 and drain electrode 20 (source / drain formation step), step of forming gate insulating film layer 16 (insulating film layer forming step), and step of forming gate electrode 14 (gate forming step) Are preferably carried out in this order. The procedure of each process is the same as the procedure of each process in the first embodiment described above.

  Note that the organic semiconductor layer 22 is not limited to the mode shown in FIG. 3, and the organic semiconductor layer is formed in a region sandwiched between the source electrode 18 and the drain electrode 20 as shown in the organic thin film transistor 300 in FIG. 4. It is sufficient that at least 22 is formed.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.

[Preparation of composition for forming conductive film]
<Composition 1 for electrically conductive film formation>
Copper oxide particles (CAI Kasei Co., Ltd., NanoTek CuO; average primary particle size 48 nm) (45 parts by mass) and water (20 parts by mass) are mixed, and a revolving mixer (Sinky Corp., Awatori Kentaro ARE-310) Was treated for 5 minutes to obtain an aqueous dispersion of copper oxide particles. Trimethylolpropane (225 parts by weight) and palladium acetate (2 parts by weight) are added to an aqueous dispersion of copper oxide particles, and the mixture is processed for 5 minutes with a rotation and revolution mixer (Shinky Corporation, Awatori Neritaro ARE-310). A composition for forming a conductive film was prepared. This composition for forming a conductive film was designated as Composition 1 for forming a conductive film.

<Composition 2 for electrically conductive film formation>
A conductive film-forming composition 2 was prepared in the same manner as the conductive film-forming composition 1, except that 1,6-hexanediol (225 parts by weight) was used instead of trimethylolpropane (225 parts by weight). did.

<Composition 3 for forming conductive film>
A conductive film forming composition 3 was prepared in the same manner as the conductive film forming composition 1 except that 1,7-heptanediol (225 parts by weight) was used in place of trimethylolpropane (225 parts by weight). did.

<Composition 4 for forming conductive film>
A conductive film forming composition 4 was prepared in the same manner as the conductive film forming composition 1 except that triruthenium dodecacarbonyl (2 parts by weight) was used instead of palladium acetate (2 parts by weight).

<Conductive film forming composition 5>
A conductive film forming composition 5 was prepared in the same manner as the conductive film forming composition 1 except that palladium acetate was not used.

  Table 1 summarizes the compositions of the conductive film forming compositions 1 to 5.

[Example 1]
1. Production of Organic Semiconductor Transistor Element (Organic Thin Film Transistor) The bottom gate / bottom contact type organic semiconductor transistor element shown in FIG. 1 was produced.
(Gate electrode formation)
On a non-alkali glass substrate (5 cm × 5 cm), silver nanoink (silver nanocolloid H-1, manufactured by Mitsubishi Materials Corporation) is printed by DMP2831 (1 picoliter head) by ink jet printing with a width of 100 μm and a film thickness of 100 nm. After forming a pattern, the gate electrode wiring was formed by baking at 200 degreeC for 90 minute (s) on a hotplate in air | atmosphere.
(Gate insulation film layer formation)
A 10% by mass (solid content concentration) ethanol solution (5 parts by mass as solid content) of an alkyl acetalized polyvinyl alcohol (ESREC ^(R) KS-3, manufactured by Sekisui Chemical Co., Ltd .; solid content 97% by mass) The glass substrate was dropped on the glass substrate, coated by spin coating (1000 rpm, 120 seconds), and heated at 150 ° C./30 minutes to form a gate insulating film layer (film thickness: 500 nm).
(Source / drain electrode formation)
A metal mask having a plurality of patterns shown in FIG. 5 was placed on the center of the substrate coated with the insulating film and irradiated with UV ozone for 30 minutes to modify the mask opening to a hydrophilic treatment surface. In FIG. 5, the metal mask 51 includes a mask portion 52 that blocks light and openings 53 and 54.
The conductive film forming composition 1 was ejected by inkjet printing using DMP2831 (1 picoliter head) around the modified portion to form source / drain electrode patterns having a channel length of 50 μm and a channel width of 320 μm. The obtained substrate was heated and fired at 200 ° C. for 90 minutes on a hot plate in an N ₂ atmosphere (in the glove box, an environment having an oxygen concentration of 20 ppm or less), thereby forming a copper electrode having a thickness of 200 nm.
(Organic semiconductor layer formation)
A benzene 0.5 wt% solution of TIPS pentacene (manufactured by Sigma-Aldrich) was prepared, and filtered through a 0.2 μm membrane filter to prepare an organic semiconductor solution. The obtained solution was dropped on the substrate on which the source / drain electrodes were formed, and coated by spin coating (1000 rpm, 120 seconds). The organic semiconductor layer was produced by drying at room temperature for 2 hours as it was.

2. Evaluation of migration resistance Under the condition that temperature / humidity = 85 ° C./85% with 30V voltage applied to each wiring of the produced organic semiconductor transistor element, until the insulation resistance value is reduced to 10 ⁶ or less. The migration resistance was evaluated according to the following evaluation criteria. The evaluation results are shown in the column of migration resistance in Table 2.
A: Dielectric breakdown time is 1000 hours or more B: Dielectric breakdown time is 500 hours or more to less than 1000 hours C: Dielectric breakdown time is 100 hours or more to less than 500 hours D: Dielectric breakdown time is less than 100 hours

3. Electrode Adhesion Evaluation Tape in accordance with JIS K 6854-1: 1999, using the substrate at the stage where the source / drain electrodes were prepared on the gate insulating film layer before forming the organic semiconductor layer as a test piece for electrode adhesion evaluation A peeling test was conducted, and the level of peeling of the wiring portion (source / drain electrode) was evaluated according to the following evaluation criteria. The evaluation results are shown in the column of electrode adhesion in Table 2.
A: No peeling at all B: Peeling at an area of less than 5% C: Peeling at an area of 5% or more and less than 20% D: Peeling at an area of 20% or more and less than 90% E: Peeling of an area of 90% or more Yes

4). Carrier Mobility Evaluation Carrier mobility was measured using a semiconductor device analyzer B1500A (manufactured by Agilent). The measurement results are shown in the carrier mobility column of Table 2.

[Examples 2 and 3]
An organic thin film transistor was fabricated and evaluated in the same manner as in Example 1 except that the thickness of the gate insulating film layer was changed to 300 nm and 1000 nm, respectively. The evaluation results are shown in Table 2.

[Example 4]
As in Example 1, except that an amorphous fluororesin solution (Cytop ^(R) CTX-807AP, manufactured by Asahi Glass Co., Ltd.) was used as a solution for forming the gate insulating film layer. The organic thin film transistor was fabricated and evaluated in various ways. The evaluation results are shown in Table 2.

[Example 5]
Except for the point that the gate insulating film layer was formed using an amorphous fluororesin solution (Teflon ^(R) AF-1601S, manufactured by Mitsui DuPont Fluorochemical Co., Ltd.) as a solution for forming the gate insulating film layer. In the same manner as in Example 1, an organic thin film transistor was prepared and various evaluations were performed. The evaluation results are shown in Table 2.

[Example 6]
As a solution for forming a gate insulating film layer, a solution in which polysilsesquioxane (HBSQ101, manufactured by Arakawa Chemical Industries, Ltd.) (100 parts by mass), isophorone diisocyanate (10 parts by mass) and 100 parts by weight of dimethyl glycol is mixed. An organic thin film transistor was prepared and evaluated in the same manner as in Example 1 except that the gate insulating film layer was formed by using it. The evaluation results are shown in Table 2.

[Examples 7 to 9]
In Examples 7 to 9, organic thin film transistors were prepared and evaluated in the same manner as in Example 4 except that the conductive film forming compositions 2 to 4 were used as the conductive film forming compositions, respectively. . The evaluation results are shown in Table 2.

[Examples 10 to 12]
In Examples 10 to 12, firing at the time of forming the source / drain electrodes is performed by heat treatment to light irradiation treatment with pulsed light (Xenon's light sintering apparatus Sinteron 2000, irradiation energy: 5 J / m ² , pulse width: 2 msec. The organic thin film transistor was prepared and various evaluations were performed in the same manner as in Examples 7 to 9 except for the points changed to (1). The evaluation results are shown in Table 2.

[Example 13]
In Example 13, firing during the formation of the source / drain electrodes is changed from heat treatment to light irradiation treatment with pulsed light (Xenon's photosintering apparatus Sinteron 2000, irradiation energy: 5 J / m ² , pulse width: 2 msec). Except for the changed points, the organic thin film transistor was produced and evaluated in the same manner as in Example 6. The evaluation results are shown in Table 2.

[Comparative Example 1]
In Comparative Example 1, an organic thin film transistor was fabricated and evaluated in the same manner as in Example 1 except that the gate insulating film layer was a SiO ₂ vapor deposition film. The evaluation results are shown in Table 2.

[Comparative Example 2]
In Comparative Example 2, an organic thin film transistor was produced and evaluated in the same manner as in Example 1 except that the source electrode and the drain electrode were produced using silver nanocolloid H-1. The evaluation results are shown in Table 2.

[Comparative Example 3]
In Comparative Example 3, as the conductive film forming composition, a conductive film forming composition 5 (containing no metal particles of Group 8 to 11 elements or salts of Group 8 to 11 elements) was used, In the same manner as in Example 1, an organic thin film transistor was produced and carrier mobility was evaluated. The evaluation results are shown in Table 2.

[Comparative Example 4]
In Comparative Example 4, firing during the formation of the source / drain electrodes is changed from heat treatment to light irradiation treatment with pulsed light (Xenon's light sintering apparatus Sinteron 2000, irradiation energy: 5 J / m ² , pulse width: 2 msec). Except for the changed points, the organic thin film transistor was produced and evaluated in the same manner as in Comparative Example 1. The evaluation results are shown in Table 2.

From the comparison between Examples and Comparative Examples, it can be seen that the transistor manufactured by the method for manufacturing an organic thin film transistor of the present invention is excellent in carrier mobility, migration resistance, and electrode adhesion.
From the comparison of Examples 1 to 3, it can be seen that good electrode adhesion is obtained when the thickness of the gate insulating film layer is at least 200 nm to 1 μm.
From the comparison between Example 1 and Examples 4 to 6, it is understood that better electrode adhesion and carrier mobility can be obtained by using a siloxane group-containing polymer or a perfluoro group-containing polymer as a gate insulating film material. .
From the comparison between Example 1 and Examples 7 and 8, it can be seen that when the alcohol compound in the composition for forming a conductive film is a trivalent alcohol, migration resistance superior to that of a divalent alcohol can be obtained. .
From the comparison between Example 1 and Example 9, it can be seen that when a palladium salt is included as a salt of the Group 8-11 element, migration resistance and electrode adhesion are more excellent than when a ruthenium complex is included.
From the comparison between Comparative Example 1 and Example 1, it can be seen that when the gate insulating film layer does not contain an organic compound, the electrode adhesion and the carrier mobility are inferior.
From the comparison between Comparative Example 2 and Example 1, it can be seen that when the source electrode and the drain electrode are formed using silver nanoparticles, the migration resistance, the electrode adhesion, and the carrier mobility are all inferior.
From the comparison between Comparative Example 3 and Example 1, it is understood that the carrier mobility is inferior when neither the metal particles of Group 8-11 elements nor the salt of Group 8-11 elements are contained.
From the comparison between Examples 7 to 9 and Examples 10 to 12, the formation of the source / drain electrodes can be performed by either heat baking or light baking, but it is understood that migration resistance is more excellent when performed by light baking. .

10, 100, 200, 300 Organic thin-film transistor 12 Support 14 Gate electrode 16 Gate insulating film layer 18 Source electrode 20 Drain electrode 22 Organic semiconductor layer 51 Metal mask 52 Mask portions 53, 54 Openings

Claims (9)

A gate electrode, a gate insulating film layer containing an organic insulating material, a source electrode, a drain electrode, and an organic semiconductor layer, the gate insulating film layer and the source electrode, and the gate insulating film layer and the drain A method for producing a bottom gate-bottom contact type or top gate-top contact type organic thin film transistor, wherein the electrodes have a structure in contact with each other,
Copper oxide particles (A) having an average primary particle size of 100 nm or less, and metal particles or salts (B) containing at least one metal element selected from the group consisting of Group 8 to 11 elements of the periodic table; At least one of the source electrode and the drain electrode is formed by subjecting the coating film formed using the composition for forming a conductive film containing the alcohol compound (C) to heat baking or light baking. The manufacturing method of an organic thin-film transistor including a process.   The manufacturing method of the organic thin-film transistor of Claim 1 with which the said organic insulating material contains the organic insulating material which has a siloxane group or a perfluoro group.   The manufacturing method of the organic thin-film transistor of Claim 1 or 2 performed by heat-processing by the said process at the glass transition temperature or more of the said organic insulating material in the said gate insulating film layer.   The manufacturing method of the organic thin-film transistor of any one of Claims 1-3 which forms the said coating film by the printing method.   The said metal particle or salt (B) contains the metal particle or salt containing at least 1 sort (s) of metal element selected from the group which consists of a group 10 element of a periodic table. The manufacturing method of the organic thin-film transistor of description.   The manufacturing method of the organic thin-film transistor of any one of Claims 1-5 in which the said alcohol compound (C) contains trivalent alcohol.   The manufacturing method of the organic thin-film transistor of any one of Claims 1-6 whose film thickness of the said gate insulating film layer is 200 nm-1 micrometer.   The manufacturing method of the organic thin-film transistor of any one of Claims 1-7 whose thickness of the said source electrode and the said drain electrode is 50-500 nm.   The organic thin-film transistor manufactured by the manufacturing method of the organic thin-film transistor of any one of Claims 1-8.