JP2015109402A - Organic thin-film transistor, electronic paper, and display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic thin-film transistor which is more excellent in insulation reliability between electrodes, and to provide electronic paper and a display device.SOLUTION: The organic thin-film transistor includes at least an organic semiconductor layer containing an organic semiconductor material, a gate insulating film, a gate electrode, a source electrode, and a drain electrode. The organic semiconductor material contains a compound represented by general formula (X). At least one electrode selected from the group consisting of the gate electrode, the source electrode, and the drain electrode contains at least a metal selected from the group consisting of silver and copper, and an onium salt.

Description

  The present invention relates to an organic thin film transistor, and an electronic paper and a display device including the organic thin film 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 thin film transistor (organic TFT) having a semiconductor film (organic semiconductor layer) is used.
Recently, demands for smaller, higher integration and higher performance of electronic components have become stronger, and even in organic thin film transistors, miniaturization of source electrodes, drain electrodes, and gate electrodes, and narrowing between each electrode have been reduced. Progressing. Moreover, as a material used for these electrodes, silver or copper is preferably cited from the viewpoint of electrical characteristics (for example, Patent Document 1).

JP 2010-161312 A

  On the other hand, silver or copper tends to cause ion migration. Therefore, in an organic thin film transistor in which the gap between electrodes is narrowed, conduction between electrodes due to silver or copper ion migration (electrochemical migration) is likely to occur, and further improvement in insulation reliability of the organic thin film transistor has been demanded. .

  In view of the above circumstances, an object of the present invention is to provide an organic thin film transistor that is superior in insulation reliability between electrodes.

  As a result of intensive studies on the above problems, the present inventors have found that a desired effect can be obtained by selecting a specific organic semiconductor material and blending an electrode with an onium salt, and have reached the present invention. That is, the present inventors have found that the above problem can be solved by the following configuration.

(1) An organic thin film transistor having at least an organic semiconductor layer containing an organic semiconductor material, a gate insulating film, a gate electrode, a source electrode, and a drain electrode,
The organic semiconductor material contains a compound represented by the following general formula (X),
An organic thin film transistor, wherein at least one electrode selected from the group consisting of a gate electrode, a source electrode, and a drain electrode contains at least a metal selected from the group consisting of silver and copper and an onium salt.
(2) The organic thin film transistor according to (1), wherein at least one of R ¹ and R ² in the general formula (X) is a substituent represented by the general formula (W) described later.
(3) The organic thin-film transistor as described in (1) or (2) in which the compound represented by general formula (X) contains the compound represented by general formula (Y) mentioned later.
(4) The organic thin-film transistor in any one of (1)-(3) in which the compound represented by general formula (X) contains the compound represented by general formula (Z) mentioned later.
(5) R ^{3 to} R ⁶ in the general formula (X) are each independently a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, or a substituted or unsubstituted group having 2 to 3 carbon atoms. (1) to (4) which are an alkynyl group, a substituted or unsubstituted alkenyl group having 2 to 3 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 2 carbon atoms, or a substituted or unsubstituted methylthio group. ).
(6) The organic thin film transistor according to any one of (1) to (5), wherein the onium salt includes a compound represented by the general formula (I) described later.
(7) Electronic paper containing the organic thin-film transistor in any one of (1)-(6).
(8) A display device comprising the organic thin film transistor according to any one of (1) to (6).

  ADVANTAGE OF THE INVENTION According to this invention, the organic thin-film transistor which is excellent by the insulation reliability between electrodes can be provided.

It is a cross-sectional schematic diagram of one aspect | mode of the organic thin-film transistor of this invention. It is a cross-sectional schematic diagram of another one aspect | mode of the organic thin-film transistor of this invention.

Below, the suitable aspect of the organic thin-film transistor of this invention is demonstrated. In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
A feature of the present invention is that the electrode contains an onium salt and the organic semiconductor layer contains a predetermined organic semiconductor material. More specifically, in the following, the case between the source electrode and the drain electrode is taken as an example. First, when a voltage is applied to an electrode of an organic thin film transistor, silver or copper in the electrode may be ionized by the action of an electric field, and ions may migrate (migrate) in the organic semiconductor layer. When such migration occurs, the insulation between the source / drain electrodes is degraded.
First, when an onium salt is contained in the electrode, even if silver or copper in the electrode is ionized, the onium salt in the electrode traps it, thereby preventing migration itself. That is, the onium salt works as an excellent migration inhibitor (migration inhibitor). In addition, when the slightly generated silver ions or copper ions diffuse through the organic semiconductor layer, the organic semiconductor material represented by the general formula (X) exhibits excellent crystallinity. Or there are few crystal grain boundaries used as the diffusion path | route of a copper ion, the spreading | diffusion of silver ion or copper ion itself is suppressed, and the insulation between electrodes is ensured as a result by the synergistic effect.

<First Embodiment>
One embodiment of the organic thin film transistor of the present invention will be described with reference to the drawings.
FIG. 1 is a schematic cross-sectional view of one embodiment of the organic thin film transistor of the present invention.
In FIG. 1, an organic thin film transistor 100 includes a substrate 10, a gate electrode 20 disposed on the substrate 10, a gate insulating film 30 in contact with the gate electrode 20, and a gate insulating film 30 on the side opposite to the gate electrode 20 side. A source electrode 40 and a drain electrode 42 in contact with the surface, an organic semiconductor layer 50 covering the surface of the gate insulating film 30 between the source electrode 40 and the drain electrode 42, and a sealing layer 60 covering each member are provided. Here, the source electrode 40 and the drain electrode 42 include a metal selected from the above-described group consisting of silver and copper, and an onium salt. The organic thin film transistor 100 is a bottom gate-bottom contact type organic thin film transistor. These transistors can be suitably used for electronic paper and display devices.
1 illustrates an embodiment in which only the source electrode 40 and the drain electrode 42 include a metal selected from the group consisting of silver and copper, and an onium salt, but the embodiment is not limited thereto, and the source electrode 40, It is only necessary that at least one electrode selected from the group consisting of the drain electrode 42 and the gate electrode 20 contains a metal selected from the group consisting of silver and copper, and an onium salt. More specifically, a metal selected from the group consisting of silver and copper, and an onium salt may be included in three of the source electrode 40, the drain electrode 42, and the gate electrode 20, and one of the three electrodes may be included. Only metals selected from the group consisting of silver and copper and onium salts may be included.
Hereinafter, first, the organic semiconductor layer 50 that is a feature of the present invention will be described in detail.

(Organic semiconductor layer)
The organic semiconductor layer is a layer disposed between the source electrode and the drain electrode, and serves as a current path between the electrodes. Note that in FIG. 1, the gate electrode is disposed so as to cover part of the source electrode and the drain electrode and to cover the surface of the gate insulating film between the source electrode and the drain electrode. The gate insulating film may be disposed so as to cover the surface of the gate insulating film between the source electrode and the drain electrode.
The organic semiconductor layer includes an organic semiconductor material, and includes at least a compound represented by the general formula (X) described later as the organic semiconductor material. The compound represented by the general formula (X) will be described in detail later.
Content of the compound represented with general formula (X) contained in an organic-semiconductor layer is not restrict | limited especially, 20 mass% or more is preferable with respect to the organic semiconductor layer total mass, and 50 mass% or more is more preferable. The upper limit is not particularly limited, but may be 100% by mass.
In addition, as an organic-semiconductor material, other compounds other than the compound represented by general formula (X) may be used together.

The thickness of the organic semiconductor layer is not particularly limited, but is preferably 10 to 200 nm.
A method for forming the organic semiconductor layer is not particularly limited. For example, an organic semiconductor containing a compound represented by the general formula (X) on a substrate on which a gate electrode, a gate insulating film, a source electrode, and a drain electrode are formed. Examples thereof include a method of applying a composition for organic semiconductor (composition for forming an organic semiconductor layer) in which a material is dissolved in a solvent.
The organic semiconductor composition may contain a solvent (for example, an organic solvent) as necessary.
The method for applying the organic semiconductor composition is not particularly limited. For example, a double roll coater, slit coater, air knife coater, wire bar coater, slide hopper, spray coater, blade coater, doctor coater, squeeze coater, reverse roll coater, Examples thereof include transfer roll coaters, extrusion coaters, curtain coaters, dip coaters, die coaters, gravure roll coating methods, screen printing methods, dip coating methods, spray coating methods, spin coating methods, and ink jet methods.
In addition, after apply | coating the composition for organic semiconductors, you may perform a drying process in order to remove a solvent as needed. A conventionally known method can be used as the drying treatment method.

Hereinafter, the compound represented by formula (X) will be described in detail.
Since this compound has a substituent represented by the general formula (W) described later, at least one of R ^{1 to} R ⁶ is preferable from the viewpoint of solution process suitability of the material and molecular arrangement in the film. Thereby, the manufacturing efficiency of the organic thin film applicable to an organic thin-film transistor can be raised, and manufacturing cost can be suppressed. In addition, charge transport properties such as field effect mobility and chemical and physical stability of the thin film are improved. Thereby, an organic thin-film transistor with high field effect mobility can be obtained.

In General Formula (X), A ¹ and A ² each independently represent a sulfur atom, an oxygen atom, or a selenium atom. A ¹ and A ² are preferably a sulfur atom or an oxygen atom. A ¹ and A ² may be the same or different from each other, but are preferably the same.

In general formula (X), R < ¹ > -R < ⁶ > represents a hydrogen atom or a substituent each independently. However, at least one of R ^{1 to} R ⁶ is a substituent represented by the following general formula (W).
The compound represented by general formula (X) may have other substituents other than the substituent represented by general formula (W).
Examples of other substituents that R ^{1 to} R ⁶ of the general formula (X) can take include, for example, a halogen atom, an alkyl group (including a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group), and an alkenyl group (cycloalkenyl group). Group, bicycloalkenyl group), alkynyl group, aryl group, heterocyclic group (may be referred to as heterocyclic group), cyano group, hydroxy group, nitro group, carboxy group, alkoxy group, aryloxy group, silyloxy group , Heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including anilino group), ammonio group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryl Oxycarbonylamino group, sulfamo Ruamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, Alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, phosphono group, silyl group, hydrazino group, ureido group, boronic acid group (-B _(OH) 2), phosphato group (-OPO _(OH) 2), a sulfato group (-OSO ₃ H), and other known substituents.
Among these, a halogen atom, an alkyl group, and an aryl group are preferable, and a fluorine atom, an alkyl group having 1 to 3 carbon atoms, an alkynyl group having 2 to 3 carbon atoms, an alkenyl group having 2 to 3 carbon atoms, and 1 to 2 carbon atoms. More preferred are an alkoxy group, a methylthio group and a phenyl group, a fluorine atom, a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 3 carbon atoms, and a substituted group having 2 to 3 carbon atoms. Alternatively, an unsubstituted alkenyl group, a substituted or unsubstituted alkoxy group having 1 to 2 carbon atoms, or a substituted or unsubstituted methylthio group is particularly preferable.
In the compound represented by the general formula (X), the number of other substituents other than the substituent represented by the general formula (W) among R ^{1 to} R ⁶ is preferably 0 to 4, It is more preferably 0 to 2, and particularly preferably 0.
Moreover, these substituents may further have the above substituents.
Among these, R ^{3 to} R ⁶ are each independently a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 3 carbon atoms, or a carbon number. A substituted or unsubstituted alkenyl group having 2 to 3 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 2 carbon atoms, or a substituted or unsubstituted methylthio group is preferable.

Next, the substituent represented by the general formula (W) will be described.
* -LR General Formula (W)
In the general formula (W), L is a divalent linking group represented by any of the following general formulas (L-1) to (L-10), or two or more of the following general formulas (L-1) to The bivalent coupling group which the bivalent coupling group represented by either of (L-10) couple | bonded is represented.

In the general formulas (L-1) to (L-10), a wavy line part represents a bonding position with a naphthalene ring, a ring containing A ¹ , or a ring containing A ² , and * represents R in the general formula (W) Indicates the binding position. M in the general formula (L-8) represents 4, and m in the general formulas (L-9) and (L-10) represents 2. In the general formulas (L-1), (L-2), (L-8), (L-9) and (L-10), R ′ each independently represents a hydrogen atom or a substituent. However, R ′ in the general formulas (L-1) and (L-2) may be bonded to R adjacent to L to form a condensed ring.

When L forms a linking group to which a divalent linking group represented by any one of formulas (L-1) to (L-10) is bonded, formulas (L-1) to (L-10) The number of bonds of the divalent linking group represented by any of the above is preferably 2-4, more preferably 2 or 3.
In particular, in the above general formulas (L-8) to (L-10), any one of the general formulas (L-1) to (L-10) is further inserted between * and R, so that L is It is also preferable to form a linking group to which a divalent linking group represented by any one of the general formulas (L-1) to (L-10) is bonded.
As the substituent R ′ in the general formulas (L-1), (L-2), (L-8), (L-9) and (L-10), R ^{1 in the} above general formula (X) mention may be made of those to R ⁶ is exemplified as other substituents can take.
M in the general formula (L-8) represents 4, and m in the general formulas (L-9) and (L-10) represents 2.

  L is a divalent compound represented by any one of the general formulas (L-1) to (L-2), (L-5) to (L-8), (L-9) or (L-10). It is preferably a linking group or a divalent linking group in which two or more of these divalent linking groups are bonded. From the viewpoints of chemical stability and charge transportability, the compounds represented by the general formulas (L-1) to (L- 3), a divalent linking group represented by any one of (L-8), (L-9) and (L-10), or a divalent linking group in which two or more of these divalent linking groups are bonded. A linking group is more preferable, and a divalent linking group represented by any one of the general formulas (L-1) and (L-8) is particularly preferable.

In the general formula (W), R is a hydrogen atom, a substituted or unsubstituted alkyl group, an oligooxyethylene group having 2 or more repeating oxyethylene groups, an oligosiloxane group having 2 or more silicon atoms, or a substituted group. Alternatively, it represents an unsubstituted trialkylsilyl group.
However, R represents a hydrogen atom only when L is represented by the general formulas (L-1) to (L-3) or (L-8) to (L-10).

When R in the general formula (W) is a substituted or unsubstituted alkyl group, the number of carbon atoms is preferably 2 to 18 and more preferably 3 to 12 from the viewpoint of chemical stability and charge transportability. More preferably, it is 4-10.
When the compound represented by the general formula (X) includes an alkyl group in the group represented by the general formula (W), the field effect is such that the number of carbon atoms of the alkyl group represented by R is not less than the lower limit of the above range. Increases mobility. In addition, when L includes the general formula (L-1) adjacent to R, an alkyl group formed by combining an alkylene group represented by the general formula (L-1) and an alkyl group represented by R When the number of carbon atoms is equal to or greater than the lower limit of the above range, the field effect mobility is increased.
The alkyl group which R can take may be linear, branched or cyclic, and is preferably a linear alkyl group from the viewpoint of increasing the field effect mobility, and is a linear alkyl group having 1 to 12 carbon atoms. It is more preferable that it is a C3-C12 linear alkyl group, and it is especially preferable that it is a C4-C10 linear alkyl group. Examples of the substituent when R is an alkyl group having a substituent include a halogen atom, and a fluorine atom is preferable. In addition, when R is an alkyl group having a fluorine atom, all hydrogen atoms of the alkyl group may be substituted with a fluorine atom to form a perfluoroalkyl group.

When R in the general formula (W) is an oligoethyleneoxy group having 2 or more repeating oxyethylene groups, the “oligoethyleneoxy group” represented by R is — (CH ₂ CH ₂ ) _x OY in the present specification. (The repeating number x of the oxyethylene unit represents an integer of 2 or more, and Y at the terminal represents a hydrogen atom or a substituent). In addition, when Y at the terminal of the oligooxyethylene group is a hydrogen atom, it becomes a hydroxy group. The number of repeating oxyethylene units x is preferably 2 to 4, and more preferably 2 to 3. The terminal hydroxy group of the oligooxyethylene group is preferably sealed, that is, Y represents a substituent. In this case, the hydroxy group is preferably sealed with an alkyl group having 1 to 3 carbon atoms, that is, Y is preferably an alkyl group having 1 to 3 carbon atoms, and Y is a methyl group or an ethyl group. Is more preferable, and a methyl group is particularly preferable.

When R in the general formula (W) is an oligosiloxane group having 2 or more silicon atoms, the number of repeating siloxane units is preferably 2 to 4, and more preferably 2 to 3. Further, it is preferable that a hydrogen atom or an alkyl group is bonded to the Si atom. When the alkyl group is bonded to the Si atom, the alkyl group preferably has 1 to 3 carbon atoms, and for example, a methyl group or an ethyl group is preferably bonded. The same alkyl group may be bonded to the Si atom, or different alkyl groups or hydrogen atoms may be bonded to it. Moreover, although all the siloxane units which comprise an oligosiloxane group may be the same or different, it is preferable that all are the same.
R can take a substituted or unsubstituted trialkylsilyl group only when L adjacent to R is a divalent linking group represented by formula (L-3). When R is a substituted or unsubstituted trialkylsilyl group, the alkyl group bonded to the Si atom preferably has 1 to 3 carbon atoms, for example, a methyl group, an ethyl group, or an isopropyl group is preferably bonded. . The same alkyl group may be bonded to the Si atom, or different alkyl groups may be bonded thereto. There is no restriction | limiting in particular as this substituent in case R is a trialkylsilyl group which has a substituent.

In the compound represented by the general formula (X), among R ^{1 to} R ⁶ , the number of substituents represented by the general formula (W) is preferably 1 to 4, preferably 1 to 2. Is more preferable, and 2 is particularly preferable.

In the present invention, in general formula (X), at least one of R ¹ and R ² is preferably a substituent represented by general formula (W).
These positions are preferred as the substitution positions in the general formula (X) because they are excellent in chemical stability of the compound, and are suitable from the viewpoint of HOMO level and packing of molecules in the film. It is done. In particular, in the general formula (X), a high carrier concentration can be obtained by using two positions of R ¹ and R ² as substituents represented by the general formula (W).

  The compound represented by the general formula (X) is preferably a compound represented by the following general formula (Y) from the viewpoint that the insulation reliability of the organic thin film transistor is more excellent.

In the general formula ^(Y), the definition of A 1, ^{A 2,} and ^R 2 to R ⁶ have the same meanings as defined in the above general formula (X).

In General Formula (Y), La is ^a divalent linking group represented by any one of General Formulas (L-1) to (L-10), or two or more General Formulas (L-1). -The bivalent coupling group which the bivalent coupling group represented by any of (L-10) couple | bonded is represented. The preferred range of L ^a is the same as the preferred range of L in the general formula (W). In general formula represented by ^{L a (L-1) ~} (L-10) in * represents a binding site with ^{R a.} Further, formula (L-1) and (L-2) in R 'may form a condensed ring by combining with R ^a respectively adjacent to the L ^a.
In General Formula (Y), R ^a is a hydrogen atom, a substituted or unsubstituted alkyl group, an oligooxyethylene group having 2 or more repeating oxyethylene units, an oligosiloxane group having 2 or more silicon atoms, or a substituted group. Or an unsubstituted trialkylsilyl group (provided that R ^a represents ^a hydrogen atom because La represents ^a general formula (L-1) to (L-3) or (L-8) to (L-10 ) only if, the R ^a represents a substituted or unsubstituted trialkylsilyl group is a divalent linking group L ^a adjacent R ^a is represented by the following general formula (L-3) Only if.) The preferable range of R ^{a is the same as} the preferable range of R in the general formula (W).

  The compound represented by the general formula (X) is preferably a compound represented by the general formula (Z) in that the effect of the present invention is more excellent.

In the general formula ^(Z), the definition of A 1, ^{A 2,} and ^R 3 to R ⁶ have the same meanings as defined in the above general formula (X).
In General Formula (Z), L ^b and L ^c are each independently a divalent linking group represented by any one of General Formulas (L-1) to (L-10), or two or more general groups A divalent linking group to which a divalent linking group represented by any one of formulas (L-1) to (L-10) is bonded is represented. The preferable range of L ^b and L ^{c is the same as} the preferable range of L in the general formula (W). L ^b and L ^c are preferably the same as each other. In general formula represented by ^{L b} or ^{L c (L-1) ~} (L-10) * in, each represents a binding site with ^{L b} or ^{L c.} In addition, R ′ in the general formulas (L-1) and (L-2) is bonded to R ^b adjacent to L ^b or R ^c adjacent to L ^c to form a condensed ring. Also good.

In general formula (Z), R ^b and R ^c each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, an oligooxyethylene group having 2 or more repeating oxyethylene units, and a silicon atom number of 2 or more. Represents an oligosiloxane group or a substituted or unsubstituted trialkylsilyl group (provided that R ^b and R ^c represent a hydrogen atom because L ^b and L ^c are each represented by formulas (L-1) to ( Only in the case of L-3) or (L-8) to (L-10), R ^b and R ^c represent a substituted or unsubstituted trialkylsilyl group, L ^b and R adjacent to R ^b L ^c adjacent to ^c is limited to the case each is a divalent linking group represented by the following general formula (L-3).). The preferable range of R ^b and R ^{c is the same as} the preferable range of R in the general formula (W). R ^b and R ^c are preferably the same as each other.

In general formula (Y) or (Z), all of R ^a , R ^b , and R ^c are preferably substituted or unsubstituted alkyl groups, and may be substituted or unsubstituted linear alkyl groups. More preferably, it is a linear alkyl group having 1 to 12 carbon atoms, more preferably a linear alkyl group having 3 to 12 carbon atoms, and a linear alkyl group having 4 to 10 carbon atoms. More particularly preferred.
In the general formula (Y) or (Z), all of L ^a , L ^b , and L ^c are (L-1) to (L-3), (L-8), (L-9), or (L— 10) is preferably a divalent linking group represented by any one of formulas (L-1) to (L-3) and (L-8) from the viewpoints of chemical stability and charge transportability. Or (L-10) is more preferable, and general formula (L-1) or (L-8) is particularly preferable.

  Specific examples of the compound represented by the general formula (X) are shown below, but should not be construed as being limited to these specific examples.

The compound represented by the general formula (X) preferably has a molecular weight of 3000 or less, more preferably 2000 or less, still more preferably 1000 or less, and particularly preferably 850 or less. It is preferable to make the molecular weight not more than the above upper limit value because the solubility in a solvent can be increased.
On the other hand, from the viewpoint of film quality stability of the thin film, the molecular weight is preferably 300 or more, more preferably 350 or more, and further preferably 400 or more.

The compound represented by the general formula (X) can be synthesized with reference to Journal of American Chemical Society, 116, 925 (1994), Journal of Chemical Society, 221 (1951), and the like.
Any reaction conditions may be used in the synthesis of the compound represented by the general formula (X). Any solvent may be used as the reaction solvent. In order to promote the ring formation reaction, it is preferable to use an acid or a base, and it is particularly preferable to use a base.
Synthetic intermediates having various substituents can be synthesized by combining known reactions. Each substituent may be introduced at any intermediate stage. After the synthesis of the intermediate, it is preferable to purify by sublimation purification after purification by column chromatography, recrystallization or the like. By sublimation purification, not only can organic impurities be separated, but inorganic salts and residual solvents can be effectively removed.

(Source electrode, drain electrode)
The source electrode and the drain electrode include a metal selected from the group consisting of silver (Ag) and copper (Cu), and an onium salt. The onium salt will be described in detail later.
The content of the onium salt in the source electrode and the drain electrode is not particularly limited, but is 0.1% relative to 100 parts by mass of the metal selected from the group consisting of silver and copper in that the insulation reliability of the organic thin film transistor is more excellent. 1-40 mass parts is preferable, 1-20 mass parts is more preferable, and 1-10 mass parts is especially preferable.

  The channel length of the source electrode and the drain electrode is not particularly limited, but is preferably 5 to 30 μm. The channel widths of the source electrode and the drain electrode are not particularly limited, but are preferably 10 to 200 μm. The thickness of the source electrode and the drain electrode is not particularly limited, but is preferably 100 to 1000 nm.

The method for producing the source electrode and the drain electrode is not particularly limited, but an electrode-forming composition containing silver particles (or copper particles) and an onium salt is applied or printed on a substrate on which a gate electrode and a gate insulating film are formed. The method of doing is mentioned. Examples of the method for patterning the electrode include a photolithography method; ink jet printing, screen printing, offset printing, letterpress printing, and the like.
Moreover, the method in particular of apply | coating the composition for electrode formation is not restrict | limited, The method of apply | coating the composition for organic-semiconductor layer formation mentioned above is mentioned.
The electrode forming composition may contain a solvent (for example, an organic solvent) as necessary.

After applying the electrode forming composition, if necessary, a drying treatment may be applied to remove the solvent. A conventionally known method can be used as a method for the drying treatment.
Moreover, energy provision, such as heating heat and light irradiation, may be applied to the coating film of the electrode forming composition to sinter silver particles (or copper particles) in the composition.
The heating conditions are not particularly limited, but the heating temperature is preferably 100 to 300 ° C., and the heating time is more preferably 10 to 60 minutes.
The heating means is not particularly limited, and known heating means such as an oven and a hot plate can be used.
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 (Xe) lamp, a chemical lamp, and a carbon arc lamp.

Hereinafter, the onium salt will be described in detail. As described above, the onium salt functions as a migration inhibitor that traps silver ions or copper ions.
The kind of onium salt is not particularly limited, and a known onium salt can be used, and examples thereof include iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, pyridinium salts, and the like.
Especially, the compound represented by general formula (I) is mentioned preferably as an onium salt at the point which the insulation reliability of an organic thin-film transistor is more excellent.
cC ^{n +} aA ^m- general formula (I)

(Cation)
In general formula (I), C ^{n +} represents an n-valent cation. Here, n represents an integer of 1 to 6. That is, C ^{n +} is a 1 to 6 valent cation.
When n in the general formula (I) is 1 (that is, when C ^{n +} is a monovalent cation), the C ^{n +} is a cation selected from the group consisting of the following general formulas (A) to (E). Represent. Especially, it is preferable that it is a cation selected from the group which consists of general formula (A)-(C), and since the organic thin-film transistor obtained shows the more superior insulation reliability, general formula (A) or general formula It is more preferable that it is a cation represented by (B).

In General Formula (A), R _{1 to} R ₄ each independently represent a hydrogen atom or a hydrocarbon group that may have a substituent (excluding a hydroxyalkyl group). However, all of R _{1 to} R ₄ are not simultaneously hydrogen atoms.

The hydrocarbon group is not particularly limited, and examples thereof include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group obtained by combining these.
The aliphatic hydrocarbon group may be linear, branched or cyclic. The number of carbon atoms of the aliphatic hydrocarbon group is not particularly limited, but is preferably 1-12. Specific examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group.
The number of carbon atoms of the aromatic hydrocarbon group is not particularly limited, but is preferably 6-18. Specific examples of the aromatic hydrocarbon group include an aryl group (phenyl group, tolyl group, xylyl group, etc.), a naphthyl group, and the like.

As said substituent, the substituent Q etc. which are mentioned later are mentioned, for example.
The substituent is preferably a substituent other than a hydroxy group because the mobility of the organic thin film transistor obtained is more excellent.

It is preferable that at least one of the R _{1 to} R ₄ is an aromatic hydrocarbon group because the resulting organic thin film transistor exhibits higher mobility.

As described above, R _{1 to} R ₄ in the general formula (A) are not hydroxyalkyl groups. Here, the hydroxyalkyl group is an alkyl group having a hydroxy group, and examples thereof include a hydroxyethyl group (—C ₂ H ₄ —OH).
When any of R _{1 to} R ₄ is a hydroxyalkyl group, carriers moving between the electrodes are trapped, and as a result, the mobility of the obtained organic thin film transistor is lowered.

Moreover, as above-mentioned, all of R < ₁ > -R < ₄ > in general formula (A) is not a hydrogen atom simultaneously. That is, C ^{n +} is not NH ₄ ⁺ . When C ^{n +} is NH ₄ ⁺ , the liberated ammonia is likely to volatilize, so that the thermal stability is lowered, and the compound (B) is easily decomposed when a conductive film (electrode) is formed by sintering or the like. As a result, the insulation reliability of the organic thin film transistor obtained is lowered.

In general formula (A), R _{1 to} R ₄ may be bonded to each other to form a ring structure. That is, two or more groups selected from the group consisting of R _{1 to} R ₄ may be bonded to each other to form a ring structure. In this specification, the term “bonded together to form a ring structure” means that two or more groups are bonded at any position via a single bond, a double bond, a triple bond or a divalent linking group to form a ring structure. It represents forming.
The divalent linking group is not particularly limited. For example, -CO-, -NH-, -NR- (R: substituent (for example, substituent Q described later)), -O-, -S-, or Examples include a combination of these.

The suitable aspect of the cation represented by general formula (A) below is shown. Here, each R _p is independently a group represented by the above-described R _{1 to} R ₄ (for example, a hydrogen atom or a hydrocarbon group which may have a substituent (excluding a hydroxyalkyl group). )). A plurality of R _p may be the same or different. Each R independently represents a hydrogen atom or a substituent (for example, a substituent Q described later).

In the general formula (B), R ₅ may have a substituent a hydrocarbon _{group, -NR 19 R 20, -N =} CR 21 R 22, -CR 23 = NR 24 or,, -CR _B1 R _B2— NR _B3 R _B4 is represented. Specific examples and preferred embodiments of the hydrocarbon group which may have the above substituent are the same as R _{1 to} R ₄ in the general formula (A).
R _{19 to} R ₂₄ and R _{B1 to} R _B4 each independently represent a hydrogen atom or a hydrocarbon group that may have a substituent. Specific examples and preferred embodiments of the hydrocarbon group which may have the above substituent are the same as R _{1 to} R ₄ in the general formula (A). R ₁₉ and R ₂₀ may combine with each other to form a ring structure.

In general formula (B), R ₆ represents a hydrogen atom or a hydrocarbon group which may have a substituent. Specific examples and preferred embodiments of the hydrocarbon group which may have the above substituent are the same as R _{1 to} R ₄ in the general formula (A).

In the general formula (B), R ₇ represents a hydrogen atom, a hydrocarbon group which may have a substituent, an alkoxy group, an alkylthio group, a hydroxy group, a mercapto group, or —NR ₂₅ R ₂₆ . Specific examples and preferred embodiments of the hydrocarbon group which may have the above substituent are the same as R _{1 to} R ₄ in the general formula (A).
R ₂₅ and R ₂₆ each independently represent a hydrogen atom or a hydrocarbon group which may have a substituent, and may be bonded to each other to form a ring structure. Specific examples and preferred embodiments of the hydrocarbon group which may have the above substituent are the same as R _{1 to} R ₄ in the general formula (A).

In general formula (B), R ₈ represents a hydrogen atom, a hydrocarbon group which may have a substituent, an alkoxy group, an alkylthio group, a hydroxy group, a mercapto group, —NR ₂₇ R ₂₈ , —N═CR ₂₉ R. _30, or represents a -CR ₃₁ = NR _32. Specific examples and preferred embodiments of the hydrocarbon group which may have the above substituent are the same as R _{1 to} R ₄ in the general formula (A).
R _{27 to} R ₃₂ each independently represent a hydrogen atom or a hydrocarbon group that may have a substituent. Specific examples and preferred embodiments of the hydrocarbon group which may have the above substituent are the same as R _{1 to} R ₄ in the general formula (A). R ₂₇ and R ₂₈ may combine with each other to form a ring structure.

However, R ₇ and R _{8 in} the general formula (B) are not simultaneously an alkoxy group, a hydroxy group, an alkylthio group or a mercapto group.
Further, R ₅ , R ₇ and R _{8 in} the general formula (B) are not all —NR ₁₉ R ₂₀ , —NR ₂₅ R ₂₆ or —NR ₂₇ R ₂₈ at the same time. That, R ₅ is the above -NR ₁₉ R _20, at the same time R ₇ is the -NR ₂₅ R _26, never R ₈ is at the same time is the -NR ₂₇ R _28.

In general formula (B), R _{5 to} R ₈ may be bonded to each other to form a ring structure. That is, two or more groups selected from the group consisting of R _{5 to} R ₈ may be bonded to each other to form a ring structure.
Two or more groups selected from the group consisting of R _{5 to} R ₈ are preferably bonded to each other to form a ring structure.

When R ₅ forms a ring structure, the divalent group derived from R ₅ in the ring structure is preferably a group selected from the group consisting of the following general formulas (a) to (f).
When R ₆ forms a ring structure, the divalent group derived from R ₆ in the ring structure may be a divalent group selected from the group consisting of the following general formulas (a) to (d). preferable.
When R ₇ forms a ring structure, the divalent group derived from R ₇ in the ring structure is selected from the group consisting of the following general formulas (a) to (e), (g) and (h) A divalent group is preferred.
When R ₈ forms a ring structure, the divalent group derived from R ₈ in the ring structure may be a divalent group selected from the group consisting of the following general formulas (a) to (h). preferable.

However, both “a divalent group derived from R ₇ in the ring structure” and “a divalent group derived from R ₈ in the ring structure” are simultaneously represented by the following general formula (g) or (h). It is not a group. In addition, “a divalent group derived from R ₅ in the ring structure”, “a divalent group derived from R ₇ in the ring structure” and “a divalent group derived from R ₈ in the ring structure” Not all are groups represented by the following general formula (e) at the same time.

In general formulas (a) to (f), R _{35 to} R ₄₈ each independently represent a hydrogen atom or a substituent. Examples of the substituent include a substituent Q described later.
In general formulas (a) to (h), an asterisk (asterisk) represents a bonding position, one of the two asterisks represents a bonding position of each group in general formula (B), and the other asterisk represents a ring. It represents the bonding position when bonding together to form a structure. For example, R ₅ and R ₆ in general formula (B) are bonded to each other to form a ring structure, and a divalent group derived from R ₅ in the ring structure is a group represented by general formula (a) When the divalent group derived from R ₆ in the ring structure is a group represented by the general formula (b), one asterisk in the general formulas (a) and (b) is represented by the general formula (B ) Represents the bonding position with N ^+, and the other asterisk in the general formulas (a) and (b) represents the bonding position when R ₅ and R ₆ are bonded to each other.

The suitable aspect of the cation represented by general formula (B) below is shown. Here, R _p is a group represented by R ₅ or R ₆ described above (for example, a hydrogen atom, an optionally substituted hydrocarbon group, —NR ₁₉ R ₂₀ , —N═CR ₂₁ R ₂₂ -CR ₂₃ = NR ₂₄ or -CR _B1 R _B2 -NR _B3 R _B4 ), and R _s represents a group represented by R ₇ or R ₈ (for example, a hydrogen atom or a substituent). hydrocarbon group which may be an alkoxy group, an alkylthio group, hydroxy group, a mercapto _{group, -NR 27 R 28, -N =} CR 29 R 30 , or represents a -CR ₃₁ = NR _32), R are each Independently, it represents a hydrogen atom or a substituent (for example, substituent Q described later).

In general formula (C), R ₉ represents a hydrocarbon group which may have a substituent, or —NR _C1 R _C2 . Specific examples and preferred embodiments of the hydrocarbon group which may have the above substituent are the same as R _{1 to} R ₄ in the general formula (A).
R _C1 and R _C2 each independently represent a hydrogen atom or a hydrocarbon group that may have a substituent. Specific examples and preferred embodiments of the hydrocarbon group which may have the above substituent are the same as R _{1 to} R ₄ in the general formula (A).

In general formula (C), R ₁₀ represents a hydrogen atom or a hydrocarbon group which may have a substituent. Specific examples and preferred embodiments of the hydrocarbon group which may have the above substituent are the same as R _{1 to} R ₄ in the general formula (A).

In general formula (C), R ₁₁ represents a hydrocarbon which may have a substituent, —CR ₃₃ ═NR ₃₄ , or —NR _C3 R _C4 . Specific examples and preferred embodiments of the hydrocarbon group which may have the above substituent are the same as R _{1 to} R ₄ in the general formula (A).
R ₃₃ , R ₃₄ , R _C3 and R _C4 each independently represent a hydrogen atom or a hydrocarbon group which may have a substituent. Specific examples and preferred embodiments of the hydrocarbon group which may have the above substituent are the same as R _{1 to} R ₄ in the general formula (A).

In general formula (C), R _{9 to} R ₁₁ may be bonded to each other to form a ring structure. That is, two or more groups selected from the group consisting of R _{9 to} R ₁₁ may be bonded to each other to form a ring structure.

The suitable aspect of the cation represented by general formula (C) below is shown. Here, R _p represents a group represented by R ₉ or R ₁₀ described above (for example, a hydrogen atom, a hydrocarbon group which may have a substituent, or —NR _C1 R _C2 ), and R is , Each independently represents a hydrogen atom or a substituent (for example, substituent Q described later).

In general formula (D), R < ₁₂ > -R < ₁₅ > represents the hydrocarbon group which may have a hydrogen atom or a substituent each independently. Specific examples and preferred embodiments of the hydrocarbon group which may have the above substituent are the same as R _{1 to} R ₄ in the general formula (A).

However, not all of R _{12 to} R _{15 in} the general formula (D) are hydrogen atoms at the same time. That is, C ^{n +} is not PH ₄ ⁺ . When C ^{n +} is PH ₄ ⁺ , the thermal stability is lowered, and the compound (B) is easily decomposed when a conductive film (electrode) is formed by sintering or the like. As a result, the insulation reliability of the organic thin film transistor obtained is lowered.

In the general formula (D), R ₁₂ ~R ₁₅ may respectively be bonded together to form a ring structure. That is, two or more groups selected from the group consisting of R _{12 to} R ₁₅ may be bonded to each other to form a ring structure.

In the general formula (E), R _{16 to} R ₁₈ each independently represents an alkyl group which may have a substituent. The alkyl group may be linear, branched or cyclic. The number of carbon atoms of the alkyl group is not particularly limited, but is preferably 1-12. Examples of the substituent include a substituent Q described later.

As described above, the general formula (E) in the R ₁₆ to R ₁₈ each independently represent an optionally substituted alkyl group. When any of R _{16 to} R ₁₈ is a hydrocarbon group other than an alkyl group (for example, an aromatic hydrocarbon group), the stability in the electrode is lowered, and as a result, the mobility of the organic thin film transistor is lowered. .

In the general formula (E), R _{16 to} R ₁₈ may be bonded to each other to form a ring structure. That is, two or more groups selected from the group consisting of R _{16 to} R ₁₈ may be bonded to each other to form a ring structure.

The R _{5 to} R ₃₄ , the R _{B1 to} R _B4, and the R _{C1 to} R _C4 may be hydroxyalkyl groups.

When n in the general formula (I) is 2 to 6 (that is, when C ^{n +} is a divalent to hexavalent cation), C ^{n +} is selected from the group consisting of the general formulas (A) to (E). A cation having n cations as a partial structure in the same molecule is represented. That is, when n in the general formula (I) is 2 to 6, C ^{n +} is obtained by removing one or more hydrogen atoms from a cation selected from the group consisting of the general formulas (A) to (E). It represents a cation having n partial structures in the same molecule. It may be a cation having n types of partial structures or a cation having a total of n types of two or more partial structures.
When n in the general formula (I) is 2 to 6, C ^{n +} is a group in which n cations selected from the group consisting of the general formulas (A) to (E) are single bonds, two A cation bonded through a heavy bond, a triple bond or a divalent linking group is preferred. Specific examples of the divalent linking group are as described above. In addition, it may be a cation in which one kind of n cations are bonded, or a cation in which two or more kinds of n cations in total are bonded.

(Anion)
In the general formula (I), A ^m− represents an m-valent anion. Here, m represents an integer of 1 to 3. That is, A ^m− is a 1-3 valent anion.

The above A ^m− is not an anion selected from the group consisting of Cl ⁻ , Br ⁻ , I ⁻ , PF ₆ ⁻ , R _A1 CO ₃ ⁻ , R _A10 NHCOO ⁻ , SbF ₆ ⁻ , and AsF ₆ ⁻ . Here, R _A1 and R _A10 each independently represent a hydrogen atom or a hydrocarbon group that may have a substituent. The specific example of the hydrocarbon group which may have the said substituent is the same as R < ₁ > -R < ₄ > in the general formula (A) mentioned above.
A ^m− is an anion selected from the group consisting of Cl ⁻ , Br ⁻ , I ⁻ , PF ₆ ⁻ , R _A1 CO ₃ ⁻ , R _A10 NHCOO ⁻ , SbF ₆ ⁻ , and AsF ₆ ^−. The mobility or insulation reliability of the obtained organic thin film transistor becomes insufficient.

The above A ^m− is SO ₄ ²⁻ , R _A2 SO ₄ ⁻ , R _A3 SO ₃ ⁻ , PO ₄ ³⁻ , R _A4 PO ₄ ²⁻ , (R _A5 ) ₂ PO ₄ ⁻ , PO ₃ ³⁻ , R _A6 PO ₃ ²⁻ , (R _A7 ) ₂ PO ₃ ⁻ , [BF ₄ ] ⁻ , [B (CN) ₄ ] ⁻ , [B (C ₆ H ₅ ) ₄ ] ⁻ , CN ⁻ , OCN ⁻ , SCN ⁻ , [R _A8 —COO] ⁻ , [(R _A9 —SO ₂ ) ₂ N] ⁻ and N (CN) ₂ ^— are preferred, and SO ₄ ²⁻ , R _A2 SO ₄ ⁻ , R _A3 SO ₃ ^— and (R _A5 ) ₂ PO ₄ ^— are more preferably anions selected from the group consisting of SO ₄ ^2- and the resulting organic thin film transistor exhibits higher mobility. , R _A2 SO ₄ ^- and R _A3 SO ₃ ^- and more preferably an anion selected from the group consisting of. Here, R _{A2 to} R _A9 each independently represent a hydrogen atom or a hydrocarbon group that may have a substituent. The specific example of the hydrocarbon group which may have the said substituent is the same as R < ₁ > -R < ₄ > in the general formula (A) mentioned above.
R _A2 is preferably a hydrogen atom or an alkyl group.
R _A3 is an alkyl group (particularly having 1 to 12 carbon atoms) which may have a substituent or an aromatic hydrocarbon group (particularly having 6 to 18 carbon atoms) which may have a substituent. Preferably there is. Examples of the substituent include the substituent Q described later.
R _A4 and R _A5 are preferably each independently a hydrogen atom or an alkyl group.
R _A6 and R _A7 are preferably each independently an aliphatic hydrocarbon group (particularly having 1 to 12 carbon atoms) which may have a substituent.

R _{A1 to} R _A10 may be a hydroxyalkyl group.

In general formula (I), c represents an integer of 1 to 3, a represents an integer of 1 to 6, and in general formula (I), c, n, a and m are c × n = a × m Is satisfied. That is, the compound (B) is a charge neutral salt composed of c cations (C ^{n +} ) and a anions (A ^m− ).
It is preferable that all of c, n, a and m are 1.

(Substituent Q)
As the substituent Q in the present specification, a halogen atom, an alkyl group (including a cycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group, an aryl group, a heterocyclic group, a cyano group, Hydroxy group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy, amino group (including anilino group), Acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfur Amoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphine group Examples thereof include a finyloxy group, a phosphinylamino group, a silyl group, or a combination thereof.

  More specifically, as the substituent Q, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group [(a linear, branched, cyclic substituted or unsubstituted alkyl group is represented. Is an alkyl group (preferably an alkyl group having 1 to 30 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl) A cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), a bicycloalkyl group (preferably having 5 to 30 carbon atoms). A substituted or unsubstituted bicycloalkyl group, that is, a bicycloalkali having 5 to 30 carbon atoms A monovalent group in which one hydrogen atom is removed from, for example, bicyclo [1.2.2] heptan-2-yl, bicyclo [2.2.2] octane-3-yl), and more ring structures It also includes a tricyclo structure, etc. An alkyl group (for example, an alkyl group of an alkylthio group) in a substituent described below also represents such an alkyl group.

Alkenyl group [represents a linear, branched, or cyclic substituted or unsubstituted alkenyl group. They are alkenyl groups (preferably substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, oleyl), cycloalkenyl groups (preferably substituted or substituted groups having 3 to 30 carbon atoms). An unsubstituted cycloalkenyl group, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms (for example, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl), Bicycloalkenyl group (a substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, i.e., a monovalent group obtained by removing one hydrogen atom of a bicycloalkene having one double bond. For example, bicyclo [2.2.1] hept-2-en-1-yl, bicyclo [2. .2] is intended to encompass oct-2-en-4-yl). An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as ethynyl, propargyl, trimethylsilylethynyl group),

An aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), a heterocyclic group (preferably 5 or 6 A monovalent group obtained by removing one hydrogen atom from a substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, and more preferably a 5- or 6-membered aromatic having 3 to 30 carbon atoms Heterocyclic groups such as 2-furanyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolinyl),

A cyano group, a hydroxy group, a nitro group, a carboxyl group, an alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, such as methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy), an aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, such as phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2 -Tetradecanoylaminophenoxy), silyloxy groups (preferably silyloxy groups having 3 to 20 carbon atoms, such as trimethylsilyloxy, t-butyldimethylsilyloxy), heterocyclic oxy groups (preferably having 2 to 30 carbon atoms) A substituted or unsubstituted heterocyclic oxy group, 1-phenyl te Razole-5-oxy, 2-tetrahydropyranyloxy), acyloxy group (preferably formyloxy group, substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, substituted or unsubstituted group having 6 to 30 carbon atoms Arylcarbonyloxy groups such as formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), carbamoyloxy groups (preferably substituted or unsubstituted carbamoyloxy groups having 1 to 30 carbon atoms) , For example, N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy), alkoxycal Nyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms such as methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy), aryloxycarbonyloxy group (preferably Is a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy),

An amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted anilino group having 6 to 30 carbon atoms, such as amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino), acylamino group (preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms) Groups such as formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino), aminocarbonylamino groups (preferably substituted with 1 to 30 carbon atoms) Or unsubstituted aminocarbonylamino, eg , Carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino), an alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, for example, Methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino), aryloxycarbonylamino group (preferably substituted or unsubstituted having 7 to 30 carbon atoms) Aryloxycarbonylamino groups such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino), sulfamoyla Group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, such as sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino), alkyl And an arylsulfonylamino group (preferably substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms, such as methylsulfonylamino, butylsulfonylamino, phenylsulfonyl Amino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino),

Mercapto group, alkylthio group (preferably substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, such as methylthio, ethylthio, n-hexadecylthio), arylthio group (preferably substituted or unsubstituted group having 6 to 30 carbon atoms) Arylthio such as phenylthio, p-chlorophenylthio, m-methoxyphenylthio), heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms such as 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio), a sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, such as N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N , N-dimethylsulfamoyl, N-acetylsulfur Moyl, N-benzoylsulfamoyl, N- (N′-phenylcarbamoyl) sulfamoyl), sulfo group, alkyl and arylsulfinyl group (preferably substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, 6 30 substituted or unsubstituted arylsulfinyl groups such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl)

Alkyl and arylsulfonyl groups (preferably substituted or unsubstituted alkylsulfonyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonyl groups having 6 to 30 carbon atoms such as methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p- Methylphenylsulfonyl), acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, substitution having 4 to 30 carbon atoms) Or a heterocyclic carbonyl group bonded to a carbonyl group with an unsubstituted carbon atom, such as acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2- Furylcarbonyl), ally An oxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms such as phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl), alkoxy A carbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl),

A carbamoyl group (preferably a substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methyl Sulfonyl) carbamoyl), aryl and heterocyclic azo groups (preferably substituted or unsubstituted arylazo groups having 6 to 30 carbon atoms, substituted or unsubstituted heterocyclic azo groups having 3 to 30 carbon atoms, such as phenylazo, p- Chlorophenylazo, 5-ethylthio-1,3,4-thiadiazol-2-ylazo), imide group (preferably N-succinimide, N-phthalimide), phosphino group (preferably substituted or unsubstituted 2 to 30 carbon atoms) Substituted phosphino groups such as dimethylphosphino, diphenylphosphino, Tilphenoxyphosphino), phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, such as phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl), phosphinyloxy group (preferably Is a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, such as diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), a phosphinylamino group (preferably having 2 to 30 carbon atoms). A substituted or unsubstituted phosphinylamino group such as dimethoxyphosphinylamino, dimethylaminophosphinylamino), a silyl group (preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms, such as Trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl And the like.

(substrate)
The substrate plays a role of supporting a gate electrode, a source electrode, a drain electrode, and the like.
The kind of board | substrate is not restrict | limited in particular, For example, a plastic substrate, a glass substrate, a ceramic substrate etc. are mentioned. Among these, a glass substrate or a plastic substrate is preferable from the viewpoint of applicability to each device and cost.
The material of the plastic substrate includes a thermosetting resin (for example, epoxy resin, phenol resin, polyimide resin, polyester resin (for example, PET, PEN)) or thermoplastic resin (for example, phenoxy resin, polyether sulfone, polysulfone, Polyphenylene sulfone).
Examples of the material for the ceramic substrate include alumina, aluminum nitride, zirconia, silicon, silicon nitride, silicon carbide, and the like.
Examples of the glass substrate material include soda glass, potash glass, borosilicate glass, quartz glass, aluminum silicate glass, and lead glass.

(Gate electrode)
Examples of the material for the gate electrode include gold (Au), silver, aluminum, copper, chromium, nickel, cobalt, titanium, platinum, magnesium, calcium, barium, sodium, and other metals; InO ₂ , SnO ₂ , ITO, etc. Examples include conductive oxides; conductive polymers such as polyaniline, polypyrrole, polythiophene, polyacetylene, and polydiacetylene; semiconductors such as silicon, germanium, and gallium arsenide; carbon materials such as fullerene, carbon nanotube, and graphite. Especially, it is preferable that it is a metal, and it is more preferable that they are silver and aluminum.

The thickness of the gate electrode is not particularly limited, but is preferably 20 to 200 nm.
A method for forming the gate electrode is not particularly limited, and examples thereof include a method of vacuum depositing or sputtering an electrode material on a substrate, a method of applying or printing an electrode forming composition, and the like. In the case of patterning the electrode, examples of the patterning method include a photolithography method; a printing method such as ink jet printing, screen printing, offset printing, letterpress printing; and a mask vapor deposition method.

  Note that, as described above, the gate electrode may include a metal selected from the group consisting of silver and copper, and an onium salt.

(Gate insulation film)
Materials for the gate insulating film include polymethyl methacrylate, polystyrene, polyvinyl phenol, polyimide, polycarbonate, polyester, polyvinyl alcohol, polyvinyl acetate, polyurethane, polysulfone, polybenzoxazole, polysilsesquioxane, epoxy resin, phenol resin And the like; oxides such as silicon dioxide, aluminum oxide, and titanium oxide; and nitrides such as silicon nitride. Of these materials, a polymer is preferable in view of compatibility with the organic semiconductor layer.
When a polymer is used as the material for the gate insulating film, it is preferable to use a crosslinking agent (for example, melamine) in combination. By using a crosslinking agent in combination, the polymer is crosslinked and the durability of the formed gate insulating film is improved.

The thickness of the gate insulating film is not particularly limited, but is preferably 100 to 1000 nm.
The method for forming the gate insulating film is not particularly limited, and examples thereof include a method for applying a gate insulating film forming composition on a substrate on which a gate electrode is formed, and a method for depositing or sputtering a gate insulating film material. It is done. The method for applying the gate insulating film forming composition is not particularly limited, and known methods (bar coating method, spin coating method, knife coating method, doctor blade method) can be used.
When a gate insulating film forming composition is applied to form a gate insulating film, it may be heated (baked) after application for the purpose of solvent removal, crosslinking, and the like.

(Sealing layer)
The organic thin film transistor of the present invention preferably includes a sealing layer as the outermost layer from the viewpoint of durability. A well-known sealing agent can be used for a sealing layer.
The thickness of the sealing layer is not particularly limited, but is preferably 0.2 to 10 μm.
The method for forming the sealing layer is not particularly limited. For example, the composition for forming the sealing layer is applied onto the substrate on which the gate electrode, the gate insulating film, the source electrode, the drain electrode, and the organic semiconductor layer are formed. The method etc. are mentioned. The specific example of the method of apply | coating the composition for sealing layer formation is the same as the method of apply | coating the composition for organic semiconductors. When the sealing layer-forming composition is applied to form the sealing layer, it may be heated (baked) after application for the purpose of solvent removal, crosslinking, and the like.

<Second Embodiment>
FIG. 2 is a schematic cross-sectional view of another embodiment of the organic thin film transistor of the present invention.
In FIG. 2, the organic thin film transistor 200 is opposite to the substrate 10, the gate electrode 20 disposed on the substrate 10, the gate insulating film 30 in contact with the gate electrode 20, and the side of the gate insulating film 30 where the gate electrode 20 is present. An organic semiconductor layer 50 in contact with the surface on the side, a source electrode 40 and a drain electrode 42 in contact with the organic semiconductor layer 50, and a sealing layer 60 that covers each member are provided. Here, the organic semiconductor layer 50 is formed using the composition of the present invention described above. The organic thin film transistor 200 is a bottom gate-top contact type organic thin film transistor.
The substrate, the gate electrode, the gate insulating film, the source electrode, the drain electrode, the organic semiconductor layer and the sealing layer are as described above, and at least one electrode selected from the group consisting of the source electrode, the drain electrode and the gate electrode is silver. And a metal selected from the group consisting of copper and onium salts, and a compound represented by the general formula (X) as an organic semiconductor material in the organic semiconductor layer.

1 and 2, the embodiments of the bottom gate-bottom contact type organic thin film transistor and the bottom gate-top contact type organic thin film transistor have been described in detail. However, the top gate-bottom contact type organic thin film transistor, It can also be applied to top gate-top contact type organic thin film transistors.
That is, in the top gate-bottom contact type organic thin film transistor and the top gate-top contact type organic thin film transistor, at least one electrode selected from the group consisting of a source electrode, a drain electrode and a gate electrode is made of silver and copper. A metal selected from the group and an onium salt are included, and a compound represented by the general formula (X) is included as an organic semiconductor material in the organic semiconductor layer.

Note that in the top gate-bottom contact type organic thin film transistor and the top gate-top contact type organic thin film transistor, as in FIGS. 1 and 2, the substrate, gate electrode, gate insulating film, source electrode, drain electrode, organic A semiconductor layer is used and only the stacking order is different.
More specifically, in a top gate-bottom contact type organic thin film transistor, a substrate, a source electrode and a drain electrode arranged on the substrate, a source electrode and a drain electrode, and a source electrode and a drain electrode are connected. An organic semiconductor layer covering the surface of the substrate in between, a gate insulating film in contact with the surface of the organic semiconductor layer opposite to the substrate side, and a gate electrode in contact with the surface of the gate insulating film opposite to the organic semiconductor layer side Prepare.
Further, in a top gate-top contact type organic thin film transistor, a substrate, an organic semiconductor layer disposed on the substrate, a source electrode and a drain electrode in contact with the surface of the organic semiconductor layer opposite to the substrate side, and a source electrode And a gate insulating film in contact with the drain electrode and covering the surface of the organic semiconductor layer between the source electrode and the drain electrode, and a gate electrode in contact with the surface of the gate insulating film opposite to the organic semiconductor layer.

  Examples are shown below, but the present invention is not limited thereto.

<Synthesis Example 1: Synthesis of Compound 7>
In accordance with the specific synthesis procedure shown in the following scheme, Compound 7, which is a compound represented by the general formula (X), was synthesized.
The compounds up to compound 7c were synthesized with reference to the following paper.
Journal of American Chemical Society, 116, 925 (1994)
Journal of Chemical Society, 221 (1951)

(Synthesis of Compound 7a)
To a pyridine solution (125 ml) of 1,5-diaminonaphthalene (10 g), p-toluenesulfonyl chloride (34 g) was slowly added and stirred at room temperature for 2 hours. The reaction solution was poured into ice water, and the precipitate was filtered under reduced pressure. The obtained crude crystals were washed with methanol to obtain Compound 7a (29 g).

(Synthesis of Compound 7b)
A glacial acetic acid solution of compound 7a (10 g) was heated and stirred at 95 ° C., and bromine (2 mL) diluted with 10 mL of glacial acetic acid was slowly added dropwise thereto. The reaction was carried out for 10 minutes, and after cooling, filtration was performed to obtain an elementary crystal as a gray solid. The crude crystal was recrystallized in nitrobenzene to obtain Compound 7b (6.8 g).

(Synthesis of Compound 7c)
A concentrated sulfuric acid solution of compound 7b (5 g) was stirred at room temperature for 24 hours. The reaction solution was poured into ice water, and the precipitated solid was collected by filtration. The solid was dispersed again in ice water and neutralized with aqueous ammonia to obtain Compound 7c (0.5 g).

(Synthesis of Compound 7d)
Butyryl chloride (2.6 mL) was added dropwise to a pyridine solution of 7c (2 g) at room temperature, and the mixture was stirred for 2 hours. The reaction solution was poured into ice water, and the solid was filtered under reduced pressure. After dispersing in methanol and stirring for 1 hour, Compound 7d (1.39 g) was obtained by filtering the solid.

(Synthesis of Compound 7e)
Compound 7d (1.2 g) and Lawesson's reagent (1.48 g) were added to a mixed solution of THF (360 mL) and toluene (72 mL), and the mixture was stirred for 3 hours while heating under reflux. After removing only THF by evaporation to form a toluene solution, the mixture was stirred at 60 ° C. for 1 hour. Thereafter, the insoluble material was filtered to obtain Compound 7e (0.5 g).

(Synthesis of Compound 7)
Compound 7e (0.4 g) and cesium carbonate (1.33 g) were reacted in dimethylacetamide at 120 ° C. for 2 hours. The reaction solution was poured into water and the precipitate was filtered. The filtered solid was repeatedly recrystallized in THF to synthesize target compound 7 (0.12 g). The obtained compound was identified by H-NMR and Mass spectrum.

  Compound 8, Compound 9, Compound 34, Compound 37, and Compound 38 used in Examples were synthesized in the same manner as Compound 7. The structural formulas of the above compounds are shown below.

  Further, as a comparative example compound, the following comparative example compound 1 was synthesized according to DT2224746, and comparative example compound 2 was synthesized according to JP-A-6-073065.

<Example 1>
(Preparation of silver ink A1)
Dispersbyk-190 (manufactured by Big Chemie) as a dispersant (7.36 g as a nonvolatile material) was dissolved in water (100 mL) (solution a). Next, 50.00 g (294.3 mmol) of silver nitrate was dissolved in water (200 mL) (solution b). Solution a and solution b were mixed and stirred. To the resulting mixture, 85 mass% N, N-diethylhydroxylamine aqueous solution (78.71 g) (750.5 mmol as N, N-diethylhydroxylamine) was slowly added dropwise at room temperature. Further, a solution prepared by dissolving Disperbyk-190 (7.36 g) in water (1000 mL) was slowly added dropwise at room temperature.
The obtained suspension was passed through an ultrafiltration unit (Saltrius Stedim Vivaflow 50, molecular weight cut off: 100,000, number of units: 4) and purified until about 5 L of exudate was produced from the ultrafiltration unit. Purified by passing water through. The supply of purified water was stopped and concentrated to obtain 50 g of a silver nanoparticle dispersion (silver ink A1). The solid content in the silver ink A1 was 32% by mass. Moreover, it was 97.0 mass% when the content of silver in solid content was measured by TG-DTA.
Next, an onium salt-containing silver ink was prepared by adding pyridinium tosylate, which is a migration inhibitor, to the silver ink A1 at a ratio of 2.0 mass% with respect to silver.

(Production of organic thin film transistor)
Al serving as a gate electrode was deposited on a glass substrate (Eagle XG: Corning) (thickness: 50 nm). On top of that, a composition for forming a gate insulating film (polyvinylphenol / melamine = 1 part by weight / 1 part by weight (w / w) PGMEA (propylene glycol monomethyl ether acetate) solution (solid content concentration: 2% by weight)) is spun Coating was performed and baking was performed at 150 ° C. for 60 minutes to form a gate insulating film having a thickness of 400 nm. An onium salt-containing silver ink prepared thereon was drawn on a source electrode and a drain electrode having a channel length of 60 μm and a channel width of 150 μm using an inkjet apparatus DMP-2831 (manufactured by Fuji Film Dimatics). Thereafter, baking was performed in an oven at 180 ° C. for 30 minutes, and sintering was performed.
A toluene solution of compound 7 (concentration of compound 7: 0.5 mass%) was spin-coated thereon and baked at 140 ° C. for 10 minutes to form an organic semiconductor layer having a thickness of 100 nm. Cytop CTL-107MK (manufactured by AGC) is spin-coated thereon and baked at 140 ° C. for 20 minutes to form a sealing layer (top layer) having a thickness of 1 μm to obtain an organic thin film transistor (bottom contact type). It was.

<Examples 2-14, Comparative Examples 1-14>
The organic semiconductor material shown in the following Table 1 was used instead of the pyridinium tosylate salt, and the migration inhibitor (onium salt) shown in the following Table 1 was used instead of the compound 7, and the same as in Example 1 An organic thin film transistor was prepared according to the procedure.

(Insulation reliability evaluation (migration suppression effect evaluation))
About the organic thin-film transistor obtained by each Example and the comparative example, the lifetime test was conducted on condition of the following using EHS-221MD (made by ESPEC Co., Ltd.), and the resistance value between source / drain electrodes was set to 1 × 10 ⁵ Ω. The time to become was measured. At this time, the measurement result (time) of Comparative Example 1 was set to 1, and Table 1 shows the relative time of each Example and Comparative Example.
・ Temperature: 60 ℃
・ Humidity: RH 60%
・ Pressure: 1.0 atm
・ Gate voltage: -40V
・ Voltage between source / drain electrodes: 50V

The detail of each component shown by the said Table 1 is as follows.
A-1: Compound 7
A-2: Compound 8
A-3: Compound 9
A-4: Compound 34
A-5: Compound 37
A-6: Compound 38
A-7: Comparative Compound 1
A-8: Comparative compound 2
A-9: TIPS pentacene (6,13-bis (triisopropylsilylethynyl) pentacene, manufactured by Sigma-Aldrich)
B-1: pyridinium tosylate

B-2: Tetramethylammonium salt tosylate

B-3: Diethylphosphonic acid tetramethylammonium salt

B-4: dimethylphenylammonium tosylate salt

As shown in Table 1, it was confirmed that the organic thin film transistor of the present invention exhibits excellent insulation reliability.
Especially, when the general formula (L-8) was contained in the compound represented by general formula (X), it was confirmed that the insulation reliability was more excellent.
On the other hand, as shown in Comparative Examples 1 to 14, the desired effect was not obtained in the organic thin film transistor having no predetermined configuration.

10: substrate 20: gate electrode 30: gate insulating film 40: source electrode 42: drain electrode 50: organic semiconductor layer 60: sealing layer 100, 200: organic thin film transistor

Claims (8)

An organic thin film transistor having at least an organic semiconductor layer containing an organic semiconductor material, a gate insulating film, a gate electrode, a source electrode, and a drain electrode,
The organic semiconductor material includes a compound represented by the general formula (X),
An organic thin film transistor, wherein at least one electrode selected from the group consisting of the gate electrode, the source electrode, and the drain electrode contains at least a metal selected from the group consisting of silver and copper, and an onium salt.

(In General Formula (X), A ¹ and A ² each independently represents a sulfur atom, an oxygen atom, or a selenium atom. R ^{1 to} R ⁶ each independently represents a hydrogen atom or a substituent. However, at least one of R ^{1 to} R ⁶ is a substituent represented by the following general formula (W).)
* -LR General Formula (W)
(In General Formula (W), * represents a bonding site with a naphthalene ring, a ring containing A ¹ , or a ring containing A ² in General Formula (X), and L is the following General Formula (L-1) To (L-10), or a divalent linking group represented by any of the following general formulas (L-1) to (L-10). And R represents a hydrogen atom, a substituted or unsubstituted alkyl group, an oligooxyethylene group having 2 or more repeating oxyethylene units, and an oligosiloxane group having 2 or more silicon atoms. Or a substituted or unsubstituted trialkylsilyl group, wherein R represents a hydrogen atom, L is represented by the general formulas (L-1) to (L-3) or (L-8) to (L -10) only when R represents a substituted or unsubstituted trialkylsilyl group , Only if L adjacent to R is a divalent linking group represented by the following general formula (L-3).)

(In the general formula (L-1) ~ (L -10), the ring wavy line portion includes a naphthalene ring, the ^{A 1} or represents a binding site to the ring containing ^{A 2,} * the general formula (W) In the general formula (L-8), m represents 4 and m in the general formulas (L-9) and (L-10) represents 2. General formula (L-1) , (L-2), (L-8), (L-9) and (L-10), each independently represents a hydrogen atom or a substituent, represented by the general formula (L-1) And R ′ in (L-2) may be bonded to R adjacent to L to form a condensed ring.) ^2. The organic thin film transistor according to claim 1, wherein at least one of R ¹ and R ² in the general formula (X) is a substituent represented by the general formula (W). The organic thin-film transistor of Claim 1 or 2 in which the compound represented by the said general formula (X) contains the compound represented by the following general formula (Y).

(In General Formula (Y), A ¹ and A ² each independently represent a sulfur atom, an oxygen atom, or a selenium atom. R ^{2 to} R ⁶ each independently represent a hydrogen atom or a substituent. La is ^a divalent linking group represented by any one of the following general formulas (L-1) to (L-10), or any of two or more of the following general formulas (L-1) to (L-10). R ^a represents ^a hydrogen atom, a substituted or unsubstituted alkyl group, or an oligooxyethylene group having 2 or more repeating oxyethylene units. Represents an oligosiloxane group having 2 or more silicon atoms, or a substituted or unsubstituted trialkylsilyl group, provided that Ra represents ^a hydrogen atom because La represents ^a general formula (L-1) to ( L-3) or (L-8) to (L-10) As long as the R ^a represents a substituted or unsubstituted trialkylsilyl group, only if L ^a adjacent R ^a is a divalent linking group represented by the following general formula (L-3). )

(In the general formula (L-1) ~ (L -10), the ring wavy line portion includes a naphthalene ring, the ^{A 1} or represents a binding site to the ring containing ^{A 2,} * the binding site for ^{R a} M in the general formula (L-8) represents 4, and m in the general formulas (L-9) and (L-10) represents 2. General formulas (L-1) and (L-2) , (L-8), (L-9) and (L-10) each independently represents a hydrogen atom or a substituent, wherein the general formulas (L-1) and (L-2) R 'in may form a condensed ring by combining with R ^a respectively adjacent to the L ^a.) The organic thin-film transistor of any one of Claims 1-3 in which the compound represented by the said general formula (X) contains the compound represented by the following general formula (Z).

(In General Formula (Z), A ¹ and A ² each independently represent a sulfur atom, an oxygen atom, or a selenium atom. R ^{3 to} R ⁶ each independently represent a hydrogen atom or a substituent. L ^b and L ^c are each independently a divalent linking group represented by any one of the following general formulas (L-1) to (L-10), or two or more of the following general formulas (L-1). ) .R ^b and R ^c represents a divalent linking group is a divalent linking group represented by any one bound of ~ (L-10) each independently represent a hydrogen atom, a substituted or unsubstituted alkyl Represents an oligooxyethylene group having 2 or more repeating oxyethylene units, an oligosiloxane group having 2 or more silicon atoms, or a substituted or unsubstituted trialkylsilyl group, provided that R ^b and R ^c are represent a hydrogen atom, L And ^{L c} are each formula (L-1) only when the ~ (L-3) or (L-8) ~ (L -10), substitution ^{R b} and ^{R c} or unsubstituted trialkylsilyl group It represents the only if L ^c adjacent to L ^b and R ^c adjacent R ^b is a divalent linking group each represented by the following general formula (L-3).)

(In the general formulas (L-1) to (L-10), the wavy line represents a binding site with a naphthalene ring, a ring containing A ¹ or a ring containing A ² , and * represents R ^b or R ^c and In general formula (L-8), m represents 4 and m in general formulas (L-9) and (L-10) represents 2. General formulas (L-1) and (L -2), (L-8), (L-9), and (L-10) each independently represents a hydrogen atom or a substituent, R 'represents a general formula (L-1) and (L -2) may be bonded to R ^b adjacent to L ^b or R ^c adjacent to L ^c to form a condensed ring. R ^{3 to} R ⁶ in the general formula (X) are each independently a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, or a substituted or unsubstituted alkynyl group having 2 to 3 carbon atoms. The group according to any one of claims 1 to 4, which is a group, a substituted or unsubstituted alkenyl group having 2 to 3 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 2 carbon atoms, or a substituted or unsubstituted methylthio group. 2. The organic thin film transistor according to item 1. The organic thin-film transistor of any one of Claims 1-5 in which the said onium salt contains the compound represented by general formula (I).
cC ^{n +} aA ^m- general formula (I)
(In general formula (I), C ^{n +} represents an n-valent cation. N represents an integer of 1 to 6. When n is 1, C ^{n +} represents the following general formulas (A) to (E). If .n representing a cation selected from the group consisting of 2 to 6, C n ⁺ is, n a cation selected from the group consisting of the following general formula (a) ~ (E) as a partial structure in the molecule This represents a cation having one.
A ^m− is selected from the group consisting of m-valent anions (provided that Cl ⁻ , Br ⁻ , I ⁻ , PF ₆ ⁻ , R _A1 CO ₃ ⁻ , R _A10 NHCOO ⁻ , SbF ₆ ⁻ , and AsF ₆ ^−). Wherein R _A1 and R _A10 each independently represents a hydrogen atom or a hydrocarbon group which may have a substituent. m represents an integer of 1 to 3.
c represents an integer of 1 to 3, a represents an integer of 1 to 6, and c, n, a, and m satisfy the relational expression of c × n = a × m. )

(In the general formula (A), R _{1 to} R ₄ each independently represent a hydrogen atom or a hydrocarbon group that may have a substituent (excluding a hydroxyalkyl group). ₍ Not all of _{1 to} R ₄ are hydrogen atoms at the same time. R _{1 to} R ₄ may be bonded to each other to form a ring structure.)
(In general formula (B), R ₅ is a hydrocarbon group which may have a substituent, —NR ₁₉ R ₂₀ , —N═CR ₂₁ R ₂₂ , —CR ₂₃ = NR ₂₄ , or —CR _B1. R _B2 —NR _B3 R _B4 , wherein R _{19 to} R ₂₄ and R _{B1 to} R _B4 each independently represent a hydrogen atom or an optionally substituted hydrocarbon group. ₁₉ and R ₂₀ may combine with each other to form a ring structure.
R ₆ represents a hydrogen atom or a hydrocarbon group which may have a substituent.
R ₇ represents a hydrogen atom, a hydrocarbon group that may have a substituent, an alkoxy group, an alkylthio group, a hydroxy group, a mercapto group, or —NR ₂₅ R ₂₆ . Here, R ₂₅ and R ₂₆ each independently represent a hydrogen atom or a hydrocarbon group which may have a substituent, and may be bonded to each other to form a ring structure.
R ₈ represents a hydrogen atom, an optionally substituted hydrocarbon group, an alkoxy group, an alkylthio group, a hydroxy group, a mercapto group, —NR ₂₇ R ₂₈ , —N═CR ₂₉ R ₃₀ , or —CR _31. = NR ₃₂ . Here, R ₂₇ to R ₃₂ each independently represent a hydrogen atom or may have a substituent hydrocarbon group. R ₂₇ and R ₂₈ may combine with each other to form a ring structure.
However, R ₇ and R ₈ are not both an alkoxy group, a hydroxy group, an alkylthio group or a mercapto group at the same time, and R ₅ , R ₇ and R ₈ are all simultaneously —NR ₁₉ R ₂₀ , —NR ₂₅ R never ₂₆ or -NR ₂₇ R _28.
R _{5 to} R ₈ may be bonded to each other to form a ring structure. )
(In the general formula (C), R ₉ represents a hydrocarbon group which may have a substituent, or —NR _C1 R _C2 . Here, R _C1 and R _C2 each independently represents a hydrogen atom. Or a hydrocarbon group which may have a substituent.
R ₁₀ represents a hydrogen atom or a hydrocarbon group which may have a substituent.
R ₁₁ represents an optionally substituted hydrocarbon, —CR ₃₃ ═NR ₃₄ , or —NR _C3 R _C4 . Here, R ₃₃ , R ₃₄ , R _C3 and R _C4 each independently represent a hydrogen atom or a hydrocarbon group which may have a substituent.
R _{9 to} R ₁₁ may be bonded to each other to form a ring structure. )
(In the general formula (D), R _{12 to} R ₁₅ each independently represents a hydrogen atom or a hydrocarbon group which may have a substituent. However, all of R _{12 to} R ₁₅ are hydrogen at the same time. (It is not an atom. R _{12 to} R ₁₅ may be bonded to each other to form a ring structure.)
(In general formula (E), R _{16 to} R ₁₈ each independently represents an alkyl group which may have a substituent. R _{16 to} R ₁₈ are bonded to each other to form a ring structure. May be good.)   Electronic paper containing the organic thin-film transistor of any one of Claims 1-6.   A display device comprising the organic thin film transistor according to claim 1.