JP2014198682A - Aromatic heterocyclic compound and production method thereof, and organic semiconductor material and organic semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: an aromatic heterocyclic compound which has oxidation stability, high solubility, favorable film production properties and high charge transfer properties, and is suitable as an organic semiconductor material; and organic semiconductor devices using the same, such as an organic field effect transistor and an organic thin film solar cell.SOLUTION: The invention provides: an aromatic heterocyclic compound represented by the specified general formula (1) and having a six-ring fused structure in which a dibenzofuran ring and a carbazole ring are fused; and an organic semiconductor material containing this aromatic heterocyclic compound. In the formula, R is a hydrogen atom or a monovalent group.

Description

  The present invention relates to a novel aromatic heterocyclic compound, an organic semiconductor material containing the same, an organic semiconductor film obtained by using the organic semiconductor material, and an organic semiconductor device such as an organic field effect transistor.

  In general, in a semiconductor element using silicon as an inorganic semiconductor material, a high temperature process and a high vacuum process are indispensable for forming a thin film. Since a high-temperature process is required, it is difficult to form a thin film of silicon on a plastic substrate or the like. Therefore, it has been difficult to impart flexibility and weight reduction to a product incorporating a semiconductor element. In addition, since a high vacuum process is required, it is difficult to increase the area and cost of a product incorporating a semiconductor element.

  In recent years, therefore, research has been conducted on organic semiconductor devices (for example, organic electroluminescence (EL) elements, organic field effect transistor elements, or organic thin film photoelectric conversion elements) that use organic semiconductor materials as organic electronic components. Since these organic semiconductor materials can significantly reduce the manufacturing process temperature as compared with inorganic semiconductor materials, they can be formed on a plastic substrate or the like. Furthermore, by using an organic semiconductor having high solubility in a solvent and good film formability, a thin film can be formed using a coating method that does not require a vacuum process, for example, an inkjet apparatus. As described above, it is expected to realize an increase in area and cost, which has been difficult in a semiconductor element using silicon which is an inorganic semiconductor material. As described above, organic semiconductor materials are advantageous in terms of large area, flexibility, weight reduction, cost reduction, and the like compared to inorganic semiconductor materials. Applications such as information tags, large-area sensors such as electronic artificial skin sheets and sheet-type scanners, displays such as liquid crystal displays, electronic paper, and organic EL panels are expected.

  Thus, a high charge mobility is required for a fixed-term semiconductor material used for a fixed-term semiconductor element that is expected to have a wide range of applications. For example, in an organic FET device, since it directly affects the switching speed and the performance of the driven device, improvement of charge mobility is an essential issue for practical use. Furthermore, as described above, solvent solubility, oxidation stability, and good film forming properties are required in order to enable the production of a semiconductor element by a coating method.

  In particular, high charge mobility is a required characteristic for organic semiconductors. From this viewpoint, in recent years, organic semiconductor materials having charge transport properties comparable to amorphous silicon have been reported. For example, in organic field effect transistor elements (OFETs) using pentacene, a hydrocarbon-based acene-type polycyclic aromatic molecule in which five benzene rings are linearly condensed, the charge mobility is similar to that of amorphous silicon. Has been reported (Non-patent Document 1). However, when pentacene is used as an organic semiconductor material for OFETs, the organic semiconductor thin film layer is formed by an ultra-high vacuum deposition method, which is disadvantageous in terms of large area, flexibility, weight reduction, and cost reduction. It is. In addition, a method of forming a pentacene crystal in a dilute solution of trichlorobenzene without using a vacuum deposition method has been proposed, but a manufacturing method is difficult and a stable element has not been obtained (Patent Document 1). A hydrocarbon-based acene-type polycyclic aromatic molecule such as pentacene also has a low oxidation stability.

  In addition, polythiophene derivatives having a long-chain alkyl group such as poly (3-hexylthiophene) are soluble in a solvent, and it has been reported that organic semiconductor devices are produced by a coating method. However, charge mobility is higher than that of crystalline compounds. Since it was low, there existed a problem that the characteristic of the obtained organic-semiconductor device was low (nonpatent literature 2).

  In addition, pentathienoacene condensed with a thiophene ring has improved oxidation resistance as compared with pentacene, but has low carrier mobility and requires multiple steps for its synthesis (Non-patent Document 3). It was not a preferable material.

  Recently, very high mobility has been reported due to the single crystal of rubrene, which is a highly soluble acene, but the rubrene film formed by solution casting does not take such a single crystal structure and is sufficient. Mobility is not obtained (Non-Patent Document 4).

  As an example of a hydrocarbon-based acene-type compound that has high solvent solubility and is relatively stable against oxidation, some compounds in which the 6- and 13-positions of pentacene are substituted with silylethynyl groups have good coating film stability. Has been reported (Non-patent Document 5). However, these reports only describe the qualitative properties in the text that the stability against oxidation has been improved, and the stability to the extent that it can withstand practical use has not yet been obtained.

  Against this background, a heteroacene skeleton in which a heteroatom such as nitrogen or sulfur is introduced into a hydrocarbon-based acene polycyclic aromatic skeleton has been recently reported as a material that is stable and exhibits high carrier mobility. ing.

  For example, a polycyclic fused ring compound obtained by condensing two benzofuran skeletons or indole skeletons with a naphthalene ring has been proposed as a material for an organic semiconductor layer of an organic TFT. There is no description (Patent Document 2).

WO2003 / 01659A WO2011 / 074232A

Journal of Applied Physics, Vol.92, 5259 (2002) Science, Vol.280, (5370) 1741 (1998) Journal Of American Chemical Society, Vol.127, 13281 (2005) Science, Vol.303 (5664), 1644 (2004) Org. Lett., Vol.4, 15 (2002)

  The present invention provides an organic semiconductor material having high charge mobility, oxidation stability and solvent solubility, an organic semiconductor element using the same, a novel aromatic heterocyclic compound used therefor, and a method for producing the same. Objective.

  As a result of intensive studies, the present inventors have found an aromatic heterocyclic compound suitable as an organic semiconductor material having high charge mobility, oxidation stability, and solvent solubility, and use this for an organic semiconductor material and an organic semiconductor element. Thus, the inventors have found that an organic semiconductor element having high characteristics can be obtained, and reached the present invention.

ここで、Ｒは、それぞれ独立に、水素原子又は１価の基を示す。ａ、ｃは1〜4の整数、ｂ、ｄは1又は2の整数である。 The present invention is an aromatic heterocyclic compound represented by the following general formula (1).

Here, each R independently represents a hydrogen atom or a monovalent group. a and c are integers of 1 to 4, and b and d are integers of 1 or 2.

Preferred embodiments of the aromatic heterocyclic compound of the present invention are shown below.
1) In general formula (1), at least one of R is a monovalent group.
2) In general formula (1), at least one of R is a halogen atom, a hydroxyl group, a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 30 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms. Substituted or unsubstituted amino group, thiol group, substituted or unsubstituted sulfonyl group, cyano group, substituted or unsubstituted aromatic hydrocarbon group having 6 to 48 carbon atoms, substituted or unsubstituted carbon number 2 to 48 Aromatic heterocyclic group, substituted or unsubstituted C 8-50 aromatic hydrocarbon substituted alkynyl group, substituted or unsubstituted C 4-50 aromatic heterocyclic substituted alkynyl group, substituted or unsubstituted carbon Aromatic hydrocarbon substituted alkenyl group having 8 to 50 carbon atoms, substituted or unsubstituted aromatic heterocyclic substituted alkenyl group having 4 to 50 carbon atoms, substituted or unsubstituted alkylsilylalkynyl group having 5 to 30 carbon atoms, substituted or Unsubstituted charcoal An alkylsilyl group having 3 to 30 primes, a substituted or unsubstituted siloxane group having 1 to 30 silicon atoms, a substituted or unsubstituted siloxane alkyl group having 1 to 30 silicon atoms, and a substituted or unsubstituted silicon group having 1 to 30 silicon atoms. A monovalent group selected from the group consisting of polysilane groups;

ここで、Ｒ₁〜Ｒ₄はそれぞれ独立に、水素原子又は１価の基を示す。 3) In general formula (1), at least one of R is a group represented by formula (2) or (3).

Here, R < ₁ > -R < ₄ > shows a hydrogen atom or monovalent group each independently.

ここで、Ｒは一般式（１）のＲと同意である。 4) General formula (1) is shown by the following general formula (4).

Here, R is the same as R in the general formula (1).

ここで、Ｒ及びａ、ｂ、ｃは、一般式（１）のＲ及びａ、ｂ、ｃと同意である。 Moreover, this invention is an aromatic heterocyclic compound characterized by being shown by following General formula (5).

Here, R and a, b, and c are the same as R and a, b, and c in the general formula (1).

ここで、Ｒは一般式（５）のＲと同意である。 As a preferable form of the general formula (5), there is the following general formula (6).

Here, R is the same as R in the general formula (5).

  The present invention also provides an aromatic heterocyclic compound represented by the general formula (1) or (4), wherein the aromatic heterocyclic compound represented by the general formula (5) or (6) is dehydrogenated. It is a manufacturing method.

ここで、Ｒは一般式（１）のＲと同意である。Ｘは、それぞれ独立に、ハロゲン原子、水酸基、-Ｂ(ＯＨ)₂、スルホニル基、トリフルオロメタンスルホナート、ノナフルオロブタンスルホナート、フルオロスルホン酸エステル、トシラートから選ばれる反応性基、又は一般式（１）のＲを示し、少なくとも１つはＲ以外の反応性基である。ｅ、ｇは1〜4の整数、ｆ、ｈは1又は2の整数である。
Ｒ―Ｙ （８）
ここで、Ｒは一般式（１）の水素原子を除くＲと同意であり、Ｙは一般式（７）のＸと反応して、Ｘ-Ｙとして離脱し、ＸをＲに置換可能とする基である。 Moreover, this invention makes the aromatic heterocyclic compound shown by following General formula (7), the compound shown by General formula (8), and making it the compound which substituted X in General formula (7) by R Is a method for producing an aromatic heterocyclic compound represented by the general formula (1) or (4).

Here, R is the same as R in the general formula (1). X is independently a reactive group selected from a halogen atom, a hydroxyl group, —B (OH) ₂ , a sulfonyl group, trifluoromethanesulfonate, nonafluorobutanesulfonate, fluorosulfonate, tosylate, or a general formula ( 1) R is shown, and at least one is a reactive group other than R. e and g are integers of 1 to 4, and f and h are integers of 1 or 2.
RY (8)
Here, R is synonymous with R excluding the hydrogen atom of general formula (1), Y reacts with X of general formula (7) to leave as XY, and X can be replaced with R. It is a group.

ここで、Ｒ₁〜Ｒ₄は、式（２）、（３）のＲ₁〜Ｒ₄と同意であり、Ｙは一般式（８）のＹと同意である。 Examples of the compound represented by the general formula (8) include compounds represented by the following formula (9) or (10).

Wherein, R ₁ to R ₄ in Formula (2) is synonymous with R ₁ to R ₄ in (3), Y is the same meaning as Y in the general formula (8).

  Furthermore, this invention is an organic semiconductor material characterized by containing the aromatic heterocyclic compound shown by General formula (1).

  Moreover, this invention is an organic-semiconductor film formed from said organic-semiconductor material. Further, the organic semiconductor film is formed through a step of dissolving the organic semiconductor material in an organic solvent and applying and drying the prepared solution. The present invention also provides an organic semiconductor device characterized by using the organic semiconductor material described above, and further an organic field effect transistor or organic photovoltaic element characterized by using the organic semiconductor material described above as a semiconductor layer. is there.

  The aromatic heterocyclic compound of the present invention has a structure in which a benzofuran ring and an indole ring are condensed in the central naphthalene ring, and introduces two types of heteroatoms to make it asymmetrical, thereby providing oxidation stability, high solubility, Good film forming properties and high charge transfer properties. Therefore, it is suitable as an organic semiconductor material, and the organic semiconductor device of the present invention can exhibit high characteristics. For example, it can be applied to organic field effect transistors, organic thin film solar cells, information tags, large area sensors such as electronic artificial skin sheets and sheet type scanners, displays such as liquid crystal displays, electronic paper, and organic EL panels. Technical value is great.

The schematic cross section which showed an example of the organic field effect transistor element is shown. The schematic cross section which showed another example of the organic field effect transistor element is shown. The schematic cross section which showed another example of the organic field effect transistor element is shown. The schematic cross section which showed another example of the organic field effect transistor element is shown. The schematic cross section which showed one structural example of the organic photovoltaic element is shown. The schematic cross section which showed another structural example of the organic photovoltaic element is shown. The NMR spectrum data of the aromatic heterocyclic compound H are shown. The NMR spectrum data of the aromatic heterocyclic compound 101 are shown. The NMR spectrum data of the aromatic heterocyclic compound 201 are shown. The NMR spectrum data of the aromatic heterocyclic compound L are shown. The NMR spectrum data of the aromatic heterocyclic compound M are shown. The NMR spectrum data of the aromatic heterocyclic compound 301 are shown.

The aromatic heterocyclic compound of the present invention is represented by the general formula (1).
In General formula (1), R shows a hydrogen atom or monovalent group each independently. A and c are integers of 1 to 4, and b and d are integers of 1 or 2.
All of R may be hydrogen atoms, but if one or more are monovalent groups, the characteristics as a semiconductor material can be advantageously adjusted. When R is a monovalent group and the monovalent groups are adjacent to each other, they may be combined to form a ring.

  When R is a monovalent group, examples of the monovalent group include a halogen atom, a hydroxyl group, a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 30 carbon atoms, and a substituted or unsubstituted carbon group having 1 to 30 carbon atoms. Alkoxy group, substituted or unsubstituted amino group, thiol group, substituted or unsubstituted sulfonyl group, cyano group, substituted or unsubstituted aromatic hydrocarbon group having 6 to 48 carbon atoms, substituted or unsubstituted carbon number 2 -48 aromatic heterocyclic group, substituted or unsubstituted C 8-50 aromatic hydrocarbon substituted alkynyl group, substituted or unsubstituted C 4-50 aromatic heterocyclic substituted alkynyl group, substituted or unsubstituted An aromatic hydrocarbon substituted alkenyl group having 8 to 50 carbon atoms, a substituted or unsubstituted aromatic heterocyclic substituted alkenyl group having 4 to 50 carbon atoms, an alkylsilylalkynyl group having 5 to 30 carbon atoms, and 3 to 30 carbon atoms Alkylsilyl group of Or unsubstituted siloxane group silicon atoms from 1 to 30, a substituted or unsubstituted siloxane alkyl groups of silicon atoms from 1 to 30, or a substituted or unsubstituted polysilane group silicon atoms 1-30 are preferred.

  When R is a halogen atom, preferred specific examples include fluorine, bromine, chlorine, or iodine.

  When R is an unsubstituted aliphatic hydrocarbon group, an aliphatic hydrocarbon group having 1 to 30 carbon atoms is preferable, more preferably an aliphatic hydrocarbon group having 1 to 12 carbon atoms, and still more preferably an alkyl group. . Specific examples include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-dodecyl group, n-tetradecyl group, n-octadecyl group. Linear saturated hydrocarbon groups such as n-docosyl group and n-tetracosyl group, branched saturated hydrocarbons such as isopropyl group, isobutyl group, neopentyl group, 2-ethylhexyl group, 2-hexyloctyl group and 4-decyldodecyl group Group, cyclopentyl group, cyclohexyl group, cyclooctyl group, 4-butylcyclohexyl group, saturated alicyclic hydrocarbon group such as 4-dodecylcyclohexyl group, vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, octenyl group, Cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, cyclooctenyl group, ethynyl group, Pinyl group, butynyl group, pentynyl group, hexynyl group, can be exemplified unsaturated hydrocarbon groups such as octynyl group.

  When R is an unsubstituted alkoxy group, a C1-C30 alkoxy group is preferable, More preferably, it is a C1-C12 alkoxy group. Specific examples include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, butoxy group, pentyloxy group, n-hexyloxy group, octyloxy group and the like.

  When R is an unsubstituted aromatic hydrocarbon group or an aromatic heterocyclic group, an aromatic hydrocarbon group having 6 to 48 carbon atoms or an aromatic heterocyclic group having 2 to 48 carbon atoms is preferable, and more preferable. Is an aromatic hydrocarbon group having 6 to 24 carbon atoms or an aromatic heterocyclic group having 3 to 24 carbon atoms. Specific examples include benzene, pentalene, indene, naphthalene, azulene, heptalene, octalene, indacene, acenaphthylene, phenalene, phenanthrene, anthracene, tridene, fluoranthene, acephenanthrylene, asanthrylene, triphenylene, pyrene, chrysene, tetraphene. , Tetracene, preaden, picene, perylene, pentaphen, pentacene, tetraphenylene, helicene, hexaphen, rubicene, coronene, trinaphthylene, heptaphene, pyrantolene, ovalene, coranulene, fluorene, anthanthrene, zetrene, terylene, naphthacenonaphthacene, truxene , Furan, furofuran, difurofuran, benzofuran, isobenzofuran, benzofurobenzofuran, xanthene, oki Tren, dibenzofuran, perixanthenoxanthene, thiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzothienobenzothiophene, thioxanthene, thianthrene, phenoxathiin, thionaphthene, isothianaphthene, thiophantene, thiophantrene , Dibenzothiophene, pyrrole, pyrrolopyrrole, indoloindole, dipyrropyrrole, pyrazole, tellurazole, selenazole, thiazole, isothiazole, oxazole, furazane, pyridine, pyrazine, pyrimidine, pyridazine, triazine, indolizine, indole, isoindole, Indazole, purine, quinolidine, isoquinoline, carbazole, imidazole, naphthyridine, phthalazine, quinazoly , Benzodiazepine, quinoxaline, cinnoline, quinoline, pteridine, phenanthridine, acridine, perimidine, phenanthroline, phenazine, carboline, phenotelrazine, phenoselenazine, phenothiazine, phenoxazine, antilysine, thebenidine, quindrine, quinindrine, acrindrin, phthaloprin Nodithiazine, triphenodioxazine, phenanthrazine, anthrazine, thiazole, thiadiazole, benzothiazole, benzothiadiazole, benzimidazole, benzoxazole, benzisoxazole, benzoisothiazole, indolocarbazole, or a combination of these aromatic rings Groups generated by removing hydrogen from an aromatic compound. More preferably, hydrogen is removed from benzene, naphthalene, phenanthrene, anthracene, chrysene, furan, thiophene, thienothiophene, dithienothiophene, pyrrole, carbazole, indolocarbazole, or an aromatic compound in which a plurality of these aromatic rings are connected. The resulting group is mentioned. In addition, when the aromatic ring is a group generated from a linked aromatic compound, the number to be linked is preferably 2 to 10, more preferably 2 to 7, and the linked aromatic rings may be the same. It may be different. When it is a condensed ring, it is preferably a condensed ring in which 2 to 5 rings are condensed. In addition, when an aromatic ring is connected, when it includes a heterocyclic ring, it is included in the aromatic heterocyclic group. Moreover, an aromatic ring is the meaning containing an aromatic hydrocarbon ring, an aromatic heterocyclic ring, or both, and an aromatic group and an aromatic compound are the same.

（Ａｒ₁〜Ａｒ₅は、置換又は無置換の芳香環を示す） Here, a group formed by connecting a plurality of aromatic rings is represented by the following formula, for example.

(Ar _{1 to} Ar ₅ represent a substituted or unsubstituted aromatic ring)

  Specific examples of the group formed by connecting a plurality of the aromatic rings include, for example, biphenyl, terphenyl, terthiophene, bipyridine, bipyrimidine, phenylnaphthalene, diphenylnaphthalene, phenylphenanthrene, pyridylbenzene, pyridylphenanthrene, bithiophene, Examples thereof include groups generated by removing hydrogen from terthiophene, vidhienothiophene, phenylindolocarbazole and the like.

  When R is an unsubstituted aromatic hydrocarbon-substituted alkynyl group or alkenyl group, or an unsubstituted aromatic heterocyclic-substituted alkynyl group or alkenyl group, the aromatic hydrocarbon-substituted alkenyl group or alkenyl group having 8 to 50 carbon atoms Or an aromatic heterocyclic substituted alkynyl group or alkenyl group having 6 to 50 carbon atoms, more preferably an aromatic hydrocarbon-substituted alkenyl group or alkenyl group having 8 to 26 carbon atoms, or an aromatic group having 6 to 26 carbon atoms. Heterocyclic substituted alkynyl group or alkenyl group. The aromatic hydrocarbon group or aromatic heterocyclic group substituted with the alkynyl group or alkenyl group is the same as the aromatic hydrocarbon group or aromatic heterocyclic group. Specific examples include phenylethenyl, naphthylethenyl, phenylethynyl, naphthylethynyl, thienylethenyl, furanylethenyl, thienylethynyl, furanylethynyl and the like.

  When R is an unsubstituted alkylsilylalkynyl group, an alkylsilylalkynyl group having 5 to 30 carbon atoms is preferable, and an alkylsilylalkynyl group having 5 to 20 carbon atoms is more preferable. Specific examples include trimethylsilylethynyl group, triethylsilylethynyl group, triisopropylsilylethynyl group, triisobutylsilylethynyl group and the like.

  When R is an unsubstituted alkylsilyl group, an alkylsilyl group having 3 to 30 carbon atoms is preferable, and an alkylsilyl group having 3 to 20 carbon atoms is more preferable. Specific examples include trimethylsilyl group, triethylsilyl group, triisopropylsilyl group, triisobutylsilyl group and the like.

  When R is an unsubstituted siloxane group, a siloxane group having 1 to 30 silicon atoms is preferable, and a siloxane group having 1 to 20 silicon atoms is more preferable. Specific examples include disiloxane, trisiloxane, tetrasiloxane, pentamethyldisiloxane, heptamethyltrisiloxane, nonamethyltetrasiloxane, pentaphenyldisiloxane, heptaphenyltrisiloxane, nonaphenyltetrasiloxane and the like.

  When R is an unsubstituted siloxyalkyl group, silicon is preferably a siloxyalkyl group having 1 to 30 silicon atoms, more preferably a siloxyalkyl group having 1 to 20 silicon atoms. The siloxyalkyl group is understood as a group in which the siloxane group is substituted with the linear saturated hydrocarbon group. Specific examples include disiloxane ethyl, trisiloxane ethyl, tetrasiloxane ethyl, disiloxane butyl, trisiloxane butyl, tetrasiloxane butyl, pentamethyldisiloxane ethyl, heptamethyltrisiloxane ethyl, nonamethyltetrasiloxane ethyl, pentamethyldi Examples thereof include siloxane butyl, heptamethyltrisiloxane butyl, nonamethyltetrasiloxane butyl and the like.

  When R is an unsubstituted polysilane group, a polysilane group having 1 to 30 silicon atoms is preferable, and a polysilane group having 1 to 20 silicon atoms is more preferable. Specific examples include silane, disilane, trisilane, tetrasilane, pentamethyldisilane, heptamethyltrisilane, nonamethyltetrasilane, triphenylsilane, pentaphenyldisilane, heptaphenyltrisilane, nonaphenyltetrasilane, and the like.

  R is an aliphatic hydrocarbon group, an alkoxy group, an amino group, a sulfonyl group, an aromatic hydrocarbon group, an aromatic heterocyclic group, an aromatic hydrocarbon substituted alkynyl group, an aromatic heterocyclic substituted alkynyl group, an aromatic hydrocarbon substituted If it is an alkenyl group, an aromatic heterocyclic substituted alkenyl group, an alkylsilylalkynyl group, an alkylsilyl group, a siloxane group, a siloxane alkyl group, or a polysilane group, it may have a substituent, and the total number of substituents is 1-4, preferably 1-2. In addition, the group which arises from the aromatic compound with which multiple aromatic rings were connected can also have a substituent. Preferred substituents include alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 1 to 20 carbon atoms, alkynyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, alkylamino groups having 1 to 20 carbon atoms, C1-C20 aromatic amino group, C1-C20 alkylthio group, hydroxyl group, C2-C10 alkoxycarbonyl group, C1-C10 alkylsulfonyl group, C1-C10 haloalkyl group An alkylamide group having 2 to 10 carbon atoms, a trialkylsilyl group having 3 to 20 carbon atoms, a trialkylsilylalkyl group having 4 to 20 carbon atoms, a trialkylsilylalkenyl group having 5 to 20 carbon atoms, and 5 to 5 carbon atoms 20 trialkylsilylalkynyl groups, C2-C20 aromatic hydrocarbon groups, C2-C20 aromatic heterocyclic groups, C4-C22 aromatic hydrocarbon groups Alkynyl group, aromatic heterocyclic substituted alkynyl group having 4 to 22 carbon atoms, an aromatic hydrocarbon substituted alkenyl group having 4 to 22 carbon atoms and an aromatic heterocyclic substituted alkenyl group having 4 to 22 carbon atoms. Specific examples include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-dodecyl group, n-tetradecyl group. Branched saturated groups such as linear saturated hydrocarbon groups such as n-octadecyl group, n-docosyl group and n-tetracosyl group, isobutyl group, neopentyl group, 2-ethylhexyl group, 2-hexyloctyl group and 4-decyldodecyl group Saturated alicyclic hydrocarbon group such as hydrocarbon group, cyclopentyl group, cyclohexyl group, cyclooctyl group, 4-butylcyclohexyl group, 4-dodecylcyclohexyl group, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-hexyloxy group, methylamino group, dimethylamino group, ethylamino group, dimethylamino group, phenylamino group, diphenyl Mino group, methylthio group, ethylthio group, ethenyl group, 1-propenyl group, 2-propenyl group, i-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, methoxycarbonyl group, ethoxycarbonyl group, methoxycarbonyloxy group, ethoxycarbonyloxy group, methylsulfonyl group, ethylsulfonyl group, chloromethyl group, Chloroethyl, chloropropyl, chlorobutyl, chloropentyl, chlorohexyl, chlorooctyl, chlorododecyl, bromomethyl, bromoethyl, bromopropyl, bromobutyl, bromopentyl, bromohexyl, bromooctyl , Bromododecyl group, iodomethyl group, iodoethyl group, Dodopropyl group, iodobutyl group, iodopentyl group, iodohexyl group, iodooctyl group, iodododecyl group, methylamide group, dimethylamide group, ethylamide group, diethylamide group, trimethylsilyl group, triethylsilyl group, triisopropylsilyl group, triisobutylsilyl group Group, trimethylsilylethyl group, triethylsilylethyl group, triisopropylsilylethyl group, triisobutylsilylethyl group, trimethylsilylethenyl group, triethylsilylethenyl group, triisopropylsilylethenyl group, triisobutylsilylethenyl group, trimethylsilylethynyl Group, triethylsilylethynyl group, triisopropylsilylethynyl group, triisobutylsilylethynyl group, benzene, naphthalene, phenanthrene, anthra Sen, chrysene, furan, thiophene, thienothiophene, dithienothiophene, pyrrole, carbazole, indolocarbazole, biphenyl, terphenyl, terthiophene, bipyridine, bipyrimidine, phenylnaphthalene, diphenylnaphthalene, phenylphenanthrene, pyridylbenzene, pyridyl Examples thereof include phenanthrene, bithiophene, terthiophene, biditienothiophene, phenylindolocarbazole, phenylethenyl, naphthylethenyl, thienylethenyl, furanylethenyl, phenylethynyl, naphthylethynyl, thienylethynyl, furanylethynyl and the like. When it has two or more substituents, they may be the same or different.

In general formula (1), at least one of R is preferably a group represented by formula (2) or (3). R _{1 to} R _{4 in} formula (2) or (3) each independently represent a hydrogen atom or a monovalent substituent, and preferred substituents are the same as those described above for R. More preferably, when R is an unsubstituted aromatic hydrocarbon-substituted alkynyl group or alkenyl group, or an unsubstituted aromatic heterocyclic-substituted alkynyl group or alkenyl group, the aromatic hydrocarbon group or aromatic It is a heterocyclic group.

  Furthermore, the compound represented by the general formula (1) is more preferably a compound represented by the general formula (4). R in the general formula (4) is the same as R described in the general formula (1), and at least one of them preferably has a group represented by the formula (2) or (3).

The aromatic heterocyclic compound represented by the general formula (5) or (6) is useful as an intermediate of the aromatic heterocyclic compound represented by the general formula (1) or (4). An aromatic heterocyclic compound represented by the general formula (1) or (4) can be obtained by dehydrogenating the aromatic heterocyclic compound represented by the general formula (5) or (6). R in the general formula (5) or (6) is the same as R in the general formula (1).
In order to distinguish the aromatic heterocyclic compound represented by the general formula (1) or (4) from the aromatic heterocyclic compound represented by the general formula (5) or (6), the general formula (1) or (4) Is also referred to as an aromatic heterocyclic compound A, and the aromatic heterocyclic compound represented by the general formula (5) or (6) is also referred to as an aromatic heterocyclic compound B.

In addition, the method for producing the aromatic heterocyclic compound A of the present invention in which at least one of R is a monovalent group is an aromatic heterocyclic compound represented by the general formula (7) (hereinafter referred to as aromatic heterocyclic compound C). And the compound represented by the general formula (8) are reacted with each other. R in the general formula (8) is the same as R in the general formula (1). X is each independently a reactive group selected from a halogen atom, a hydroxyl group, —B (OH) ₂ , a sulfonyl group, trifluoromethanesulfonate, nonafluorobutanesulfonate, fluorosulfonate, and tosylate or a general formula ( 1) R represents at least one reactive group other than R; In addition, R _{1 to} R ₄ in the general formulas (9) and (10) are preferably groups similar to the substituent that gives a substituted alkenyl group or an alkynyl group in R described in the general formula (1).

The aromatic heterocyclic compound B of the present invention can be synthesized, for example, by the method shown in the following reaction formula (I).

  That is, by synthesizing a compound obtained by aldehyde-forming an unsubstituted or substituted dibenzofuran and a Wittig salt, a compound in which cyclohexanone is condensed with dibenzofuran is synthesized, and further reacted with an unsubstituted or substituted phenylhydrazine hydrochloride. Thus, the aromatic heterocyclic compound B can be synthesized.

Then, as shown in the following reaction formula (II), the aromatic heterocyclic compound A can be synthesized by the dehydrogenation reaction of the aromatic heterocyclic compound B.

Moreover, the aromatic heterocyclic compound C and the compound represented by the general formula (8) or (9) to (10) are reacted to produce an aromatic heterocyclic compound A in which at least one of R is a monovalent group. As a method of synthesis, there is a method as shown in the following reaction formula (III) or (IV).

  That is, when at least one of X in the general formula (7) is a leaving functional group such as a halogen atom, the compound (RY) represented by the general formula (8) and the dehydrohalogenated group The aromatic heterocyclic compound A can be synthesized by a cross-coupling reaction such as a reaction. Is the cross-coupling reaction, for example, Tamao? Kumada? Corriu reaction, Negishi reaction, Kosugi-Migita-Stille reaction, Suzuki-Miyaura reaction, Hiyama reaction, Sonogashira reaction, Mizoroki-Heck reaction, etc. can be exemplified, and the target product is obtained by selecting and reacting as necessary be able to. At that time, the reaction is carried out by selecting a metal catalyst, a reaction solvent, a base, a reaction temperature, a reaction time, etc. according to each reaction. Then, the target object of desired purity can be obtained by performing post-processing operations, such as extraction, and refinement | purification operations as needed.

  Although the preferable specific example of a compound shown by General formula (1) is shown below, it is not limited to these.

  Although the organic-semiconductor material of this invention contains the compound of General formula (1), it is preferable to contain 50 wt% or more of this compound, It is good to contain 90 wt% or more more preferably. It is also preferred that the compound of general formula (1) itself is an organic semiconductor material. The component contained together with the compound of the general formula (1) in the organic semiconductor material is not particularly limited as long as it does not impair the performance as the organic semiconductor material, but the organic semiconductor material comprising a charge transporting compound It is good to be.

  The organic semiconductor film of the present invention is formed from the above organic semiconductor material. Preferably, the organic semiconductor material is formed by dissolving the organic semiconductor material in an organic solvent and applying and drying the prepared solution. This organic semiconductor film is useful as an organic semiconductor layer in an organic semiconductor device.

  Subsequently, an organic semiconductor device including an organic semiconductor material formed from the organic semiconductor material of the present invention will be described based on FIGS. 1 to 4 by taking an organic field effect transistor element (OTFT element) as an example.

  1, 2, 3, and 4 exemplify embodiments of the OTFT device of the present invention, and all are schematic cross-sectional views showing the structure of the OTFT device.

  The OTFT device shown in FIG. 1 includes a gate electrode 2 on the surface of a substrate 1, an insulating film layer 3 is formed on the gate electrode 2, and a source electrode 5 and a drain electrode 6 are formed on the insulating film layer 3. And an organic semiconductor layer 4 is formed.

  The OTFT device shown in FIG. 2 includes a gate electrode 2 on the surface of a substrate 1, an insulating film layer 3 is formed on the gate electrode 2, and an organic semiconductor layer 4 is formed thereon. On 4, a source electrode 5 and a drain electrode 6 are provided.

  In the OTFT device shown in FIG. 3, a source electrode 5 and a drain electrode 6 are provided on the surface of a substrate 1, and a gate electrode 2 is formed on the outermost surface via an organic semiconductor layer 4 and an insulating film layer 3.

  In the OTFT device shown in FIG. 4, the organic semiconductor device according to the present invention is provided with an organic semiconductor layer 4, a source electrode 5, and a drain electrode 6 on the surface of the substrate 1, and the outermost surface through the insulating film layer 3. A gate electrode 2 is formed on the substrate.

  As a material used for the substrate 1, for example, a ceramic substrate such as glass, quartz, aluminum oxide, sapphire, silicon nitride, silicon carbide, a semiconductor substrate such as silicon, germanium, gallium silicon, gallium phosphorus, gallium nitrogen, polyethylene terephthalate, Examples thereof include polyesters such as polynaphthalene terephthalate, resin substrates such as polyethylene, polypropylene, polyvinyl alcohol, ethylene vinyl alcohol copolymer, cyclic polyolefin, polyimide, polyamide, and polystyrene. The thickness of the substrate can be from about 10 μm to about 2 mm, but is preferably about 50 to about 100 μm, particularly for flexible plastic substrates, and about 0.1 for a rigid substrate such as a glass plate or silicon wafer. 1 to about 2 mm.

  The gate electrode 2 may be a metal thin film, a conductive polymer film, a conductive film made from a conductive ink or paste, or the substrate itself as a gate electrode, such as heavily doped silicon. can do. Examples of gate electrode materials include aluminum, copper, stainless steel, gold, chromium, n-doped or p-doped silicon, indium tin oxide, conductive polymers such as poly (3,4-polystyrene) doped with polystyrene sulfonic acid. Examples thereof include a conductive ink / paste containing ethylenedioxythiophene), carbon black / graphite, or a colloidal silver dispersed in a polymer binder.

  The gate electrode 2 can be formed by using vacuum deposition, sputtering of a metal or conductive metal oxide, spin coating of a conductive polymer solution or conductive ink, inkjet, spraying, coating, casting, or the like. The thickness of the gate electrode 2 is preferably in the range of about 10 nm to 10 μm, for example.

  The insulating film layer 3 can generally be an inorganic material film or an organic polymer film. Examples of inorganic materials suitable for the insulating film layer 3 include silicon oxide, silicon nitride, aluminum oxide, barium titanate, and barium zirconium titanate. Examples of organic compounds suitable for the insulating film layer 3 include polyesters, polycarbonates, poly (vinylphenol), polyimides, polystyrene, poly (methacrylates), poly (acrylates), and epoxy resins. Further, an inorganic material may be dispersed in an organic polymer and used as an insulating layer film. The thickness of the insulating film layer varies depending on the dielectric constant of the insulating material used, but is, for example, about 10 nm to 10 μm.

  Examples of the means for forming the insulating film layer include dry film formation methods such as vacuum deposition, CVD, sputtering, and laser deposition, spin coating, blade coating, screen printing, ink jet printing, and stamping. Examples include a wet film forming method such as a method, which can be used depending on the material.

  The source electrode 5 and the drain electrode 6 can be made of a material that provides a low-resistance ohmic contact to the organic semiconductor layer 4 described later. As a preferable material for the source electrode 5 and the drain electrode 6, those exemplified as a preferable material for the gate electrode 2 can be used, and examples thereof include gold, nickel, aluminum, platinum, a conductive polymer, and a conductive ink. The thicknesses of the source electrode 5 and the drain electrode 6 are typically about 40 nm to about 10 μm, and more preferably about 10 nm to 1 μm, for example.

  Examples of means for forming the source electrode 5 and the drain electrode 6 include a vacuum deposition method, a sputtering method, a coating method, a thermal transfer method, a printing method, a sol-gel method, and the like. It is preferable to perform patterning as needed during film formation or after film formation. As a patterning method, for example, a photolithography method in which patterning and etching of a photoresist are combined can be used. Also, patterning can be performed using a printing method such as ink jet printing, screen printing, offset printing, soft lithography method such as a micro contact printing method, or a combination of these methods.

  As a means for forming the organic semiconductor layer 4, for example, a dry film forming method such as a vacuum deposition method, a CVD method, a sputtering method, or a laser deposition method, or after applying a solution or dispersion on a substrate, a solvent or dispersion medium is used. There is a wet film formation method in which a thin film is formed by removing the film, but it is preferable to use a wet film formation method. Examples of the wet film forming method include spin coating, blade coating, screen printing, ink jet printing, and stamping. For example, when the spin coating method is used, an insulating film formed on the substrate 1 after preparing a solution having a concentration of 0.01 wt% to 10 wt% by dissolving the organic semiconductor material of the present invention in an appropriate solvent having solubility. The organic semiconductor material solution is dropped on the layer 3 and then treated at 500 to 6000 RPM for 5 to 120 seconds. The solvent is selected depending on the solubility of each organic semiconductor material in each solvent and the film quality after film formation. For example, water, alcohols typified by methanol, aromatic hydrocarbons typified by toluene, hexane Aliphatic hydrocarbons such as cyclohexane, organic nitro compounds such as nitromethane and nitrobenzene, cyclic ether compounds such as tetrahydrofuran and dioxane, nitrile compounds such as acetonitrile and benzonitrile, ketones such as acetone and methyl ethyl ketone, acetic acid A solvent selected from esters such as ethyl, aprotic polar solvents represented by dimethyl sulfoxide, dimethylacetamide, sulfolane, N-methylpyrrolidone, dimethylimidazolidinone, and the like can be used. These solvents may be used in combination of two or more.

  By the above-described method, an organic field effect transistor element using the organic semiconductor material of the present invention can be produced. In the obtained organic field effect transistor element, the organic semiconductor layer forms a channel region, and the on / off operation is controlled by controlling the current flowing between the source electrode and the drain electrode by the voltage applied to the gate electrode. To do.

  Another preferred embodiment of the organic semiconductor device obtained from the organic semiconductor material of the present invention is an organic photovoltaic element. Specifically, an organic photovoltaic device having a positive electrode, an organic semiconductor layer, and a negative electrode on a substrate, wherein the organic semiconductor layer includes the organic semiconductor material of the present invention described above.

  The structure of the organic photovoltaic element of the present invention will be described with reference to the drawings, but the structure of the organic photovoltaic element of the present invention is not limited to the illustrated one.

  FIG. 5 is a cross-sectional view showing an example of the structure of a general organic photovoltaic element used in the present invention, wherein 7 is a substrate, 8 is a positive electrode, 9 is an organic semiconductor layer, and 10 is a negative electrode. FIG. 6 is a cross-sectional view showing an example of a structure in which organic semiconductor layers are stacked, where 9-a is a p-type organic semiconductor layer and 9-b is an n-type organic semiconductor layer.

  A board | substrate is not specifically limited, For example, it can be set as a conventionally well-known structure. It is preferable to use a glass substrate or a transparent resin film having mechanical and thermal strength and transparency. Transparent resin films include polyethylene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polypropylene, polystyrene, polymethyl methacrylate, polyvinyl chloride, polyvinyl alcohol, polyvinyl butyral, nylon, polyether ether ketone. , Polysulfone, polyethersulfone, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, polyvinyl fluoride, tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene, Polyvinylidene fluoride, polyester, polycarbonate, polyurethane, polyimide, polyetherimide, polyimide, polypropylene, etc. It is.

  As an electrode material, it is preferable to use a conductive material having a high work function for one electrode and a conductive material having a low work function for the other electrode. An electrode using a conductive material having a large work function is a positive electrode. Conductive materials with a large work function include metals such as gold, platinum, chromium and nickel, transparent metal oxides such as indium and tin, composite metal oxides (indium tin oxide (ITO), indium Zinc oxide (IZO) or the like is preferably used. Here, the conductive material used for the positive electrode is preferably an ohmic junction with the organic semiconductor layer. Furthermore, when a hole transport layer described later is used, it is preferable that the conductive material used for the positive electrode is an ohmic contact with the hole transport layer.

  An electrode using a conductive material having a low work function serves as a negative electrode. As the conductive material having a low work function, alkali metal or alkaline earth metal, specifically, lithium, magnesium, or calcium is used. Tin, silver, and aluminum are also preferably used. Furthermore, an electrode made of an alloy made of the above metal or a laminate of the above metal is also preferably used. In addition, it is possible to improve the extraction current by introducing a metal fluoride such as lithium fluoride or cesium fluoride at the interface between the negative electrode and the electron transport layer. Here, the conductive material used for the negative electrode is preferably one that is in ohmic contact with the organic semiconductor layer. Furthermore, when an electron transport layer described later is used, it is preferable that the conductive material used for the negative electrode is in ohmic contact with the electron transport layer.

  The organic semiconductor layer contains the aromatic heterocyclic compound A of the present invention. That is, it is formed using the organic semiconductor material of the present invention including the aromatic heterocyclic compound A represented by the general formula (1). The organic semiconductor material of the present invention is used for a p-type organic semiconductor material (hereinafter referred to as a p-type organic material), an n-type organic semiconductor material (hereinafter referred to as an n-type organic material), or both. Two or more compounds represented by the general formula (1) can be used, one or more of which can be a p-type organic material component and the other one or more can be an n-type organic material component. One of the p-type organic material and the n-type organic material may be a compound that does not include the compound represented by the general formula (1).

  The organic semiconductor layer is formed using an organic semiconductor material containing at least one compound represented by the formula (1). The compound represented by the formula (1) functions as a p-type organic material or an n-type organic material.

  P-type organic material and n-type organic material These materials are preferably mixed, and it is preferable that the p-type organic material and the n-type organic material are compatible or phase-separated at the molecular level. The domain size of this phase separation structure is not particularly limited, but is usually 1 nm or more and 50 nm or less. Further, when the p-type organic material and the n-type organic material are laminated, it is preferable that the layer having the p-type organic material is on the positive electrode side and the layer having the n-type organic material is on the negative electrode side. The organic semiconductor layer preferably has a thickness of 5 nm to 500 nm, more preferably 30 nm to 300 nm. When laminated, the layer having the p-type organic material of the present invention preferably has a thickness of 1 nm to 400 nm, more preferably 15 nm to 150 nm, among the above thicknesses.

  As the p-type organic material, a compound exhibiting p-type semiconductor characteristics among the compounds represented by the formula (1) may be used alone, or other p-type organic materials may be included. Examples of other p-type organic materials include polythiophene polymers, benzothiadiazole-thiophene derivatives, benzothiadiazole-thiophene copolymers, poly-p-phenylene vinylene polymers, poly-p-phenylene polymers, Conjugated polymers such as polyfluorene polymers, polypyrrole polymers, polyaniline polymers, polyacetylene polymers, polythienylene vinylene polymers, H2 phthalocyanine (H2Pc), copper phthalocyanine (CuPc), zinc phthalocyanine Phthalocyanine derivatives such as (ZnPc), porphyrin derivatives, N, N′-diphenyl-N, N′-di (3-methylphenyl) -4,4′-diphenyl-1,1′-diamine (TPD), N, N′-dinaphthyl-N, N′-diphenyl-4,4′-diphenyl-1,1 Triarylamine derivatives such as' -diamine (NPD), carbazole derivatives such as 4,4'-di (carbazol-9-yl) biphenyl (CBP), oligothiophene derivatives (terthiophene, quarterthiophene, sexithiophene, octi Low molecular organic compounds such as thiophene).

  As the n-type organic material, among the compounds represented by the formula (1), those showing n-type semiconductor characteristics may be used alone, or other n-type organic materials may be used. Other n-type organic materials include, for example, 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTCDA), 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA), 3,4, 9,10-perylenetetracarboxylic bisbenzimidazole (PTCBI), N, N′-dioctyl-3,4,9,10-naphthyltetracarboxydiimide (PTCDI-C8H), 2- (4-biphenylyl) -5 Oxazole derivatives such as (4-t-butylphenyl) -1,3,4-oxadiazole (PBD), 2,5-di (1-naphthyl) -1,3,4-oxadiazole (BND), 3- (4-Biphenylyl) -4-phenyl-5- (4-tert-butylphenyl) -1,2,4-triazole (T AZ) and other triazole derivatives, phenanthroline derivatives, phosphine oxide derivatives, fullerene compounds (unsubstituted ones including C60, C70, C76, C78, C82, C84, C90, C94, and [6,6] -phenyl C61 Butyric acid methyl ester ([6,6] -PCBM), [5,6] -phenyl C61 Butyric acid methyl ester ([5,6] -PCBM), [6,6] -phenyl C61 Butyric acid hexyl Ester ([6,6] -PCBH), [6,6] -phenyl C61 butyric acid dodecyl ester ([6,6] -PCBD), phenyl C71 butyric acid methyl ester (PC70BM), phenyl C85 butyric acid Methyl ester (PC84BM) Etc.), carbon nanotubes (CNT), poly -p- phenylene vinylene-based polymer derivatives obtained by introducing cyano group into (CN-PPV) and the like.

  In the organic photovoltaic device of the present invention, a hole transport layer may be provided between the positive electrode and the organic semiconductor layer. As a material for forming the hole transport layer, conductive polymers such as polythiophene polymers, poly-p-phenylene vinylene polymers, polyfluorene polymers, phthalocyanine derivatives (H2Pc, CuPc, ZnPc, etc.), Low molecular organic compounds exhibiting p-type semiconductor properties such as porphyrin derivatives are preferably used. In particular, polyethylenedioxythiophene (PEDOT), which is a polythiophene polymer, or PEDOT to which polystyrene sulfonate (PSS) is added is preferably used. The hole transport layer preferably has a thickness of 5 nm to 600 nm, more preferably 30 nm to 200 nm.

  Moreover, the organic photovoltaic element of this invention may provide an electron carrying layer between an organic-semiconductor layer and a negative electrode. Although it does not specifically limit as a material which forms an electron carrying layer, The above-mentioned n-type organic material (NTCDA, PTCDA, PTCDI-C8H, an oxazole derivative, a triazole derivative, a phenanthroline derivative, a phosphine oxide derivative, a fullerene compound, CNT An organic material exhibiting n-type semiconductor characteristics such as CN-PPV) is preferably used. The thickness of the electron transport layer is preferably 5 nm to 600 nm, more preferably 30 nm to 200 nm.

  The organic photovoltaic element of the present invention may form a series junction by laminating (tandemizing) two or more organic semiconductor layers via one or more intermediate electrodes. For example, a laminated structure of substrate / positive electrode / first organic semiconductor layer / intermediate electrode / second organic semiconductor layer / negative electrode can be given. By laminating in this way, the open circuit voltage can be improved. Note that the hole transport layer described above may be provided between the positive electrode and the first organic semiconductor layer and between the intermediate electrode and the second organic semiconductor layer, and between the first organic semiconductor layer and the intermediate electrode. The hole transport layer described above may be provided between the second organic semiconductor layer and the negative electrode.

  In the case of such a laminated structure, at least one layer of the organic semiconductor layer contains the compound of the present invention represented by the formula (1), and the other layer does not reduce the short-circuit current. It is preferable to include a p-type organic material having a different band gap from the organic material. Examples of such p-type organic materials include the polythiophene polymers, poly-p-phenylene vinylene polymers, poly-p-phenylene polymers, polyfluorene polymers, polypyrrole polymers, and polyaniline polymers described above. Conjugated polymers such as polymers, polyacetylene polymers, polythienylene vinylene polymers, phthalocyanine derivatives such as H2 phthalocyanine (H2Pc), copper phthalocyanine (CuPc), zinc phthalocyanine (ZnPc), porphyrin derivatives, N, N′-diphenyl-N, N′-di (3-methylphenyl) -4,4′-diphenyl-1,1′-diamine (TPD), N, N′-dinaphthyl-N, N′-diphenyl-4 Triarylamine derivatives such as 4,4′-diphenyl-1,1′-diamine (NPD), 4,4′-di (carbazo Carbazole derivatives such as Le-9-yl) biphenyl (CBP), oligothiophene derivatives (terthiophene, quarter thiophene, sexithiophene, etc. oct thiophene) include low molecular weight organic compounds, such as.

  In addition, the material for the intermediate electrode used here is preferably a material having high conductivity, for example, the above-mentioned metals such as gold, platinum, chromium, nickel, lithium, magnesium, calcium, tin, silver, aluminum, and transparent Metal oxides such as indium and tin, composite metal oxides (indium tin oxide (ITO), indium zinc oxide (IZO), etc.), alloys composed of the above metals and laminates of the above metals, polyethylene Examples include dioxythiophene (PEDOT) and those obtained by adding polystyrene sulfonate (PSS) to PEDOT. The intermediate electrode preferably has a light transmission property, but even a material such as a metal having a low light transmission property can often ensure a sufficient light transmission property by reducing the film thickness.

  For organic semiconductor layer formation, spin coating, blade coating, slit die coating, screen printing coating, bar coater coating, mold coating, printing transfer method, dip pulling method, ink jet method, spray method, vacuum deposition method, etc. This method may be used, and the formation method may be selected according to the characteristics of the organic semiconductor layer to be obtained, such as film thickness control and orientation control.

  The organic semiconductor device of the present invention uses the organic semiconductor material of the present invention. The organic semiconductor device is preferably an organic field effect transistor or an organic photovoltaic element.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is of course not limited to these examples, and can be implemented in various forms as long as the gist thereof is not exceeded. is there. The compound number corresponds to the number given to the above chemical formula.

Example 1

  Under a nitrogen gas stream, dibenzofuran (A) (3448 mmol, 580 g) and dehydrated THF (2260 mL) were added to a 10 L reactor and stirred at 0 ° C. for 30 minutes. To this, 1.6 M BuLi-heptane solution (3414 mmol, 2134 mL) was added dropwise. After stirring at −78 ° C. for 30 minutes, DMF (5173 mmol, 401 mL) was added dropwise. After the temperature was raised to room temperature, stirring was continued for 2 hours. The reaction solution was poured into 6 M hydrochloric acid and adjusted to pH1. This was extracted with ethyl acetate, washed with water and brine, dried over sodium sulfate, filtered and concentrated to obtain 690 g of a crude compound (B) as a pale yellow solid.

  Under a nitrogen gas stream, 3-bromopropionic acid (C) (5719 mmol, 874 g), triphenylphosphine (5719 mmol, 1500 g), and dehydrated acetonitrile (2390 mL) were added to a 10 L reactor. After completion of the addition, the mixture was stirred for 22 hours under heating and reflux. The reaction liquid was concentrated after standing_to_cool to room temperature. Acetonitrile was added thereto, and the concentrate was dissolved with heating and stirring, and a seed solid was added thereto. The mixture was stirred overnight while allowing it to cool naturally to room temperature, yielding 2043 g of wittig-salt (D).

  Under a nitrogen gas stream, a 20 L reactor was charged with compound (B) (3411 mmol, 690 g) and wittig-salt (D) (3377 mmol, 1402 g), dehydrated THF (6 L), dehydrated DMSO (6 L). ) And stirred at 27 ° C. (water bath) for 30 minutes. To this was added sodium hydride (7164 mmol, 286 g) in small portions and stirred for 20 hours. The reaction solution was poured into 1M aqueous hydrochloric acid, extracted with toluene, washed with water, dried over sodium sulfate, filtered and concentrated to obtain 1545 g of a crude compound (E) as a yellow viscous liquid. It was.

  Under a nitrogen gas stream, compound (E) (198 mmol, 50 g), dehydrated ethanol (280 mL) and dehydrated ethyl acetate (280 mL) were added to a 1 L eggplant flask and stirred at room temperature for 1 hour. Nitrogen gas bubbling was performed. Subsequently, 10% Pd / C (31 g) was added, and hydrogen gas bubbling was performed while stirring at room temperature for 1 hour. Thereafter, the mixture was stirred at room temperature for 22 hours under a hydrogen gas atmosphere (using a 1 L balloon, 1 atm). The insoluble material was removed by celite filtration, and the filtrate was concentrated after washing with ethyl acetate to obtain a crude compound (F) as a yellow liquid.

  In a 1 L reactor under a nitrogen gas stream, compound (F) (161 mmol, 41 g) and 2,4,6-trichloro-1,3,5-triazine (322 mmol, 59.4 g) were dehydrated. Dichloromethane (415 mL) was added and stirred at room temperature for 5 minutes. Then, dehydrated pyridine (484 mmol, 39.1 mL) was slowly added at room temperature and stirred for 20 hours. Subsequently, aluminum chloride (322 mmol, 43 g) was slowly added at room temperature and stirred for 4 hours. The reaction solution was poured into acetone cooled to 0 ° C. to stop the reaction. After stirring for a while, the suspended solution was filtered through Celite. Methanol was added thereto, and the precipitated solid was removed by celite filtration. The obtained filtrate was concentrated, extracted with toluene, washed with 1M aqueous hydrochloric acid, dried over sodium sulfate, filtered, concentrated, and washed with methanol to obtain 46.4 g of Compound (G).

  Under a nitrogen gas stream, Compound (G) (77 mmol, 46.5 g), phenylhydrazine hydrochloride (77 mmol, 11.1 g) and dehydrated ethanol (538 mL) were added to a 1 L reactor at room temperature. For 5 minutes. Thereafter, glacial acetic acid (30.7 mmol, 1.75 mL) was added, and the mixture was stirred at 90 ° C. for 5 hours. After allowing to cool to room temperature, the solvent was distilled off with an evaporator, the precipitated solid was dissolved in toluene, and this was washed with a 2M aqueous sodium hydroxide solution. After drying, filtering and concentrating the organic phase with sodium sulfate, the obtained solid was suspended and washed with methanol to obtain 20.1 g of Compound (H). The NMR spectrum data of the obtained compound (H) is shown in FIG.

窒素ガス雰囲気下、２ Ｌ のナスフラスコに、化合物（Ｈ）（４５３ ｍｍｏｌ, １４０ ｇ）とクロラニル（６３４ ｍｍｏｌ, １５５グラム）、キシレン（５０２８ ｍＬ）を加え、１５０℃にて４ 時間撹拌した。析出した固体を濾別、メタノールで洗浄し、化合物（１０１）を１００ ｇ 得た。得られた化合物（１０１）のＮＭＲスペクトルデータを図８に示す。

Under a nitrogen gas atmosphere, compound (H) (453 mmol, 140 g), chloranil (634 mmol, 155 grams), and xylene (5028 mL) were added to a 2 L eggplant flask, and the mixture was stirred at 150 ° C. for 4 hours. The precipitated solid was separated by filtration and washed with methanol to obtain 100 g of compound (101). The NMR spectrum data of the obtained compound (101) are shown in FIG.

Example 2

  In a 300 mL three-necked flask under a nitrogen gas atmosphere, compound (101) (7.8 mmol, 2.4 g), DMF (70 mL), 59.6% NaH (8.6 mmol, 0.35 g), Iodooctane (8.6 mmol, 2.1 g) was added and stirred at room temperature overnight. After adding a small amount of methanol to the reaction solution and confirming that no bubbles appeared, the reaction mixture was poured into water and the precipitate was filtered off and washed with methanol and hexane to obtain 2.5 g of compound (201). . The NMR spectrum data of the obtained compound (201) are shown in FIG.

Example 3

  In a 300 mL three-necked flask under a nitrogen gas stream, compound (G) (22.4 mmol, 5.3 g), 3-bromophenylhydrazine hydrochloride (22.4 mmol, 5.0 g), dehydrated ethanol (140 mL) was added and stirred at room temperature for 5 minutes. Glacial acetic acid (9.0 mmol, 0.54 g) was then added, and the mixture was heated and stirred overnight at 90 ° C. After allowing to cool to room temperature, the solvent was distilled off with an evaporator, the precipitated solid was dissolved in toluene, and this was washed with a 2M aqueous sodium hydroxide solution. The organic phase was dried over sodium sulfate, filtered and concentrated, and then the resulting solid was suspended and washed with ethanol to obtain 3.4 g of compound (K).

  Under a nitrogen gas stream, compound (K) (8.1 mmol, 3.2 g), chloranil (12.2 mmol, 3.0 g), and xylene (90 mL) were added to a 300 mL three-necked flask at 150 ° C. For 20 hours. The precipitated solid was separated by filtration and washed with methanol to obtain 2.6 g of Compound (L). The NMR spectrum data of the obtained compound (L) are shown in FIG.

  In a 300 mL three-necked flask under a nitrogen gas atmosphere, compound (101) (6.2 mmol, 2.4 g), DMF (60 mL), 59.6% NaH (6.8 mmol, 0.28 g), Iodooctane (6.8 mmol, 1.7 g) was added and stirred overnight at room temperature. After adding a small amount of methanol to the reaction solution and confirming that no bubbles appeared, the reaction mixture was poured into water and the precipitate was filtered off and washed with methanol and hexane to obtain 2.5 g of compound (M). . The NMR spectrum data of the obtained compound (M) are shown in FIG.

  In a 100 mL eggplant flask under a nitrogen gas atmosphere, compound (M) (4.8 mmol, 2.4 g), dehydrated THF (25 mL), diisopropylamine (25 mL), ethynylbenzene (5.8 mmol, 0.6 g), copper iodide (1.0 mmol, 0.18 g), and tetrakistriphenylphosphine palladium (0.5 mmol, 0.6 g) were added, and the mixture was stirred at 85 ° C. for 6 hours. The reaction mixture was concentrated under reduced pressure, the residue was dissolved in dichloromethane, washed with water, concentrated under reduced pressure and dried. The obtained solid was subjected to column chromatography to obtain 1.3 g of a compound (Compound 301). The NMR spectrum data of the compound (301) is shown in FIG.

Example 4
The characteristics of the organic semiconductor material of the present invention were evaluated by preparing an organic field effect transistor having the configuration shown in FIG. First, a silicon wafer (n-doped) having a thermally grown silicon oxide layer having a thickness of about 300 nm was washed with a sulfuric acid-hydrogen peroxide aqueous solution, boiled with isopropyl alcohol, and then dried. On the silicon wafer (n-doped) having the thermally grown silicon oxide layer obtained, a chlorobenzene solution (2 Wt%) of the compound (201) was formed by spin coating and then heat-treated at 80 ° C. to obtain a thickness of 50 A thin film of nm compound (201) was formed. Furthermore, gold was deposited on the surface of this film using a mask to form source and drain electrodes. An organic field effect transistor having a width of 100 μm, a thickness of 200 nm, a channel width W = 2 mm, and a channel length L = 50 μm was prepared.

A voltage of −100 V is applied between the source electrode and the drain electrode of the obtained organic field effect transistor, the gate voltage is changed in the range of −20 to −100 V, and the voltage-current curve is set to a temperature of 25 ° C. And the transistor characteristics were evaluated. The field effect mobility (μ) was calculated using the following formula (I) representing the drain current I _d .
I _d = (W / 2L) μC _i (V _g −V _t ) ² (I)

In the above formula (I), L is the channel length and W is the channel width. C _i is a capacitance per unit area of the insulating layer, V _g is a gate voltage, and V _t is a threshold voltage. Table 1 shows the calculated field effect mobility.

Examples 5-10
In Example 4, instead of the chlorobenzene solution (2 wt%) of the compound (201), a solution (2 wt%) of the compound (301), (401), (501), (601), (701), or (801) ) Were used in the same manner except that each was used to produce an organic field effect transistor. The transistor characteristics of the obtained device were evaluated in the same manner as in Example 4. Table 1 shows the calculated field effect mobility.

Comparative Examples 1 and 2
In Example 4, a similar operation was performed except that the following compound (H1) or (H2) solution (2 wt%) was used instead of the chlorobenzene solution (2 wt%) of the compound (201), respectively. An effect transistor was fabricated. The transistor characteristics of the obtained device were evaluated in the same manner as in Example 4. Table 1 shows the calculated field effect mobility.

  From the results of Examples 4 to 9 and Comparative Examples 1 and 2, it was revealed that the organic field effect transistor using the aromatic heterocyclic compound represented by the formula (1) has high characteristics.

  1 substrate, 2 gate electrode, 3 insulating layer, 4 organic semiconductor, 5 source electrode, 6 drain electrode, 7 substrate, 8 positive electrode, 9 organic semiconductor layer, 9-a electron donating organic semiconductor layer, 9-b electron accepting property Organic semiconductor layer, 10 negative electrode

Claims (16)

An aromatic heterocyclic compound represented by the following general formula (1).

Here, each R independently represents a hydrogen atom or a monovalent group. a and c are integers of 1 to 4, and b and d are integers of 1 or 2.   The aromatic heterocyclic compound according to claim 1, wherein in general formula (1), at least one of R is a monovalent group.   In general formula (1), at least one of R is a halogen atom, a hydroxyl group, a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, or a substituted group. Or an unsubstituted amino group, a thiol group, a substituted or unsubstituted sulfonyl group, a cyano group, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 48 carbon atoms, a substituted or unsubstituted aromatic group having 2 to 48 carbon atoms. Aromatic heterocyclic group, substituted or unsubstituted C 8-50 aromatic hydrocarbon substituted alkynyl group, substituted or unsubstituted C 4-50 aromatic heterocyclic substituted alkynyl group, substituted or unsubstituted carbon 8 -50 aromatic hydrocarbon substituted alkenyl group, substituted or unsubstituted C4-C50 aromatic heterocyclic substituted alkenyl group, substituted or unsubstituted C5-C30 alkylsilylalkynyl group, substituted or unsubstituted Carbon An alkylsilyl group of 3 to 30; a substituted or unsubstituted siloxane group having 1 to 30 silicon; a substituted or unsubstituted siloxane alkyl group having 1 to 30 silicon; and a substituted or unsubstituted silicon having 1 to 30 silicon. The aromatic heterocyclic compound according to claim 1, which is a monovalent group selected from the group consisting of polysilane groups. The aromatic heterocyclic compound according to claim 1, wherein at least one of R in the general formula (1) is a group represented by the formula (2) or (3).

Here, R < ₁ > -R < ₄ > shows a hydrogen atom or monovalent group each independently. The aromatic heterocyclic compound in any one of Claims 1-4 shown by following General formula (4).

Here, R is the same as R in the general formula (1). An aromatic heterocyclic compound represented by the following general formula (5):

Here, each R independently represents a hydrogen atom or a monovalent group. a and c are integers of 1 to 4, and b is an integer of 1 or 2. The aromatic heterocyclic compound of Claim 6 shown by following General formula (6).

Here, R is the same as R in the general formula (5).   The method for producing an aromatic heterocyclic compound according to any one of claims 1 to 5, wherein the aromatic heterocyclic compound according to claim 6 or 7 is dehydrogenated. The aromatic heterocyclic compound represented by the following general formula (7) and the compound represented by the general formula (8) are reacted to form a compound in which X in the general formula (7) is substituted with R. 2. A process for producing an aromatic heterocyclic compound according to 2.

Here, R is the same as R in the general formula (1). X is independently a reactive group selected from a halogen atom, a hydroxyl group, —B (OH) ₂ , a sulfonyl group, trifluoromethanesulfonate, nonafluorobutanesulfonate, fluorosulfonate, tosylate, or a general formula ( 1) R is shown, and at least one is a reactive group other than R. e and g are integers of 1 to 4, and f and h are integers of 1 or 2.
RY (8)
Here, R is the same as R in the general formula (1) (except when it is a hydrogen atom), Y reacts with X in the general formula (7) to leave as XY, and X is R Is a group that can be substituted. The method for producing an aromatic heterocyclic compound according to claim 8, wherein the compound represented by the general formula (8) is a compound represented by the following formula (9) or (10).

Here, R < ₁ > -R < ₄ > shows a hydrogen atom or monovalent group each independently. Y is the same as Y in the general formula (8).   An organic semiconductor material comprising the aromatic heterocyclic compound according to any one of claims 1 to 5.   An organic semiconductor film formed from the organic semiconductor material according to claim 11.   An organic semiconductor film formed by dissolving the organic semiconductor material according to claim 11 in an organic solvent and applying and drying the prepared solution.   An organic semiconductor device comprising the organic semiconductor material according to claim 11.   An organic field effect transistor using the organic semiconductor material according to claim 11 for a semiconductor layer.   An organic photovoltaic element, wherein the organic semiconductor material according to claim 11 is used for a semiconductor layer.

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