JP6259527B2 - Organic electronic devices, organic thin film transistors, electronic paper, display devices - Google Patents

Description

  The present invention relates to an organic electronic device, an organic thin film transistor, electronic paper, and a display device.

Equipment that uses logic circuits such as TFTs (Thin Film Transistors), RFIDs (Radio Frequency Identifiers), and memories used in liquid crystal displays and organic EL (Electro Luminescence) displays because they can be reduced in weight, cost, and flexibility. In addition, an organic electronic device having an organic semiconductor film (organic semiconductor layer) made of an organic semiconductor material is used.
In recent years, with increasing expectations for organic electronic devices, organic electronic devices are required to have improved mobility (particularly field effect mobility) and stability.
Under such circumstances, Patent Document 1 discloses an organic thin film transistor in which an organic semiconductor layer is formed of a composition containing an antioxidant in order to reduce oxidative degradation of the organic semiconductor layer. More specifically, in the Example column of Patent Document 1, a hindered phenol-based antioxidant (manufactured by Nagase Sangyo Co., Ltd .: Irganox 1076) is used.

Japanese Patent Laid-Open No. 2005-5582

On the other hand, in recent years, there has been a demand for further improvement in the performance of organic electronic devices, and in particular, there has been a demand for further improving insulation reliability between electrodes without lowering mobility. For example, in the form of an organic thin film transistor, it is required to further improve the insulation reliability between the source electrode and the drain electrode without reducing the mobility via the organic semiconductor layer.
When the present inventors produced an organic electronic device (particularly, an organic thin film transistor) using the above-described composition containing the antioxidant (Irganox 1076) specifically disclosed in Patent Document 1, an organic electronic device ( In particular, it has been clarified that both the mobility of the organic thin film transistor) and the insulation reliability between the electrodes (in the case of the organic thin film transistor, between the source electrode and the drain electrode) are not satisfied at the level required recently. In particular, regarding the insulation reliability, there has been a problem that metal ion migration proceeds between the electrodes.

Accordingly, in view of the above circumstances, an object of the present invention is to provide an organic electronic device having improved insulation reliability between electrodes without greatly reducing mobility.
Another object of the present invention is to provide an organic thin film transistor, electronic paper, and a display device.

As a result of intensive studies on the above problems, the present inventors have found that a predetermined effect can be obtained by including a compound having a phenolic hydroxyl group in the organic semiconductor layer and the electrode layer, 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 semiconductor layer containing an organic semiconductor material, and an electrode layer arranged adjacent to the organic semiconductor layer and containing a metal,
An organic electronic device in which a compound having a phenolic hydroxyl group is contained in both the organic semiconductor layer and the electrode layer.
(2) The compound having a phenolic hydroxyl group is at least selected from the group consisting of a compound represented by formula (I) described later and a compound having a repeating unit represented by formula (II) described later The organic electronic device according to (1), comprising one kind.
(3) The organic electron according to (1) or (2), wherein the content of the compound having a phenolic hydroxyl group contained in the organic semiconductor layer is 10 to 300% by mass relative to the total mass of the organic semiconductor material. device.
(4) The mass ratio of the content Ms of the compound having a phenolic hydroxyl group contained in the organic semiconductor layer to the content Mm of the compound having a phenolic hydroxyl group contained in the electrode layer is 5.0 or more. The organic electronic device according to any one of 1) to (3). In addition, mass ratio intends content Ms / content Mm.
(5) The organic semiconductor material is a low molecular compound, and the compound having a phenolic hydroxyl group contained in the organic semiconductor layer is a low molecular compound, or
The organic electronic device according to any one of (1) to (4), wherein the organic semiconductor material is a polymer compound, and the compound having a phenolic hydroxyl group contained in the organic semiconductor layer is a polymer compound.
(6) The organic electronic device according to any one of (1) to (5), wherein the metal contained in the electrode layer is a metal selected from the group consisting of silver, copper, aluminum, nickel, and tantalum.
(7) The organic electronic device according to any one of (1) to (6), which is applied to at least one selected from the group consisting of an organic thin film transistor, an organic solar battery, and an organic EL device.
(8) An organic thin film transistor including the organic electronic device according to any one of (1) to (6).
(9) An organic thin film transistor comprising a source electrode, a drain electrode, a gate electrode, a gate insulating film, and an organic semiconductor layer,
The organic semiconductor layer contains a compound having a phenolic hydroxyl group,
An organic thin film transistor, wherein a compound having a phenolic hydroxyl group is contained in at least one of a source electrode and a drain electrode arranged adjacent to an organic semiconductor layer.
(10) Electronic paper comprising the organic thin film transistor according to (8) or (9).
(11) A display device comprising the organic thin film transistor according to (8) or (9).

ADVANTAGE OF THE INVENTION According to this invention, the organic electronic device which improved the insulation reliability between electrodes can be provided, without reducing a mobility significantly.
Moreover, according to this invention, an organic thin-film transistor, electronic paper, and a display device can also be provided.

It is a cross-sectional schematic diagram of the 1st embodiment of the organic thin-film transistor of this invention. It is a cross-sectional schematic diagram of the 2nd embodiment of the organic thin-film transistor of this invention.

The organic electronic device of the present invention will be described below.
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.
First, a feature of the present invention is that a compound having a phenolic hydroxyl group (hereinafter simply referred to as “phenol compound”) is contained in both the organic semiconductor layer and the electrode layer. When a phenol compound is contained in both the organic semiconductor layer and the electrode layer, ion migration of the metal is further suppressed, and the insulation reliability is greatly improved. Moreover, when a phenol compound is contained in both the organic semiconductor layer and the electrode layer, a decrease in mobility is suppressed to a minimum. The reason is that the phenol compound added to the electrode layer tends to be unevenly distributed on the electrode layer surface, and the phenol compound unevenly distributed on the electrode layer surface side and the phenol compound contained in the organic semiconductor layer have similar properties. Therefore, the adhesion at the interface between the adjacent electrode layer and the organic semiconductor layer is improved, and as a result, the movement of electrons and holes between them is promoted, and the decrease in mobility is suppressed. It is speculated that it was done.

The organic electronic device of the present invention includes at least an organic semiconductor layer containing an organic semiconductor material and an electrode layer disposed adjacent to the organic semiconductor layer. As will be described later, the organic electronic device can be applied for various uses including an organic thin film transistor.
Hereinafter, first, the organic semiconductor layer and the electrode layer will be described in detail.

<Organic semiconductor layer>
The organic semiconductor layer includes an organic semiconductor material and a compound having a phenolic hydroxyl group. Exchange of electrons and holes to the electrode layer is performed through the organic semiconductor layer.
Below, the material which comprises an organic-semiconductor layer is explained in full detail first.

[Organic semiconductor materials]
The organic semiconductor layer includes an organic semiconductor material. The kind in particular is not restrict | limited, A well-known organic-semiconductor material can be used, A low molecular compound or a high molecular compound (preferably conjugated polymer) may be sufficient. Specifically, pentacenes such as 6,13-bis (triisopropylsilylethynyl) pentacene (TIPS pentacene), tetramethylpentacene, perfluoropentacene, TES-ADT, diF-TES-ADT (2,8-difluoro- 5,11-bis (triethylsilylethynyl) anthradithiophene) and the like, DPh-BTBT (2,7-diphenyl [1] benzothieno [3,2-b] [1] benzothiophene), Cn- Benzthienobenzothiophenes such as BTBT, dinaphthothienothiophenes such as Cn-DNTT (dinaphtho [2,3-b: 2 ′, 3′-f] thieno [3,2-b] thiophene), and perixantheno Fullerenes such as dioxaanthanthrenes such as xanthene, rubrenes, C60, PCBM ([6,6] -Phenyl-C61-Butyric Acid Methyl Ester), Phthalocyanines such as copper phthalocyanine and fluorinated copper phthalocyanine, P3RT (poly (3-alkylthiophene)), PQT (poly [5,5′-bis (3-dodecyl-2-thienyl1) -2,2′-bithiophene) ]), Polythiophenes such as P3HT (poly (3-hexylthiophene)), poly [2,5-bis (3-dodecylthiophen-2-yl) thieno [3,2-b] thiophene] (PBTT), etc. Examples include polythienothiophenes.
As described above, the organic semiconductor material may be a low molecular compound or a high molecular compound. In addition, a low molecular compound intends the compound whose molecular weight is 2000 or less. Moreover, the high molecular compound intends the compound whose molecular weight exceeds 2000. In addition, when the polymer compound is a compound having a plurality of predetermined repeating units, the number average molecular weight may be more than 2000.
In addition, the measuring method of a number average molecular weight is the same as the measuring method of the number average molecular weight of the high molecular compound which has a repeating unit represented by general formula (II) mentioned later.

  The content of the organic semiconductor material in the organic semiconductor layer is not particularly limited, but the mobility and / or insulation reliability of the obtained organic electronic device is more excellent (hereinafter simply referred to as “the effect of the present invention is more excellent”). 20 to 95% by mass, more preferably 30 to 95% by mass, and still more preferably 33 to 75% by mass with respect to the total mass of the organic semiconductor layer.

[Compound having phenolic hydroxyl group]
The organic semiconductor layer contains a compound having a phenolic hydroxyl group. A phenol compound is a compound that functions as a so-called migration inhibitor (migration inhibitor). As described above, in the prior art, as one of the factors that decrease the insulation reliability of the electrode layer, ion migration of the metal constituting the electrode layer can be considered. The phenol compound has a function of suppressing ion migration of the metal.
A phenol compound is a compound having a phenolic hydroxyl group. The phenolic hydroxyl group means a hydroxyl group directly bonded to an aromatic hydrocarbon ring (aromatic hydrocarbon nucleus) exemplified by a benzene ring, naphthalene ring, anthracene ring and the like.
The phenol compound only needs to contain at least one phenolic hydroxyl group. When the phenol compound is a low molecular weight compound, 1 to 4 is preferable and 1 to 2 is preferable in that the effect of the present invention is more excellent. .
A plurality of phenolic hydroxyl groups may be substituted on one aromatic hydrocarbon ring.
The phenol compound may be a low molecular compound or a high molecular compound. In addition, a low molecular compound intends the compound whose molecular weight is 2000 or less. Moreover, the high molecular compound intends the compound whose molecular weight exceeds 2000. In addition, when the polymer compound is a compound having a plurality of predetermined repeating units, the number average molecular weight may be more than 2000.

  One preferred embodiment of the phenolic hydroxyl group is a group represented by the general formula (A) in that the effect of the present invention is more excellent. That is, the phenol compound is preferably a compound having a group represented by the general formula (A).

In general formula (A), R < ₁ > -R < ₄ > represents a hydrogen atom or a substituent each independently.
Examples of the substituent include 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, a hydroxyl 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, sulfamoy 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 include a ruoxy group, a phosphinylamino group, a silyl group, or a combination thereof.
Note that the substituents exemplified above may include heteroatoms such as —O—, —S—, and —NH—. Moreover, the above-described substituents may be further substituted with the substituents exemplified above.

  More specifically, examples of the substituent include a halogen atom (for example, a chlorine atom, a bromine atom, and an iodine atom), an alkyl group [a linear, branched, cyclic substituted or unsubstituted alkyl group. They are alkyl groups (preferably alkyl groups 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 monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms, such as bicyclo [1.2.2] heptan-2-yl, Bicyclo [2.2.2] octane-3-yl) and a tricyclo structure having more ring structures. It is intended to encompass such. An alkyl group (for example, an alkyl group of an alkylthio group) in the substituents 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 A monovalent group obtained by removing one hydrogen atom from a 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, and more preferably a 5- or 6-membered group having 3 to 30 carbon atoms Aromatic heterocyclic groups such as 2-furanyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolinyl),

A cyano group, a hydroxyl 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) Substituted or unsubstituted heterocyclic oxy group, 1-phenyl Tolazole-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), alkoxyca Bonyloxy 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 a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, carbon number 6 to 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, 4 to 30 carbon atoms) A heterocyclic carbonyl group bonded to a carbonyl group at a substituted or unsubstituted carbon atom such as acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl), A reeloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, such as phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl), An alkoxycarbonyl 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 , Or a combination thereof.

  Among the above functional groups, those having a hydrogen atom may be substituted with the above groups by removing this. Examples of such functional groups include alkylcarbonylaminosulfonyl groups, arylcarbonylaminosulfonyl groups, alkylsulfonylaminocarbonyl groups, arylsulfonylaminocarbonyl groups, and the like. Examples thereof include methylsulfonylaminocarbonyl, p-methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl, benzoylaminosulfonyl groups and the like.

  In the present specification, the “substituent” has the above meaning.

Y represents a single bond or a divalent linking group. Examples of the divalent linking group include a divalent hydrocarbon group (for example, a linear, branched or cyclic divalent aliphatic hydrocarbon group (for example, an alkylene group having 1 to 12 carbon atoms (more specifically, In particular, a methylene group, an ethylene group, a propylene group, etc.)), a divalent aromatic hydrocarbon group (for example, a phenylene group), or a combination thereof (a divalent aliphatic hydrocarbon group and a divalent group). A combination of aromatic hydrocarbon groups)), —O—, —S—, —SO ₂ —, —NR ₂₀ —, —CO—, —NH—, —COO—, —CONR ₂₀ —, —O—CO —O—, —SO ₃ —, —NHCO—, —SO ₂ NR ₂₀ —, —NH—CO—NH—, or a combination thereof (for example, an alkyleneoxy group, an alkyleneoxycarbonyl group, an alkylenecarbonyloxy group) Group etc.) It is. Here, R ₂₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
The divalent linking group may be substituted with the above-described substituent.
Among them, Y is a divalent hydrocarbon group (preferably an alkylene group) which may have a single bond or a substituent (for example, an alkyl group or a hydroxyl group) in that the effect of the present invention is more excellent. Or a phenylene group which may have a substituent, or a combination thereof), —O—, —CO—, —COO—, —NHCO—, or a combination thereof. It is done. More preferably, -valent hydrocarbon group -Lx-, -valent hydrocarbon group -Lx -valent hydrocarbon group -Lx-, etc. are mentioned. Lx represents -O-, -CO-, -COO-, or -NHCO-.
* Indicates a binding position.

  Among them, the group represented by the general formula (A) is a group represented by the general formula (A-1) or a group represented by the general formula (A-2) in that the effect of the present invention is more excellent. And a group selected from the group consisting of groups represented by formula (A-3) is preferable. * Represents a binding position.

In general formula (A-1), R ₁₁ and R ₁₃ each independently represents an alkyl group or an alkoxy group. R ₁₂ and R ₁₄ represent a hydrogen atom, an alkyl group, or an alkoxy group.
Y represents a single bond or a divalent linking group, and the definition thereof is as described above.

In general formula (A-2), R ₁₁ and R ₁₅ each independently represents an alkyl group or an alkoxy group. R ₁₂ and R ₁₄ represent a hydrogen atom, an alkyl group, or an alkoxy group.
Y represents a single bond or a divalent linking group, and the definition thereof is as described above.

In General Formula (A-3), R _{16 to} R ₁₈ each independently represents a hydrogen atom, a hydroxy group, an alkyl group, or an alkoxy group.
Y represents a single bond or a divalent linking group, and the definition thereof is as described above.

(Preferred embodiment of phenol compound)
As a preferred embodiment of the phenol compound, a compound represented by the general formula (I) and a polymer compound having a repeating unit represented by the general formula (II) in that the effect of the present invention is more excellent. And at least one selected from the group consisting of:
Hereinafter, each compound will be described in detail.

(Compound represented by formula (I))
Formula (I) (Rx) _n -L- (Ry) _m
In general formula (I), Rx represents a group represented by general formula (A). The definition of group represented by general formula (A) is as above-mentioned, and its suitable aspect is also the same. When n is 2 or more, the plurality of Rx may be the same or different.

Ry represents a hydrogen atom or a substituent. The definition of the substituent is as described above. When m is 2 or more, the plurality of Ry may be the same or different.
Especially, the group which combined the alkyl group, the polyalkyleneoxy group, or these is mentioned by the point which the effect of this invention is more excellent.
Here, the polyalkyleneoxy group is a group having a plurality of alkyleneoxy repeating units represented by-(La-O)-. La represents an alkylene group, preferably having 1 to 4 carbon atoms, more preferably 2 to 3 carbon atoms. As a suitable aspect of a polyalkyleneoxy group, group represented by the following general formula (V) is mentioned.
Formula (V) *-(La-O) _p -R ₃₁
R ₃₁ represents a hydrogen atom or an alkyl group. p represents an integer greater than or equal to 2, and 4-50 are preferable and 5-30 are more preferable at the point which the effect of this invention is more excellent.

L represents a single bond or an n + m-valent linking group. Note that when L is a single bond, n = 1 and m = 1. That is, Rx-Ry is represented.
Examples of the n + m-valent linking group include a divalent linking group when n + m = 2, a trivalent linking group when n + m = 3, a tetravalent linking group when n + m = 4, and n + m = 5 represents a pentavalent linking group, and n + m = 6 represents a hexavalent linking group. The definition of the divalent linking group in the case of n + m = 2 is synonymous with the definition of the divalent linking group represented by Y.
One preferred embodiment of the n + m-valent linking group is a group selected from the group consisting of groups represented by general formula (1) to general formula (10) in that the effect of the present invention is more excellent. It is done. * Indicates a binding position.
In the general formulas (1), (2), (8), and (9), n + m = 2, and in the general formulas (3) to (5), n + m = 3, and the general formula (6 ) Is n + m = 4, and in the case of general formulas (7) and (10), n + m = 6.
In general formula (10), L ₁ represents a single bond or a divalent linking group. The definition of a bivalent coupling group is synonymous with the definition of the bivalent coupling group represented by Y.

n represents an integer of 1 to 6, m represents an integer of 0 to 5, and satisfies 2 ≦ n + m ≦ 6.
Especially, it is preferable that n represents the integer of 1-4 in the point which the effect of this invention is more excellent. Moreover, m preferably represents an integer of 0 to 2, and m is preferably 0 or 1.
As for the suitable aspect of the relationship between n and m, n represents the integer of 1-4, m represents the integer of 0 or 1, and the aspect which satisfy | fills 2 <= n + m <= 4 is mentioned.

  Although the molecular weight of the compound represented by the general formula (I) is not particularly limited, 2000 or less is preferable and 1000 or less is more preferable in that the effect of the present invention is more excellent. The lower limit is not particularly limited, but is preferably 200 or more from the viewpoint of crystallinity of the organic semiconductor material.

(Polymer compound having a repeating unit represented by formula (II))

In general formula (II), R ₅ represents a hydrogen atom or an alkyl group.
In general formula (II), Rx represents a group represented by general formula (A). The definition of group represented by general formula (A) is as above-mentioned.

The general formula (II) is more specifically expressed as the following formula. The definitions of R _{1 to} R ₄ and Y in the following formulas are as described above.

The content of the repeating unit represented by the general formula (II) in the polymer compound is not particularly limited, but all the repeating units in the polymer compound are more advantageous in terms of the effect of the present invention and solubility. 10-90 mol% is preferable with respect to a unit, and 20-80 mol% is more preferable.
The polymer compound may contain a repeating unit other than the repeating unit represented by the general formula (II).

The number average molecular weight of the polymer compound having a repeating unit represented by the general formula (II) is not particularly limited, but is preferably more than 2000, more preferably from 10,000 to 1,000,000, more preferably from 100,000 to 10,000 in terms of more excellent effects of the present invention. 500,000 is more preferable.
The weight average molecular weight of the polymer compound is not particularly limited, but is preferably more than 2,000, more preferably 10,000 to 1,000,000, and even more preferably 100,000 to 500,000, from the viewpoint that the effect of the present invention is more excellent.
The number average molecular weight and the weight average molecular weight are measured using GPC (gel permeation chromatography) under the following conditions.
Equipment: HLC-8320GPC manufactured by Tosoh Corporation
Column: TSK-GEL G3000PWXL manufactured by Tosoh Corporation
Column temperature: 35 ° C
Flow rate: 0.5 mL / min
Calibration curve: POLY SODIUM ACRYLATE STANDARD
Eluent: sodium dihydrogen phosphate 12 hydrate / disodium hydrogen phosphate dihydrate (34.
A solution obtained by diluting a mixture of 5 g / 46.2 g) with pure water to 5000 g.

  A preferred embodiment of the organic semiconductor layer is an embodiment in which the organic semiconductor material is a low-molecular compound and the phenol compound contained in the organic semiconductor layer is a low-molecular compound (Aspect A). Or the organic semiconductor material is a polymer compound and the phenol compound contained in the organic semiconductor layer is a polymer compound (embodiment B).

  Although content in particular of a phenolic compound in an organic-semiconductor layer is not restrict | limited, 10-300 mass% is preferable with respect to the total mass of organic-semiconductor material by the point which the effect of this invention is more excellent, and 30-300 mass% is more. Preferably, 50 to 250 mass% is more preferable, and 50 to 150 mass% is particularly preferable.

  The thickness of the organic semiconductor layer is not particularly limited and varies depending on the application, but is preferably 10 to 200 nm in terms of a balance between thinning and performance.

The manufacturing method in particular of an organic-semiconductor layer is not restrict | limited, A well-known method is employable. For example, preparing a composition (a composition for forming an organic semiconductor layer) containing a predetermined amount of the organic semiconductor material and the phenol compound, applying the composition to a predetermined position, and performing a drying treatment as necessary Can be manufactured. In addition, as a method of providing the said composition, inkjet printing, screen printing, etc. are applicable, for example.
The composition for forming an organic semiconductor layer preferably contains a solvent from the viewpoint of homogeneity and crystallinity of the formed organic semiconductor layer.
Although it does not restrict | limit especially as a solvent, For example, aromatic compounds, such as toluene, xylene, mesitylene, 1,2,3,4-tetrahydronaphthalene (tetralin), chlorobenzene, dichlorobenzene, anisole, are illustrated suitably.

<Electrode layer>
The electrode layer is disposed adjacent to the organic semiconductor layer and includes a metal. The electrode layer serves as a conductive portion (metal wiring layer) that conducts electricity in the organic electronic device. A plurality of electrode layers may be arranged. For example, when used in an organic thin film transistor as described later, a source electrode and a drain electrode may correspond to this electrode layer.

  The electrode layer includes a metal. Examples of the metal include gold, silver, aluminum, copper, chromium, nickel, tantalum, cobalt, titanium, platinum, and magnesium, and silver, copper, aluminum, nickel, and tantalum in terms of more excellent conductivity.

  The metal content in the electrode layer is not particularly limited, but is preferably 30 to 97% by mass and more preferably 50 to 95% by mass with respect to the total mass of the electrode layer in terms of more excellent effects of the present invention.

The electrode layer contains the above-described phenol compound (compound having a phenolic hydroxyl group). The definition of the phenol compound is as described above.
Although content in particular of a phenolic compound in an electrode layer is not restrict | limited, 3-70 mass% is preferable with respect to the metal total mass contained in an electrode layer at the point which the effect of this invention is more excellent, and 5-30 mass. % Is more preferable.

The method for producing the electrode layer is not particularly limited, and a known method can be adopted. For example, a metal particle containing a predetermined metal and a composition containing a predetermined amount of a phenol compound (a composition for forming an electrode layer) are prepared, and the composition is applied to a predetermined position. For example, an electrode layer can be manufactured by performing heat treatment or light irradiation treatment. The composition may contain a solvent (for example, water or an organic solvent) as necessary.
As a method for applying the composition, for example, inkjet printing, screen printing, or the like can be applied.
In addition, although the aspect which uses a metal particle was described above, it is not limited to this aspect, The metal oxide particle containing a predetermined metal is used instead of a metal particle, and a metal oxide particle is heat-processed. An electrode layer containing a metal and a phenol compound may be formed by reduction by light irradiation treatment.

<Organic electronic devices>
The organic electronic device includes the organic semiconductor layer and the electrode layer.
As one of the preferred embodiments of the organic electronic device, the content Ms of the phenol compound contained in the organic semiconductor layer with respect to the content Mm of the phenol compound contained in the electrode layer is more excellent in the effect of the present invention. The mass ratio (content Ms / content Mm) is preferably 5.0 or more, more preferably 10 to 5000, and still more preferably 20 to 1000.

The organic electronic device only needs to include the organic semiconductor layer and the electrode layer, and may include other layers depending on the application.
For example, organic thin film transistors, organic solar cells, and organic EL devices can be used, and in particular, it can be suitably applied to organic thin film transistors. The organic thin film transistor can be suitably applied to electronic paper, a display device, and the like.
Hereinafter, the aspect which applied the said organic electronic device to the organic thin-film transistor is explained in full detail.

<Organic thin film transistor (organic transistor)>
As a preferred embodiment of the organic thin film transistor of the present invention, the organic thin film transistor includes a source electrode, a drain electrode, a gate electrode, a gate insulating film, and an organic semiconductor layer, and the organic semiconductor layer includes a phenol compound, A phenol compound is contained in at least one of the source electrode and the drain electrode arranged adjacent to the layer.
Hereinafter, preferred embodiments of the organic thin film transistor will be described with reference to the drawings.

[First Embodiment]
FIG. 1 is a schematic cross-sectional view of a first embodiment of the organic thin film transistor of the present invention.
In FIG. 1, an organic thin film transistor 100 is disposed on a substrate 10, a gate electrode 20 disposed on the substrate 10, a gate insulating film 30 disposed so as to cover the gate electrode 20, and a gate insulating film 30. The source electrode 40 and the drain electrode 42 that are spaced apart from each other, and at least the gate insulating film 30 between the source electrode 40 and the drain electrode 42 are covered, and the source electrode 40 and the drain electrode 42 are in contact with each other. The organic semiconductor layer 50 and the sealing layer 60 covering each member are provided. Here, the organic semiconductor layer 50 includes an organic semiconductor material and a phenol compound. Moreover, both the source electrode 40 and the drain electrode 42 contain a metal and a phenol compound. The organic thin film transistor 100 is a so-called bottom contact-bottom gate type organic thin film transistor.

The organic semiconductor layer 50 is synonymous with the organic semiconductor layer included in the organic electronic device described above, and the definition of the phenol compound included in the organic semiconductor layer 50 is also as described above.
The mass of the phenol compound contained in the organic semiconductor layer 50 and the mass of the phenol compound contained in the source electrode 40 satisfy the relationship of the above-described content Ms / content Mm. Further, the relationship between the mass of the phenol compound contained in the organic semiconductor layer 50 and the mass of the phenol compound contained in the drain electrode 42 also satisfies the relationship of content Ms / content Mm, as described above.
The thickness of the organic semiconductor layer 50 is not particularly limited, but is preferably 10 to 200 nm.

Moreover, the source electrode 40 and the drain electrode 42 are synonymous with the electrode layer contained in the organic electronic device mentioned above, and the definition of the phenol compound contained in the source electrode 40 and the drain electrode 42 is also as above-mentioned.
The channel length of the source electrode 40 and the drain electrode 42 is not particularly limited, but is preferably 5 to 30 μm.
The channel width of the source electrode 40 and the drain electrode 42 is not particularly limited, but is preferably 10 to 200 μm.
In addition, in the said aspect, although the aspect in which a phenol compound is contained in both the source electrode 40 and the drain electrode 42 was described, the phenol compound should just be contained in at least one of the source electrode 40 and the drain electrode 42. FIG.
If it is the organic thin-film transistor of the said structure, a desired effect will be acquired.
Hereinafter, configurations other than the source electrode 40, the drain electrode 42, and the organic semiconductor layer 50 will be described in detail.

(substrate)
The substrate plays a role of supporting a gate electrode, a source electrode, a drain electrode, and the like described later.
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.

(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 is preferably provided with a sealing layer as the outermost layer from the viewpoint of durability. A well-known sealing agent can be used for a sealing layer. If the durability of the organic thin film transistor is sufficient, the sealing layer may not be provided.
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. A specific example of the method of applying the sealing layer forming composition is the same as the method of applying the gate insulating film forming composition. When a sealing layer forming composition is applied to form a 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 a second embodiment of the organic thin film transistor of the present invention.
In FIG. 2, the organic thin film transistor 200 is disposed on the substrate 10, the gate electrode 20 disposed on the substrate 10, the gate insulating film 30 disposed so as to cover the gate electrode 20, and the gate insulating film 30. The organic semiconductor layer 50 includes a source electrode 40 and a drain electrode 42 that are disposed on the organic semiconductor layer 50 and spaced apart from each other, and a sealing layer 60 that covers each member. The organic thin film transistor 200 corresponds to a so-called top contact-bottom gate type organic thin film transistor.
The second embodiment of the organic thin film transistor has the same configuration as that of the first embodiment of the organic thin film transistor except that the positions of the layers used are different. The description is omitted.
Also in the second embodiment, as in the first embodiment, the organic semiconductor layer 50, the source electrode 40, and the drain electrode 42 contain a phenol compound.

  In the above description, the bottom contact-bottom gate type organic thin film transistor is described with reference to FIG. 1 and the top contact-bottom gate type organic thin film transistor is described with reference to FIG. Organic thin film transistors and top contact-top gate type organic thin film transistors may also be used.

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

In the examples and comparative examples described later, the materials exemplified below were used.
(A) Phenol compound (M-1 to M-3) contained in the electrode layer

(Synthesis Example 1: Phenol Compound M-1)
In a reaction vessel, 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid (5.0 g, 18.0 mmol), polyethylene glycol monomethyl ether (average molecular weight 550, manufactured by FLUKA) (9. 88 g, 18.0 mmol), dichloromethane (20 ml) and tetrahydrofuran (10 ml) were added, and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (3.62 g, 18.9 mmol), 4 was added under ice cooling. -Dimethylaminopyridine (0.07 g, 0.54 mmol) was added and stirred for 30 minutes. The reaction solution was further stirred at room temperature for 3 hours and then concentrated under reduced pressure to obtain a crude product. The obtained crude product was purified by silica gel column chromatography (mobile phase: methanol / ethyl acetate = 1/9) to obtain 10 g of phenol compound M-1 (yield 64%).

(Synthesis Example 2: Phenol Compound M-2)
In a reaction vessel, 3- (3,4-dihydroxyphenyl) propionic acid (5.0 g, 27.5 mmol), polyethylene glycol monomethyl ether (average molecular weight 350, manufactured by FLUKA) (9.61 g, 27.5 mmol), Phenylphosphine (12.96 g, 49.4 mmol) and tetrahydrofuran (100 ml) were added, and a toluene solution of diisopropyl azodicarboxylate (1.9 mol / L) (21.7 ml, 41.2 mmol) was added under ice cooling. Stir for minutes. The reaction solution was further stirred at room temperature for 3 hours and then concentrated under reduced pressure to obtain a crude product. The obtained crude product was purified by silica gel column chromatography (mobile phase: methanol / ethyl acetate = 1/9) to obtain 7 g of phenol compound M-2 (yield 51%).

  In addition, the phenol compound M-3 was synthesize | combined in the procedure similar to the said phenol compound M-1.

The following M-4 (tetramethylammonium tosylate) was used as a comparative migration inhibitor contained in the electrode layer.

(B) Organic semiconductor material O-1: 5,11-bis (triethylsilylethynyl) anthradithiophene (TES-ADT) (manufactured by Aldrich)
O-2: Compound of the following formula (synthesized according to the method described in JP2009-190999A)

O-3: P3HT (poly (3-hexylthiophene)) (manufactured by Aldrich: Mn = 54,000-75000)

(C) Phenol compound S-1 contained in the organic semiconductor layer: IRGANOX 1010 (manufactured by BASF)
S-2: 2,6-Dimethoxy-p-cresol (manufactured by Tokyo Chemical Industry)
S-3: IRGANOX 1076 (manufactured by BASF)
S-4: Polymer of the following formula

(Synthesis example: S-4)
The following compound Z-1 (3.51 g), 3.60 g of methyl methacrylate, and 6.1 g of toluene were placed in a 100 mL three-necked flask, and heated to 80 ° C. under a nitrogen stream. Thereto, 148 mg of azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd.) and 1.0 g of toluene were added and stirred for 16 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and diluted with 18.0 g of toluene. After reprecipitation with hexane, molecular weight fractionation was performed by preparative chromatography to obtain 4.8 g of S-4 (Mw = 470,000, Mn = 290,000) having the above structure. The measuring method of Mw (weight average molecular weight) and Mn (number average molecular weight) is as described above.
In addition, S-4 corresponds to the high molecular compound containing the repeating unit represented by general formula (II).

  The following S-5 (dodecyltrimethylammonium tosylate salt) was used as a comparative migration inhibitor contained in the organic semiconductor layer.

<Example 1>
(Method for preparing electrode layer forming composition A1)
“Disperbyk-190” (7.36 g as a non-volatile material manufactured by Big Chemie) was used as a nanoparticle dispersant, dissolved in 100 mL of water, and a solution of 50.00 g (294.3 mmol) of silver nitrate in 200 mL of water was added. Stir. To this mixture, a solution prepared by dissolving 78.71 g (750.5 mmol) of 85% N, N-diethylhydroxylamine and 7.36 g of “Disperbyk-190” in 1000 mL of water was slowly added dropwise at room temperature.
The obtained suspension was passed through an ultrafiltration unit (Sartorius Stedim Vivaflow 50, molecular weight cut off 100,000, 4 pieces), and purified water was passed through until about 5 L of exudate appeared from the ultrafiltration unit. Purified. The supply of purified water was stopped and concentrated to obtain 50 g of a silver nanoparticle dispersion (silver ink A1).
The solid content of the silver ink A1 was 32% by mass, and the silver content in the solid content measured by TG-DTA was 97.0% by mass.
Phenol compound M-1 was added to the obtained silver ink A1 so as to satisfy the mass ratio relationship shown in Table 1 to be described later to produce an electrode layer forming composition A1.

(Preparation of organic semiconductor composition (composition for forming an organic semiconductor layer))
The organic semiconductor material O-1 and the phenol compound S-1 are dissolved in toluene (organic semiconductor material O-1 / phenol compound S-1 = 100 parts by mass / 30 parts by mass (w / w), organic semiconductor) Material concentration: 2% by mass), an organic semiconductor composition 1 was prepared.

(Production of organic thin film transistor)
Al serving as a gate electrode was deposited on a glass substrate (Eagle XG: Corning) (thickness: 50 nm). A gate insulating film composition (polyvinylphenol / melamine = 1 part by weight / 1 part by weight (w / w) PGMEA (propylene glycol monomethyl ether acetate) solution (solution concentration: 2% by weight)) was spin-coated thereon. Then, baking was performed at 150 ° C. for 60 minutes to form a gate insulating film having a thickness of 300 nm. On top of that, the electrode layer forming composition A1 was drawn in the form of a source electrode and a drain electrode having a channel length of 40 μm and a channel width of 250 μm using an inkjet apparatus DMP-2831 (manufactured by Fujifilm Dimatics: 1 pL head used). Thereafter, baking was performed at 180 ° C. for 30 minutes in an oven, sintering was performed, and a source electrode and a drain electrode were manufactured. The organic semiconductor composition 1 was spin coated thereon 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, and an organic thin film transistor (bottom contact-bottom gate type) )
In the electrode layer (source electrode and drain electrode) included in the organic thin film transistor, the content of the phenol compound was 6% by mass with respect to the total mass of the metal included in the electrode layer.

<Evaluation of mobility>
Each electrode of the obtained organic thin film transistor was connected to each terminal of a manual prober connected to a semiconductor parameter analyzer (4155C, manufactured by Agilent Technologies) to evaluate a field effect transistor (FET). Specifically, the field effect mobility ([cm ² / V · sec]) was calculated by measuring the drain current-gate voltage (Id-Vg) characteristics. Similarly, the average value of the five manufactured elements is defined as field effect mobility μ1.
Moreover, according to the procedure similar to the above, the composition for electrode formation and the organic-semiconductor composition which do not contain a phenol compound were prepared, respectively. More specifically, a silver ink A1 that does not contain a phenol compound is prepared as an electrode layer forming composition, and the organic semiconductor material O-1 is dissolved in toluene (organic semiconductor material concentration: 2% by mass). Product 1 was prepared. Next, according to the same procedure as the production of the organic thin film transistor of Example 1, except that the silver ink A1 was used instead of the electrode layer forming composition 1 and the comparative composition 1 was used instead of the organic semiconductor composition 1. An organic thin film transistor was produced. About the obtained organic thin-film transistor, field effect mobility was computed according to the procedure similar to said μ1. The calculated field effect mobility is defined as μ2.
Μ1 / μ2 was obtained from the calculated μ1 and μ2, and evaluated according to the following criteria. The results are shown in Table 1. Practically, from the viewpoint of mobility, A or B is preferable, and A is more preferable.
“A”: μ1 / μ2 ≧ 0.8
“B”: 0.8> μ1 / μ2 ≧ 0.5
“C”: 0.5> μ1 / μ2 ≧ 0.1
“D”: 0.1> μ1 / μ2

<Evaluation of insulation reliability>
The durability test of the obtained organic thin film transistor was performed according to the following method. The obtained organic thin film transistor was placed in a constant temperature and humidity chamber with a temperature of 60 ° C. and a humidity of 60%, and voltages of Vs = −20 V, Vd = 0 V, and Vg = −20 V were applied. Meanwhile, the transistor characteristics were measured every 10 minutes, and the time when the threshold voltage Vth was observed to be shifted by 10 V or more with respect to the initial value was calculated as the lifetime of the transistor (T1). According to the same procedure as the evaluation, an organic thin film transistor using a composition for forming an electrode layer and an organic semiconductor composition that does not contain a phenol compound was produced. For the obtained organic thin film transistor, the time when the threshold voltage Vth was observed to be shifted to 10 V or more with respect to the initial value was calculated as the lifetime (T2) of the transistor. T1 / T2 was calculated from the calculated T1 and T2, and the following: Evaluation was performed according to the criteria. The results are shown in Table 1. From the viewpoint of insulation reliability, A or B is preferable, and A is more preferable.
“A”: T1 / T2 ≧ 10
“B”: 10> T1 / T2 ≧ 5
“C”: 5> T1 / T2 ≧ 1.5
“D”: 1.5> T1 / T2

<Examples 2-9, Comparative Examples 1-3>
Regarding Examples 2 to 9 and Comparative Examples 1 to 3, the type of phenol compound, the type of organic semiconductor material, the mass ratio of the phenol compound and organic semiconductor material, the phenol compound in the organic semiconductor layer and the phenol compound in the electrode layer The organic thin film transistor was manufactured according to the same procedure as in Example 1 except that the mass ratio was changed as described in Table 1, and various evaluations were performed. The results are summarized in Table 1.

In Table 1, “(mass of phenol compound (F2) (Ms) / mass of organic semiconductor material) × 100” represents the content ratio (mass%) of the phenol compound with respect to the total mass of the organic semiconductor material.
In Table 1, “mass of phenol compound (F2) (Ms) / (mass of phenol compound (F1) (Mm)” is the mass of phenol compound contained in the electrode layer (source electrode or drain electrode), This represents the mass ratio of the phenolic compound contained in the organic semiconductor layer with respect to the mass of the phenolic compound, since in the above Example and Comparative Example 3, the source electrode and the drain electrode are formed using the same electrode forming composition. The ratio (Ms / Mm) between the electrode and the organic semiconductor layer and the ratio (Ms / Mm) between the drain electrode and the organic semiconductor layer show the same value.

As shown in Table 1 above, in the organic electronic device (organic thin film transistor) of the present invention, the insulation reliability was improved without greatly reducing the mobility.
Especially, from the comparison of Examples 1 to 3, it was confirmed that the effect was more excellent when the content of the phenol compound contained in the organic semiconductor layer was 50 to 250% by mass with respect to the total mass of the organic semiconductor.
On the other hand, in Comparative Examples 1 and 2 in which only the organic semiconductor layer contains a phenol compound, and in Comparative Example 3 in which no phenol compound is used, the desired effect was not obtained. In particular, Comparative Example 2 corresponds to the aspect of Patent Document 1, and it was confirmed that a desired effect could not be obtained.
In addition, comparison between Example 6 and Comparative Example 1 revealed that both the mobility and the insulation reliability were improved when both the organic semiconductor layer and the electrode layer contained a phenol compound. Thus, when a phenol compound is further added to the electrode layer of Comparative Example 1, the insulation reliability is improved and, as described above, the adhesion between the organic semiconductor layer and the electrode layer is improved, and as a result, the mobility is increased. Is estimated to have improved.

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 (11)

An organic semiconductor layer including an organic semiconductor material, and an electrode layer disposed adjacent to the organic semiconductor layer and including a metal;
An organic electronic device in which a compound having a phenolic hydroxyl group is contained in both the organic semiconductor layer and the electrode layer. The compound having a phenolic hydroxyl group includes at least one selected from the group consisting of a compound represented by general formula (I) and a compound having a repeating unit represented by general formula (II). The organic electronic device described in 1.
Formula (I) (Rx) _n -L- (Ry) _m
In general formula (I), Rx represents a group represented by general formula (A).

In general formula (A), R < ₁ > -R < ₄ > represents a hydrogen atom or a substituent each independently.
In general formula (A), Y represents a single bond or a divalent linking group. In the general formula (A), * indicates a bonding position.
Ry represents a hydrogen atom or a substituent.
L represents a single bond or an n + m-valent linking group. Note that when L is a single bond, n = 1 and m = 1.
When L represents an n + m-valent linking group, n represents an integer of 1 to 6, m represents an integer of 0 to 5, and satisfies 2 ≦ n + m ≦ 6.

In general formula (II), R ₅ represents a hydrogen atom or an alkyl group. Rx represents a group represented by the general formula (A).   The organic electronic device according to claim 1 or 2, wherein the content of the compound having a phenolic hydroxyl group contained in the organic semiconductor layer is 10 to 300% by mass with respect to the total mass of the organic semiconductor material.   The mass ratio of the content Ms of the compound having a phenolic hydroxyl group contained in the organic semiconductor layer to the content Mm of the compound having a phenolic hydroxyl group contained in the electrode layer is 5.0 or more. The organic electronic device according to any one of claims 1 to 3. In addition, the said mass ratio intends content Ms / content Mm. The organic semiconductor material is a low molecular compound, and the compound having the phenolic hydroxyl group contained in the organic semiconductor layer is a low molecular compound, or
5. The organic electron according to claim 1, wherein the organic semiconductor material is a polymer compound, and the compound having the phenolic hydroxyl group contained in the organic semiconductor layer is a polymer compound. device.   The organic electronic device according to claim 1, wherein the metal contained in the electrode layer is a metal selected from the group consisting of silver, copper, aluminum, nickel, and tantalum.   The organic electronic device of any one of Claims 1-6 applied to at least one selected from the group which consists of an organic thin-film transistor, an organic solar cell, and an organic EL device.   The organic thin-film transistor containing the organic electronic device of any one of Claims 1-6. An organic thin film transistor comprising a source electrode, a drain electrode, a gate electrode, a gate insulating film, and an organic semiconductor layer,
The organic semiconductor layer contains a compound having a phenolic hydroxyl group,
An organic thin film transistor, wherein a compound having a phenolic hydroxyl group is contained in at least one of the source electrode and the drain electrode arranged adjacent to the organic semiconductor layer.   An electronic paper comprising the organic thin film transistor according to claim 8. A display device comprising the organic thin film transistor according to claim 8.