JP6986692B2 - Nitrogen-containing heterocyclic alkenyl compounds, organic semiconductor materials and organic semiconductor devices - Google Patents

Description

The present invention is a novel nitrogen-containing conjugated alkenyl compound, an organic semiconductor material containing the same, an organic semiconductor film obtained by using this organic semiconductor material, and an organic electric field effect transistor obtained by using this organic semiconductor material. It is related to organic semiconductor devices such as.

Generally, in a semiconductor device using silicon, which is 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 not possible to form a thin film of silicon on a plastic substrate or the like, so it has been difficult to impart flexibility or reduce the weight of products incorporating semiconductor devices. .. Further, since a high vacuum process is required, it is difficult to increase the area and reduce the cost of the product incorporating the semiconductor element.

Therefore, in recent years, research has been conducted on organic semiconductor devices (for example, organic electroluminescence (EL) elements, organic field effect transistor elements, organic CMOS circuits, organic thin film solar cells, etc.) that utilize organic semiconductor materials as organic electronic components. .. Since these organic semiconductor materials can significantly reduce the manufacturing process temperature as compared with the inorganic semiconductor materials, they can be formed on a plastic substrate or the like. Further, by using an organic semiconductor material having high solubility in a solvent and good film forming property, a thin film can be formed by a coating method that does not require a vacuum process, for example, an inkjet device or the like. As a result, it is expected that the area and cost will be reduced, which was difficult with semiconductor devices using silicon, which is an inorganic semiconductor material. As described above, the organic semiconductor material is advantageous in terms of large area, flexibility, weight reduction, cost reduction, etc. as compared with the inorganic semiconductor material, and therefore, an organic semiconductor product utilizing these characteristics can be obtained. It is expected to be applied to information tags, large area sensors such as electronic artificial skin sheets and sheet-type scanners, liquid crystal displays, displays such as electronic paper and organic EL panels, and the like.

The organic semiconductor material used in the above-mentioned organic semiconductor device, which is expected to have a wide range of applications, exhibits characteristics by transferring charges in the organic semiconductor material. Further, it is divided into two types according to the type of electric charge to be moved. That is, it is a P-type organic semiconductor material in which holes having a positive charge move and an N-type organic semiconductor material in which electrons having a negative charge move. High charge mobility is required for both P-type organic semiconductor materials and N-type organic semiconductor materials. Further, in organic semiconductor materials, it is also an issue to stably exhibit semiconductor functions even in the atmosphere. In general, organic semiconductor materials have the characteristics of organic semiconductor devices in the atmosphere due to the interaction between positive charges (holes) and negative charges (electrons) transported in the semiconductor and oxygen molecules and water molecules. It had the problem of rapid deterioration.

Countermeasures include improving atmospheric stability by controlling the highest occupied molecular orbital energy level and the lowest unoccupied molecular orbital energy level of organic semiconductor materials, improving charge transfer characteristics by expanding the π-conjugated structure of semiconductor materials, and introducing soluble functional groups. Studies have been made on the addition of solvent solubility. As a result, polyacenes and heterocyclic aromatic derivatives have been developed as P-type semiconductor materials (Patent Document 1, Non-Patent Documents 1 and 2). In recent years, studies including a film forming process have been conducted for further high mobility and drive stabilization.

On the other hand, in the field of N-type organic semiconductor materials, although the above-mentioned studies are underway, as materials applicable to the solution method, naphthalene tetracarboxylic acid perylene imide derivative and fullerene (C60) derivative are being focused on. However, we have not yet developed a useful material. For example, naphthalenetetracarboxylic dianimide and fullerene themselves have been reported to have high charge mobilities, but they are unstable in the atmosphere. It has been reported that atmospheric stability is improved by derivatization of C60 and perylene diimide, but the charge mobility is lowered (Non-Patent Document 3).

In recent years, a cyanostyryl derivative has been developed as an N-type organic semiconductor material (Non-Patent Document 4), and the present inventors have a device using the cyanostyryl derivative as a semiconductor and its high electron mobility in the atmosphere. (Patent Document 2).

WO2003 / 016599 Japanese Patent No. 5533185

Org. Lett., Vol.4, 15 (2002) J. Am. Chem. Soc., 129 (51), 15732 (2007) Chem. Rev., Vol.107, 1066 (2007) J. Mater. Chem., 20, 6472 (2010)

The present invention has been made for the purpose of further improving the properties of the cyanostyryl derivative, and is a novel compound having high charge transfer and atmospheric stability and suitable for an organic semiconductor material, and an organic semiconductor material containing the same. , And an organic semiconductor device using this organic semiconductor material.

As a result of diligent studies, the present inventors have found an organic semiconductor material in which a specific nitrogen-containing heterocyclic alkenyl compound has high charge transfer and atmospheric stability as an organic semiconductor material, and uses this as an organic semiconductor device. As a result, they have found that an organic semiconductor device having high characteristics can be obtained, and have reached the present invention.

The present invention is a nitrogen-containing heterocyclic alkenyl compound represented by the following general formula (1).

Here, Ar ¹ is independently a divalently substituted or unsubstituted unsaturated cyclic hydrocarbon group having 4 to 22 carbon atoms, and a divalently substituted or unsubstituted unsaturated complex having 2 to 21 carbon atoms. A divalently substituted or unsubstituted linked ring group formed by arbitrarily linking 2 to 7 rings selected from a ring group or a ring constituting these unsaturated cyclic hydrocarbon groups and unsaturated heterocyclic groups. Is shown.
Ar ² is an unsaturated heterocyclic group containing nitrogen having an unshared electron pair having 1 to 21 carbon atoms substituted or unsubstituted, respectively, or a ring constituting the unsaturated heterocyclic group and substituted or absent. Substituentally substituted or unsubstituted, in which 2 to 7 rings selected from the substituted aromatic hydrocarbon rings having 6 to 22 carbon atoms are optionally linked and have at least one ring constituting the unsaturated heterocyclic group. Indicates a linked ring group.
B represents a vinylene group (-CH = CH-) or an ethynylene group (-C≡C-).
R ¹ independently represents a halogen atom, a cyano group, a nitro group, a carboxy group, a formyl group, or a hydrocarbon substituted carbonyl group having 2 to 30 carbon atoms.
a represents the number of repetitions and is an integer of 0 to 3.
When a is 0, R ¹ is a cyano group, Ar ¹ is an unsubstituted phenylene, and Ar ² is an unsubstituted pyridyl group, the pyridyl group is bonded to the vinylene group at the 2- or 3-position of the pyridyl group. There is no such thing.

The nitrogen-containing heterocyclic alkenyl compound has an energy level of -3.0 eV or less at the lowest unoccupied molecular orbital (LUMO) obtained by the structural optimization calculation by the density general function calculation B3LYP / 6-31G (d). good.
In the above general formula (1)
If Ar ¹ is an unsaturated cyclic hydrocarbon group, Ar ¹ is a monocyclic unsaturated cyclic hydrocarbon group or the 5 to 8 membered ring consisting of monocyclic 5- to 8-membered ring substituted or unsubstituted is It is an unsaturated cyclic hydrocarbon group formed by arbitrarily condensing 2 to 6 groups.
When Ar ¹ is an unsaturated heterocyclic group, Ar ¹ is an unsaturated heterocyclic group consisting of a substituted or unsubstituted 5- to 7-membered monocycle or a 2 to 6 ring containing one or more of the unsaturated heterocycles. Is a fused heterocyclic group of
When Ar ² is an unsaturated heterocyclic group, Ar ² is a heterocyclic group represented by any of the following formulas (C-1) to (C-3) containing nitrogen having an unshared electron pair, or It is preferably an aromatic heterocyclic group represented by any of the following formulas (A-1) to (A-16) containing nitrogen having an unshared electron pair.

^{Here, X 1} in the formulas (C-1) to (C-3) independently represents CH or N, and at least one represents N. X ² represents NH, O or S. ^One of CH of X ^{1 and NH of X 2} has H removed and becomes a bond. ^{X 3} in the formula (A-1) ~ (A -16) each independently represents CH or N, at least one represents a N. X ⁴ each independently represent NH, O or S. CH of X ^3, one of NH of ^{X 4} is a bond 0.00 H.

In the general formula (1), a is an integer of 0 or 1, R ¹ is a cyano group, and Ar ¹ is a substituted or unsubstituted phenylene group, a biphenylene group, a terphenylene group, or a single 5- or 6-membered ring. An unsaturated heterocyclic group consisting of a ring, a fused heterocyclic group of 2 or 3 rings containing one or more of the unsaturated heterocycles, or a phenylene group, the unsaturated heterocyclic group or the condensed heterocyclic group is optionally 2 Alternatively, it is a divalent linked ring group composed of three linked rings, and Ar ² is a heterocycle represented by any of the formulas (C-1) to (C-3) or the formula (A-1). An unsaturated heterocyclic group composed of an aromatic heterocycle represented by (A-4), (A-13), and (A-14), or the unsaturated heterocyclic group and the phenylene group are optionally 2 or 3 It can be a linked ring group configured by connecting the individual rings.

The following general formula (2) is a preferred embodiment of the general formula (1).

Here, X ¹¹ , X ¹² , and X ¹³ independently indicate CR or N, and X ¹² and X ¹³ independently indicate at least one N and at least one CR. be. R is independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted fluorinated alkyl group having 1 to 30 carbon atoms, a pentafluorosulfanyl group, a substituted or substituted group. An unsubstituted 1 to 30 carbon number alkoxy group, a substituted or unsubstituted fluorinated alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted hydrocarbon substituted carbonyl group having 2 to 30 carbon atoms, a nitro group, a thionitroso group, Or indicates a cyano group.

Further, the present invention is an organic semiconductor material characterized by containing the above-mentioned nitrogen-containing heterocyclic alkenyl compound. Further, the present invention is an organic semiconductor membrane characterized by containing the above-mentioned nitrogen-containing heterocyclic alkenyl compound.

Further, the present invention is a method for producing an organic semiconductor film, which comprises dissolving the above-mentioned organic semiconductor material in an organic solvent and applying and drying the prepared solution to form the organic semiconductor film. Further, in the present invention, the above organic semiconductor material is dissolved in an organic solvent having a boiling point of 50 ° C. or higher to prepare a solution having a concentration of 0.01 to 10 wt%, which is 30 ° C. to 20 ° C. or lower than the boiling point of the solvent. It is a method for producing an organic semiconductor film, which comprises applying it to a substrate heated to a temperature range and drying the solvent.

Further, the present invention is an organic semiconductor device, an organic thin film transistor, or an organic photovoltaic element, which is characterized by using the above-mentioned organic semiconductor film. The organic thin film transistor can be an N-type organic thin film transistor or an organic complementary transistor using the N-type organic thin film transistor.

The nitrogen-containing heterocyclic alkenyl compound of the present invention has a structure in which an alkenyl group is bonded to the nitrogen-containing heterocycle at both ends, and an electron-attracting group is introduced as a substituent of the alkenyl group to charge the entire molecule. The π electron orbit involved in the movement expands, and the energy level of that orbit becomes deeper. Therefore, the organic semiconductor material containing this compound exhibits higher atmospheric stability while maintaining high charge transfer characteristics as compared with the organic semiconductors containing cyanostyryl derivatives reported so far.
In addition, in order to fabricate the device in the coating process, high solubility of the organic semiconductor material is required, and the crystallinity when forming the thin film is not destroyed so as not to deteriorate the charge transfer characteristics (for example, the end in the long axis direction of the molecule). ) Must have a soluble functional group (alkyl group, etc.). Conventional N-type organic semiconductors, which have particularly atmospheric stability, have fluorine, which is an electron-withdrawing group, at the end in the long axis direction of the molecule in order to ensure crystallinity and maintain a deep LUMO energy level. It has a trifluoromethyl group, and it was difficult to impart solubility. Since the compound of the present invention has a nitrogen-containing heterocycle having a high electron-attracting property in the matrix, even if the electron-withdrawing group attached to the terminal in the long axis direction of the molecule is replaced with a soluble functional group, LUMO Energy level can be kept deep. Therefore, the organic semiconductor material containing the compound of the present invention can be imparted with functions such as solubility while maintaining high charge transfer characteristics and atmospheric stability.

Therefore, since the compound of the present invention exhibits good properties as an organic semiconductor material, an organic semiconductor device using the compound can exhibit high properties. For example, application to organic field effect transistors, organic thin film solar cells, organic complementary circuits, information tags, large area sensors such as electronic artificial skin sheets and sheet scanners, liquid crystal displays, electronic paper and displays such as organic EL panels. Is conceivable, and its technical value is great.

A schematic cross-sectional view showing an example of an organic field effect transistor element is shown. A schematic cross-sectional view showing another example of the organic field effect transistor element is shown. A schematic cross-sectional view showing another example of the organic field effect transistor element is shown. A schematic cross-sectional view showing another example of the organic field effect transistor element is shown. A schematic cross-sectional view showing an example of an organic thin-film solar cell is shown. A schematic cross-sectional view showing another example of the organic thin-film solar cell is shown. The result of the thin film X-ray diffraction of the organic thin film transistor 4 is shown. The result of the atmospheric operation test of the organic thin film transistor 1 is shown.

The nitrogen-containing heterocyclic alkenyl compound of the present invention is represented by the above general formula (1). Since the nitrogen-containing heterocyclic alkenyl compound of the present invention is preferably a compound containing an aromatic group (referring to an aromatic hydrocarbon group, an aromatic heterocyclic group, or both), the nitrogen-containing heterocyclic alkenyl compound of the present invention is preferable. The compound is also referred to as a nitrogen-containing heterocyclic aromatic alkenyl compound.
In the present specification, the unsaturated cyclic hydrocarbon group and the unsaturated heterocyclic group can be aromatic groups. In order to enhance charge transfer, it is preferable to use a conjugated group such as a conjugated double bond, an aromatic group, or a group containing these.

In the general formula (1), Ar ¹ is a divalent group, which is independently substituted or unsubstituted unsaturated cyclic hydrocarbon group having 4 to 22 carbon atoms, or substituted or unsubstituted carbon number 2 to 2. 21 shows a linked ring group composed of 2 to 7 unsaturated heterocyclic groups, or a hydrocarbon ring constituting these unsaturated cyclic hydrocarbon groups, or a complex ring constituting an unsaturated heterocyclic group. ..

Here, the linked ring group has a structure in which the rings of an unsaturated cyclic hydrocarbon group or an unsaturated heterocyclic group are directly linked by a direct bond, and may have a substituent. The linking ring group may be linear or branched, the linking rings may be the same or different, and m + 1 bond exists in any ring. Is also good. Unless otherwise specified, the linking ring group referred to herein is understood to have the above meaning.

（Ａは、不飽和複素環又は不飽和炭化水素環を示す） In the case of a linking ring group, as a specific linking pattern, the one shown in the following formula can be given as an example.

(A indicates an unsaturated heterocycle or an unsaturated hydrocarbon ring)

Ar ² is an unsaturated heterocyclic group containing nitrogen having a substituted or unsubstituted unshared electron pair having 1 to 21 carbon atoms, or a heterocycle constituting at least one unsaturated heterocyclic group. A linked ring group composed of 2 to 7 aromatic hydrocarbon rings having 6 to 22 carbon atoms is shown.

B represents a vinylene group (-CH = CH-) or an ethynylene group (-C≡C-).
R ¹ independently represents a halogen atom, a cyano group, a nitro group, a carboxy group, a formyl group, or a hydrocarbon substituted carbonyl group having 2 to 30 carbon atoms.
When a is 0, R ¹ is a cyano group, Ar ¹ is a divalent unsubstituted benzene, and Ar ² is an unsubstituted pyridine, this pyridine is bonded to an adjacent vinyl group at the 2- or 3-position. There is nothing to do.

Here, nitrogen having an unshared electron pair is nitrogen that is bonded to two adjacent elements by a single bond or a double bond (including an equivalent bond) and is not bonded to other elements. Say. The unsaturated cyclic hydrocarbon group and the unsaturated heterocyclic group are a cyclic hydrocarbon group containing a double bond or a triple bond, and a heterocyclic group containing a double bond or a triple bond, respectively, and have the formula (1). ), ^{Each of Ar 1} and Ar ² is a group conjugated via an R ^1- substituted vinylene group or the like. Conjugated refers to a state in which double bonds or triple bonds (including equivalent bonds) and single bonds are alternately linked.

In the nitrogen-containing heterocyclic alkenyl compound of the present invention, the energy level of the lowest empty orbital (LUMO) obtained as a result of the structure optimization calculation by the density general function calculation B3LYP / 6-31G (d) is -3.0 eV or less. It is preferably present, and more preferably -3.1 eV or less.

The unsaturated cyclic hydrocarbon group, the unsaturated heterocyclic group, and the linked cyclic group constituting ^{Ar 1} and Ar ² of the general formula (1) may independently have any substituents and are adjacent to each other. Substituents may be integrated to form a ring. When these have substituents, the number of substituents is preferably 1 to 4 independently.

Examples of the substituent include a halogen atom, a substituted or unsubstituted hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted fluorinated alkyl group having 1 to 30 carbon atoms, and a pentafluorosulfanyl group. , Substituent or unsubstituted 1 to 30 carbon number alkoxy group, substituted or unsubstituted 1 to 30 carbon number fluorinated alkoxy group, carboxy group, formyl group, substituted or unsubstituted hydrocarbon group having 2 to 30 carbon atoms Carbonyl group, substituted or unsubstituted amino group, substituted or unsubstituted thiol group, nitro group, thionitroso group, cyano group, substituted or unsubstituted aromatic hydrocarbon substituted alkynyl group, substituted or unsubstituted. Aromatic heterocyclic substituted alkynyl groups having 4 to 50 carbon atoms, substituted or unsubstituted aromatic hydrocarbon substituted alkenyl groups having 8 to 50 carbon atoms, substituted or unsubstituted aromatic heterocyclic substituents having 4 to 50 carbon atoms. An alkenyl group, an alkylsilylalkynyl group having 5 to 56 carbon atoms, a hydrocarbon substituted silyl group having 3 to 54 carbon atoms, a substituted or unsubstituted siloxane group having 2 to 30 silicon atoms, or a substituted or unsubstituted silicon number 2 to 30 It is preferably a polysilane group of 30, more preferably a halogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a fluorinated alkyl group having 1 to 30 carbon atoms, a pentafluorosulfanyl group, a substituted or unsubstituted group. Substituted 1-30 alkoxy groups, substituted or unsubstituted fluorinated alkoxy groups with 1 to 30 carbon atoms, substituted or unsubstituted hydrocarbon substituted carbonyl groups with 2 to 30 carbon atoms, nitro groups, thionitroso groups, or It is a cyano group.

When the substituent is a halogen atom, preferable specific examples thereof include fluorine, bromine, chlorine, and iodine.

In the case of an unsubstituted alkyl group, an alkyl group having 1 to 30 carbon atoms is preferable, and an alkyl group having 1 to 12 carbon atoms is more preferable. Specific examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-octyl group, an n-dodecyl group, an n-tetradecyl group and an n-octadecyl group. , N-docosyl group, linear saturated hydrocarbon group such as n-tetracosyl group, isopropyl group, isobutyl group, neopentyl group, 2-ethylhexyl group, 2-hexyloctyl group, 4-decyldodecyl group and other branched saturated hydrocarbons. Examples thereof include saturated alicyclic hydrocarbon groups such as a group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a 4-butylcyclohexyl group and a 4-dodecylcyclohexyl group.

In the case of a fluorinated alkyl group, a fluorinated alkyl group having 1 to 30 carbon atoms is preferable, and a fluorinated alkyl group having 1 to 12 carbon atoms is more preferable. As a specific example, a group in which the hydrogen atom of the group shown as a specific example of the above alkyl group is completely or partially replaced with a fluorine atom can be exemplified.

In the case of an unsubstituted alkoxy group, an alkoxy group having 1 to 30 carbon atoms is preferable, and an alkoxy group having 1 to 12 carbon atoms is more preferable. Specific examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, a butoxy group, a pentyloxy group, an n-hexyloxy group, an octyloxy group and the like.

In the case of an unsubstituted fluorinated alkoxy group, a fluorinated alkoxy group having 1 to 30 carbon atoms is preferable, and a fluorinated alkoxy group having 1 to 12 carbon atoms is more preferable. As a specific example, a group in which all or part of the hydrogen atom of the group shown as a specific example of the alkoxy group is replaced with a fluorine atom can be exemplified.

In the case of an unsubstituted hydrocarbon-substituted carbonyl group, a hydrocarbon-substituted carbonyl group having 2 to 30 carbon atoms is preferable, and a hydrocarbon-substituted carbonyl group having 2 to 12 carbon atoms is more preferable. Specific examples thereof include an acetyl group, a propionyl group, a butanoyl group, a pentanoyl group, a hexanoyl group, an octanoyl group, a benzoyl group and the like.

In the case of an unsubstituted aromatic hydrocarbon-substituted alkynyl group or an alkenyl group, or an unsubstituted aromatic heterocyclic substituted alkynyl group or an alkenyl group, an aromatic hydrocarbon-substituted alkenyl group or an alkenyl group having 8 to 50 carbon atoms, or an alkenyl group. An aromatic heterocyclic substituted alkynyl group or alkenyl group having 6 to 50 carbon atoms is preferable, and an aromatic hydrocarbon substituted alkenyl group or alkenyl group having 8 to 26 carbon atoms or an aromatic heterocyclic ring having 6 to 26 carbon atoms is more preferable. It is a substituted alkynyl group or an alkenyl group. Specific examples include benzene, naphthalene, octalen, indacene, phenanthrene, anthracene, triphenylene, chrysen, tetraphene, tetracene, pisen, pentacene, azulene, acephenantrylene, preadene, pentaphene, tetraphenylene, helicen, hexaphene, rubisene. , Coronen, Trinaphthylene, Heptaphene, Pyrantren, Ovalen, Coranulene, Fluminen, Antantren, Zetren, Terylene, Naftasenonaphthacene, Fran, Flofran, Diflofuran, Benzothiophene, Isobenzofuran, Benzoflobenzofuran, Xanthene, Oxatren, Dibenzofuran, Perixan Tenoxanthene, thiophene, thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene, benzothienobenzothiophene, benzothienodibenzothiophene, dinaphthothienothiophene, thioxanthene, thiantolene, phenoxatiin, thionaphthene, isotianaften, thioften , Thiophanthrene, dibenzothiophene, pyrrol, pyrrolopyrrole, indoloindole, dipyrrolopyrrole, indole, isoindole, carbazole, indolocarbazole, indridin, quinolidine, phenothiazine, phenoxazine, acrindrin, pyrazole, triazole, thiazole, Isothiazole, oxazol, flazan, pyridine, pyrazine, pyrimidine, pyridazine, triazine, tetrazine, indazole, purine, isoquinoline, imidazole, naphthylidine, phthalazine, quinazoline, quinoxalin, cinnoline, quinoline, pteridine, phenanthridin, acrydin, perimidine, phenanthroline. , Phenazine, carboline, antilysine, tebenidine, kindrin, quinindrin, thiadiazol, benzothiazole, benzothiazol, benzoimidazole, benzoxazole, benzoisoxazole, benzoisothiazole, isooxazole, thiazolothiazole, benzofrazan, frazolofurazole, An alkynyl group or an alkynyl group in an aromatic ring such as pyrazorothiazole, pyrazolopyrimidine, triphenodithiazine, triphenodioxazine, phenanthrazine, anthrazine, tellurazole, serenazole, benzoterlazole, benzoserenazole, phenotellazine, or phenoselenazine. Addition of alkenyl group The group can be exemplified. More preferably, a group in which an alkynyl group or an alkenyl group is added to an aromatic ring of benzene, naphthalene, furan, thiophene, pyridine, or pyrazine can be mentioned.

In the case of an alkylsilyl alkynyl group, an alkylsilyl alkynyl group having 5 to 30 carbon atoms is preferable, and an alkylsilyl alkynyl group having 5 to 20 carbon atoms is more preferable. Specific examples thereof include a trimethylsilylethynyl group, a triethylsilylethynyl group, a triisopropylsilylethynyl group, a triisobutylsilylethynyl group and the like.

In the case of a hydrocarbon-substituted silyl group, a hydrocarbon-substituted silyl group having 3 to 30 carbon atoms is preferable, and a hydrocarbon-substituted silyl group having 3 to 20 carbon atoms is more preferable. Specific examples thereof include a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, a triisobutylsilyl group, a triphenylsilyl group and the like.

In the case of an unsubstituted siloxane group, a siloxane group having 2 to 30 silicon atoms is preferable, and a siloxane group having 2 to 20 silicon atoms is more preferable. Specific examples thereof include disiloxane, trisiloxane, tetrasiloxane, pentamethyldisiloxane, heptamethyltrisiloxane, nonamethyltetrasiloxane, pentaphenyldisiloxane, heptaphenyltrisiloxane, nonaphenyltetrasiloxane and the like.

When it is an unsubstituted polysilane group, a polysilane group having 2 to 30 silicon atoms is preferable, and a polysilane group having 2 to 20 silicon atoms is more preferable. Specific examples thereof include disilane, trisilane, tetrasilane, pentamethyldisilane, heptamethyltrisilane, nonamethyltetrasilane, triphenylsilane, pentaphenyldisilane, heptaphenyltrisilane, and nonaphenyltetrasilane.

The above substituents are hydroxyl group, alkyl group, fluorinated alkyl group, alkoxy group, carboxy group, formyl group, hydrocarbon substituted carbonyl group, amino group, thiol group, aromatic hydrocarbon substituted alkynyl group, aromatic hydrocarbon substituted alkenyl. When it is a group, an aromatic heterocyclic substituted alkynyl group, an aromatic heterocyclic substituted alkenyl group, a siloxane group, or a polysilane group, it may further have a substituent (b), and the total number of substituents (b). Is 1 to 4, preferably 1 to 2, respectively.

Preferred substituents (b) include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an alkynyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an alkyl having 1 to 20 carbon atoms. Amino group, aromatic amino group with 1 to 20 carbon atoms, alkylthio group with 1 to 20 carbon atoms, hydroxyl group, alkoxycarbonyl group with 2 to 10 carbon atoms, alkylsulfonyl group with 1 to 10 carbon atoms, 1 to 10 carbon atoms Haloalkyl group, alkylamide group with 2 to 10 carbon atoms, trialkylsilylalkyl group with 3 to 20 carbon atoms, trialkylsilylalkyl group with 4 to 20 carbon atoms, trialkylsilylalkenyl group with 5 to 20 carbon atoms, carbon Examples thereof include a trialkylsilylalkynyl group having a number of 5 to 20.

Specific examples of the substituent (b) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-octyl group and an n-dodecyl. Group, n-tetradecyl group, n-octadecyl group, n-docosyl group, linear saturated hydrocarbon group such as n-tetracosyl group, isobutyl group, neopentyl group, 2-ethylhexyl group, 2-hexyloctyl group, 4-decyl Branched saturated hydrocarbon group such as dodecyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, 4-butylcyclohexyl group, saturated alicyclic hydrocarbon group such as 4-dodecylcyclohexyl group, perfluoromethyl group, perfluoroethyl group, Perfluorobutyl group, perfluorohexyl group, perfluoloctyl group, tetrafluoro-4-hexyloctyl group, tetrafluoro-4-octyldodecyl group, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-hexyloxy group, methylamino group, dimethylamino group, ethylamino group dimethylamino group, phenylamino group, diphenylamino group, methylthio group, ethylthio group, methoxycarbonyl group, ethoxycarbonyl group, methoxycarbonyloxy group, ethoxycarbonyl Oxy group, methyl sulfonyl group, ethyl sulfonyl group, chloromethyl group, chloroethyl group, chloropropyl group, chlorobutyl group, chloropentyl group, chlorohexyl group, chlorooctyl group, chlorododecyl group, bromomethyl group, bromoethyl group, bromopropyl group. , Bromobutyl group, bromopentyl group, bromohexyl group, bromooctyl group, bromododecyl group, iodomethyl group, iodoethyl group, iodopropyl 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, trimethylsilylethyl group, triethylsilylethyl group, triisopropylsilylethyl group, triisobutylsilylethyl group, Examples thereof include trimethylsilylethenyl group, triethylsilylethenyl group, triisopropylsilylethenyl group, triisobutylsilylethenyl group, trimethylsilylethynyl group, triethylsilylethynyl group, triisopropylsilylethynyl group, triisobutylsilylethynyl group and the like. Wear. When it has two or more substituents, it may be the same or different.

In the general formula (1), Ar ¹ is a divalent group. When Ar ¹ is an unsaturated cyclic hydrocarbon ring group, the unsaturated cyclic hydrocarbon ring group independently condenses 2 to 6 single rings of 5 to 8 member rings or 2 to 6 member rings of 5 to 8 members. It is preferably an unsaturated cyclic hydrocarbon group composed of a fused ring.

Preferred specific examples of the unsaturated cyclic hydrocarbon group include benzene, naphthalene, anthanthrene, octalene, phenanthrene, triphenylene, indacene, chrysene, tetraphenyl, tetracene, picene, pentacene, azulene, acephenantrylene, and preadene. Examples thereof include pentaphene, tetraphenylene, helicene, hexaphen, anthanthrene and zethrene. Also, they can have substituents as described above.

In the general formula (1), when Ar ¹ is an unsaturated heterocyclic group, the unsaturated heterocyclic group is independently an unsaturated heterocyclic group consisting of a 5- to 8-membered monocycle or the unsaturated heterocyclic group. It is preferably a fused heterocyclic group of 2 to 6 rings containing one or more rings.

Preferred specific examples of the unsaturated heterocyclic group or condensed heterocyclic group include pyrrol, furan, thiophene, pyrrolopyrrole, flofran, thienothiophene, indol, benzofuran, benzothiophene, dipyrrolopyrrole, difluorofuran, dithienothiophene, benzo. Dipyrol, benzodifuran, benzodithiophene, carbazole, dibenzofuran, dibenzothiophene, bistienothioenothiophene, indroindole, benzoflobenzofuran, benzothioenobenzothiophene, naphthodithiophene, naphthodifuran, indrocarbazole, benzobisbenzofuran, benzobis Benzothiophene, imidazole, pyrazole, triazole, oxazole, isooxazole, oxadiazol, thiazole, isothiazole, thiadiazol, imidazole imidazole, thiazothiazole, oxazolooxazole, pyrazolopyrazole, isooxazoloisoxazole, isothiazoloisothiazole. , Benzoimidazole, benzoxazole, benzothiazole, benzopyrazole, benzoisoxazole, benzoisothiazole, benzotriazole, benzoxaziazole, benzothiazol, thiathiazolopyridine, flobisoxazole, thienovistiazole, flodiimidazole, pyrrolo Bistiazole, flobistiazole, benzodiimidazole, benzodioxazole, benzodithiazole, benzodipyrazole, benzobisthiazol, dipyrrolopyrazine, diflopyrazine, dithienopyrazine, pyrorobispyridine, flobispyridine, thienobispyridine, bistiazorotienothiophene , Thienopyridylthienopyridine, Nachtbisoxazole, Nachtbisthiazole, Difronaftilysin, Dithienonaphtilidine, Benzobispyrrolopyridine, Benzobisflopyridine, Benzobisthienopyridine, Bisbenzothienopyrazine, Pyridine, Pyrimidine, Pyridazine, Pyrazine, Triazine, Examples thereof include groups derived from quinoline, isoquinolin, naphthylidine, tetraazanaphthalene, acrydin, diazaanthracene, tetraazaanthracene, azaphenanthrene, diazaphenanthrene, tetraazaphenanthrene and the like. Also, they can have substituents as described above.

Ar ¹ is substituted or unsubstituted, benzene, naphthalene, anthracene, phenanthrene, chrysen, pisen, azulene, biphenyl, triphenyl, pyridine, pyrazine, pyrimidine, bipyridine, bipyrazine, bipyrimidine, pyrazolopyrazole, diphenylpyrazolopyrazole, More preferably, it is a group derived from imidazoloimidazole, diphenylimidazoloimidazole, thiazolothiazole, diphenylthiazolothiazole, benzobisthiazol, or diphenylbenzobisthiazol.

In the general formula (1), Ar ² is a monovalent group, an unsaturated heterocyclic group, or a linked ring group containing an unsaturated heterocycle, which can have a substituent.

The unsaturated heterocyclic group is independently represented by any of the above formulas (C-1) to (C-3), or any of the above formulas (A-1) to (A-16). It is preferably an aromatic heterocyclic group represented by the above, and the heterocyclic group represented by any of the formulas (C-1) to (C-3) or the formulas (A-1) to (A-). 4) It is more preferable that it is an aromatic heterocyclic group represented by any one of (A-13) and (A-14).

In the case of the heterocyclic group represented by the formulas (C-1) to (C-3), specific examples thereof include groups generated from the following heterocyclic compounds and the like.

In the case of the aromatic heterocyclic group represented by the formula (A-1), specific examples thereof include a group derived from imidazole, pyrazole, triazole, oxazole, isoxazole, oxadiazole, thiazole, isothiazole, or thiadiazole. It can be exemplified.

In the case of the aromatic heterocyclic group represented by the formula (A-2), specific examples thereof include imidazole imidazole, thiazothiazole, oxazolooxazole, pyrazolopyrazole, isooxazoloisoxazole, and isothiazoloisothiazole. Examples thereof include groups derived from imidazole oxazole, imidazole thiazole, thiazolooxazole, pyrazoloisoxazole, pyrazoloisothazole, isothiazoloisoxazole and the like.

When the aromatic heterocyclic group is represented by the formulas (A-3) and (A-4), specific examples thereof include benzimidazole, benzoxazole, benzothiazole, benzopyrazole, benzoisothazole, and benzoisothiazole. Examples thereof include groups derived from benzotriazole, benzoxaziazole, benzothiazole, pyrrolopyridine, flopyridine, thienopyridine, thiathiazolopyridine, purine and the like.

In the case of the aromatic heterocyclic group represented by the formula (A-5), specific examples thereof include a group derived from flobisoxazole, thienobithiazole, fluoridiimidazole, pyrolobistiazole, flobisthiazole and the like. can.

When the aromatic heterocyclic group is represented by the formula (A-6), specific examples thereof include benzodiimidazole, benzodioxazole, benzodithiazole, benzodipyrazole, benzodiisoxazole, and benzodiisothiazole. Examples thereof include groups derived from benzobistriazole, benzobisthiadiazole, dipyrrolopyrazine, difluoropyrazine, dithienopyrazine and the like.

In the case of the aromatic heterocyclic group represented by the formula (A-7), specific examples thereof include pyrrolobispyridine, pyrorobispyrazine, flobispyridine, flobispyrazine, thienobispyridine, thienobispyrazine and the like. The resulting groups can be exemplified.

In the case of the aromatic heterocyclic group represented by the formula (A-8), specific examples thereof include groups derived from thienothiophenobisoxazole, bistiazorothienothiophene and the like.

In the case of the aromatic heterocyclic group represented by the formulas (A-9) to (A-11), specific examples thereof include indole, benzoflobenzofuran, benzothienobenzothiophene, naphthodithiophene, naphthodifuran and thieno. Examples thereof include groups derived from pyridylthienopyridines, difronafutilidines, dithienonaphthalidines and the like.

In the case of the aromatic heterocyclic group represented by the formula (A-12), specific examples thereof include a group derived from benzobispyrrolopyridine, benzobisflopyridine, benzobisthienopyridine, bisbenzothienopyrazine and the like. ..

In the case of the aromatic heterocyclic group represented by the formulas (A-13) to (A-16), specific examples thereof include pyridine, pyrimidine, pyridazine, pyrazine, triazine, tetrazine, quinoline, isoquinoline, naphthylidine and tetraaza. Examples thereof include groups derived from naphthalene, acrydin, diazaanthracene, tetraazaanthracene, azaphenanthrene, diazaphenanthrene, tetraazaphenanthrene and the like.

Preferred specific examples of the unsaturated heterocycle constituting Ar ² are imidazole, pyrazole, triazole, oxazole, isooxazole, oxadiazol, thiazole, isothiazole, thiazylazole, imidazole imidazole, thiazothiazole, oxazolooxazole and pyra. Zolopyrazole, isooxazoloisoxazole, isothiazoloisothiazole, benzimidazole, benzoxazole, benzothiazole, benzopyrazole, benzoisoxazole, benzoisothiazole, benzotriazole, benzoxaziazole, benzothiazol, thiathiazolopyridine, Frobisoxazole, Thienobisthiazole, Frodiimidazole, Pyrrolobisthiazole, Frobisthiazole, Benzimidazole, Benzodixazole, Benzodithiazole, Benzodipyrazole, Benzobistiazol, Dipyrrolopyrazine, Diflopyrazine, Dithienopyrazine, Pyrrolobispyridine, Frobispyridine, Thienobispyridine, Bistiazolothienothiophene, Thienopyridylthienopyridine, Nachtbisoxazole, Nachtbisthiazole, Difluoronaphthylidine, Dithienonaphthylidine, Benzobispyrrolopyridine, Benzobisflopyridine, Benzobisthienopyridine, Bisbenzo Examples thereof include thienopyrazine, pyridine, pyrimidine, pyridazine, pyrazine, triazine, quinoline, isoquinoline, naphthylidine, tetraazanaphthalene, aclysine, diazaanthracene, tetraazaanthracen, azaphenanthrene, diazaphenanthrene and tetraazafenantrene.

Ar ² is substituted or unsubstituted, pyridine, pyrazine, pyrimidine, bipyridine, bipyrazine, bipyrimidine, phenylpyridine, phenylpyrazine, phenylpyrimidine, bipyridine, bipyrazine, bipyrimidine, pyrazolopyrazole, phenylpyrazolopyrazole, imidazoloimidazole, More preferably, it is phenylimidazoloimidazole, thiazolothiazole, or benzobistiasiazol.

In the general formula (1), a represents the number of repetitions, is an integer of 0 to 3, and is preferably 0 or 1.

In the general formula (1), R ¹ independently represents a halogen atom, a cyano group, a nitro group, a carboxy group, a formyl group, or a hydrocarbon substituted carbonyl group having 2 to 30 carbon atoms. It is preferably a cyano group.

In the case of a halogen atom, preferred specific examples include fluorine, bromine, chlorine, or iodine.

In the case of a hydrocarbon-substituted carbonyl group, preferred specific examples thereof include an acetyl group, a propionyl group, a butanoyl group, a pentanoyl group, a hexanoyl group, an octanoyl group, a benzoyl group and the like.

The nitrogen-containing heterocyclic aromatic alkenyl compound of the present invention is more preferably the compound represented by the above general formula (2).

In the general formula (2), X ¹¹ , X ¹² , and X ¹³ each independently represent CR or N, and X ¹² and X ¹³ each independently have at least one N and at least one. CR. That is, the 6-membered ring at both ends contains at least one N as an heteroatom. Preferably, the 6-membered ring at both ends is a pyridine ring, a pyrimidine ring or a triazine ring. Since the ^{6-membered ring including the central X 11 corresponds to Ar 1} in the general formula (1), it is not essential to have N.

R is independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted fluorinated alkyl group having 1 to 30 carbon atoms, a pentafluorosulfanyl group, a substituted or substituted group. An unsubstituted 1 to 30 carbon number alkoxy group, a substituted or unsubstituted fluorinated alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted hydrocarbon substituted carbonyl group having 2 to 30 carbon atoms, a nitro group, a thionitroso group, Or indicates a cyano group. At ^{least one of the Rs of CR in X 11} , X ¹² and X ¹³ is fluorine, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, pentafluorosulfanyl group, substituted or unsubstituted carbon number. It may be 1 to 30 fluorinated alkoxy groups, nitro groups, thionitroso groups, or cyano groups.

R is a halogen atom, an alkyl group having 1 to 30 carbon atoms, a fluorinated alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a fluorinated alkoxy group having 1 to 30 carbon atoms, or 2 to 2 carbon atoms. As a specific example in the case of the hydrocarbon-substituted carbonyl group of 30, the substituent of the unsaturated cyclic hydrocarbon group, the unsaturated heterocyclic group, and the linking ring group constituting ^{Ar 1} and Ar ^{2 is a halogen atom.} An alkyl group having 1 to 30 carbon atoms, a fluorinated alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a fluorinated alkoxy group having 1 to 30 carbon atoms, or a hydrocarbon substituted carbonyl having 2 to 30 carbon atoms. The same as the case where it is a group can be exemplified.

（Ａｒ^１及びＡｒ^２は、一般式（１）と同意である。）
すなわち、シアノメチル基を官能基として有する含窒素芳香族複素環化合物と、２つのホルミル基を有する芳香族化合物の縮合反応により得ることができる。 In the nitrogen-containing heterocyclic alkenyl compound represented by the general formula (1) of the present invention, when Ar ¹ is an aromatic ring, Ar ² is a nitrogen-containing aromatic heterocycle, R ¹ is a cyano group, and a = 0, for example. , Can be synthesized by the method shown in the following reaction formula (A).

(Ar ¹ and Ar ² are in agreement with the general formula (1).)
That is, it can be obtained by a condensation reaction between a nitrogen-containing aromatic heterocyclic compound having a cyanomethyl group as a functional group and an aromatic compound having two formyl groups.

Preferred specific examples of the compound represented by the general formula (1) are shown below, but the present invention is not limited thereto.

The organic semiconductor material of the present invention contains a compound represented by the general formula (1), and preferably contains 50 wt% or more of this compound, and more preferably 90 wt% or more. .. The component contained in the organic semiconductor material together with the compound of the general formula (1) is not particularly limited as long as it does not impair the performance as the organic semiconductor material.

An organic semiconductor device including an organic semiconductor material formed of the organic semiconductor material of the present invention will be described with reference to FIGS. 1 to 4 by taking an organic field effect transistor element (OFET element) as an example.

1, FIG. 2, FIG. 3 and FIG. 4 exemplify an embodiment of the OFET element of the present invention, all of which are schematic cross-sectional views showing the structure of the OFET element.

The OFET element shown in FIG. 1 is provided with a gate electrode 2 on the surface of the 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. Is provided, and the organic semiconductor layer 4 is further formed.

The OFET element shown in FIG. 2 is provided with a gate electrode 2 on the surface of the substrate 1, an insulating film layer 3 is formed on the gate electrode 2, and an organic semiconductor layer 4 is formed on the insulating film layer 3. A source electrode 5 and a drain electrode 6 are provided on the 4.

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

In the OFET element shown in FIG. 4, in the organic semiconductor device according to the present invention, the organic semiconductor layer 4, the source electrode 5 and the drain electrode 6 are provided on the surface of the substrate 1, and the organic semiconductor device is formed on the outermost surface via the insulating film layer 3. The gate electrode 2 is formed.

Examples of the material used for the substrate 1 include ceramic substrates such as glass, quartz, aluminum oxide, sapphire, silicon nitride and silicon carbide, semiconductor substrates such as silicon, germanium, gallium hydride, gallium phosphorus and gallium nitrogen, and polyethylene terephthalate. Examples thereof include polyesters such as polynaphthalene terephthalate, polyethylene, polypropylene, polyvinyl alcohol, ethylene vinyl alcohol copolymers, cyclic polyolefins, polyimides, polyamides, resin substrates such as polystyrene, and the like. The thickness of the substrate can be about 10 μm to about 2 mm, but particularly a flexible plastic substrate is preferably about 50 to about 100 μm, and a rigid substrate such as a glass plate or a silicon wafer is about 0. It can be 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 may be a gate electrode, for example, as in 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, for example, polystyrene sulfonic acid-doped poly (3,4-). Ethylenedioxythiophene), a conductive ink / paste containing carbon black / graphite, or a polymer in which colloidal silver is dispersed in a polymer binder can be exemplified.

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

The insulating film layer 3 can generally be an inorganic material film or an organic polymer film. Examples of the inorganic material suitable for the insulating film layer 3 include silicon oxide, silicon nitride, aluminum oxide, barium titanate, and barium titanate. Examples of organic compounds suitable for the insulating film layer 3 include polyesters, polycarbonates, poly (vinylphenols), polyimides, polystyrenes, poly (methacrylates), poly (acrylates), polyvinylidene fluoride, and CYTOP. Fluororesin, epoxy resin, etc. Further, the inorganic material may be dispersed in the organic material and used as an insulating layer film, or the inorganic material and the organic material may be laminated and used. 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.

As means for forming the insulating film layer, for example, a dry film forming method such as a vacuum vapor deposition method, a CVD method, a sputtering method, a laser vapor deposition method, a spin coating method, a blade coating method, screen printing, ink jet printing, and stamping. Wet film forming methods such as the method can be mentioned and can be used depending on the material.

The source electrode 5 and the drain electrode 6 can be made of a material that provides low resistance ohmic contact to the organic semiconductor layer 4 described later. As the preferred material for the source electrode 5 and the drain electrode 6, those exemplified as the preferred material for the gate electrode 2 can be used, and examples thereof include gold, nickel, aluminum, platinum, conductive polymer, and conductive ink. The thickness of the source electrode 5 and the drain electrode 6 is typically, for example, about 40 nm to about 10 μm, more preferably about 10 nm to 1 μm. Further, the surfaces of the source and drain electrodes may be treated with a charge transfer barrier reducing material for the purpose of reducing the charge transfer barrier between the source and drain electrodes and the organic semiconductor layer. As the charge transfer barrier reducing material, for example, 4-dimethylaminobenzenethiol can be used.

Examples of the means for forming the source electrode 5 and the drain electrode 6 include a vacuum vapor 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 necessary during or after film formation. Examples of the patterning method include a photolithography method in which patterning and etching of a photoresist are combined. Further, it is also possible to perform patterning by using a soft lithography method such as an inkjet printing, a screen printing, an offset printing printing method, a microcontact printing method, or a method in which a plurality of these methods are combined.

As the organic semiconductor layer 4, a semiconductor material containing a compound represented by the general formula (1) is used. As a means for forming the organic semiconductor layer, for example, a dry film forming method such as a vacuum vapor deposition method, a CVD method, a sputtering method, or a laser vapor deposition method, or a solvent or a dispersion medium after applying a solution or a dispersion liquid on a substrate is used. A wet film forming method in which a thin film is formed by removing the film can be mentioned. Since the compound represented by the general formula (1) has excellent solubility in various organic solvents, a wet film forming method can be preferably applied. Examples of the wet film forming method include a spin coating method, a drop coating method, a blade coating method, screen printing, ink jet printing, a stamping method, a die coating method, a capillary coating method, and an edge casting method. For example, when the spin coating method is used, a solution having a concentration of 0.01 wt% to 10 wt% is prepared by dissolving the organic semiconductor material of the present invention in an appropriate solvent, and then on the insulating film layer 3 formed on the substrate 1. It is carried out by dropping an organic semiconductor material solution into the mixture and then treating the mixture at 500 to 6000 rpm for 5 to 120 seconds. The solvent is selected depending on the solubility of the organic semiconductor material of the present invention in each solvent and the film quality after film formation. For example, water, alcohols typified by methanol, and aromatic hydrocarbons typified by toluene are selected. Classes, aliphatic hydrocarbons such as hexane and cyclohexane, organic nitro compounds such as nitromethane and nitrobenzene, cyclic ether compounds such as tetrahydrofuran and dioxane, nitrile compounds such as acetonitrile and benzonitrile, and ketones such as acetone and methyl ethyl ketone. , Esters such as ethyl acetate, asolvents selected from aprotonic polar solvents such as dimethylsulfoxide, dimethylacetamide, sulfolane, N-methylpyrrolidone, dimethylimidazolidinone and the like can be used. Further, these solvents may be used in combination of two or more kinds. Further, in these wet film forming methods, the solubility of the organic semiconductor material of the present invention, the drying rate of the solvent, and the drying direction can be controlled by forming the film while heating the substrate. The organic semiconductor layer is preferably in a state where charge transfer is easy, and more preferably formed of an alignment film in which molecules are arranged in a certain direction. Therefore, as a method for forming an organic semiconductor layer, a method for forming an alignment film is more preferable. Specifically, the organic semiconductor material of the present invention is dissolved in an organic solvent having a boiling point of 50 ° C. or higher, and the concentration is 0.01. Examples thereof include a method in which a solution of 10 wt% is applied to a substrate heated in a temperature range of 30 ° C. to 20 ° C. or lower than the boiling point of the solvent and dried.

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

Further, since the compound represented by the general formula (1) has a deep energy level of the lowest unoccupied molecular orbital (LUMO), the organic semiconductor material containing the compound of the present invention is particularly preferably used as an N-type semiconductor, and is preferably used as the N-type semiconductor of the present invention. An organic thin film using an organic semiconductor material containing a compound as a semiconductor layer can be suitably used as an N-type organic thin film.

Further, an element or the like (for example, an organic complementary transistor) composed of a combination of a single organic field effect transistor is also included in the organic field effect transistor of the present invention.

Another preferred embodiment of the organic semiconductor device using the organic semiconductor material of the present invention is an organic photovoltaic device. Specifically, it is an organic photovoltaic element (organic thin film solar cell) having a positive electrode, an organic semiconductor layer and a negative electrode on a substrate, and the organic semiconductor layer contains the above-mentioned organic semiconductor material of the present invention. It is a device.

An example of the structure of the organic photovoltaic device to which the organic semiconductor material of the present invention can be applied will be described with reference to the drawings, but the structure of the organic photovoltaic device of the present invention is not limited to the one shown in the drawing. ..

FIG. 5 is a cross-sectional view showing a structural example of a general organic photovoltaic device used in the present invention, in which 7 is a substrate, 8 is a positive electrode, 9 is an organic semiconductor layer, and 10 is a negative electrode. Further, FIG. 6 is a cross-sectional view showing a structural example when the organic semiconductor layers are laminated, 9-a is a P-type organic semiconductor layer, and 9-b is an N-type organic semiconductor layer.

The substrate is not particularly limited, and may have, for example, a conventionally known configuration. It is preferable to use a glass substrate or a transparent resin film having mechanical and thermal strength and transparency. The transparent resin film includes polyethylene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polypropylene, polystyrene, polymethyl methacrylate, polyvinyl chloride, polyvinyl alcohol, polyvinyl butyral, nylon, and polyether ether ketone. , Polysulfone, polyether sulfone, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, polyvinylfluoride, tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene, Examples thereof include polyvinylidene fluoride, polyester, polycarbonate, polyurethane, polyimide, polyetherimide, polyimide, polypropylene and the like.

As the electrode material, it is preferable to use a conductive material having a large work function for one electrode and a conductive material having a small work function for the other electrode. An electrode made of a conductive material having a large work function becomes a positive electrode. In addition to metals such as gold, platinum, chromium, and nickel, transparent metal oxides such as indium and tin, and composite metal oxides (indium tin oxide (ITO), indium) are examples of conductive materials with a large work function. (Zinc oxide (IZO), etc.) is preferably used. Here, the conductive material used for the positive electrode is preferably ohmic-bonded to the organic semiconductor layer. Further, when the hole transport layer described later is used, it is preferable that the conductive material used for the positive electrode is ohmic-bonded to the hole transport layer.

An electrode using a conductive material having a small work function serves as a negative electrode, and an alkali metal or an alkaline earth metal, specifically lithium, magnesium, or calcium is used as the conductive material having a small work function. Further, tin, silver and aluminum are also preferably used. Further, an electrode made of the above-mentioned metal alloy or a above-mentioned metal laminate is also preferably used. It is also possible to improve the take-out 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 ohmic-bonded to the organic semiconductor layer. Further, when the electron transport layer described later is used, it is preferable that the conductive material used for the negative electrode is ohmic-bonded to the electron transport layer.

The organic semiconductor layer contains the compound of the present invention. That is, the organic semiconductor material of the present invention containing the nitrogen-containing heterocyclic alkenyl compound represented by the formula (1) is used. The organic semiconductor material of the present invention is used for a P-type organic semiconductor material (hereinafter, also referred to as P-type organic material), an N-type organic semiconductor material (hereinafter, also referred to as N-type organic material), or both. For example, two or more compounds represented by the general formula (1) can be used, one or more of which can be used as a P-type organic material component, and the other one or more can be used as an N-type organic material component. Further, a compound represented by the general formula (1) containing only one of the P-type organic material and the N-type organic material can be contained as an organic semiconductor material component.

The organic semiconductor material containing the compound represented by the formula (1) functions as a P-type organic material or an N-type organic material, but is preferably used as an N-type material.

The organic semiconductor layer is formed by containing at least one organic semiconductor material containing a compound represented by the general formula (1), and is known or known as an N-type organic material containing a compound represented by the general formula (1), for example. It is composed of a new P-type organic material.

In the case of the organic photovoltaic device of the structural example shown in FIG. 5, it is preferable that the P-type material and the N-type organic material are mixed, and whether the P-type organic material and the N-type organic material are compatible at the molecular level. , Preferably phase-separated. The domain size of this phase-separated structure is not particularly limited, but is usually 1 nm or more and 50 nm or less. Further, in the case of an organic photovoltaic element in which the P-type organic material and the N-type organic material of the structural example shown in FIG. 6 are laminated, the layer having the P-type organic material is on the positive electrode side, and the layer having the N-type organic material. Is preferably on the negative electrode side. The thickness of the organic semiconductor layer is preferably 5 nm to 500 nm, more preferably 30 nm to 300 nm. In the case of being laminated, when the organic semiconductor material of the present invention is used as an N-type organic material, the layer having the N-type organic material preferably has a thickness of 1 nm to 400 nm among the above thicknesses. , More preferably 15 nm to 150 nm.

As the P-type organic material, among the compounds represented by the general formula (1), those exhibiting P-type semiconductor characteristics may be used alone, or other P-type organic materials may be used. Examples of other P-type organic materials include polythiophene-based polymers, benzothiasiazol-thiophene-based derivatives, benzothiasiazol-thiophene-based copolymers, poly-p-phenylene vinylene-based polymers, poly-p-phenylene-based polymers, and the like. Conjugate polymers such as polyfluorene-based polymers, polypyrrole-based polymers, polyaniline-based polymers, polyacetylene-based polymers, polythienylene vinylene-based 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, Triarylamine derivatives such as N'-dinaphthyl-N, N'-diphenyl-4,4'-diphenyl-1,1'-diamine (NPD), 4,4'-di (carbazole-9-yl) biphenyl ( Examples thereof include carbazole derivatives such as CBP) and oligothiophene derivatives (terthiophene, quarterthiophene, sexithiophene, octthiophene, etc.).

As the N-type organic material, among the compounds represented by the general formula (1), those exhibiting N-type semiconductor characteristics may be used alone, or other N-type organic materials may be mixed and used. Other N-type organic materials include, for example, 1,4,5,8-naphthalenetetracarboxylicdiane hydride (NTCDA), 3,4,9,10-perylenetetracarboxylicdiane hydride (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), Triazole derivatives such as 3- (4-biphenylyl) -4-phenyl-5- (4-t-butylphenyl) -1,2,4-triazole (TAZ), phenanthroline derivatives, phosphine oxide derivatives, fullerene compounds (C60, Unsubstituted ones such as 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 Estel ([5,6] -PCBM), [6,6] -Phenyl C61 Butyric Acid Hexyl Estel ([6,6] -PCBH), [6,6] -Phenyl C61 Butylic Acid Desylester ([6,6] -PCBD), Phenyl C71 Butyric Acid Methyl Estel (PC70BM), Phenyl C85 Butyric Acid Methyl Estel (PC84BM), etc.), Carbon Nanotubes (CNT), Poly-p-Phenylene Examples thereof include a derivative (CN-PPV) in which a cyano group is introduced into a vinylene-based polymer.

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. Materials for forming the hole transport layer include conductive polymers such as polythiophene-based polymers, poly-p-phenylene vinylene-based polymers, and polyfluorene-based polymers, and phthalocyanine derivatives (H2Pc, CuPc, ZnPc, etc.). Low molecular weight organic compounds exhibiting P-type semiconductor properties such as porphyrin derivatives are preferably used. In particular, polyethylenedioxythiophene (PEDOT), which is a polythiophene-based 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.

Further, in the organic photovoltaic device of the present invention, an electron transport layer may be provided between the organic semiconductor layer and the negative electrode. The material for forming the electron transport layer is not particularly limited, but is not limited to the above-mentioned N-type organic materials (NTCDA, PTCDA, PTCDI-C8H, oxazole derivative, triazole derivative, phenanthroline derivative, phosphine oxide derivative, fullerene compound, CNT). , CN-PPV, etc.), and organic materials exhibiting N-type semiconductor characteristics are preferably used. The electron transport layer preferably has a thickness of 5 nm to 600 nm, more preferably 30 nm to 200 nm.

Further, in the organic photovoltaic device of the present invention, two or more organic semiconductor layers may be laminated (tandemized) via one or more intermediate electrodes to form a series junction. For example, a laminated structure of a substrate / positive electrode / first organic semiconductor layer / intermediate electrode / second organic semiconductor layer / negative electrode can be mentioned. By stacking in this way, the open circuit voltage can be improved. The hole transport layer 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. , And the hole transport layer described above may be provided between the second organic semiconductor layer and the negative electrode.

The organic semiconductor layer can be formed by spin coating, blade coating, slit die coating, screen printing, bar coater coating, mold coating, print transfer method, immersion pulling method, inkjet method, spray method, vacuum vapor deposition method, etc. 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. However, when the organic semiconductor material of the present invention is used, spin coating is applied. , Blade coat coating, slit die coating coating, screen printing coating, bar coater coating, mold coating, printing transfer method, immersion pulling method, inkjet method, spray method and other wet film forming methods can be preferably applied.

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 device.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.

Example 1
In a DMSO (10 ml) suspension of sodium hydride (580 mg (60% oil suspension), 14.5 mmol) at room temperature and in an argon atmosphere, tert-butyl cyanoacetate (2.11 mg, 14.9 mmol). The DMSO solution (3 ml) was added dropwise over 30 minutes, and then the mixture was stirred at room temperature for 30 minutes. A DMSO solution (5 ml) of 5- (trifluoromethyl) -2-chloropyridine (1.00 g, 5.51 mmol) was added to the reaction mixture, and the mixture was stirred at 120 ° C. for 2 hours. After cooling the reaction solution, a saturated aqueous solution of ammonium chloride was added, and the precipitated solid was filtered, washed with water and dried to obtain a crude product. Next, p-toluenesulfonic acid monohydrate (5.79 g) was added to an acetonitrile solution (13 ml) of the dried crude product, and the mixture was heated under reflux for 1 hour. The reaction mixture was diluted with ethyl acetate, washed with water and saturated brine, and dried over anhydrous sodium sulfate. Anhydrous sodium sulfate was filtered and concentrated under reduced pressure to obtain a crude product of 5- (trifluoromethyl) -2-pyridine acetonitrile. The obtained crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 3: 1) to obtain 5- (trifluoromethyl) -2-pyridine acetonitrile. Yield 836 mg, yield 82%, white solid.
^{1 1} H-NMR (400 MHz, CDCl ₃ )
δ (ppm): 8.87 (s, 1H), 8.00 (dd, 1H, J = 2.1,8.0Hz), 7.60 (d, 1H, J = 8.1Hz), 4. 04 (s, 2H)

Ethanol solution of 2,5-difluorobenzene-1,4-dicarbaldehyde (50 mg, 0.29 mmol), 5- (trifluoromethyl) -2-pyridin acetonitrile (109 mg, 0.59 mmol) at room temperature and nitrogen atmosphere. Sodium ethoxide (0.29 ml, 0.059 mmol) was added to (5 ml), the mixture was shielded from light, and the mixture was stirred for 1 hour. Then, the mixture was cooled to 0 ° C., methanol was added, and the mixture was filtered and dried to obtain a crude product. The obtained crude product was purified by recrystallization (hexane: chloroform) to obtain the target compound (45). Yield 100 mg, yield 68%, yellow solid.
^{1 1} H-NMR (400 MHz, CDCl ₃ )
δ (ppm): 8.94 (s, 1H), 8.84 (s, 1H), 8.26 (t, 1H, J = 8.3Hz), 8.10 (d, 1H, J = 8. 1Hz), 7.94 (d, 1H, J = 8.3Hz)
MS (EI): m / z = 506

Example 2
Bredereck reagent (3.0 ml, 14.6) in a DMF solution (3.0 ml) of 5,5'-dimethyl-2,2'-bipyridyl (300 mg, 1.63 mmol) at room temperature and in an argon atmosphere. mmol) was added, the temperature was raised to 120 ° C., and the mixture was stirred for 72 hours. Then, the temperature was returned to room temperature with stirring, the precipitate was filtered, and then washed with diethyl ether to obtain 5,5'-bis (2-dimethylaminovinyl) -2,2'-bipyridine. Yield 257 mg, 54% yield, yellow solid.
^{1 1} H-NMR (500 MHz, CDCl ₃ )
δ (ppm): 8.41 (d, 2H, J = 2.4 Hz), 8.10 (d, 2H, J = 8.4 Hz), 7.54 (dd, 2H, J = 2.4) , 8.4 Hz), 6.86 (d, 2H, J = 13.8 Hz), 5.11 (d, 2H, J = 13.8 Hz), 2.85 (s, 12H)

5,5'-Bis (2-dimethylaminovinyl) -2,2'-bipyridine (100 mg, 0.34 mmol) in dichloromethane (4.5 ml), THF (15 ml), at room temperature and in a nitrogen atmosphere, Add to a mixed solution of distilled water (3 ml), add sodium periodate (553 mg, 2.59 mmol) to it, and stir for 22 hours. Then, after filtering the precipitate, the filtrate was concentrated under reduced pressure. The concentrated filtrate was subjected to a liquid separation operation to extract the organic layer and then concentrated under reduced pressure to obtain a crude product. The obtained crude product was purified by silica gel column chromatography (chloroform: methanol = 95: 5) to obtain 2,2'-bipyridine-5,5'-dicarbaldehyde. Yield 68 mg, 60% yield, white solid.
^{1 1} H NMR (500 MHz, CDCl ₃ )
δ (ppm): 10.21 (s, 2H), 9.175 (dd, 2H, J = 0.9, 2.2 Hz), 8.72 (dd, 2H, J = 0.9, 8. 2 Hz), 8.34 (dd, 2H, J = 2.2, 8.2 Hz)

In a THF solution (8 ml) of 6- (trifluoromethyl) -3-pyridinecarboxylic acid (504 mg, 2.64 mmol) at room temperature and a nitrogen atmosphere, cool to 0 ° C. and dimethyl sulfide borane complex (401 mg). 5.27 mmol) was added, the temperature was raised to room temperature, and the mixture was stirred for 18.5 hours. Then, the mixture was cooled to 0 ° C., methanol was added, and the mixture was concentrated under reduced pressure. Then, 1% hydrochloric acid / methanol was added, and the mixture was heated under reflux at 60 ° C., cooled to 0 ° C., triethylamine was added, and concentrated under reduced pressure to obtain a crude product. The obtained crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 1: 1) to obtain [6- (trifluoromethyl) pyridin-3-yl] methanol. Yield 369 mg, yield 92%, yellow liquid.
^{1 1} H-NMR (400 MHz, CDCl ₃ )
δ (ppm): 8.67 (s, 1H), 7.91 (d, 1H, J = 8.0 Hz), 7.68 (d, 1H, J = 8.0 Hz), 4.83 ( s, 2H) 2.85 (bs, 1H)
¹³ C-NMR (125 MHz, CDCl ₃ )
δ (ppm): 61.2, 120.4, 121.4 (q, 272 Hz), 136.0, 140.4, 146.4 (q, 34 Hz), 147.9
MS (EI): m / z = 177
IR (KBr): 3357, 1405, 1337 cm ^-1

Triethylamine (4.2 ml) was added to a dichloromethane solution (82.5 ml) of [6- (trifluoromethyl) pyridin-3-yl] methanol (4.41 g, 24.9 mmol) at room temperature and a nitrogen atmosphere. 30.1 mmol), dimethylaminopyridine (21.5 mg, 0.176 mmol) is added. The mixture was cooled to 0 ° C., methanesulfonyl chloride (3.0 ml, 38.8 mmol) was added, and the mixture was stirred for 1 hour, heated to room temperature, and stirred for 22 hours. Then, the mixture was concentrated under reduced pressure to obtain a crude product. The obtained crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 9: 1 → 1: 1) to obtain 5- (chloromethyl) -2-trifluoromethylpyridine. Yield 3.99 g, yield 84%, yellow liquid.
^{1 1} H-NMR (400 MHz, CDCl ₃ )
δ (ppm): 8.75 (s, 1H), 7.95 (d, 1H, J = 8.0 Hz), 7.72 (d, 1H, J = 8.0 Hz), 4.67 ( s, 2H)
MS (EI): m / z = 195
IR (KBr): 1399, 1337, 707 cm ^-1

_{CH 3} CN: phosphate buffer (pH 7) = 3: 1 solution (100) of 5- (chloromethyl) -2-trifluoromethylpyridine (3.99 g, 20.9 mmol) at room temperature and nitrogen atmosphere. To (ml), sodium cyanide (3.18 g, 64.9 mmol) and tetrabutylammonium bromide (678 mg, 2.1 mmol) were added, and the mixture was stirred at 60 ° C. for 5 hours. Then, the mixture was cooled to 0 ° C., phosphate buffer (pH 7) was added, the mixture was extracted with dichloromethane, washed with saturated brine, and dried over anhydrous sodium sulfate. Anhydrous sodium sulfate was filtered and concentrated under reduced pressure to obtain a crude product. The obtained crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 4: 1) followed by activated carbon to obtain [6- (trifluoromethyl) pyridin-3-yl] acetonitrile. Yield 2.47 g, 77% yield, yellow liquid.
^{1 1} H-NMR (400 MHz, CDCl ₃ )
δ (ppm): 8.71 (s, 1H), 7.94 (d, 1H, J = 8.0 Hz), 7.76 (d, 1H, J = 8.1 Hz), 3.89 ( s, 2H)
MS (EI): m / z = 186
IR (KBr): 2928, 2260 cm ^-1

2,2'-Bipyridine-5,5'-dicarbaldehyde (25 mg, 0.12 mmol), [6- (trifluoromethyl) pyridin-3-yl] acetonitrile (44 mg,) at room temperature, under nitrogen atmosphere. Sodium ethoxydo (0.12 ml, 0.024 mmol) was added to an ethanol solution (5 ml) of 0.24 mmol), the mixture was shielded from light, and the mixture was stirred for 4 hours. Then, the mixture was cooled to 0 ° C., methanol was added, and the mixture was filtered and dried to obtain a crude product. The obtained crude product was purified by recrystallization (chloroform) to obtain the target compound (245). Yield 35 mg, yield 54%, yellow solid.
^{1 1} H NMR (500 MHz, CDCl ₃ )
δ (ppm): 9.12 (d, 2H, J = 1.80 Hz), 8.93 (s, 2H), 8.73 (dd, 2H, J = 2.10, 8.40 Hz), 8.71 (s, 2H), 8.68 (d, 2H, J = 8.55 Hz), 8.08 (d, 2H, J = 8.15 Hz), 2.67 (d, 2H, J) = 8.15 Hz)
MS (ESI +): m / z = 549
HRMS (ESI +): Calcd for C ₂₈ H ₁₅ F ₆ N ₆ ; 549.1262, Found; 549.1283
IR (KBr): 3069, 2220 cm ^-1

Example 3
_{Cyanide in CH 3} CN: phosphate buffer (pH 7) = 3: 1 solution (100 ml) of 2-bromo-5- (bromomethyl) pyridine (630 mg, 2.46 mmol) at room temperature and nitrogen atmosphere. Sodium phosphate (366 mg, 7.38 mmol) and tetrabutylammonium bromide (90 mg, 0.24 mmol) were added, and the mixture was stirred at 60 ° C. for 5 hours. Then, the mixture was cooled to 0 ° C., phosphate buffer (pH 7) was added, the mixture was extracted with dichloromethane, washed with saturated brine, and dried over anhydrous sodium sulfate. Anhydrous sodium sulfate was filtered and concentrated under reduced pressure to obtain a crude product. The obtained crude product was purified by column chromatography (hexane: ethyl acetate = 2: 1) to obtain (6-bromopyridin-3-yl) acetonitrile. Yield 432 mg, yield 87%, white solid.
^{1 1} H-NMR (400 MHz, CDCl ₃ )
δ (ppm): 8.36 (s, 1H), 7.59 (dd, 1H, J = 2.4,8.2 Hz), 7.55 (d, 1H, J = 8.1 Hz), 3.75 (s, 2H)

Room temperature, under nitrogen atmosphere, (6-bromopyridine-3-yl) acetonitrile (120 mg, 0.61 mmol), 1-octin (134 mg, 1.22 mmol), PdCl ₂ (32 mg, 0.18 mmol) ), Triphenylphosphine (96 mg, 0.37 mmol), CuI (70 mg, 0.37 mmol) and triethylamine (1.2 ml) were added, and the mixture was stirred at room temperature for 3 hours. Then, the mixture was extracted with dichloromethane, washed with water, and the organic layer was dried over anhydrous sodium sulfate. Anhydrous sodium sulfate was filtered and concentrated under reduced pressure to obtain a crude product. The obtained crude product was purified by thin layer column chromatography (hexane: ethyl acetate = 2: 1) to obtain 1- [5- (cyanomethyl) pyridin-2-yl] -1-octyne. Yield 72 mg, yield 53%, yellow liquid.
^{1 1} H-NMR (500 MHz, CDCl ₃ )
δ (ppm): 8.49 (m, 1H), 7.64 (dd, 1H, J = 2.5, 8.1 Hz), 7.40 (d, 1H, J = 8.1 Hz), 3.76 (s, 2H), 2.44 (t, 2H, J = 7.2 Hz), 3.89 (quin, 2H, J = 5.0 Hz), 1.45 (m, 2H), 1.32 (m, 4H), 0.90 (t, 3H, J = 7.0 Hz)

室温、窒素雰囲気下、２，５−ジフルオロベンゼン−１，４−ジカルボアルデヒド （２１ ｍｇ、０．１２ ｍｍｏｌ）、１−（５−シアノメチル−ピリジン−２−イル）−１−オクチン（５７ ｍｇ、０．２５ ｍｍｏｌ）のエタノール溶液（４ ｍｌ）に、ナトリウムエトキシド（０．１２ ｍｌ、０．０２４ ｍｍｏｌ）を加え、遮光し、１時間半撹拌した。その後、０℃に冷却してメタノールを加え、濾過、乾燥し、粗生成物を得た。得られた粗生成物を再結晶（ヘキサン：クロロホルム）により精製することで目的物である化合物（７４）を得た。収量５５ｍｇ、収率７５％、黄色固体。
^１Ｈ−ＮＭＲ（５００ ＭＨｚ、ＣＤＣｌ_３）
δ（ｐｐｍ）：８．８９（ｄ，２Ｈ，Ｊ＝２．１５ Ｈｚ）、８．１８（ｔ，２Ｈ，Ｊ＝８．３０ Ｈｚ）、７．９４（ｄｄ，２Ｈ，Ｊ＝２．５０，８．２５ Ｈｚ）、７．７７（ｓ，２Ｈ）、７．４８（ｄ，２Ｈ，Ｊ＝８．２５ Ｈｚ）、２．４８（ｔ，４Ｈ，Ｊ＝７．１５ Ｈｚ）、１．６６（ｑｕｉｎ，４Ｈ，Ｊ＝７．２５ Ｈｚ）、１．４７（ｑｕｉｎ，４Ｈ，Ｊ＝ ７．３５ Ｈｚ）、１．２９−１．３８（ｍ，８Ｈ）、０．９０（ｔ，６Ｈ，Ｊ＝６．９５ Ｈｚ）
^１３Ｃ−ＮＭＲ（１２６ ＭＨｚ、ＣＤＣｌ_３）
δ（ｐｐｍ）：１５７．９、１５５．９、１５５．８、１４７．４、１４５．４、１３３．５， １３１．９， １３１．９， １２７．８４， １２６．８１， １２５．１０， １２５．０１、１２４．９、１１２．５、９４．６、８０．１、３１．３、２８．７、２８．２、２２．５、１９．５、１４．１
ＭＳ（ＥＩ）：ｍ／ｚ＝５８６
ＨＲＭＳ（ＥＩ）：Ｃａｌｃｄ ｆｏｒ Ｃ_３８Ｈ_３６Ｆ_２Ｎ_４；５８６．２９０８、Ｆｏｕｎｄ； ５８６．２８９７
ＩＲ（ＫＢｒ）：２９１８、２２２４ ｃｍ^−１

2,5-Difluorobenzene-1,4-dicarbaldehyde (21 mg, 0.12 mmol), 1- (5-cyanomethyl-pyridin-2-yl) -1-octin (57 mg) at room temperature and in a nitrogen atmosphere. , 0.25 mmol) of ethanol solution (4 ml) was added with sodium ethoxydo (0.12 ml, 0.024 mmol), shielded from light, and stirred for 1 and a half hours. Then, the mixture was cooled to 0 ° C., methanol was added, and the mixture was filtered and dried to obtain a crude product. The obtained crude product was purified by recrystallization (hexane: chloroform) to obtain the target compound (74). Yield 55 mg, 75% yield, yellow solid.
^{1 1} H-NMR (500 MHz, CDCl ₃ )
δ (ppm): 8.89 (d, 2H, J = 2.15 Hz), 8.18 (t, 2H, J = 8.30 Hz), 7.94 (dd, 2H, J = 2.50) , 8.25 Hz), 7.77 (s, 2H), 7.48 (d, 2H, J = 8.25 Hz), 2.48 (t, 4H, J = 7.15 Hz), 1. 66 (quin, 4H, J = 7.25 Hz), 1.47 (quin, 4H, J = 7.35 Hz), 1.29-1.38 (m, 8H), 0.90 (t, 6H) , J = 6.95 Hz)
¹³ C-NMR (126 MHz, CDCl ₃ )
δ (ppm): 157.9, 155.9, 155.8, 147.4, 145.4, 133.5, 131.9, 131.9, 127.84, 126.81, 125.10, 125 0.01, 124.9, 112.5, 94.6, 80.1, 31.3, 28.7, 28.2, 22.5, 19.5, 14.1
MS (EI): m / z = 586
HRMS (EI): Calcd for C ₃₈ H ₃₆ F ₂ N ₄ ; 586.2908, Found; 586.2897
IR (KBr): 2918, 2224 cm ^-1

Example 4
To a solution of 2,5-dimethylpyrazine (500 mg, 5.36 mmol) in ethyl acetate (7 ml) at room temperature, m-chloroperbenzoic acid (1.27 g, 7.36 mmol) was added and stirred for 24 hours. did. The reaction system was then filtered and the solid washed with ethyl acetate to give 2,5-dimethylpyrazine-N, N'-dioxide. Yield 517 mg, yield 80%, white solid.
_{^{1 H-NMR (200 MHz,}} D 2 O)
δ (ppm): 8.48 (s, 2H), 2.42 (s, 6H)

An acetic anhydride solution (2.5 ml) of 2,5-dimethylpyrazine-N, N'-dioxide (500 mg, 3.57 mmol) was heated to reflux at room temperature for 7 hours. Then, the mixture was stirred at room temperature for 12 hours and concentrated under reduced pressure. Diethyl ether was added thereto, and the mixture was stirred for 3 hours, and the solid was filtered. The filtrate was concentrated and purified by silica gel column chromatography (hexane: ethyl acetate = 3: 1) to give 2,5-di (acetoxymethyl) pyrazine. Yield 166 mg, yield 21%, yellow solid.
^{1 1} H-NMR (300 MHz, CDCl ₃ )
δ (ppm): 8.59 (s, 2H), 5.23 (s, 4H), 2.13 (s, 6H)

Sodium methoxide (29 mg, 0.54 mg) was added to a methanol solution (4 ml) of 2,5-di (acetoxymethyl) pyrazine (150 mg, 0.67 mmol) at room temperature, and the mixture was stirred for 3 hours. .. Then, ammonium chloride (60 mg, 1.12 mmol) was added, and the mixture was concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (chloroform: methanol = 9: 1) to obtain 2,5-di (hydroxymethyl) pyrazine. Yield 85 mg, yield 91%, white solid.
^{1 1} H-NMR (300 MHz, acetone-d ₆ )
δ (ppm): 8.63 (s, 2H), 4.89 (s, br, 2H), 4.75 (s, 4H)

A 1,4-dioxane suspension (15 ml) of 2,5-di (hydroxymethyl) pyrazine (300 mg, 2.14 mmol) and manganese dioxide (3.72 g, 42.8 mmol) at room temperature. , Stirred for 1.5 hours. Then, the reaction system was filtered through Celite, and the filtrate was purified by thin layer chromatography (chloroform: methanol = 9: 1) to obtain 2,5-pyrazine dicarbaldehyde. Yield 168.9 mg, 58% yield, yellow solid.
^{1 1} H-NMR (300 MHz, CDCl ₃ )
δ (ppm): 10.23 (s, 2H), 9.30 (s, 2H)

Room temperature, under nitrogen atmosphere, (6-bromopyridine-3-yl) acetonitrile (433 mg, 2.20 mmol), 1-octine (484 mg, 4.39 mmol), PdCl ₂ (195 mg, 1.10 mmol). ), Triphenylphosphine (576 mg, 2.20 mmol), CuI (418 mg, 2.20 mmol), and triethylamine (2.2 ml) were added, and the mixture was stirred at room temperature for 20 hours. Then, the mixture was concentrated under reduced pressure and purified by thin layer column chromatography (hexane: ethyl acetate = 2: 1) to remove the catalyst and the like to obtain a crude product. Next, Pd / C (10%) (40 mg) was added to an ethanol solution (16 ml) of the obtained crude product to create a hydrogen atmosphere, and the mixture was stirred at room temperature for 17 hours. After completion of the reaction, filtration through Celite is performed, the filtrate is concentrated, and purified by column chromatography (hexane: ethyl acetate = 4: 1) to give 1- [5- (cyanomethyl) pyridin-2-yl] octane. Obtained. Yield 180 mg, yield 35%, yellow liquid.
^{1 1} H-NMR (500 MHz, CDCl ₃ )
δ (ppm): 8.47 (d, 1H, J = 2.2), 7.61 (dd, 1H, J = 2.4,8.0 Hz), 7.19 (d, 1H, J = 8.1 Hz), 3.73 (s, 2H), 2.79 (t, 2H, J = 7.7 Hz), 1.71 (quin, 2H, J = 7.0 Hz), 1.28 (M, 10H), 0.87 (t, 3H, J = 6.8 Hz)

2,5-Di (hydroxymethyl) pyrazine (16 mg, 0.12 mmol), 1- [5- (cyanomethyl) pyridin-2-yl] octane (54 mg, 0.24 mmol) at room temperature and in a nitrogen atmosphere. Sodium ethoxide (0.12 ml, 0.024 mmol) was added to the ethanol solution (3 ml) of the above, shielded from light, and stirred for 21 hours. Then, the mixture is cooled to 0 ° C., methanol is added, and the mixture is filtered and dried to obtain a crude product. The obtained crude product was purified by recrystallization (hexane: chloroform) to obtain the target compound (235). Yield 19 mg, yield 29%, yellow solid.
^{1 1} H-NMR (500 MHz, CDCl ₃ )
δ (ppm): 9.05 (s, 2H), 8.94 (d, 2H, J = 2.45 Hz), 7.99 (dd, 2H, J = 2.45, 8.20 Hz), 7.62 (s, 2H), 7.29 (d, 2H, J = 8.05 Hz), 2.87 (t, 4H, J = 7.80 Hz), 1.76 (quin, 4H, J) = 6.30 Hz), 1.32 (m, 10H), 0.88 (t, 6H, J = 6.85 Hz)
MS (ESI +): m / z = 561
HRMS (ESI +): Calcd for C ₃₆ H ₄₅ N ₆ ; 561.37057, Found; 561.37000
IR (KBr): 3019, 3071, 2954, 2919, 2850, 2222 cm ^-1

Example 5
2,5-Difluorobenzene-1,4-dicarbaldehyde (25 mg, 0.15 mmol), 1- [5- (cyanomethyl) pyridin-2-yl] octane (68 mg, 0) at room temperature and nitrogen atmosphere. To a mixed solution of ethanol (5 ml) and DMF (3 ml) of .29 mmol), sodium ethoxide (0.15 ml, 0.029 mmol) was added, the mixture was shielded from light, and the mixture was stirred for 4 hours. Then, the mixture was cooled to 0 ° C., methanol was added, and the mixture was filtered and dried to obtain a crude product. The obtained crude product was purified by recrystallization (hexane: chloroform) to obtain the target compound (61). Yield 64 mg, 74% yield, yellow solid.
^{1 1} H-NMR (500 MHz, CDCl ₃ )
δ (ppm): 8.87 (d, 2H, J = 2.25 Hz), 8.16 (t, 2H, J = 8.35 Hz), 7.90 (dd, 2H, J = 2.45) , 8.20 Hz), 7.73 (s, 2H), 7.27 (d, 2H, J = 9.90 Hz), 2.86 (t, 4H, J = 7.70 Hz), 1. 75 (quin, 4H, J = 6.90 Hz), 1.32 (m, 10H), 0.88 (t, 6H, J = 6.60 Hz)
¹³ C-NMR (126MHz, CDCl ₃ )
δ (ppm): 164.8, 146.9, 133.8, 127.0, 122.9, 113.0, 38.3, 31.9, 29.7, 29.4, 29.4, 29 .2, 22.7, 14.1
MS (EI): m / z = 594
HRMS (EI): Calcd for C ₃₈ H ₄₄ F ₂ N ₄ ; 594.3534, Found; 594.3512
IR (KBr): 2953, 2920, 2850, 2221 cm ^-1

Example 6
In a DMSO (2 ml) suspension of sodium hydride (53 mg (60% oil suspension), 1.34 mmol) at room temperature and in a nitrogen atmosphere, tert-butyl cyanoacetate (197 mg, 1. A DMSO solution (1 ml) of 39 mmol) was added dropwise over 15 minutes and then stirred at room temperature for 1 hour. After adding 5-bromo-2-chloropyrimidine (100 mg, 0.52 mmol) to the reaction mixture, the mixture was stirred at room temperature for 8 hours. Next, a saturated aqueous solution of ammonium chloride was added to the reaction system, the mixture was extracted with ethyl acetate, washed with water, and then concentrated under reduced pressure to obtain a crude product. Subsequently, trifluoroacetic acid (1.8 ml) was added to a dried crude product in dichloromethane (2.3 ml) at 0 ° C., and the mixture was stirred for 1 hour, heated to room temperature, and then stirred for 15 hours. did. The reaction mixture was neutralized with saturated aqueous sodium hydrogen carbonate solution, extracted with ethyl acetate, washed with water and saturated brine, and dried over anhydrous sodium sulfate. Anhydrous sodium sulfate was filtered and concentrated under reduced pressure to obtain a crude product of (5-bromopyrimidine-2-yl) acetonitrile. The obtained crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 3: 1) to obtain (5-bromopyrimidine-2-yl) acetonitrile. Yield 46 mg, 45% yield, white solid.
^{1 1} H-NMR (500 MH, CDCl ₃ )
δ (ppm): 8.81 (s, 2H), 4.08 (s, 2H)

At room temperature, under nitrogen atmosphere, (5-bromopyrimidine-2-yl) acetonitrile (150 mg, 0.76 mmol), 1-octine (167 mg, 1.51 _{mmol), PdCl 2} (13 mg, 0.08 mmol). , Triphenylphosphine (40 mg, 0.15 mmol), CuI (7 mg, 0.04 mmol), triethylamine (0.81 ml), THF (1.8 ml) were added, and the mixture was stirred at 40 ° C. for 3 hours. did. Then, Celite filtration was performed, and the filtrate was concentrated under reduced pressure to obtain a crude product. The obtained crude product was purified by thin layer column chromatography (hexane: ethyl acetate = 2: 1) to obtain [5- (1-octynyl) pyrimidin-2-yl] acetonitrile. Yield 138 mg, 80% yield, yellow liquid.
^{1 1} H-NMR (500 MHz, CDCl ₃ )
δ (ppm): 8.70 (s, 2H), 4.10 (s, 2H), 2.45 (t, 2H, J = 7.7 Hz), 1.63 (quin, 2H, J = 7) .3 Hz), 1.45 (m, 2H), 1.33 (m, 4H), 0.91 (t, 3H, J = 6.8 Hz)

Pd / C (10%) (3 mg) in an ethanol solution (10 ml) of [5- (1-octynyl) pyrimidin-2-yl] acetonitrile (16 mg, 0.07 mmol) at room temperature and hydrogen atmosphere. Was added, and the mixture was stirred at room temperature for 33 hours. After completion of the reaction, the mixture was filtered through Celite, the filtrate was concentrated, and purified by column chromatography (hexane: ethyl acetate = 4: 1) to obtain (5-octylpyrimidine-2-yl) acetonitrile. Yield 10 mg, yield 60%, yellow liquid.
^{1 1} H-NMR (500 MHz, CDCl ₃ )
δ (ppm): 8.56 (s, 2H), 4.08 (s, 2H), 2.61 (t, 2H, J = 7.6 Hz), 1.63 (quin, 2H, J = 7) .0 Hz), 1.29 (m, 10H), 0.88 (t, 3H, J = 6.9 Hz)

2,5-Difluorobenzene-1,4-dicarbaldehyde (13 mg, 0.08 mmol), (5-octylpyrimidine-2-yl) acetonitrile (35.1 mg, 0.15) at room temperature and nitrogen atmosphere. Sodium ethoxydo (0.08 ml, 0.015 mmol) was added to an ethanol solution (5 ml) of mmol), the mixture was shielded from light, and the mixture was stirred for 1 hour. Then, the mixture was cooled to 0 ° C., methanol was added, and the mixture was filtered and dried to obtain a crude product. The obtained crude product was purified by recrystallization (hexane: chloroform) to obtain the target compound (106). Yield 27 mg, yield 60%, yellow solid.
^{1 1} H-NMR (500 MHz, CDCl ₃ )
δ (ppm): 8.87 (s, 2H), 8.66 (s, 4H), 8.37 (t, 2H, J = 8.25 Hz), 2.67 (t, 4H, J = 7) .60 Hz), 1.67 (quin, 4H, J = 6.75 Hz), 1.29 (m, 10H), 0.89 (t, 6H, J = 6.80 Hz)
¹³ C NMR (126 MHz, CDCl ₃ )
δ (ppm): 158.3, 157.3, 136.7, 135.1, 125.3, 116.4, 115.4, 115.2, 115.0, 31.8, 30.9, 30 .7, 30.3, 29.3, 29.2, 29.0, 22.6, 14.1
MS (EI): m / z = 596
HRMS (EI): Calcd for C ₃₆ H ₄₂ F ₂ N ₆ ; 596.3439, Found; 596.3452
IR (KBr): 2927, 2857, 2227 cm ^-1

Example 7
A silicon wafer (n-doped) with a thermal oxide film of 300 nm is used as a gate electrode and a gate insulating film, and the vapor deposition rate is ^{applied to the surface of the oxide film by a vacuum vapor deposition method (deposited condition: under reduced pressure (about 4.0 × 10-6 torr)).} The compound (45) was formed into a film under the condition that the film thickness was about 50 nm at 0.5 nm / min, substrate temperature: room temperature (about 25 ° C.)) to form an organic semiconductor layer.
By forming a source electrode and a drain electrode having a film thickness of about 50 nm made of Au by a vacuum vapor deposition method on the surface of this organic semiconductor layer using a shadow mask, the above-mentioned embodiment of the shape of FIG. 1 can be obtained. The organic thin film transistor 1 was obtained. The channel length (L) of the formed source electrode and drain electrode is 20 μm, and the channel width (W) is 2 mm.

Example 8
A silicon wafer with a thermal oxide film similar to that in Example 7 was used as a gate electrode and a gate insulating film. This silicon wafer is heated to 80 ° C. on a hot plate with the oxide film facing up, and a chlorobenzene solution (0.5 wt%) of the compound (45) is dropped onto the oxide film surface from above, and a solvent is added. Was dried to form an organic semiconductor layer. The formation of the source electrode and the drain electrode was carried out in the same manner as in Example 7 to produce the organic thin film transistor 2.

Example 9
In Example 7, the organic field effect transistor 3 was produced by performing the same operation except that the compound (61) was used instead of the compound (45).

Example 10
In Example 8, the organic field effect transistor 4 was produced by performing the same operation except that the compound (61) was used instead of the compound (45).

Comparative Example 1
In Example 7, the organic field effect transistor 5 was produced by performing the same operation except that the following compound (H1) was used instead of (45).

Comparative Example 2
In Example 7, the organic field effect transistor 6 was produced by performing the same operation except that the following compound (H2) was used instead of the compound (45).

The organic field effect transistors produced in Examples and Comparative Examples were evaluated.
Using Keithley's 2612A type 2ch system source meter, apply a voltage of 100V between the source and drain electrodes of the organic thin film transistor ^{under vacuum (10-5 torr or less), and set the gate voltage from -20V to 100V.} The transfer characteristics of each organic thin film transistor were evaluated by changing the range. The carrier (electron) mobility of each organic thin film transistor was calculated from the saturation region of the transfer characteristics. Table 1 shows the carrier (electron) mobility of each organic thin film transistor. The organic transistor 6 did not have transfer characteristics.

Example 11
The crystallinity of the organic semiconductor layer in the organic thin film transistor 4 was evaluated by measuring out-of-plane X-ray diffraction. The results are shown in FIG. As a result of FIG. 7, it was confirmed that the diffraction profile showed a fifth-order peak or higher, and the organic semiconductor layer in the organic thin film transistor 4 was a thin film having extremely high crystallinity.

Example 12
An atmospheric operation test was performed on the organic thin film transistor 1. The organic thin film transistor 1 was exposed to the atmosphere, and immediately after that, the characteristics were evaluated, and then the characteristics were evaluated every few hours in the atmosphere as it was. Storage in the air was done in the dark. The characteristic evaluation was carried out by the same method as the above evaluation except that the evaluation was performed in the atmosphere. The result of mobility with respect to air exposure time. It is shown in FIG. As is clear from FIG. 8, the mobility deterioration from the characteristics immediately after exposure to the atmosphere is about 10% in about 300 hours, and it is confirmed that the n-type characteristics are very stable even in the atmosphere.

Comparative Example 3
In Example 12, the same operation was performed except that the organic thin film transistor 5 was used instead of the organic thin film transistor 1, and the characteristics were evaluated by exposure to the atmosphere. The mobility deterioration from the characteristics immediately after exposure to the atmosphere was about 10% in about 24 hours.

Based on the characteristics evaluation results of the organic thin film transistors manufactured in Examples 7 to 10 and Comparative Examples 1 and 2, and the comparison between Example 12 and Comparative Example 3, the organic field effect transistor using the organic semiconductor material of the present invention has high characteristics. It became clear.

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 organic semiconductor Layer 10 Negative

Claims (9)

Including the energy level of the lowest unoccupied molecular orbital (LUMO) expressed by the following general formula (2) and obtained by the structural optimization calculation by the density general function calculation B3LYP / 6-31G (d) is -3.1 eV or less. An organic semiconductor material comprising a nitrogen heterocyclic alkenyl compound.

Here, X ¹¹ , X ¹² , and X ¹³ independently indicate CR or N, and X ¹² and X ¹³ independently indicate 1 to 3 N, and the rest are CR. However, the number of CRs other than CH is at most 1.
R each independently represent a hydrogen atom, a fluorine atom, an unsubstituted alkyl group having a carbon number of 1-12, or an unsubstituted fluoroalkyl group having a carbon number of 1-12.
The ^{number in which X 11} becomes N is at most two, and when ^{any one of X 11} is N, the other X ¹¹ is CH. When ^{all X 11s} are CR, X ¹¹ is CH or CF, and at least one is CF. The organic semiconductor material according to claim 1, wherein the nitrogen-containing heterocyclic alkenyl compound is any compound selected from the compounds represented by the following formulas.

An organic semiconductor film comprising the organic semiconductor material according to claim 1 or 2. A method for producing an organic semiconductor film, which comprises dissolving the organic semiconductor material according to claim 1 or 2 in an organic solvent, and applying and drying the prepared solution to form the organic semiconductor film. The organic semiconductor material according to claim 1 or 2 is dissolved in an organic solvent having a boiling point of 50 ° C. or higher to prepare a solution having a concentration of 0.01 to 10 wt%, which is 30 ° C. to 20 ° C. or lower than the boiling point of the solvent. A method for producing an organic semiconductor film, which comprises applying to a substrate heated to a temperature range and drying the solvent. An organic semiconductor device according to claim 3, wherein the organic semiconductor film is used. An organic thin film transistor using the organic semiconductor film according to claim 3 for a semiconductor layer. The organic thin film transistor according to claim 7, which is an N-type organic thin film transistor or an organic complementary transistor using the N-type organic thin film transistor. An organic photovoltaic device according to claim 3, wherein the organic semiconductor film is used for the semiconductor layer.

Images