JP6143698B2 - Wiring pattern forming method, organic transistor manufacturing method, and organic transistor - Google Patents

Description

  The present invention relates to a wiring pattern forming method, an organic transistor manufacturing method, and an organic transistor.

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 transistor having a semiconductor film (organic semiconductor layer) is used.
Here, from the viewpoint of improving the performance of the organic transistor, the electrode of the organic transistor is required to have high conductivity and accuracy. Further, high adhesion (electrode adhesion) to the gate insulating film layer or the like is required.
Under such circumstances, Patent Document 1 discloses a method of forming an electrode of an organic transistor by a relief offset method, and describes that a precise electrode (wiring pattern) can be formed by the above method.

JP 2009-224665 A

  On the other hand, when the present inventor formed a wiring pattern using the relief offset method with reference to Patent Document 1, a defect may be found in the formed wiring pattern, or a remaining pattern may be seen in an unnecessary portion. It became clear. That is, it has become clear that printability may be insufficient. In addition, even when a high-precision wiring pattern is formed without any problem in printability, it has been clarified that the conductivity and adhesion of the formed wiring pattern do not always satisfy the level required recently. . And when it used for formation of the electrode of an organic transistor, it became clear that the mobility of an organic transistor may become inadequate.

  Therefore, in view of the above circumstances, the present invention manufactures a wiring pattern forming method excellent in printability, conductivity and adhesion, and an organic transistor excellent in mobility for forming electrodes by the wiring pattern forming method. It aims at providing the manufacturing method of an organic transistor, and the organic transistor manufactured by the said manufacturing method.

As a result of intensive studies on the above problems, the present inventor has, as a wiring pattern formation by a relief offset method, a composition for wiring pattern formation containing two kinds of solvents having specific boiling points and specifying the amount ratio of components. Further, the present inventors have found that the above problems can be solved by using photo-sintering, and have reached the present invention.
That is, the present inventor has found that the above problem can be solved by the following configuration.

(1) Copper nanoparticles (A) having an average primary particle diameter of less than 100 nm, a surfactant (B), a water-soluble organic solvent (C) having a boiling point of 120 ° C. or less, and a water-soluble organic having a boiling point of 200 ° C. or more. The mass ratio (mass ratio X) of the content of the water-soluble organic solvent (D) having a boiling point of 200 ° C. or higher and the content of the copper nanoparticles (A) is 1: 1. A coating film forming step of applying a wiring pattern forming composition of ˜1: 30 on a temporary support and forming a coating film on the temporary support;
A removal step of pressing a plate on which convex portions are formed in a pattern shape against the coating film, and removing a part of the coating film,
A transfer step of transferring the coating film remaining on the temporary support onto a substrate and forming a wiring pattern precursor on the substrate;
A wiring pattern forming method comprising: a photosintering step of photo-sintering the wiring pattern precursor to form a wiring pattern.
(2) In the transfer step, the total content of the water-soluble organic solvent (C) having a boiling point of 120 ° C. or lower and the water-soluble organic solvent (D) having a boiling point of 200 ° C. or higher in the coating film to be transferred and the above The wiring pattern forming method according to (1), wherein a mass ratio (mass ratio Y) with respect to the content of the copper nanoparticles (A) is 1: 1 to 1:33.
(3) The difference between the SP value of the temporary support and the SP value of the water-soluble organic solvent (C) having a boiling point of 120 ° C. or lower is 3.0 to 15.0 [MPa] ^1/2. (1) The wiring pattern forming method according to (2).
(4) The wiring pattern forming method according to any one of (1) to (3), wherein the wiring pattern forming composition further contains water.
(5) The wiring pattern forming method according to any one of (1) to (4), wherein the water-soluble organic solvent (C) having a boiling point of 120 ° C. or lower is ethanol or isopropyl alcohol.
(6) The wiring pattern forming method according to any one of (1) to (5), wherein the water-soluble organic solvent (D) having a boiling point of 200 ° C. or higher is an alcohol.
(7) The wiring pattern forming method according to any one of (1) to (6), wherein the water-soluble organic solvent (D) having a boiling point of 200 ° C. or higher is a divalent or trivalent alcohol.
(8) The wiring pattern forming method according to any one of (1) to (7), wherein a main component of a material forming the temporary support is polydimethylsiloxane.
(9) A method of manufacturing an organic transistor comprising at least a gate electrode, a gate insulating film layer, a source electrode, a drain electrode, and an organic semiconductor layer,
Production of an organic transistor, wherein at least one electrode selected from the group consisting of the gate electrode, the source electrode and the drain electrode is formed by the wiring pattern forming method according to any one of (1) to (8) above Method.
(10) The method for producing an organic transistor according to (9), wherein the gate insulating film layer is formed using a solution containing an insulating material containing an organic substance as a main component.
(11) The organic transistor according to (9) or (10), wherein the organic transistor has a structure in which the gate insulating film layer and the source electrode, and the gate insulating film layer and the drain electrode are in contact with each other. Manufacturing method of organic transistor.
(12) The method for producing an organic transistor according to any one of (9) to (11), wherein the gate insulating film layer has a thickness of 200 to 1000 nm.
(13) The method for producing an organic transistor according to any one of (9) to (12), wherein the gate electrode, the source electrode, and the drain electrode have a thickness of 50 to 500 nm.
(14) An organic transistor manufactured by the method for manufacturing an organic transistor according to any one of (9) to (13).

  As shown below, according to the present invention, a wiring pattern forming method excellent in printability, conductivity, and adhesion, and an organic transistor excellent in mobility for forming electrodes by the wiring pattern forming method are manufactured. The manufacturing method of an organic transistor and the organic transistor manufactured by the said manufacturing method can be provided.

FIG. 1 is a schematic view showing a process of forming a wiring pattern precursor by a reverse printing method. FIG. 2 is a cross-sectional view of one embodiment of a bottom gate-bottom contact organic transistor. FIG. 3 is a cross-sectional view of another embodiment of a bottom gate-bottom contact type organic transistor. FIG. 4 is a cross-sectional view of an embodiment of a top gate-top contact type organic transistor. FIG. 5 is a cross-sectional view of another embodiment of a top gate-top contact type organic transistor. FIG. 6 is a plan view of a glass plate having convex portions formed in the pattern used in the examples.

Below, the wiring pattern formation method of this invention and the manufacturing method of an organic 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.

[Wiring pattern forming method]
The wiring pattern forming method of the present invention (hereinafter, also simply referred to as the method of the present invention) includes a copper nanoparticle (A) having an average primary particle diameter of less than 100 nm, a surfactant (B), and a boiling point of 120 ° C. or lower. It contains at least a water-soluble organic solvent (C) and a water-soluble organic solvent (D) having a boiling point of 200 ° C. or higher. The content of the water-soluble organic solvent (D) having a boiling point of 200 ° C. or higher and the copper nanoparticles (A ) Content ratio of 1: 1 to 1:30 on the temporary support, and a coating film forming step of forming a coating film on the temporary support,
A removal step of pressing a plate on which convex portions are formed in a pattern shape against the coating film, and removing a part of the coating film,
A transfer step of transferring the coating film remaining on the temporary support onto a substrate and forming a wiring pattern precursor on the substrate;
A photo-sintering step of photo-sintering the wiring pattern precursor to form a wiring pattern.

Since the method of this invention takes such a structure, it is thought that it is excellent in printability, electroconductivity, and adhesiveness. The reason is not clear, but it is presumed that it is as follows.
In the method of the present invention, a water-soluble organic solvent (C) having a boiling point of 120 ° C. or lower and a water-soluble organic solvent (D) having a boiling point of 200 ° C. or higher are used in combination, and the water-soluble organic solvent having a boiling point of 200 ° C. or higher ( The composition for wiring pattern formation whose mass ratio of content of D) and content of copper nanoparticles (A) is a specific range is used.
When a coating film is formed on the temporary support using the wiring pattern forming composition, the water-soluble organic solvent (C) having a boiling point of 120 ° C. or less contained in the wiring pattern forming composition is appropriate for the temporary support. Therefore, the coating film is precisely removed by a subsequent removal step. That is, the accuracy of the shape of the coating film remaining on the temporary support is high. Furthermore, since the water-soluble organic solvent (D) having a boiling point of 200 ° C. or higher is contained in the coating film remaining on the temporary support, the coating film has high flexibility, and in the subsequent transfer process, with high accuracy. Transcribed.
And since the coating film (wiring pattern precursor) transferred onto the substrate with such high accuracy is sintered by light sintering, it is possible to form a precise pattern while suppressing damage to the substrate. It becomes possible. As a result, it is considered that a wiring pattern excellent in printability, conductivity, and adhesion can be formed.
Below, after explaining the composition for wiring pattern formation used at a coating-film formation process first, each process is demonstrated.

[Composition for wiring pattern formation]
The composition for forming a wiring pattern (hereinafter also simply referred to as a composition) comprises a copper nanoparticle (A) having an average primary particle size of less than 100 nm, a surfactant (B), and a water-soluble organic compound having a boiling point of 120 ° C. or lower. It contains at least a solvent (C) and a water-soluble organic solvent (D) having a boiling point of 200 ° C. or higher. Here, the mass ratio of the content of the water-soluble organic solvent (D) having a boiling point of 200 ° C. or higher and the content of the copper nanoparticles (A) is 1: 1 to 1:30.

<Copper nanoparticles (A)>
The copper nanoparticles (A) are not particularly limited as long as they are particulate copper having an average primary particle diameter of less than 100 nm. The particulate form refers to a small granular form, and specific examples thereof include a spherical shape and an ellipsoidal shape. It does not have to be a perfect sphere or ellipsoid, and a part may be distorted.
The “copper” in the present invention is a compound that does not substantially contain copper oxide. Although it does not contain copper oxide substantially, it means that content of copper oxide is 1 mass% or less with respect to a copper particle. The content of copper oxide with respect to the copper particles is measured by XRD.
As described above, the average primary particle diameter of the copper nanoparticles (A) is less than 100 nm. Especially, it is preferable that it is 1-90 nm, and it is more preferable that it is 5-60 nm. In addition, the average primary particle diameter in this invention measures the particle diameter (diameter) of at least 50 or more copper particles by transmission electron microscope (TEM) observation, and calculates | requires them by arithmetic average. In addition, when the shape of a copper particle is not a perfect circle shape in an observation figure, a major axis is measured as a diameter.

  Although content of the copper nanoparticle (A) in a composition will not be restrict | limited especially if mass ratio X mentioned later is a predetermined range, It is preferable that it is 1-40 mass%, and it is 5-30 mass%. It is more preferable.

<Surfactant (B)>
The kind of surfactant (B) is not particularly limited. For example, an anionic surfactant, a nonionic surfactant, a cationic surfactant, an amphoteric surfactant, etc. are mentioned.
Specific examples of the anionic surfactant include fatty acid salts, alkyl sulfate esters, alkylbenzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfosuccinates, alkyl diphenyl ether disulfonates, alkyl phosphates, polyoxyethylenes. Alkyl sulfate ester salt, polyoxyethylene alkyl allyl sulfate ester salt, naphthalene sulfonic acid formalin condensate, polycarboxylic acid type polymer surfactant, polyoxyethylene alkyl phosphate ester and the like can be mentioned.

Specific examples of nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene acetylenic glycol ether, polyoxyethylene derivative, oxyethylene / oxypropylene block copolymer, sorbitan fatty acid Examples include esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene alkylamines, and alkyl alkanolamides.
More specifically, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, polyoxyethylene lauryl ether and the like can be mentioned.

  Specific examples of the cationic surfactant and the amphoteric surfactant include alkylamine salts, quaternary ammonium salts, alkylbetaines, amine oxides and the like.

In addition to these, fluorine-based surfactants and silicon-based surfactants (for example, BYK306 (manufactured by Big Chemie Japan)) can also be used. Among the above surfactants, nonionic surfactants and silicon-based surfactants are preferable in that the conductivity of the conductive film to be formed is more excellent.
As the nonionic surfactant, polyoxyethylene alkyl ether and polyoxyethylene acetylenic glycol ether are preferable.

The surfactant (B) can be used alone or in combination of two or more.
Although content in particular of surfactant (B) in a composition is not restrict | limited, It is preferable that it is 0.01-2.0 mass%.

<Water-soluble organic solvent (C) having a boiling point of 120 ° C. or lower>
The water-soluble organic solvent (C) (hereinafter also simply referred to as solvent (C)) is not particularly limited as long as it is a water-soluble organic solvent having a boiling point of 120 ° C. or lower. In the present specification, the boiling point is a value at 1 atmosphere. Moreover, in this specification, water-soluble means that the solubility with respect to 25 degreeC water is 10 mass% or more.
Examples of the water-soluble organic solvent (C) include methanol, ethanol, isopropyl alcohol, butyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, isobutyl ketone, and cyclohexanone. Of these, ethanol and isopropyl alcohol are preferable.

The difference (absolute value) between the SP value of the temporary support described later and the SP value (solubility parameter) of the solvent (C) (hereinafter also referred to as SP value difference) is not particularly limited, but the solvent (C ) because the print is further improved by a more familiar, it is preferably from 3.0 to 15.0 ^{[MPa] 1/2,} which is from 4.0 to 15.0 ^{[MPa] 1/2} Is more preferably 10.0 to 15.0 [MPa] ^1/2 , and particularly preferably 10.0 to 14.0 [MPa] ^1/2 .
Here, the SP value of the temporary support represents the SP value of the material of the temporary support.
In addition, the SP value is Michael M. Collman, John F. Graf, Paul C.M. "SPECIFIC Interactions and the Miscibility of Polymer Blends" (1991), Technological Publishing Co., by Painter (Pensylvania State Univ.). Inc. It is a value obtained by the calculation described in. However, since -COOH group and -OH group are not described, R.I. F. Values described in Polymer Engineering and Science by Fedors, 14 (2), 147 (1974) are used.

  The content of the solvent (C) in the composition is not particularly limited, but is preferably 30 to 80% by mass.

<Water-soluble organic solvent (D) having a boiling point of 200 ° C. or higher>
The water-soluble organic solvent (D) (hereinafter also simply referred to as the solvent (D)) is not particularly limited as long as it is a water-soluble organic solvent having a boiling point of 200 ° C. or higher.
The water-soluble organic solvent (D) is preferably an alcohol having a boiling point of 200 ° C. or higher, especially a divalent or higher alcohol (an alcohol having two or more hydroxy groups in one molecule). Of these, divalent or trivalent alcohols are more preferred, and trivalent alcohols are particularly preferred.
Specific examples of the water-soluble organic solvent (D) include trimethylolethane, trimethylolpropane (above 250 ° C.), glycerin (above 250 ° C.), 1,4-butanediol (230 ° C.), 1,5-pentanediol. (242 ° C.), 1,6-hexanediol (250 ° C.), 1,7-heptanediol (258 ° C.), diethylene glycol (244 ° C.), triethylene glycol (over 250 ° C.) and the like. Methylolpropane is preferred. In addition, the inside of a parenthesis represents a boiling point.

  The content of the solvent (D) having a boiling point of 200 ° C. or higher in the composition is not particularly limited as long as the mass ratio X described later is within a predetermined range, but is preferably 0.05 to 10% by mass.

<Mass ratio X>
The mass ratio (mass ratio X) of the content of the solvent (D) and the content of the copper nanoparticles (A) described above is 1: 1 to 1:30.
The mass ratio X is preferably 1: 1 to 1:20, and more preferably 1: 2 to 1:20, because the conductivity and the printability are more excellent.

<Optional component>
The composition may contain components (arbitrary components) other than the components described above as long as the effects of the present invention are not impaired. Examples of such an optional component include a solvent (for example, water) other than the solvent (C) and the solvent (D) described above, a dispersant, and the like.
The composition preferably contains a dispersant. The dispersant is preferably a polyalkylene glycol.
The polyalkylene glycol is not particularly limited as long as it is a compound having a repeating unit of oxyalkylene (—R—O—, wherein R represents an alkylene group) and having two or more hydroxy groups in one molecule. The alkylene group is not particularly limited. For example, a C1-C10 alkylene group like an ethylene group and a propylene group is mentioned.
Examples of the polyalkylene glycol include polyethylene glycol and polypropylene glycol. Of these, polyethylene glycol is preferable.
The weight average molecular weight (Mw) of the polyalkylene glycol is not particularly limited, but is preferably 1,000 or more, more preferably 3000 to 500000, and further preferably 4000 to 30000. In addition, the said weight average molecular weight is a polystyrene conversion value obtained by GPC method (solvent: N-methylpyrrolidone).

<Method for Preparing Composition for Forming Wiring Pattern>
The preparation method of the composition for wiring pattern formation is not specifically limited, A well-known method is employable. For example, after mixing each of the above components, the composition is obtained by dispersing the components by a known means such as an ultrasonic method (for example, treatment with an ultrasonic homogenizer), a mixer method, a three-roll method, or a ball mill method. Can do.
In preparing the wiring pattern forming composition, it is preferable to prepare a dispersion of copper nanoparticles and then mix it with other components. The solvent of the copper nanoparticle dispersion is preferably water.

[Each step of the manufacturing method]
Next, each step in the method of the present invention will be described with reference to the drawings. In addition, the method of manufacturing a wiring pattern precursor film on a substrate, which will be described in detail below, corresponds to a so-called reverse printing method.

<Coating film formation process>
FIG. 1 is a schematic view showing a process of forming a wiring pattern precursor by a reverse printing method.
First, in the coating film forming step, the above-described composition is applied on a temporary support to form a coating film on the temporary support. More specifically, as shown in FIG. 1A, the composition is applied to the temporary support 1 to form a coating film 2 on the temporary support 1.
As a temporary support used in the reversal printing method, a blanket having a liquid repellent surface is mentioned as one of preferred embodiments. Specifically, a silicone blanket is mentioned.
As the main component of the material of the temporary support, for example, silicone elastomers such as vinyl silicone rubber and fluorinated silicone rubber, various fluororesin elastomers, ethylene propylene rubber, olefin elastomers and the like are used. Of these, silicone elastomers and fluorine elastomers can be suitably used because of their excellent liquid repellency and excellent releasability. In particular, silicone elastomers have appropriate liquid repellency, solvent resistance, and solvent swelling properties, and are more excellent as rubbers for release surfaces of blankets. Among them, polydimethylsiloxane (polydimethylsilicone) (PDMS) rubber has high liquid repellency and moderate solvent absorbability, and is excellent in fine pattern formation and pattern transfer. As a reversal printing blanket material, it has particularly excellent characteristics. The main component is intended to occupy 80% by mass or more.

In the present invention, the method for applying the composition to the temporary support is not particularly limited. For example, a coating film having a predetermined film thickness can be formed by slit coating, bar coating, or spin coating.
The film thickness of the applied coating is preferably adjusted to 0.1 μm to 15 μm, more preferably 0.15 μm to 10 μm, from the viewpoint of conductivity obtained by subsequent fine pattern formability and drying properties.
In addition, you may provide the drying process which dries a coating film between a coating-film formation process and the removal process mentioned later so that it may mention later.

<Removal process>
Next, in the removing step, a plate on which convex portions are formed in a pattern is pressed onto the coating film formed on the temporary support to remove a part of the coating film. More specifically, as shown in FIGS. 1B and 1C, a plate 4 having convex portions 6 formed in a pattern is pressed against the coating film 2, and the coating film in contact with the convex portions 6 is pressed. Part 2a is removed. As a result, the patterned coating film 2 b remains on the temporary support 1.

The material of the plate is not particularly limited as long as a part of the coating film can be removed from the temporary support, and for example, various metals such as glass, silicon, stainless steel, and various resins can be used.
Further, the processing method of the plate surface is not particularly limited, and an optimum method can be selected depending on the material, pattern accuracy, relief plate depth, and the like. For example, when glass or silicon is used as a material, a processing method such as wet etching or dry etching can be applied. In the case of metal, wet etching, electroforming, sandblasting, etc. can be applied. Further, when a resin is used as a material, a processing method such as photolithography etching, laser, or focused ion beam can be suitably applied.

<Drying process>
As described above, the method of the present invention can further include a drying step of drying the temporary support after the coating film forming step between the coating film forming step and the removing step. By providing the drying step, transferability can be further improved.
The temperature in the drying step is preferably less than 100 ° C. By being within this temperature range, the organic solvent can be removed from the composition.

<Transfer process>
The transfer step is a step of transferring the coating film (patterned coating film) remaining on the temporary support obtained in the removing step onto the substrate to form a wiring pattern precursor on the substrate. More specifically, first, as shown in FIG. 1D, the temporary support 1 on which the patterned coating film 2b is formed and the substrate 8 are opposed to each other, and then as shown in FIG. The temporary support 1 on which the patterned coating film 2b is formed and the substrate 8 are brought into contact with each other, and the patterned coating film 2b is transferred onto the substrate 8 as shown in FIG. The transferred pattern-like coating film 2b is a wiring pattern precursor, and becomes a wiring pattern through a photo-sintering process described later.
The procedure of the transfer process is not particularly limited, but usually, the coating film on the temporary support after the removal process is opposed to the substrate, and both are lightly pressed, and the coating film remaining on the temporary support is the substrate. It is preferable to transfer all the images to

The kind of base material used in the reverse printing method is not particularly limited, and examples thereof include a metal base material and a resin base material, and a resin base material is preferable from the viewpoint of handleability. Examples of the resin substrate include polyolefin resins such as low density polyethylene resin, high density polyethylene resin, polypropylene and polybutylene; methacrylic resins such as polymethyl methacrylate; polystyrene resins such as polystyrene, ABS and AS; acrylic resins; Polyamide resin selected from styrene resin, vinyl chloride resin, polyester resin (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, poly 1,4-cyclohexyldimethylene terephthalate, etc.), nylon resin and nylon copolymer; polyvinyl chloride resin Polyoxymethylene, polycarbonate resin, polyphenylene sulfide resin, modified polyphenylene ether resin, polyacetal resin, polysulfone resin, polyester Polysulfone resins; Polyketone resins; Polyether nitrile resins; Polyether ether ketone resins; Polyether imide resins, polyether ketone resins, polyether ketone ketone resins; Polyimide resins, polyamide imide resins; Fluorine resins; The
In the transfer step, the total content of the water-soluble organic solvent (C) having a boiling point of 120 ° C. or lower and the water-soluble organic solvent (D) having a boiling point of 200 ° C. or higher in the coating film to be transferred and the copper nanoparticles (A) The mass ratio with respect to the content (mass ratio Y) is not particularly limited, but is preferably 1: 1 to 1:33, and is preferably 1: 1 to 1:22 because the conductivity and printability are more excellent. It is more preferable that the ratio is 1: 2 to 1:22.

<Photo sintering process>
Next, in the photosintering step, the wiring pattern precursor is photosintered to form a wiring pattern. More specifically, a wiring pattern is formed by irradiating the wiring pattern precursor with light and fusing the copper nanoparticles (A) in the wiring pattern precursor.

The light source used for light irradiation 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 (eg, pulsed light irradiation with a Xe 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 0.5~100J / cm ^2, more preferably 0.5~30J / cm ^2, preferably 1μ seconds ~100m sec as a pulse width, and more is 10μ seconds ~10m seconds preferable. The irradiation time of the pulsed light is preferably 0.1 to 100 msec, more preferably 0.1 to 50 msec, and further preferably 0.1 to 10 msec.

  One preferred embodiment is that light irradiation is performed twice or more using a flash lamp at an exposure time of 0.5 msec or more.

  The atmosphere in which the light irradiation is performed is not particularly limited, and examples thereof include an air atmosphere, an inert atmosphere, and a reducing atmosphere. The inert atmosphere is, for example, an atmosphere filled with an inert gas such as argon, helium, neon, or nitrogen, and the reducing atmosphere is a reducing gas such as hydrogen or carbon monoxide. It refers to the atmosphere.

[Wiring pattern]
A wiring pattern (patterned copper wiring) is formed on the substrate by the above process.
The thickness of the wiring pattern is not particularly limited, and is appropriately adjusted to an optimal thickness depending on the intended use, but is preferably 50 to 500 nm.

[Method of manufacturing organic transistor]
An organic transistor manufacturing method of the present invention (hereinafter also simply referred to as a manufacturing method of the present invention) includes an organic transistor including at least a gate electrode, a gate insulating film layer, a source electrode, a drain electrode, and an organic semiconductor layer. In the manufacturing method, at least one electrode selected from the group consisting of the gate electrode, the source electrode, and the drain electrode is formed by the method of the present invention described above.
The organic transistor preferably has a structure in which a gate insulating film layer and a source electrode, and a gate insulating film layer and a drain electrode are in contact with each other.
Hereinafter, the manufacturing method of the bottom gate-bottom contact type organic transistor will be described in detail as the first mode, and the manufacturing method of the top gate-top contact type organic transistor will be described as the second mode.

<First aspect>
FIG. 2 shows a cross-sectional view of one embodiment of a bottom gate-bottom contact type organic transistor.
As shown in FIG. 2, the organic 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.
In the manufacturing method of the present invention, at least one electrode selected from the group consisting of a gate electrode, a source electrode, and a drain electrode may be formed by the above-described method of the present invention. The method of forming the film layer 16 and the organic semiconductor layer 22) is not particularly limited, but usually, a step of forming the gate electrode 14 (gate forming step), a step of forming the gate insulating film layer 16 (insulating film layer forming step), The step of forming the source electrode 18 and the drain electrode 20 (source / drain formation step) and the step of forming the organic semiconductor layer 22 (organic semiconductor formation step) are preferably performed 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 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.
The gate electrode may be formed by the method of the present invention described above. In this case, a gate electrode precursor (wiring pattern precursor) is formed on a support (base material), and a gate electrode (wiring pattern) is formed by photo-sintering this.
The thickness of the gate electrode is not particularly limited, but is preferably 20 to 200 nm.

(Insulating film layer forming process)
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 is not particularly limited, but is preferably formed using a solution containing an insulating material containing an organic substance as a main component. That is, the gate insulating film layer preferably contains an organic insulating material. Here, the main component is intended to be 75% by mass or more, preferably 90% by mass or more, and more preferably 100% by mass.

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 the drain electrode and the gate insulating film layer is more excellent, or the mobility of the organic 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)
A method for forming the source electrode and the drain electrode is not particularly limited, but the method of the present invention described above is preferable. In this case, a source electrode precursor and a drain electrode precursor (wiring pattern precursor) are formed on the gate insulating film layer (base material), and the source electrode and the drain electrode (wiring pattern) are formed by photo sintering. It is formed.
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 of FIG. 2. For example, as shown in the organic transistor 100 of FIG. 3, 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 and the like); polymers such as polyvinyl carbazole, polyphenylene sulfide and 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-kinkethiophene, 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 above-mentioned condensed polycyclic aromatic compound and a 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. 4 shows a schematic diagram of an embodiment of a top gate-top contact type organic transistor.
As shown in FIG. 4, the organic 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 transistor 200 shown in FIG. 4 are the same as the members constituting the organic transistor 10 shown in FIG. 2 described above, and the same members are denoted by the same reference numerals and description thereof is omitted. . The organic transistor 200 shown in FIG. 4 is different from the organic transistor 10 shown in FIG.
Similar to the first embodiment described above, at least one electrode selected from the group consisting of a gate electrode, a source electrode and a drain electrode may be formed by the method of the present invention described above. Step of forming organic semiconductor layer 22 (organic semiconductor forming step), step of forming source electrode 18 and drain electrode 20 (source / drain forming step), step of forming gate insulating film layer 16 (insulating film layer forming) Step) and the step of forming the gate electrode 14 (gate formation step) are preferably performed in this order. The procedure of each process is the same as the procedure of each process in the first embodiment described above.

  In forming the organic semiconductor layer 22, the organic semiconductor layer 22 is not limited to the embodiment shown in FIG. 4 and is formed in a region sandwiched between the source electrode 18 and the drain electrode 20 as shown in the organic transistor 300 in FIG. 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 copper nanoparticle dispersion (dispersion 1)>
In a glass container, 115 g of copper (II) acetate hydrate was dissolved in 1700 g of distilled water and 30 g of formic acid to prepare an aqueous solution containing copper ions. The pH of the aqueous solution was 2.7. While stirring the aqueous solution, the aqueous solution was heated to 40 ° C., and 240 g of a 50 mass% hypophosphorous acid aqueous solution was added. Five minutes after the addition, the color of the aqueous solution changed from blue to green to brown. After stirring for 30 minutes at 40 ° C., copper nanoparticles were synthesized by heating at 80 ° C. for 60 minutes. Thereafter, 20 g of polyethylene glycol (weight average molecular weight 20000) was added and stirred at room temperature for 20 minutes. Then, particle recovery by pressure filtration, ultrasonic dispersion in polyethylene glycol 2% by mass solution is repeated twice, washing is performed, and finally, the copper nanoparticles concentration is diluted with water so that the concentration becomes 20% by mass, A copper nanoparticle dispersion was prepared by sonicating at room temperature for 5 minutes. The prepared copper nanoparticle dispersion is designated as Dispersion 1. When the copper nanoparticles in the dispersion 1 were observed with an SEM, the average primary particle diameter of the copper nanoparticles was 80 nm.

<Preparation of copper nanoparticle dispersion (dispersion 2)>
Instead of diluting with copper so that the copper nanoparticle concentration is 20% by mass, the copper nanoparticles are dispersed according to the same procedure as dispersion 1, except that the copper nanoparticle concentration is diluted with ethanol so that the copper nanoparticle concentration is 20% by mass. A liquid was prepared. The prepared copper nanoparticle dispersion is designated as Dispersion 2. When the copper nanoparticles in the dispersion 2 were observed with an SEM, the average primary particle diameter of the copper nanoparticles was 80 nm.

<Preparation of composition for wiring pattern formation>
10 g of the dispersion described in “Copper nanoparticle dispersion” in Table 1, 0.5 g of BYK306 (manufactured by BYK Japan) as a surfactant, and “water-soluble organic solvent having a boiling point of 120 ° C. or lower (C ) ”, 0.2 g of the solvent described in“ Water-soluble organic solvent (D) having a boiling point of 200 ° C. or higher ”in Table 1, and 0.2 g of polyethylene glycol (weight average molecular weight 20000) are mixed. A composition for forming a wiring pattern (a composition for forming a wiring pattern used in each example and comparative example) was prepared by treating for 5 minutes with a rotation and revolution mixer (manufactured by THINKY, manufactured by Awatori Nertaro ARE-310). did.
In Comparative Examples 2 and 3, the “water-soluble organic solvent (C) having a boiling point of 120 ° C. or lower” was not mixed. In Comparative Examples 1, 3 and 7, “water-soluble organic solvent (D) having a boiling point of 200 ° C. or higher” was not mixed. Moreover, about Examples 13-16 and Comparative Examples 5-6, the compounding quantity of "the water-soluble organic solvent (D) whose boiling point is 200 degreeC or more" was adjusted so that it might become "mass ratio X" of Table 1.
The dispersion 1 in Table 1 represents the dispersion 1 described above, and the dispersion 2 in Table 1 represents the dispersion 2 described above. Moreover, the mass ratio X in Table 1 represents the mass ratio X described above.

(The boiling point of the solvent described in “Water-soluble organic solvent (C) having a boiling point of 120 ° C. or lower” in Table 1)
The boiling points of the solvents described in “Water-soluble organic solvent (C) having a boiling point of 120 ° C. or lower” in Table 1 are as follows. In addition, ethanol, isopropyl alcohol, acetone, methyl ethyl ketone, and methanol have a solubility in water of 25 ° C. of 10% by mass or more and correspond to the above-mentioned solvent (C), but hexane has a solubility in water of 25 ° C. of less than 10% by mass. And does not correspond to the solvent (C) described above.
・ Ethanol: 78 ° C
Isopropyl alcohol: 82 ° C
Acetone: 57 ° C
・ Methyl ethyl ketone: 80 ℃
・ Methanol: 65 ℃
・ Hexane: 69 ℃

(The boiling point of the solvent described in “Water-soluble organic solvent (D) having a boiling point of 200 ° C. or higher” in Table 1)
The boiling points of the solvents described in “Water-soluble organic solvent (D) having a boiling point of 200 ° C. or higher” in Table 1 are as follows. Trimethylolpropane, glycerin and 1,7-heptanediol have a solubility in water at 25 ° C. of 10% by mass or more.
Trimethylolpropane: over 250 ° C Glycerin: over 250 ° C 1,7-heptanediol: 258 ° C

<Production of organic transistor>
A bottom gate-bottom contact type organic transistor (organic transistors of each example and comparative example) shown in FIG. 2 was produced using each wiring pattern forming composition as follows.

(Formation of gate electrode)
On an alkali-free glass substrate (5 cm × 5 cm), silver nanoink (silver nanocolloid H-1, manufactured by Mitsubishi Materials Corporation) is 100 μm wide and 100 nm thick by inkjet printing using DMP2831 (1 picoliter head). A gate electrode precursor was formed, and then heated and fired at 200 ° C. for 90 minutes on a hot plate in the atmosphere to form a gate electrode.

(Formation of gate insulating film layer (other than Examples 4 and 5))
Except for Examples 4 and 5, a gate insulating film layer was formed as follows.
A solution was prepared by stirring and mixing 5 parts by mass of polyvinylphenol (Mw 25000, manufactured by Aldrich), 5 parts by mass of melamine, and 90 parts by mass of polyethylene glycol monomethyl ether acetate and filtering with a 0.2 μm membrane filter. The obtained solution was dropped onto the alkali-free glass substrate on which the gate electrode was formed as described above, coated by spin coating, and heated at 150 ° C./30 minutes to form a gate insulating film layer. The spin coating conditions were adjusted to achieve the film thickness shown in Table 1.

(Formation of Gate Insulating Film Layer (Example 4))
About Example 4, as a solution for forming a gate insulating film layer, polysilsesquioxane (HBSQ101, manufactured by Arakawa Chemical Industries) (100 parts by mass), isophorone diisocyanate (10 parts by mass) and 100 parts by mass of dimethyl glycol A gate insulating film layer was formed in the same manner as in Examples 4 and 5 described above, except that the mixed solution was used.

(Formation of gate insulating film layer (Example 5))
About Example 5, as a solution for forming a gate insulating film layer, SRECK KS-3 (manufactured by Sekisui Chemical Co., Ltd.) (5 parts by mass) and toluene / ethanol 1: 1 mixed solvent (95 parts by mass) were used. A gate insulating film layer was formed in the same manner as in Examples 4 and 5 except that the mixed solution was used.

(Formation of source and drain electrodes)
1. Coating Film Formation Step The obtained wiring pattern forming composition was applied to a PDMS blanket (10 cm × 10 cm) with a coater (6 μm liquid film thickness) and dried at room temperature for 30 seconds. In this way, a coating film was formed on the PDMS blanket.
2. Removal Step Next, a glass plate (depth: 10 μm) in which convex portions are formed in the pattern shown in FIG. 6 is placed on the coating film, pressed from above for 10 seconds, and then peeled off to remove the coating film. The part which the convex part 52 contacted among these was removed. As a result, the coating film having the shape of the openings 53 and 54 in FIG. 6 remained on the PDMS blanket.
3. Transfer process 20 seconds later, the coating film remaining on the PDMS blanket is brought into contact with the gate insulating film layer, pressed for 10 seconds from the top, and then peeled off from the PDMS blanket to transfer the coating film onto the gate insulating film layer. did. Table 1 shows the mass ratio Y described above for each example and comparative example. In addition, “<1: 100” has less “total content of water-soluble organic solvent (C) having a boiling point of 120 ° C. or lower and water-soluble organic solvent (D) having a boiling point of 200 ° C. or higher” than 1: 100. Represents.
4). Photo-sintering process The transferred coating film (wiring pattern precursor) is subjected to pulsed light irradiation treatment (Xenon's photo-sintering apparatus Sinteron 2000) under the conditions of irradiation energy: 5 J / m ² and pulse width: 2 msec. A source electrode and a drain electrode (wiring pattern) were formed by performing photo-sintering. In Comparative Examples 3 and 7, since an appropriate wiring pattern precursor was not formed, photosintering was not performed. Moreover, about the comparative example 4, the source electrode and the drain electrode were formed by performing heat sintering (nitrogen atmosphere) instead of light sintering. Table 1 shows the thicknesses of the source and drain electrodes formed.

(Formation of organic semiconductor layer)
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 onto a substrate on which a source electrode and a drain electrode were formed, and was 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.
Thus, each organic transistor was produced.

<Conductivity>
About the obtained source electrode and drain electrode of each organic transistor, the volume resistivity was measured using the four-probe method resistivity meter. And conductivity was evaluated according to the following criteria. The results are shown in Table 1. Practically, it is preferably A to C. In addition, about Comparative Examples 3 and 7 which did not sinter, electroconductivity evaluation was not performed.
“A”: Volume resistivity is less than 10 μΩ · cm “B”: Volume resistivity is 10 μΩ · cm or more and less than 50 μΩ · cm “C”: Volume resistivity is 50 μΩ · cm or more and less than 100 μΩ · cm “D”: Volume resistance Rate is 100 μΩ · cm or more and less than 1000 μΩ · cm “E”: Volume resistivity is 1000 μΩ · cm or more

<Printability (Letter offset printability)>
In the production of the organic transistor, the formed source electrode and drain electrode (wiring pattern) were observed with an optical microscope without forming the organic semiconductor layer, and the printability was evaluated according to the following criteria. Practically, it is preferably A to C. The results are shown in Table 1. In addition, printability evaluation was not performed about the comparative examples 3 and 7 which did not sinter.
“A”: No defect is found in the wiring pattern, no remaining pattern is seen in unnecessary portions, and no blur or rattling is seen on the edge of the wiring pattern.
“B”: No defect is found in the wiring pattern, and no remaining pattern is seen in an unnecessary portion, but slight blurring or shading is seen in the edge portion of the wiring pattern.
“C”: No defect is found in the wiring pattern, and no remaining pattern is seen in an unnecessary portion, but bleeding and shading are seen in the edge portion of the pattern. However, within the allowable range for wiring.
“D”: Some defects are found in the wiring pattern, or some remaining patterns are seen in unnecessary portions. Alternatively, the blur and shakiness are noticeable at the edge of the pattern.
“E”: A noticeable defect is seen in the wiring pattern, or a noticeable remaining pattern is seen in an unnecessary portion, and the wiring pattern is not formed.

<Adhesion (electrode adhesion)>
In the production of the organic transistor, a tape peeling test was performed on the formed source electrode and drain electrode (wiring pattern) without forming the organic semiconductor layer. And the adhesiveness was evaluated according to the following criteria. The results are shown in Table 1. Practically, it is preferably A to C. In addition, adhesiveness was not evaluated about the comparative examples 3 and 7 which did not sinter, and the comparative example 1 whose printability evaluation was "E".
“A”: no peeling at all “B”: peeling at an area of less than 5% “C”: peeling at an area of 5% or more but less than 20% “D”: peeling of an area of 20% or more but less than 90% “ E ": There is peeling of an area of 90% or more

<Mobility>
About each obtained organic transistor, mobility was measured using semiconductor device analyzer B1500A (made by Agilent). The results are shown in Table 1. In addition, mobility was not evaluated about the comparative examples 3 and 7 which did not sinter, and the comparative example 1 whose evaluation of printability was "E".

In Table 1, the SP value difference represents the SP value difference described above. Here, the SP value of the PDMS blanket which is a temporary support is the SP value of polydimethylsiloxane, specifically 15.3 [MPa] ^1/2 .

As can be seen from Table 1, copper nanoparticles (A), surfactant (B), water-soluble organic solvent (C) having a boiling point of 120 ° C. or lower, and water-soluble organic solvent (D) having a boiling point of 200 ° C. or higher And a mass ratio (mass ratio X) of the content of the water-soluble organic solvent (D) having a boiling point of 200 ° C. or higher and the content of the copper nanoparticles (A) is 1: 1 to 1:30 All of the wiring patterns formed by the wiring pattern forming method of Examples of the present application using the pattern forming composition showed excellent conductivity, printability and adhesion. Moreover, the organic transistor which formed the source electrode and the drain electrode by the wiring pattern formation method of the said this-application Example showed high organic-semiconductor mobility.
From the comparison of Examples 1 and 13 to 16, Examples 1 and 13 to 15 having a mass ratio X of 1: 1 to 1:20 showed better conductivity. Among them, Examples 1, 13 and 15 having a mass ratio X of 1: 2 to 1:20 showed further excellent conductivity and printability.
Further, from the comparison of Examples 1, 6 and 7, Examples 1 and 6 in which the water-soluble organic solvent (D) having a boiling point of 200 ° C. or higher is a trivalent alcohol showed better adhesion. Among them, Example 1 in which the water-soluble organic solvent (D) having a boiling point of 200 ° C. or higher was trimethylolpropane showed better printability.
Further, from the comparison of Examples 1, 8 and 10 to 12, the difference (SP value difference) between the SP value of the temporary support and the SP value of the water-soluble organic solvent (C) having a boiling point of 120 ° C. or lower is 4.0 to 4.0. Examples 1, 8, 10 and 12 which were 15.0 showed better conductivity. Among them, Examples 1 and 12 having an SP value difference of 10.0 to 15.0 showed more excellent printability. Among them, Example 1 in which the SP value difference is 10.0 to 14.0 showed further excellent conductivity.
Moreover, from the comparison with Example 1 and 9, Example 1 whose solvent of the copper nanoparticle dispersion liquid is water showed more excellent printability.

On the other hand, Comparative Examples 1 to 3 and 7 in which the wiring pattern forming composition does not contain a water-soluble organic solvent (C) having a boiling point of 120 ° C. or lower or a water-soluble organic solvent (D) having a boiling point of 200 ° C. or higher are suitable without being transferred. Even if a proper wiring pattern precursor was not formed or an appropriate wiring pattern precursor was formed, the printability was insufficient.
Moreover, the comparative example 4 which sintered by heat sintering was inadequate in electroconductivity and adhesiveness.
Further, Comparative Examples 5 and 6 in which the mass ratio X is outside the range of 1: 1 to 1:30 have insufficient printability, and also have insufficient conductivity and adhesion.

1 Temporary support 2 Coating film 2a Part of coating film (removed coating film)
2b Patterned coating film 4 Plate 6 Convex 8 Base material 10, 100, 200, 300 Organic transistor 12 Support 14 Gate electrode 16 Gate insulating film layer 18 Source electrode 20 Drain electrode 22 Organic semiconductor layer 51 Glass plate 52 Convex 53, 54 opening

Claims (12)

Copper nanoparticles (A) having an average primary particle size of less than 100 nm, a surfactant (B), a water-soluble organic solvent (C) having a boiling point of 120 ° C. or lower, and a water-soluble organic solvent (D) having a boiling point of 200 ° C. or higher The mass ratio (mass ratio X) of the content of the water-soluble organic solvent (D) having a boiling point of 200 ° C. or higher and the content of the copper nanoparticles (A) is 1: 1 to 1: A coating film forming step of applying a wiring pattern forming composition of 30 on a temporary support and forming a coating film on the temporary support; and
A removal step of pressing a plate on which convex portions are formed in a pattern shape against the coating film, and removing a part of the coating film;
A transfer step of transferring the coating film remaining on the temporary support onto a substrate and forming a wiring pattern precursor on the substrate;
A photo-sintering step of photo-sintering the wiring pattern precursor to form a wiring pattern ;
And SP value of the temporary support, the difference between the SP value of the boiling point of 120 ° C. or less of the water-soluble organic solvent (C) is, 3.0 to 14.1 ^[MPa] Ru ^1/2 der, wiring patterns formed Method.   In the transfer step, the total content of the water-soluble organic solvent (C) having a boiling point of 120 ° C. or lower and the water-soluble organic solvent (D) having a boiling point of 200 ° C. or higher and the copper nanoparticles in the coating film to be transferred The wiring pattern formation method of Claim 1 whose mass ratio (mass ratio Y) with content of (A) is 1: 1-1: 33. The wiring pattern forming composition further contains water, a wiring pattern forming method according to claim 1 or 2. The boiling point of 120 ° C. or less of the water-soluble organic solvent (C) is ethanol or isopropyl alcohol, a wiring pattern forming method according to any one of claims 1-3. The boiling point of 200 ° C. or more water-soluble organic solvent (D) is an alcohol, the wiring pattern forming method according to any one of claims 1-4. The wiring pattern forming method according to any one of claims 1 to 5 , wherein the water-soluble organic solvent (D) having a boiling point of 200 ° C or higher is a divalent or trivalent alcohol. The wiring pattern formation method of any one of Claims 1-6 whose main component of the material which forms the said temporary support body is polydimethylsiloxane. A method of manufacturing an organic transistor comprising at least a gate electrode, a gate insulating film layer, a source electrode, a drain electrode, and an organic semiconductor layer,
Said gate electrode, at least one electrode selected from the group consisting of the source electrode and the drain electrode are formed by a wiring pattern forming method according to any one of claims 1 to 7 the method of manufacturing the organic transistor . The method of manufacturing an organic transistor according to claim 8 , wherein the gate insulating film layer is formed using a solution containing an insulating material containing an organic substance as a main component. The method for manufacturing an organic transistor according to claim 8 or 9 , wherein the organic transistor has a structure in which the gate insulating film layer and the source electrode, and the gate insulating film layer and the drain electrode are in contact with each other. The thickness of the gate insulating film layer is 200 to 1000 nm, a manufacturing method of an organic transistor according to any one of claims 8-10. The gate electrode, the thickness of the source electrode and the drain electrode, is 50 to 500 nm, a manufacturing method of an organic transistor according to any one of claims 8-11.

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