JP6474276B2 - Picenodithiophene compounds, organic semiconductor materials, organic semiconductor layers, organic semiconductor elements - Google Patents

Description

  The present invention relates to a picenodithiophene compound, an organic semiconductor material using the same, an organic semiconductor layer, and an organic semiconductor element.

  Conventionally, inorganic compounds have been used in electronic devices. However, when an inorganic compound is used, there are problems such as an expensive manufacturing process, difficulty in increasing the area, and a large environmental load.

  In recent years, research on organic compounds (organic molecules) instead of inorganic compounds has been actively conducted. This is because when an organic compound is used, a film can be formed at a low temperature and a rare element is not required, so that the manufacturing process becomes inexpensive. Moreover, since an organic compound does not contain a toxic element, the environmental load is reduced. Furthermore, the structure and manufacturing process of the semiconductor element are expected to reduce weight, diversify materials, increase the area, reduce the thickness, and increase the integration.

  As this organic compound, for example, condensed polycyclic aromatic compounds such as polyacene compounds and polyphenacene compounds are used. More specifically, in the following Patent Document 1, a polyacene compound is proposed.

JP 2009-218333 A

  The organic compound is required to be able to be stably manufactured using existing technology and to be effectively applicable to an electronic device. Therefore, there is still room for research on organic compounds used in electronic devices, and new organic compounds are desired.

  An object of the present invention is to provide a picenodithiophene compound that can be easily produced and is useful for an electronic device, and an organic semiconductor material, an organic semiconductor layer, and an organic semiconductor element using the same.

  As a result of intensive studies to achieve the above object, the present inventor has found that the picenodithiophene compound described below can be easily produced and is useful for an electronic device. By using this picenodithiophene compound, an organic semiconductor layer can be easily manufactured, and an organic semiconductor element using the organic semiconductor layer is expected to achieve high performance (for example, carrier mobility). .

The present invention has been made on the basis of the above findings, and the picenodithiophene compound of the present invention is a compound represented by the following formula (1) and a compound represented by the following formula (11). At least one of the following.

（式中、Ｒ₁ 〜Ｒ₁₄のそれぞれは、水素原子、ハロゲン原子、ニトロ基、水酸基、アルキルカルボニルオキシ基、アルキルシリルオキシ基、アミノ基、アルキルアミノ基、カルボキシル基、カルボン酸塩基、炭化水素基、複素環基、アルコキシ基、炭化水素基にアルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、複素環基、アシル基、アシルオキシ基、アミノ基及びハロゲン原子のうちの少なくとも１種が導入された基、並びに複素環基にアルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、複素環基、アシル基、アシルオキシ基、アミノ基及びハロゲン原子のうちの少なくとも１種が導入された基のうちのいずれかである。）

(Wherein each of R ₁ to R _14, a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, an alkylcarbonyloxy group, an alkylsilyl group, an amino group, an alkylamino group, a carboxyl group, mosquitoes carboxylic acid base, carbonized At least one of an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a heterocyclic group, an acyl group, an acyloxy group, an amino group, and a halogen atom as a hydrogen group, a heterocyclic group, an alkoxy group, and a hydrocarbon group A group into which a species is introduced, and at least one of an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a heterocyclic group, an acyl group, an acyloxy group, an amino group, and a halogen atom in the heterocyclic group; Any of the groups introduced.)

  The organic semiconductor material of the present invention contains the above-mentioned picenodithiophene compound. The organic semiconductor layer of the present invention contains an organic semiconductor material, and the organic semiconductor material contains the aforementioned picenodithiophene compound. The organic semiconductor element of the present invention includes an organic semiconductor layer containing an organic semiconductor material, and the organic semiconductor material contains the above-described picenodithiophene compound.

  According to the picenodithiophene compound of the present invention, it can be easily produced and is useful for an electronic device. Therefore, if the picenodithiophene compound of the present invention is used for an organic semiconductor material, an organic semiconductor layer, and an organic semiconductor element, it can contribute to high performance of the organic semiconductor element.

It is a figure which shows typically the structural example of the organic-semiconductor element of this invention. It is a figure which shows typically the modification regarding the structure of the organic-semiconductor element of this invention.

  Hereinafter, the present invention will be described in detail. The order of explanation is as follows. However, details regarding the present invention are not limited to the modes described below, and can be changed as appropriate.

1. Picenodithiophene compound 1-1. Configuration 1-2. Manufacturing method Organic semiconductor materials Organic semiconductor layer 4. Organic semiconductor device

<1. Picenodithiophene Compound>
The picenodithiophene compound of the present invention is used, for example, in an electronic device. Although the kind of this electronic device is not specifically limited, For example, they are semiconductor elements, such as an electroluminescent element, a photoelectric conversion element, and a thin-film transistor element. However, the use of the picenodithiophene compound is not limited to the electronic device described above.

<1-1. Configuration>
The picenodithiophene compound is one or more of the compounds shown in the above formula (1) and derivatives thereof. This is because it exhibits excellent characteristics that can be easily manufactured and can improve the performance of the electronic device. This characteristic is, for example, a semiconductor characteristic.

  The picenodithiophene compound may be only the compound represented by the formula (1), or any one or more of the derivatives of the compound represented by the formula (1). Any one kind or two kinds or more may be sufficient.

  As described above, the “derivative” is a compound in which one or more substituents are introduced into the compound represented by the formula (1), and the type of the substituent is not particularly limited.

  This substituent is, for example, one type or two or more types in a series of groups described below. Halogen atom, nitrile group, nitro group, sulfo group, amino group, carboxyl group, hydroxyl group, hydrocarbon group, hydrocarbon oxy group, thiol group, hydrocarbon thioxy group, formyl group, hydrocarbon carbonyl group, sulfino group, sulfeno group Amide group, hydrocarbon disulfide group, ester group, phosphoric acid group, thioester group, silyl group, boron group, hydrocarbon amino group, heterocyclic group and the like.

  The hydrocarbon group includes, for example, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a cycloalkyl group and the like. The heterocyclic group contains, for example, one or more of nitrogen (N), oxygen (O), and sulfur (S) as a constituent element. In addition, two or more types in the series of groups described above may be bonded so as to be monovalent as a whole. Each of the series of groups may be protected.

  Especially, it is preferable that a derivative is any 1 type in the compound represented by following formula (11), or 2 types or more. This is because it can be manufactured more easily and exhibits superior characteristics.

（式中、Ｒ₁ 〜Ｒ₁₄のそれぞれは、水素原子、ハロゲン原子、ニトロ基、保護されていてもよい水酸基、保護されていてもよいアミノ基、保護されているか又は塩を形成していてもよいカルボキシル基、置換されていてもよい炭化水素基、置換されていてもよい複素環基、置換されていてもよいアルコキシ基のうちのいずれかである。）

(In the formula, each of R _{1 to} R ₁₄ is a hydrogen atom, a halogen atom, a nitro group, an optionally protected hydroxyl group, an optionally protected amino group, protected or forming a salt. Or any of a carboxyl group which may be substituted, a hydrocarbon group which may be substituted, a heterocyclic group which may be substituted, or an alkoxy group which may be substituted.)

Details regarding R _{1 to} R ₁₄ are as follows. However, R _{1 to} R ₁₄ may be the same type (same group) or different types (different groups). Of course, some of R _{1 to} R ₁₄ may be the same type.

  The halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

  The hydroxyl group which may be protected includes a hydroxyl group which is not protected and a hydroxyl group which is protected. Examples of the protected hydroxyl group include an alkylcarbonyloxy group, an alkylsilyloxy group, and an alkoxy group. Specific examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, an acryloyl group, and a methacryloyl group. Although carbon number of this alkylcarbonyloxy group is not specifically limited, For example, it is 1-20. Specific examples of the alkylsilyloxy group include a trimethylsilyloxy group, a triethylsilyloxy group, a triisopropylsilyloxy group, a tert-butyldiphenylsilyloxy group, and the like. Although carbon number of this alkyl silyloxy group is not specifically limited, For example, it is 1-30.

  The amino group which may be protected includes an unprotected amino group and a protected amino group. The protected amino group is, for example, an alkylamino group. Specific examples of the alkylamino group include an ethylamino group, a propylamino group, a diethylamino group, a dipropylamino group, a hexylamino group, and a dicyclopentylamino group. Although carbon number of this alkylamino group is not specifically limited, For example, it is 1-20.

  The carboxyl group which may be protected or may form a salt includes a carboxyl group which is not protected and does not form a salt, a protected carboxyl group, and a carboxyl group which forms a salt ( Carboxylate group). The protected carboxyl group is, for example, a group (ester group) obtained by reacting a carboxyl group with an alcohol. Although carbon number of this ester group is not specifically limited, For example, it is 1-30. The carboxylate group is, for example, a group obtained by reacting a carboxyl group with various bases, and specifically, a group represented by -COOM1. However, since M1 is an alkali metal and quaternary ammonium, -COOM1 represents an alkali metal base and an ammonium base.

  The hydrocarbon group which may be substituted includes an unsubstituted hydrocarbon group and a substituted hydrocarbon group. Examples of the unsubstituted hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. Although carbon number of this hydrocarbon group which is not substituted is not specifically limited, For example, it is 1-30.

  The aliphatic hydrocarbon group may be linear, may be branched having one or more side chains, or may be cyclic. Specific examples of the aliphatic hydrocarbon include methyl group, ethyl group, propyl group, isopropyl group, butyl group, s-butyl group, t-butyl group, isobutyl group, amyl group, isoamyl group, t-amyl group, hexyl group. , Heptyl group, isoheptyl group, t-heptyl group, n-octyl group, isooctyl group, t-octyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, 1-butyloctyl group, 2-butyloctyl group, 3- Butyloctyl group, 1-hexyldecyl group, 2-hexyldecyl group, 3-hexyldecyl group, 1-decyltetradecyl group, 2-decylte Radeshiru group, 3-decyl tetradecyl group, a cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl and the like.

  Of these, a branched alkyl group is preferable. For example, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, 1-butyloctyl group, 2-butyloctyl group, 3-butyloctyl group, 1-hexyldecyl group, 2-hexyldecyl group, 3-hexyl A decyl group, a 1-decyltetradecyl group, a 2-decyltetradecyl group, a 3-decyltetradecyl group, and the like. This is because excellent solubility can be obtained. The solubility described here is, for example, solubility in a solvent described later, and the same applies hereinafter.

  Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, and a fluorenyl group.

  The heterocyclic group which may be substituted includes an unsubstituted heterocyclic group and a substituted heterocyclic group. Examples of the unsubstituted heterocyclic group include an aromatic heterocyclic group and a non-aromatic heterocyclic group. Although carbon number of this heterocyclic group is not specifically limited, For example, it is 1-30. Specific examples of the aromatic heterocyclic group include a thiophenyl group, a furanyl group, and a thienothiophenyl group. Specific examples of the non-aromatic heterocyclic group include a tetrahydrofuryl group, a dioxolanyl group, a tetrahydropyranyl group, a pyrrolidinyl group, a pyrazolyl group, a piperidyl group, a piperazyl group, a morpholyl group, and a tetrahydrothiophenyl group.

  The alkoxy group which may be substituted includes an unsubstituted alkoxy group and a substituted alkoxy group. Specific examples of the unsubstituted alkoxy group include the methoxy group, the ethoxy group, the propoxy group, the isopropoxy group, the butyloxy group, the second butoxy group, the third butoxy group, the isobutoxy group, the amyloxy group, Isoamyloxy group, tertiary amyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group, isoheptyloxy group, tertiary heptyloxy group, n-octyloxy group, isooctyloxy group, tertiary octyloxy group, 2 -Ethylhexyloxy group, nonyloxy group, decyloxy and the like. Although carbon number of this alkoxy group is not specifically limited, For example, it is 1-30.

  Examples of the substituent introduced into each of the above-described hydrocarbon group and heterocyclic group include an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a heterocyclic group, an acyl group, an acyloxy group, and a substituted group. And an amino group, a halogen atom, and the like.

  Specific examples of the alkylthio group include methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, secondary butylthio group, tertiary butylthio group, isobutylthio group, amylthio group, isoamylthio group, tertiary amylthio group, hexylthio group. Group, cyclohexylthio group, heptylthio group, isoheptylthio group, tertiary heptylthio group, n-octylthio group, isooctylthio group, tertiary octylthio group, 2-ethylhexylthio and the like.

  Specific examples of the aryl group include phenyl and naphthyl. Specific examples of the aryloxy group include a phenoxy group and naphthyloxy. Specific examples of the arylthio group include a phenylthio group and naphthylthio.

  Specific examples of the heterocyclic group include pyridyl group, pyrimidyl group, pyridadyl group, piperidyl group, pyranyl group, pyrazolyl group, triazyl group, pyrrolyl group, quinolyl group, isoquinolyl group, imidazolyl group, benzimidazolyl group, triazolyl group, furyl group, Furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, 2-pyrrolidinone-1- An yl group, a 2-piperidone-1-yl group, a 2,4-dioxyimidazolidin-3-yl group, a 2,4-dioxyoxazolidine-3-yl group, and the like.

  Specific examples of the acyl group include acetyl group, 2-chloroacetyl group, propionyl group, octanoyl group, acryloyl group, methacryloyl group, phenylcarbonyl (benzoyl) group, phthaloyl group, 4-trifluoromethylbenzoyl group, pivaloyl group, salicyloyl. Group, oxaloyl group, stearoyl group, methoxycarbonyl group, ethoxycarbonyl group, t-butoxycarbonyl group, n-octadecyloxycarbonyl group, carbamoyl and the like.

  Specific examples of the acyloxy group include acetyloxy group and benzoyloxy.

  The details regarding the alkoxy group, the optionally substituted amino group, and the halogen atom are as described above.

  However, specific examples of the substituted amino group include dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, chlorophenylamino group, toluidino group, anisidino group, N- Methyl-anilino group, diphenylamino group, naphthylamino group, 2-pyridylamino group, methoxycarbonylamino group, phenoxycarbonylamino group, acetylamino group, benzoylamino group, formylamino group, pivaloylamino group, lauroylamino group, carbamoylamino group N, N-dimethylaminocarbonylamino group, N, N-diethylaminocarbonylamino group, morpholinocarbonylamino group, methoxycarbonylamino group, ethoxycarbonylamino group, t-butoxycarbonylamino N-octadecyloxycarbonylamino group, N-methyl-methoxycarbonylamino group, phenoxycarbonylamino group, sulfamoylamino group, N, N-dimethylaminosulfonylamino group, methylsulfonylamino group, butylsulfonylamino group, phenyl Sulfonylamino and the like may be used.

  In addition, the substituents include sulfonamido group, sulfonyl group, carboxyl group, cyano group, sulfo group, hydroxyl group, nitro group, mercapto group, imide group, carbamoyl group, vinyl group, acrylic group, methacryl group, epoxy group, etc. is there.

  Among these, the substituent is preferably a halogen atom. This is because the picenodithiophene compound can be easily produced and the substituent can be easily changed to another substituent.

  In addition, when a substituent has 1 or 2 or more carbon atoms, it is preferable to satisfy | fill the above-mentioned conditions of carbon number including the number of the carbon atoms.

Any one or two or more of R _{1 to} R ₁₄ are preferably a group (partial structure group) represented by any of the following formulas (6) to (8). This is because the picenodithiophene compound having this partial structural group can be easily produced, and the picenodithiophene compound can be easily obtained. Moreover, it is because the outstanding solubility is obtained. In addition, * shown in the formula represents the site | part of the partial structural group introduce | transduced into the compound shown to Formula (11).

（式中、Ｒ_a 及びＲ_b のそれぞれは、水素原子、置換されていてもよいアルキル基、置換されていてもよいアルケニル基、置換されていてもよいアルキニル基のうちのいずれかである。）

(In the formula, each of R _a and R _{b is} any one of a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, and an optionally substituted alkynyl group. )

  The unsubstituted alkyl group includes an unsubstituted alkyl group and a substituted alkyl group. Details regarding the alkyl group and the substituent introduced therein are as described above. Although carbon number of this alkyl group is not specifically limited, For example, it is 1-27. However, when a substituent has 1 or 2 or more carbon atoms, it is preferable to satisfy the above-mentioned conditions for the number of carbon atoms including the number of carbon atoms.

  Unsubstituted alkenyl groups include unsubstituted alkenyl groups and substituted alkenyl groups. An alkenyl group is a group having one or more carbon-carbon double bonds (—C═C—), and specific examples of the alkynyl group include a vinyl group.

  Unsubstituted alkynyl groups include unsubstituted alkynyl groups and substituted alkynyl groups. An alkynyl group is a group having one or more carbon-carbon triple bonds (—C≡C—), and specific examples of the alkynyl group include an ethynyl group.

  The details regarding the substituent introduced into each of the alkenyl group and the alkynyl group are as described above.

  Although carbon number of the partial structure group shown to each of Formula (6)-Formula (8) is not specifically limited, Especially, it is preferable that it is 1-30. This is because excellent solubility can be obtained.

  Here, the picenodithiophene compound represented by the formula (11) preferably satisfies the following conditions. This is because it can be easily produced and exhibits excellent characteristics.

First, any one or two or more of R _{1 to} R ₁₄ are preferably hydrocarbon groups. Among them, any one or two or more of R _{1 to} R ₄ are more preferably a hydrocarbon group, and one or both of R ₁ and R ₂ may be a hydrocarbon group. Further preferred.

  In this case, the hydrocarbon group preferably has 1 to 30 carbon atoms, more preferably 6 to 30 carbon atoms, and still more preferably 8 to 25 carbon atoms.

  Secondly, the above-described hydrocarbon group is preferably an aliphatic hydrocarbon group.

  Specific examples of the picenodithiophene compound include compounds represented by the following formulas (1-1) to (1-22).

<1-2. Manufacturing method>
This picenodithiophene compound is produced, for example, by the following procedure.

Here, a manufacturing process is demonstrated in order, using the following formula | equation (1 ') and Formula (2)-Formula (5). Details regarding R ₁ , R ₃ and R _{5 to} R ₁₀ are as described above.

（式中、Ｒ₁ 、Ｒ₃ 及びＲ₅ 〜Ｒ₁₀のそれぞれは、水素原子、ハロゲン原子、ニトロ基、保護されていてもよい水酸基、保護されていてもよいアミノ基、保護されているか又は塩を形成していてもよいカルボキシル基、置換されていてもよい炭素数１〜３０の炭化水素基、炭素数１〜３０の複素環基、置換されていてもよい炭素数１〜３０のアルコキシ基のうちのいずれかである。）

(In the formula, each of R ₁ , R ₃ and R _{5 to} R ₁₀ is a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group which may be protected, an amino group which may be protected, a protected group or A carboxyl group which may form a salt, an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, a heterocyclic group having 1 to 30 carbon atoms, and an optionally substituted alkoxy having 1 to 30 carbon atoms Any of the groups.)

  First, a dibromophenanthrene derivative represented by the formula (2) and a formylthienylboronic acid derivative represented by the formula (3) are prepared. Subsequently, a dibromophenanthrene derivative and a formylthienylboronic acid derivative are reacted (Suzuki coupling reaction) to synthesize an aldehyde compound represented by the formula (4). Subsequently, the aldehyde group of the aldehyde body is epoxidized to obtain an epoxy body represented by the formula (5). Finally, the epoxy compound is cyclized to obtain a picenyl dithiophene compound represented by the formula (1 ').

In the above production process, instead of the formylthienylboronic acid derivative represented by the formula (3), the formylthienylboronic acid derivative represented by each of the following formulas (3-1) and (3-2) It may be used. In this case, a picenyl dithiophene compound represented by the formula (11) is obtained. Details regarding R _{1 to} R ₄ are as described above.

（式中、Ｒ₁ 〜Ｒ₄ のそれぞれは、水素原子、ハロゲン原子、ニトロ基、保護されていてもよい水酸基、保護されていてもよいアミノ基、保護されているか又は塩を形成していてもよいカルボキシル基、置換されていてもよい炭素数１〜３０の炭化水素基、炭素数１〜３０の複素環基、置換されていてもよい炭素数１〜３０のアルコキシ基のうちのいずれかである。）

(In the formula, each of R _{1 to} R ₄ is a hydrogen atom, a halogen atom, a nitro group, an optionally protected hydroxyl group, an optionally protected amino group, protected or forming a salt. Any one of an optionally substituted carboxyl group, an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, a heterocyclic group having 1 to 30 carbon atoms, and an optionally substituted alkoxy group having 1 to 30 carbon atoms. .)

<2. Organic semiconductor materials>
The organic semiconductor material of the present invention includes any one or two or more of the above-described picenodithiophene compounds, and is used, for example, in an organic semiconductor layer constituting an organic semiconductor element. The organic semiconductor element is, for example, an organic electroluminescent element, a photoelectric conversion element, an organic thin film transistor (OFET), or the like.

  The composition of the organic semiconductor material is not particularly limited as long as it includes any one or more of the picenodithiophene compounds. That is, the organic semiconductor material may be only one kind or two or more kinds of picenodithiophene compounds. Or the organic-semiconductor material may contain any 1 type or 2 or more types of other materials with the picenodithiophene compound.

  Another material is, for example, a solvent. Although the kind in particular of solvent is not restrict | limited, For example, it is any 1 type in water, an organic solvent, etc. or 2 types or more. Organic solvents include, for example, alcohol solvents, diol solvents, ketone solvents, ester solvents, ether solvents, aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, aromatic hydrocarbon solvents, cyano groups And hydrocarbon solvents, halogenated hydrocarbon solvents, and other organic solvents.

  Specific examples of the alcohol solvent include methanol, ethanol, propanol, isopropanol, 1-butanol, isobutanol, 2-butanol, tertiary butanol, pentanol, isopentanol, 2-pentanol, neopentanol, and third pen. Tanol, hexanol, 2-hexanol, heptanol, 2-heptanol, octanol, 2-ethylhexanol, 2-octanol, cyclopentanol, cyclohexanol, cycloheptanol, methylcyclopentanol, methylcyclohexanol, methylcycloheptanol, Benzyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, 2- (N, N- dimethylamino) ethanol, 3 (N, N-dimethylamino) propanol.

  Specific examples of the diol solvent include ethylene glycol, propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, isoprene glycol (3 -Methyl-1,3-butanediol), 1,2-hexanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,2-octanediol, octanediol (2-ethyl- 1,3-hexanediol), 2-butyl-2-ethyl-1,3-propanediol, 2,5-dimethyl-2,5-hexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and the like.

  Specific examples of ketone solvents are acetone, ethyl methyl ketone, methyl isopropyl ketone, methyl butyl ketone, methyl isobutyl ketone, methyl amyl ketone, methyl hexyl ketone, ethyl butyl ketone, diethyl ketone, dipropyl ketone, diisobutyl ketone, methyl amyl. Ketone, cyclohexanone, methylcyclohexanone and the like.

  Specific examples of the ester solvent include methyl formate, ethyl formate, methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, tributyl acetate, amyl acetate, isoamyl acetate, triamyl acetate, Phenyl acetate, methyl propionate, ethyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, butyl propionate, tert-butyl propionate, amyl propionate, isoamyl propionate, 3 amyl propionate, propionate Acid phenyl, methyl 2-ethylhexanoate, ethyl 2-ethylhexanoate, propyl 2-ethylhexanoate, isopropyl 2-ethylhexanoate, butyl 2-ethylhexanoate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethoxy Methyl lopionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monoisopropyl ether acetate, ethylene glycol monobutyl ether Acetate, ethylene glycol mono sec-butyl ether acetate, ethylene glycol monoisobutyl ether acetate, ethylene glycol mono tertiary butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl acetate Acetate, propylene glycol monoisopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol mono sec-butyl ether acetate, propylene glycol monoisobutyl ether acetate, propylene glycol mono-tert-butyl ether acetate, butylene glycol monomethyl ether acetate, butylene glycol monoethyl ether Acetate, Butylene glycol monopropyl ether acetate, Butylene glycol monoisopropyl ether acetate, Butylene glycol monobutyl ether acetate, Butylene glycol mono sec-butyl ether acetate, Butylene glycol monoisobutyl ether acetate, Butylene glycol mono-tert-butyl Examples thereof include ether acetate, methyl acetoacetate, ethyl acetoacetate, methyl oxobutanoate, ethyl oxobutanoate, γ-lactone, dimethyl malonate, dimethyl succinate, propylene glycol diacetate, and δ-lactone.

  Specific examples of the ether solvent include tetrahydrofuran, tetrahydropyran, morpholine, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, triethylene glycol dimethyl ether, dibutyl ether, diethyl ether, dioxane and the like.

  Specific examples of the aliphatic hydrocarbon solvent and the alicyclic hydrocarbon solvent include pentane, hexane, cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, heptane, octane, decalin, solvent naphtha, turpentine oil, D-limonene, Examples include pinene, mineral spirits, Swazol # 310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.), and the like.

  Specific examples of the aromatic hydrocarbon solvent include benzene, toluene, ethylbenzene, xylene, mesitylene, diethylbenzene, cumene, isobutylbenzene, cymene, tetralin and the like.

  Specific examples of the hydrocarbon solvent having a cyano group include acetonitrile, 1-cyanopropane, 1-cyanobutane, 1-cyanohexane, cyanocyclohexane, cyanobenzene, 1,3-dicyanopropane, 1,4-dicyanobutane, 1 , 6-dicyanohexane, 1,4-dicyanocyclohexane, 1,4-dicyanobenzene and the like.

  Specific examples of the halogenated hydrocarbon solvent include carbon tetrachloride, chloroform, dichloromethane, trichloroethylene, chlorobenzene, dichlorobenzene, and trichlorobenzene.

  Specific examples of other organic solvents are N-methyl-2-pyrrolidone, dimethyl sulfoxide, dimethylformamide, aniline, triethylamine, pyridine, carbon disulfide and the like.

  Of these, chloroform, dichloromethane, toluene, xylene, chlorobenzene, dichlorobenzene, trichlorobenzene and the like are preferable. This is because excellent solubility can be obtained. Moreover, since the solvent is easily removed, the film forming property is excellent.

  When the organic semiconductor material contains a solvent, the content of the solvent in the organic semiconductor material is not particularly limited as long as the content does not hinder the formation of the organic semiconductor layer. Specifically, the content of the solvent is, for example, preferably 100 parts by mass or more, and more preferably 500 parts by mass to 1000000 parts by mass with respect to 100 parts by mass of the picenodithiophene compound. This is because if the solvent content is low, the picenodithiophene compound may be precipitated, and if the solvent content is high, it may be difficult to form an organic semiconductor layer having a desired thickness.

However, among the picenodithiophene compounds, when any one or two or more of R _{1 to} R ₁₄ shown in the formula (11) are partial structural groups, the content of the solvent may be relatively small. Good. This is because this picenodithiophene compound exhibits high solubility, so that it has excellent coating properties and improves the formation efficiency of the organic semiconductor layer. Specifically, the content of the solvent is preferably 100 parts by mass to 100000 parts by mass, and more preferably 7000 parts by mass to 20000 parts by mass with respect to 100 parts by mass of the picenodithiophene compound. .

  The other material may be any material necessary for forming the organic semiconductor layer. This optional material is, for example, a metal oxide. Although content of the arbitrary material in organic-semiconductor material will not be specifically limited if it is content which does not impair the function of organic-semiconductor material, For example, it is 30 mass parts or less with respect to 100 mass parts of picenodithiophene compounds. It is preferable.

<3. Organic semiconductor layer>
The organic semiconductor layer of the present invention is a layer (thin film) containing any one or more of the above-described organic semiconductor materials, and the organic semiconductor material is formed into a film.

  Details regarding the configuration (composition) and the manufacturing method of the organic semiconductor layer are the same as the configuration and manufacturing method of a general organic semiconductor layer, except that the organic semiconductor layer contains the organic semiconductor material of the present invention.

  The organic semiconductor layer is formed on an arbitrary support, for example. This organic semiconductor layer may be used as it is formed on the support. Or after forming an organic-semiconductor layer on a support body, it may be used as an independent layer by peeling from the support body. Although the kind of support body is not specifically limited, For example, it is any 1 type or 2 types or more in glass, a resin substrate, quartz, a single crystal silicon, a polycrystalline silicon, an amorphous silicon, etc.

  In the case where the organic semiconductor material contains a solvent, the organic semiconductor layer is formed through a step of removing (volatilizing) the solvent.

  The manufacturing method of the organic semiconductor layer is, for example, any one type or two or more types among a dry process and a wet process.

  Specific examples of the dry process include vapor deposition, physical vapor deposition (PVD), chemical vapor deposition (CVD), atomic layer deposition (ALD), atomic layer epitaxy (ALE), and molecular beam epitaxy (MBE). ), Vapor phase epitaxy (VPE), sputtering, plasma polymerization, and the like.

  In the dry process, an organic semiconductor material composed of a picenodithiophene compound, that is, a picenodithiophene compound itself is used as the organic semiconductor material. However, an organic semiconductor material containing a solvent together with a picenodithiophene compound, that is, an organic semiconductor material in a state where the picenodithiophene compound is dispersed or dissolved in a solvent (solution state) may be used.

  Specific examples of the wet process include dip coating, casting, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, spin coating, LB, printing, inkjet, and ext For example, the rouge coat method. Among these, a dip coating method, a casting method, a spin coating method, a printing method, an ink jet method and the like are preferable. This is because the organic semiconductor layer can be easily manufactured.

  In the wet process, the organic semiconductor material in the solution state described above is used. In this case, after applying an organic semiconductor material to the surface of the support, the organic semiconductor material is dried. Thereby, since the solvent in the organic semiconductor material is volatilized, the organic semiconductor material becomes a film.

  The thickness of the organic semiconductor layer is not particularly limited, but is preferably 1 nm to 100 μm, and more preferably 1 nm to 500 nm. This is because when the thickness is smaller than 1 nm, defects are likely to occur in the organic semiconductor layer. On the other hand, when the thickness is larger than 100 μm, the leakage current tends to increase.

  Note that the organic semiconductor layer may be doped. That is, any one type or two or more types of dopants may be introduced into the organic semiconductor layer during or after the formation of the organic semiconductor layer.

  Examples of the dopant include a donor dopant and an acceptor dopant. Specific examples of the donor dopant include alkali metal, alkaline earth metal, rare earth metal, metal oxide, ammonium ion, phosphonium ion, and the like. Specific examples of the acceptor dopant include a halogen compound, a transition metal compound, and an electrolyte anion.

<4. Organic Semiconductor Device>
The organic semiconductor element of the present invention includes the organic semiconductor layer described above. The configuration of this organic semiconductor element is the same as that of a general organic semiconductor element, for example, except that it includes one or more organic semiconductor layers.

  1 and 2 schematically show some configuration examples of the organic semiconductor element. The types of the organic semiconductor element shown in FIG. 1 are (a) bottom gate-top contact type, (b) bottom gate-bottom contact type, (c), (d) top gate-bottom contact type, (e), (F) Bottom gate—top and bottom contact type. Note that the organic semiconductor element shown in FIG. 1G is a vertical static induction transistor (SIT). FIG. 2 is a modification of the organic semiconductor element shown in FIG.

  The organic semiconductor element includes, for example, an organic semiconductor layer 11, a drain electrode 12, a source electrode 13, an insulating layer 14, a gate electrode 15, and a support 16 as shown in FIGS. . However, the organic semiconductor element that is SIT includes, for example, the organic semiconductor layer 11, the drain electrode 12, the source electrode 13, and the gate electrode 15 as shown in FIG.

  The organic semiconductor layer 11 is the above-described organic semiconductor layer of the present invention. Each configuration of the drain electrode 12 and the source electrode 13 is the same as the configuration of the gate electrode 15 described later, for example.

  The insulating layer 14 includes one or more of various insulating materials, and the insulating material includes an inorganic insulating material and an organic insulating material. Examples of inorganic insulating materials include silicon oxide, aluminum oxide, barium strontium titanate, barium zirconate titanate, lead zirconate titanate, lead lanthanum titanate, strontium titanate, barium titanate, barium magnesium fluoride, titanium Examples thereof include bismuth oxide, strontium bismuth titanate, tantalum oxide, strontium bismuth tantalate, bismuth tantalate niobate, titanium oxide, yttrium oxide, silicon nitride, and aluminum nitride. Organic insulating materials include, for example, polyimide resin, epoxy resin, acrylic resin, acrylate resin, polysulfone resin, polyurethane resin, polyvinyl acetate resin, polyester resin, polycarbonate resin, polyvinyl phenol resin, polyvinyl alcohol resin, polystyrene resin, benzocyclo Butene resins, halogenated hydrocarbon compounds (halogen-based surfactants), and the like. In addition, the organic insulating material may be an organic silicon compound such as octyltrichlorosilane. The thickness of the insulating layer 14 is not particularly limited, but is preferably 500 nm or less, and more preferably 300 nm or less. In particular, the thickness of the insulating layer 14 is preferably as small as possible, and more specifically 100 nm or less.

  The gate electrode 15 includes one kind or two or more kinds of various conductive materials. Examples of the conductive material include noble metal materials, metal materials, carbon materials, transparent conductive materials, doped conductive polymers, highly n-type doped silicon wafers, and heavily p-type doped silicon wafers. Etc. Specific examples of the noble metal material are platinum, gold, silver and the like. Specific examples of the metal material include copper and aluminum. Specific examples of the transparent conductive material include indium tin oxide (ITO), tin oxide, and tin oxide doped with fluorine. The thickness of the gate electrode 15 is not particularly limited, but is preferably 500 nm or less, and more preferably 100 nm or less.

  The support 16 includes, for example, an insulating material or a conductive material depending on the configuration of the organic semiconductor element. Specifically, the support 16 shown in FIGS. 1A, 1B, and 1F includes, for example, any one type or two or more types of various conductive materials. The support 16 shown in FIGS. 1C, 1D, and 1E includes, for example, any one type or two or more types of various insulating materials. In FIG. 2, since the gate electrode 15 and the support 16 are integrated, the support 16 includes any one type or two or more types of various conductive materials. Details regarding each of the insulating material and the conductive material are the same as those described for each of the insulating layer 14 and the gate electrode 15.

  In addition, the intermediate compound shown in each of formula (4) and formula (5), that is, the aldehyde form shown in formula (4) and the epoxy form shown in formula (5) are useful as organic superconducting materials. .

  Hereinafter, embodiments of the present invention will be specifically described. The order of explanation is as follows. However, the aspect of the present invention is not limited to the aspect described here.

1. Synthesis Example 1: Synthesis of compound (1-1) Synthesis Examples 2 to 9: Synthesis of compounds (1-4), (1-5), (1-16) to (1-20), and (1-22) Measurement example 1, 2

<1. Synthesis Example 1: Synthesis of Compound (1-1)>
Production of compound (1-1), which is a picenodithiophene compound, was attempted by the procedure described in steps 1 to 3 below.

<Step 1: Synthesis of a compound corresponding to formula (4))
First, 2,7-dibromophenanthrene (1.86 g, 5.5 mmol, 1 equivalent), 3-formyl-2-thienylboronic acid (1.89 g, 12.1 mmol, 2.2 equivalent) as raw materials Potassium fluoride (KF: 1.4 g, 25.3 mmol, 4.6 equivalents) and bis (benzylideneacetone) palladium (Pd (dba) ₂ : 158 mg, 0.275 mmol, 5 mol%) If, tetrafluoroborate tri -t- butylphosphine _{^{(HP (t Bu) 3 ·}} BF 4: 161mg, 0.55mmol, 10mol%) and water _{(H 2 O: 0.6ml, 33mmol} , 6 eq) And tetrahydrofuran (THF: 110 ml), followed by a two-necked flask (volume 200) under an argon gas atmosphere. The raw material was added to the flask (15 ml) and refluxed (12 hours) .Then, the reaction was stopped by adding water to the two-necked flask, and methanol (100 ml) was poured into the flask to form a precipitate. Finally, the precipitate was filtered and dried, whereby the following compound (4-1) was obtained.

The compound (4-1) was a pale yellow solid, and the yield of the compound (4-1) was 84% (1.83 g, 4.6 mmol). Moreover, when the compound (4-1) was analyzed using the nuclear magnetic resonance (NMR) method, the following results were obtained.
¹ H NMR (300 MHz, CDC 1 ₃ , rt): δ 7.61 (s, 2H), 7.71 (d, J = 8.7 Hz, 2H), 8.00 (s, 2H), 8.40 ( d, j = 8.4 Hz, 2H).

<Step 2: Synthesis of a compound corresponding to formula (5)>
First, as a raw material, compound (4-1) (279 mg, 0.7 mmol, 1 equivalent), trimethylsulfonium iodide (Me ₃ SI: 371 mg, 1.8 mmol, 2.6 equivalent), Potassium hydroxide (KOH: 216 mg, 3.9 mmol, 5.5 equivalents) and dehydrated acetonitrile (MeCN: 14 ml) were prepared. Subsequently, the raw material was charged into a Schlenk tube (capacity 50 ml) under an argon atmosphere, and the raw material was stirred (60 ° C. × 3.5 hours). Subsequently, the reaction was stopped by adding water to the Schlenk tube, and then extracted with chloroform. Then, after wash | cleaning an organic phase using saturated sodium chloride aqueous solution, the organic phase was dried using anhydrous magnesium sulfate. Finally, after filtering the organic phase, the solvent in the organic phase was distilled off using a rotary evaporator. Thereby, the following compound (5-1) was obtained.

Compound (5-1) was a pale yellow solid, and the yield of compound (5-1) was 99% (294 mg, 0.69 mmol). Moreover, when the compound (5-1) was analyzed using NMR method, the following results were obtained.
¹ H NMR (400 MHz, CDC 1 ₃ , rt): δ 3.06-3.08 (m, 2H), 3.22-3.25 (m, 2H), 4.07-4.09 (m = 2H) ), 6.97 (d, j = 5.2 Hz, 2H), 7.33 (d, j = 5.2 Hz, 2H), 7.83 (s, 2H), 7.86 (dd, J = 8) .4, 1.6 Hz, 2H), 8.06 (d, J = 1.6 Hz, 2H), 8.74 (d, J = 8.4 Hz, 2H).

<Step 3: Synthesis of Compound (1-1) Corresponding to Formula (1))
First, as a raw material, compound (5-1) (256 mg, 0.6 mmol, 1 equivalent), anhydrous indium chloride (InCl ₃ : 26.4 mg, 0.12 mmol, 20 mol%), dehydrated 1,2-dichloroethane (DCE: 36 ml) was prepared. Subsequently, the raw material was charged into a Schlenk tube (capacity 50 ml) and refluxed (24 hours) in an argon atmosphere. Subsequently, the reaction was stopped by adding water to the Schlenk tube, and then the precipitate was filtered. Finally, the precipitate was washed with water and chloroform and then dried. Thereby, the compound (1-1) which is a light brown solid was obtained.

The yield (%) and yield (mg, mmol) of this compound (1-1) are as shown in Table 1. However, when obtaining the yield, the compound synthesized in Step 2 was used as the starting material, and the compound synthesized in Step 3 was used as the final target product. The compound (1-1) was purified by sublimation to obtain a high-purity compound (1-1), and then the compound (1-1) was analyzed using the NMR method. The NMR shown in Table 1 was obtained. Spectral data was obtained. Information accompanying the NMR spectrum data is as follows.
Anal. Calcd for C ₂₆ H ₁₄ S ₂ : C, 79.96%: H, 3.61%. Found: C, 79.93%: H, 3.29%.

<2. Synthesis Examples 2 to 9: Synthesis of Compounds (1-4), (1-5), (1-16) to (1-20), (1-22)>
According to the same procedure as in Synthesis Example 1, except that a derivative of 3-formyl-2-thienylboronic acid into which a predetermined substituent was introduced was used instead of 3-formyl-2-thienylboronic acid. Attempts were made to produce compounds (1-4), (1-5), (1-16) to (1-20), and (1-22), which are thiophene compounds. The above-mentioned predetermined substituent is a group bonded to the thiophene ring in each of the compounds (1-4), (1-5), (1-16) to (1-20), and (1-22). It is.

  In addition, when synthesizing the compound (1-19), after reacting two types of 3-formyl-2-thienylboronic acid derivatives having different types of substituents, the compound (1- 19) was isolated.

  The yield (%), yield (mg, mmol) and NMR spectrum data of the compounds (1-4), (1-5), (1-16) to (1-20), (1-22) As shown in Table 1 and Table 2.

  Although some differences occurred in the yield, a series of compounds (1-1), (1-4), (1-5), (1-16) to (1-20), which are picenodithiophene compounds, (1-22) could be synthesized.

<3. Measurement Example 1, 2>
An organic semiconductor element was produced by the following procedure.

  First, a support 16 on which the insulating layer 14 and the gate electrode 15 were formed was prepared. An n-type doped silicon substrate was used as the support 16 on which the gate electrode 15 was formed. The insulating layer 14 is a silicon oxide film (thickness = 200 nm). Subsequently, the support 16 and the like were subjected to ultraviolet (UV) ozone treatment, and then the support 16 and the like were processed using octyltrichlorosilane (OTS) to form a self-assembled film. Hereinafter, the support 16 and the like formed up to the self-assembled film are referred to as “Si processing substrate”. Subsequently, in the air, a picenodithiophene compound was deposited on the Si-treated substrate using an evaporation method to form an organic semiconductor layer 11 (thickness = 30 nm to 70 nm). The types of this picenodithiophene compound are as shown in Table 3. Subsequently, after arranging a nickel mask on the surface of the organic semiconductor layer 11, gold was deposited by using a vacuum evaporation method to form the drain electrode 12 and the source electrode 13 (channel width = 2 mm, channel length = 100 μm). . Finally, the nickel mask was removed. Thereby, the organic semiconductor element was completed.

The organic semiconductor element in which the organic semiconductor layer 11 contains a picenodithiophene compound exhibited operating characteristics in which the drain current increases as a negative gate voltage is applied, that is, p-channel-enhanced operating characteristics. When the mobility (carrier mobility or charge mobility: cm ² / Vs) and the On / Off ratio were examined as the organic semiconductor characteristics of the organic semiconductor element, the results shown in Table 3 were obtained. The mobility was calculated based on the saturation region of current (I) -voltage (V) characteristics. The On / Off ratio is a ratio of drain current values under the conditions of Vd = 80V and Vg = 0V to 80V. The mobility and On / Off ratio after annealing (150 ° C. × 30 minutes) of the organic semiconductor element were also examined.

  The picenodithiophene compound showed organic semiconductor properties. For this reason, the picenodithiophene compound was applicable to an organic semiconductor material, an organic semiconductor layer, and an organic semiconductor element using a known method.

  From these results, it is possible to synthesize the picenodithiophene compound and derivatives thereof represented by the formula (1), and the picenodithiophene compound and derivatives can be applied to organic semiconductor materials, organic semiconductor layers, and organic semiconductor elements. It was confirmed.

  As mentioned above, although this invention was demonstrated referring an embodiment and an Example, this invention is not limited to the aspect demonstrated in embodiment and an Example, A various deformation | transformation is possible.

  DESCRIPTION OF SYMBOLS 11 ... Organic-semiconductor layer, 12 ... Drain electrode, 13 ... Source electrode, 14 ... Insulating layer, 15 ... Gate electrode, 16 ... Support body.

Claims (4)

It is at least one of a compound represented by the following formula (1) and a compound represented by the following formula (11).
Picenodithiophene compound.

(Wherein each of R ₁ to R _14, a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, an alkylcarbonyloxy group, an alkylsilyl group, an amino group, an alkylamino group, a carboxyl group, mosquitoes carboxylic acid base, carbonized At least one of an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a heterocyclic group, an acyl group, an acyloxy group, an amino group, and a halogen atom as a hydrogen group, a heterocyclic group, an alkoxy group, and a hydrocarbon group A group into which a species is introduced, and at least one of an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a heterocyclic group, an acyl group, an acyloxy group, an amino group, and a halogen atom in the heterocyclic group; Any of the groups introduced.) Including a picenodithiophene compound that is at least one of a compound represented by the following formula (1) and a compound represented by the following formula (11):
Organic semiconductor material.

(Wherein each of R ₁ to R _14, a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, an alkylcarbonyloxy group, an alkylsilyl group, an amino group, an alkylamino group, a carboxyl group, mosquitoes carboxylic acid base, carbonized At least one of an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a heterocyclic group, an acyl group, an acyloxy group, an amino group, and a halogen atom as a hydrogen group, a heterocyclic group, an alkoxy group, and a hydrocarbon group A group into which a species is introduced, and at least one of an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a heterocyclic group, an acyl group, an acyloxy group, an amino group, and a halogen atom in the heterocyclic group; Any of the groups introduced.) Including organic semiconductor materials,
The organic semiconductor material includes a picenodithiophene compound that is at least one of a compound represented by the following formula (1) and a compound represented by the following formula (11).
Organic semiconductor layer.

(Wherein each of R ₁ to R _14, a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, an alkylcarbonyloxy group, an alkylsilyl group, an amino group, an alkylamino group, a carboxyl group, mosquitoes carboxylic acid base, carbonized At least one of an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a heterocyclic group, an acyl group, an acyloxy group, an amino group, and a halogen atom as a hydrogen group, a heterocyclic group, an alkoxy group, and a hydrocarbon group A group into which a species is introduced, and at least one of an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a heterocyclic group, an acyl group, an acyloxy group, an amino group, and a halogen atom in the heterocyclic group; Any of the groups introduced.) An organic semiconductor layer including an organic semiconductor material;
The organic semiconductor material includes a picenodithiophene compound that is at least one of a compound represented by the following formula (1) and a compound represented by the following formula (11).
Organic semiconductor element.

(Wherein each of R ₁ to R _14, a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, an alkylcarbonyloxy group, an alkylsilyl group, an amino group, an alkylamino group, a carboxyl group, mosquitoes carboxylic acid base, carbonized At least one of an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a heterocyclic group, an acyl group, an acyloxy group, an amino group, and a halogen atom as a hydrogen group, a heterocyclic group, an alkoxy group, and a hydrocarbon group A group into which a species is introduced, and at least one of an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a heterocyclic group, an acyl group, an acyloxy group, an amino group, and a halogen atom in the heterocyclic group; Any of the groups introduced.)

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