WO2012067139A1

WO2012067139A1 - Compound, field-effect transistor and process for production thereof, solar cell and process for production thereof, organic light-emitting element and process for production thereof, and composition

Info

Publication number: WO2012067139A1
Application number: PCT/JP2011/076381
Authority: WO
Inventors: 哲二伊藤; 青森　繁
Original assignee: シャープ株式会社
Priority date: 2010-11-16
Filing date: 2011-11-16
Publication date: 2012-05-24

Abstract

Provided is a compound represented by general formula (1). (In the formula, R¹ represents a C_1-20 aliphatic hydrocarbon group which may have a substituent; and R²-R¹³ independently represent a hydrogen atom, a halogen atom, or an aromatic group or a C_1-20 aliphatic hydrocarbon group each of which may have a substituent.)

Description

COMPOUND, FIELD EFFECT TRANSISTOR AND ITS MANUFACTURING METHOD, SOLAR CELL AND ITS MANUFACTURING METHOD, ORGANIC LIGHT EMITTING DEVICE AND ITS MANUFACTURING METHOD, AND COMPOSITION

The present invention relates to a novel compound, a field effect transistor using the compound and a method for producing the same, a solar cell using the compound and a method for producing the same, an organic light emitting device using the compound and a method for producing the same, and the compound. The present invention relates to a composition for an organic semiconductor layer of a field effect transistor, a composition for an organic semiconductor layer of a solar cell, and a composition for a carrier transport layer of an organic light emitting device.
This application claims priority based on Japanese Patent Application No. 2010-256098 filed in Japan on November 16, 2010, the contents of which are incorporated herein by reference.

Celebrating the ubiquitous information society, flexible, lightweight, and inexpensive devices are required as information terminals. Furthermore, when such an application as an information terminal is assumed, a process capable of quickly responding to not only mass production but also various user requests is required. Such devices and processes cannot sufficiently meet the demand by extending the conventional silicon-based device technology. In recent years, research on electronic device technology using organic materials for semiconductors has been actively conducted as a technology that can meet such demands. Among them, organic electronic devices such as organic transistors (OFETs), organic light emitting diodes (OLEDs), and organic solar cells using organic semiconductor materials have attracted attention and have already been put into practical use.

So far, various compounds having carrier transport properties have been known as organic semiconductor materials used for active layers of semiconductor devices such as field effect transistors (FETs).
For example, Patent Document 1 discloses using pentacene for a semiconductor layer of an organic semiconductor device. Patent Document 2 discloses poly (3-octylthiophene) as a polymer organic semiconductor used for a semiconductor layer of a field effect transistor. Non-Patent Document 1 discloses the use of dihydrodiazapentacene (DHDAP) as a semiconductor layer of an organic FET device. Patent Document 3 discloses that DHDAP into which an alkyl group is introduced is used for the carrier transport layer.

JP 2001-94107 A JP-A-6-177380 US Patent Application Publication No. 2005/0014018

However, since the organic semiconductor materials disclosed in Patent Documents 1 to 3 and Non-Patent Document 1 are easily oxidized in the air atmosphere, the organic semiconductor material may be decomposed during the manufacturing process, or the organic semiconductor in the semiconductor device. Device characteristics may deteriorate as materials deteriorate. For example, pentacene disclosed in Cited Document 1 has a low ionization potential and is easily oxidized in the atmosphere as shown below, resulting in a deterioration in device characteristics. In addition, it has been pointed out that DHDAP disclosed in Non-Patent Document 1 also has a low ionization potential and easily gives diazapentacene (DAP), which is a dehydrogenated oxidation product.

When an organic semiconductor material that is unstable in such an air atmosphere is used for a device, it is conceivable to provide a protective film in order to improve environmental resistance. For example, a technique is disclosed in which a protective film is provided by laminating a silicon oxide film, an alumina film, a silicon nitride film, an epoxy resin film, or the like on the device surface (Japanese Patent Laid-Open No. 2005-191077). However, even if such a protective film is used, the organic semiconductor layer cannot be sufficiently protected against oxygen and moisture in the atmosphere, and the protective film can be formed without damaging the organic semiconductor layer. A material and a method for forming such a protective film are not conventionally known.

On the other hand, a condensed ring compound such as pentacene has low solubility in a solvent. Therefore, when forming a film as a semiconductor layer, it is generally necessary to apply a vacuum deposition method, which is a vacuum process, and the production cost is high. Become. Usually, when an organic semiconductor layer is formed, a method in which a device is manufactured by dissolving an organic semiconductor material in an organic solvent and forming a film by a spin coating method, an inkjet method, or the like using the obtained solution is applied. Compared with the vacuum deposition method, the manufacturing cost can be greatly reduced, and an organic semiconductor device having a large area can be easily manufactured.

As described above, in order to manufacture a semiconductor device having low cost and excellent characteristics, an organic semiconductor material that is highly soluble in a solvent and that stably exists in an air atmosphere from the manufacturing process of the device to after it is manufactured. However, such an organic semiconductor material has not been known so far.
An aspect of the present invention has been made in view of the above circumstances, a novel compound that has high solubility in a solvent and is stable in an air atmosphere and is suitable as an organic semiconductor material, and a semiconductor device using the compound. The issue is to provide.

One embodiment of the present invention provides a compound represented by the following general formula (1).

(Wherein R ¹ is an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms; R ² to R ¹³ each independently has a hydrogen atom, a halogen atom or a substituent. An aromatic group which may be substituted or an aliphatic hydrocarbon group having 1 to 20 carbon atoms.)
Another embodiment of the present invention is the compound, wherein the R ¹ is an alkyl group having 1 to 15 carbon atoms, and the R ² to R ¹³ are each independently a hydrogen atom, a halogen atom, or a carbon number of 1 to 10 The compound which is the alkyl group of may be sufficient.
Another embodiment of the present invention is the compound, wherein the R ¹ is a linear, branched, or cyclic alkyl group having 5 to 9 carbon atoms, and the R ² to R ¹³ are each independently a hydrogen atom. Further, it may be a compound which is a halogen atom or an alkyl group having 1 to 5 carbon atoms.

Another embodiment of the present invention provides a field effect transistor including an organic semiconductor layer including the compound.
Further, one embodiment of the present invention may be a field effect transistor further including a hydrophilic film, wherein the organic semiconductor layer is provided over the hydrophilic film.
In one embodiment of the present invention, the field effect transistor further includes a gate electrode, a gate insulating film, a source electrode, and a drain electrode, and the organic semiconductor layer faces the gate electrode with the gate insulating film interposed therebetween. The field effect transistor may be provided so that the source electrode and the drain electrode are in contact with the organic semiconductor layer.
In one embodiment of the present invention, the field effect transistor further includes a gate electrode, a gate insulating film, a source electrode, and a drain electrode, and the organic semiconductor layer faces the gate electrode with the gate insulating film interposed therebetween. And the organic semiconductor layer may be a field effect transistor provided so as to cover the source electrode and the drain electrode.
One embodiment of the present invention may be the field effect transistor in which the organic semiconductor layer is formed by applying the compound.
One embodiment of the present invention may be the field effect transistor according to the field effect transistor, wherein the organic semiconductor layer is formed by vapor deposition of the compound.
Another embodiment of the present invention is a method for manufacturing a field effect transistor including an organic semiconductor layer containing the compound, and a dipping method, a spin coating method, a casting method, and an inkjet method using the composition containing the compound And the organic semiconductor layer is formed by any one of printing methods, and the composition includes at least one selected from the group consisting of toluene, chlorobenzene, dichlorobenzene, trichlorobenzene, dichloromethane, and chloroform. A manufacturing method is provided.

Another embodiment of the present invention provides a solar cell including an organic semiconductor layer containing the compound.
In one embodiment of the present invention, the solar cell may further include a hydrophilic film, and the organic semiconductor layer may be provided over the hydrophilic film.
In one embodiment of the present invention, in the solar cell, the organic semiconductor layer may be formed by applying the compound.
In one embodiment of the present invention, in the solar cell, the organic semiconductor layer may be formed by vapor deposition of the compound.
Further, one embodiment of the present invention is a method for manufacturing a solar cell including an organic semiconductor layer containing the compound, and a dipping method, a spin coating method, a casting method, an ink jet method, and a method using the composition containing the compound The organic semiconductor layer is formed by any one of printing methods, and the composition includes at least one selected from the group consisting of toluene, chlorobenzene, dichlorobenzene, trichlorobenzene, dichloromethane, and chloroform. I will provide a.
Another embodiment of the present invention is a solar cell including an organic semiconductor layer including a p-type semiconductor material and an n-type semiconductor material, and at least one of the p-type semiconductor material and the n-type semiconductor material includes the compound. May be.

Another embodiment of the present invention provides an organic light-emitting device including a carrier transport layer containing the compound.
In one embodiment of the present invention, the organic light-emitting element may further include a hydrophilic film, and the carrier transport layer may be provided on the hydrophilic film.
In one embodiment of the present invention, in the organic light emitting device, the carrier transport layer may be formed by applying the compound.
In one embodiment of the present invention, in the organic light emitting device, the carrier transport layer may be formed by depositing the compound.
Another embodiment of the present invention is a method for manufacturing an organic light-emitting element including a carrier transport layer containing the compound, and a dipping method, a spin coating method, a casting method, and an inkjet method using the composition containing the compound. And the carrier transport layer is formed by any one of printing methods, and the composition is an organic light emitting device comprising at least one selected from the group consisting of toluene, chlorobenzene, dichlorobenzene, trichlorobenzene, dichloromethane, and chloroform. A manufacturing method is provided.

Another embodiment of the present invention provides a composition for an organic semiconductor layer of a field effect transistor containing the compound.
Another embodiment of the present invention provides a composition for an organic semiconductor layer of a solar cell containing the compound.
Another embodiment of the present invention is a composition for an organic semiconductor layer of a solar cell including a p-type semiconductor material and an n-type semiconductor material, and at least one of the p-type semiconductor material and the n-type semiconductor material includes such a compound. I will provide a.
Another embodiment of the present invention provides a composition for a carrier transport layer of an organic light-emitting device comprising the compound.

According to the aspect of the present invention, a novel compound that is highly soluble in a solvent and stable in the air atmosphere and is suitable as an organic semiconductor material, and a semiconductor device using the compound can be provided.

It is a schematic sectional drawing which illustrates the principal part of the field effect transistor concerning a first embodiment. It is a schematic sectional drawing which illustrates the principal part of the other field effect transistor which concerns on 1st embodiment. It is a schematic sectional drawing which illustrates the principal part of the field effect transistor which concerns on 2nd embodiment. It is a schematic sectional drawing which illustrates the principal part of the field effect transistor which concerns on 3rd embodiment. It is a schematic sectional drawing which illustrates the principal part of the field effect transistor which concerns on 4th embodiment. It is a schematic sectional drawing which illustrates the principal part of the field effect transistor which concerns on 5th embodiment. It is a schematic sectional drawing which illustrates the principal part of the field effect transistor which concerns on 6th embodiment. It is a schematic sectional drawing for demonstrating the manufacturing method of the field effect transistor shown in FIG. It is a schematic sectional drawing for demonstrating the manufacturing method of the field effect transistor shown in FIG. It is a schematic sectional drawing for demonstrating the manufacturing method of the field effect transistor shown in FIG. It is a schematic sectional drawing for demonstrating the manufacturing method of the field effect transistor shown in FIG. It is a schematic sectional drawing for demonstrating the manufacturing method of the field effect transistor shown in FIG. It is a schematic sectional drawing for demonstrating the manufacturing method of the field effect transistor shown in FIG. It is a schematic sectional drawing for demonstrating the manufacturing method of the field effect transistor shown in FIG. It is a schematic sectional drawing for demonstrating the manufacturing method of the field effect transistor shown in FIG. It is a schematic sectional drawing for demonstrating the manufacturing method of the field effect transistor shown in FIG. It is a schematic sectional drawing for demonstrating the manufacturing method of the field effect transistor shown in FIG. It is a schematic sectional drawing for demonstrating the manufacturing method of the field effect transistor shown in FIG. It is a schematic sectional drawing for demonstrating the manufacturing method of the field effect transistor shown in FIG. It is a schematic sectional drawing for demonstrating the manufacturing method of the field effect transistor shown in FIG. It is a schematic sectional drawing for demonstrating the manufacturing method of the field effect transistor shown in FIG. It is a schematic sectional drawing for demonstrating the manufacturing method of the field effect transistor shown in FIG. It is a schematic sectional drawing for demonstrating the manufacturing method of the field effect transistor shown in FIG. It is a schematic sectional drawing for demonstrating the manufacturing method of the field effect transistor shown in FIG. It is a schematic sectional drawing for demonstrating the manufacturing method of the field effect transistor shown in FIG. It is a schematic sectional drawing for demonstrating the manufacturing method of the field effect transistor shown in FIG. It is a schematic sectional drawing which illustrates the principal part of the solar cell concerning this invention. It is a schematic sectional drawing which illustrates the principal part of the other solar cell concerning this invention. It is a schematic sectional drawing for demonstrating the manufacturing method of the solar cell shown in FIG. It is a schematic sectional drawing for demonstrating the manufacturing method of the solar cell shown in FIG. It is a schematic sectional drawing for demonstrating the manufacturing method of the solar cell shown in FIG. It is a schematic sectional drawing for demonstrating the manufacturing method of the solar cell shown in FIG. It is a schematic sectional drawing which illustrates the principal part of the organic light emitting element which concerns on this invention. FIG. 16 is a schematic cross-sectional view for explaining a method for manufacturing the organic light-emitting element shown in FIG. 15. FIG. 16 is a schematic cross-sectional view for explaining a method for manufacturing the organic light-emitting element shown in FIG. 15. FIG. 16 is a schematic cross-sectional view for explaining a method for manufacturing the organic light-emitting element shown in FIG. 15. FIG. 16 is a schematic cross-sectional view for explaining a method for manufacturing the organic light-emitting element shown in FIG. 15. FIG. 16 is a schematic cross-sectional view for explaining a method for manufacturing the organic light-emitting element shown in FIG. 15. FIG. 16 is a schematic cross-sectional view for explaining a method for manufacturing the organic light-emitting element shown in FIG. 15. FIG. 16 is a schematic cross-sectional view for explaining a method for manufacturing the organic light-emitting element shown in FIG. 15. FIG. 2 is a graph showing the results of measurement of absorption intensity immediately after solution preparation and after one month of standing for the solution of compound (1-1) in Example 1. 10 is a graph showing measurement results of gate voltage (Vg) -drain current (Id) characteristics of the field effect transistor manufactured in Example 3.

[First embodiment]
<Compound>
A compound according to one embodiment of the present invention is represented by the following general formula (1) (hereinafter abbreviated as compound (1)) and has a dibenzophenoxazine skeleton.

(Wherein R ¹ is an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms; R ² to R ¹³ each independently has a hydrogen atom, a halogen atom or a substituent. An aromatic group which may be substituted or an aliphatic hydrocarbon group having 1 to 20 carbon atoms.)

In the formula, R ¹ is an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
The aliphatic hydrocarbon group for R ¹ may be either a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, and may be linear, branched, or cyclic.

Examples of the linear or branched saturated aliphatic hydrocarbon group (alkyl group) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert group. -Butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylbutyl group, n-hexyl group, 2-methylpentyl group, 3-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, n-heptyl group, 2-methylhexyl group, 3-methylhexyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3 , 3-dimethylpentyl group, 3-ethylpentyl group, 2,2,3-trimethylbutyl group, n-octyl group, isooctyl group, nonyl group, decyl group Undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl group, eicosyl group and the like. That is, the linear or branched saturated aliphatic hydrocarbon group may have 1 to 20 carbon atoms. In view of the relationship between the carbon number and solubility of the alkyl group, the alkyl group is preferably an alkyl group having 1 to 15 carbon atoms, and more preferably an alkyl group having 5 to 9 carbon atoms. By doing in this way, it can be set as a compound with high solubility with respect to a solvent.
As a report on the relationship between the solubility of the chain length of the alkyl chain introduced into the condensed ring compound having high planarity and J. Am. Chem. Soc. 2007, 129, and 15732. According to this, the solubility is particularly good when the chain length of the alkyl chain is 5 to 9, and it is shown that the solubility decreases as the chain length becomes longer. Accordingly, the alkyl substituent to be introduced preferably has 5 to 9 carbon atoms, and it can be assumed that any carbon number has the same effect on solubility.
Examples of the linear or branched unsaturated aliphatic hydrocarbon group include a vinyl group (ethenyl group), an allyl group (2-propenyl group), a 1-propenyl group, a 1-butenyl group, a 2-butenyl group, In the linear or branched saturated aliphatic hydrocarbon group such as 3-butenyl group, a single bond (C—C) between one or more carbon atoms is a double bond (C ═C) or a triple bond (C≡C) can be exemplified, and the number and position of unsaturated bonds are not particularly limited.

The cyclic aliphatic hydrocarbon group may be monocyclic or polycyclic.
Examples of the cyclic saturated aliphatic hydrocarbon group (cycloalkyl group) include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, tricyclodecyl group, adamantyl Group, tetracyclododecyl group, isobornyl group, norbornyl group and the like.
As the cyclic unsaturated aliphatic hydrocarbon group, a double bond (C—C) between one or more carbon atoms in the cyclic saturated aliphatic hydrocarbon group is an unsaturated bond ( Examples include those substituted with C═C) or triple bonds (C≡C), and the number and position of unsaturated bonds are not particularly limited.
The cyclic aliphatic hydrocarbon group may have 3 to 20 carbon atoms. In view of the relationship between the carbon number of the cyclic aliphatic hydrocarbon group and the solubility, it is preferably a cyclic aliphatic hydrocarbon group having 3 to 15 carbon atoms, and a cyclic aliphatic carbon group having 5 to 9 carbon atoms. More preferably, it is a hydrogen group. By doing in this way, it can be set as a compound with high solubility with respect to a solvent.

In the aliphatic hydrocarbon group for R ¹ , one or more hydrogen atoms may be substituted with a substituent. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; hydroxyl group; mercapto group; nitro group; amino group; alkoxy group; aryl group; alkylamino group; arylamino group; Can be illustrated. The position and number of hydrogen atoms substituted with the substituent are not particularly limited.

Examples of the alkoxy group as the substituent in R ¹ include a monovalent group in which the alkyl group in R ¹ is bonded to an oxygen atom.
The aryl group as the substituent in R ¹ may be monocyclic or polycyclic, and may be a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, or a 2,6-dimethylphenyl group. 2,4,6-trimethylphenyl group, 1-ethylphenyl group, 1-propylphenyl group, 1-butylphenyl group, 1-naphthyl group, 2-naphthyl group, anthryl group and the like.
The alkylamino group as a substituent in R ^1, one or two hydrogen atoms, monovalent group substituted with the same alkyl group and the alkyl group in R ¹ amino group (-NH ₂₎ Can be illustrated.
Examples of the arylamino group as the substituent in R ¹ include a monovalent group in which one or two hydrogen atoms of an amino group (—NH ₂ ) are substituted with the aryl group.
Examples of the acyl group as the substituent in R ¹ include a monovalent group in which the alkyl group or aryl group in R ¹ is bonded to a carbonyl group (—C (═O) —).

R ¹ is preferably a saturated aliphatic hydrocarbon group (alkyl group).

In the formula, each of R ² to R ¹³ is independently a hydrogen atom, a halogen atom, or an optionally substituted aromatic group or an aliphatic hydrocarbon group having 1 to 20 carbon atoms.
Examples of the halogen atom in R ² to R ¹³ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
The aromatic group in R ² to R ¹³ may be monocyclic or polycyclic, and may be any of an aromatic hydrocarbon group (aryl group) and an aromatic heterocyclic group (heteroaryl group).
The aromatic hydrocarbon group for R ² to R ¹³ is the same as the aryl group as a substituent for R ¹ .
The aromatic heterocyclic group in R ² to R ¹³ is not particularly limited as long as it has a hetero atom as an atom constituting the aromatic ring. Examples of the hetero atom include a nitrogen atom, an oxygen atom, a sulfur atom, A selenium atom etc. can be illustrated. Preferred examples of the aromatic heterocyclic group include a pyridyl group, a furyl group, a thienyl group, and a selenothienyl group.

The aliphatic hydrocarbon group for R ² to R ¹³ is the same as the aliphatic hydrocarbon group for R ¹ , preferably a saturated aliphatic hydrocarbon group, and may be linear or branched. preferable. An alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable. By doing so, the influence of repulsion between molecules due to steric hindrance of the substituent can be suppressed.

In the aromatic group or aliphatic hydrocarbon group in R ² to R ¹³ , one or more hydrogen atoms may be substituted with a substituent. The substituent is the same as the substituent in R ¹ .

R ² to R ¹³ are preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an aromatic group having 3 to 12 carbon atoms which may have a substituent.

Specific examples of preferred compound (1) are shown below, but compound (1) is not limited thereto.

Compound (1) is stable even in an air atmosphere, such as high solubility in a solvent and high oxidation resistance. Therefore, as described later, it is particularly suitable as an organic semiconductor material for organic electronic devices (semiconductor devices) such as field effect transistors, solar cells, and organic light emitting elements.
The high oxidation resistance of the compound (1) is presumed to be due to the fact that the main skeleton is a dibenzophenoxazine skeleton, thereby reducing the HOMO level.
The high solubility of the compound (1) in the solvent is presumed to be because R ¹ is bonded to the nitrogen atom constituting the dibenzophenoxazine skeleton.

[Production Method of Compound (1)]
Compound (1) can be produced, for example, by the method shown below.
That is, a compound represented by the following general formula (1a) (hereinafter abbreviated as compound (1a)) and a compound represented by the following general formula (1b) (hereinafter abbreviated as compound (1b)). A step of reacting to synthesize a compound represented by the following general formula (1c) (hereinafter abbreviated as compound (1c)) (hereinafter abbreviated as compound (1c) synthesis step), and compound (1c); And a step of reacting a compound represented by the following general formula (1d) (hereinafter abbreviated as compound (1d)) to synthesize compound (1) (hereinafter abbreviated as compound (1) synthesis step). A compound (1) can be manufactured by the method which has this.

(Wherein R ¹ to R ¹³ are the same as described above; X is a chlorine atom or a bromine atom.)

(Compound (1c) synthesis step)
In the compound (1c) synthesis step, compounds (1a) and (1b) are subjected to a dehydration condensation reaction.
In the compounds (1a) and (1b), R ² to R ¹³ are the same as in the case of the compound (1).
The amount of compound (1a) used is preferably 0.5 to 1.5 times the molar amount of compound (1b).
The dehydration condensation reaction may be performed using a solvent or may be performed without a solvent, but is preferably performed without a solvent from the viewpoint that the reaction can proceed promptly. A solvent will not be specifically limited if it does not react with the raw material to be used.
The dehydration condensation reaction may be performed under normal pressure or reduced pressure. When performed under normal pressure, it is preferably performed in an inert gas atmosphere, and examples of the inert gas include nitrogen gas, argon gas, and helium gas.
What is necessary is just to set reaction temperature suitably according to the kind etc. of raw material to be used. For example, when the reaction is performed without a solvent, the temperature is preferably 150 to 260 ° C.
What is necessary is just to adjust reaction time so that reaction temperature may be considered so that the production amount of a compound (1c) may become the maximum. For example, when the reaction is carried out without a solvent, it is preferably 1 to 24 hours.
After completion of the reaction, post-treatment may be performed as necessary to take out the product compound (1c). Here, “post-treatment” refers to operations such as filtration, concentration, extraction, dehydration, and pH adjustment, and any one of these operations may be performed alone or in combination of two or more. The compound (1c) can be removed by operations such as concentration, crystallization, column chromatography, etc., and operations such as column chromatography, crystallization, extraction, and stirring and washing of the crystals with a solvent can be performed as necessary. Purification may be performed by repeating once or more. Moreover, you may post-process as needed and may perform the next process (compound (1) synthetic | combination process), without taking out a compound (1c).

(Compound (1) synthesis step)
In the compound (1) synthesis step, compounds (1c) and (1d) are reacted to introduce an aliphatic hydrocarbon group into the nitrogen atom of compound (1c).
In compound (1d), R ¹ is the same as in compound (1). X is a chlorine atom or a bromine atom.
The amount of compound (1d) used is preferably 1 to 3 times the molar amount of compound (1c).
When compound (1c) is not taken out, the amount of compound (1d) used should be set in consideration of the amount of compound (1a) used and the reaction rate of compound (1c) in the synthesis step of compound (1c). That's fine.
The reaction is preferably performed in the presence of a base. For example, it is preferable to mix the compound (1c) and a base and then add the compound (1d) to the reaction. The base is preferably a strong base such as sodium hydride (NaH) or n-butyllithium (n-BuLi). Moreover, it is preferable that the usage-amount of a base is the same as the usage-amount of a compound (1d).
The reaction is preferably performed using a solvent, and the solvent is not particularly limited as long as it does not react with the raw material used, but N, N-dimethylformamide (DMF) and the like can be exemplified as a preferable one.
The reaction is preferably performed under anhydrous conditions.
The reaction temperature may be appropriately set according to the type of raw material used, but is preferably 15 to 30 ° C.
The reaction time may be adjusted so as to maximize the amount of compound (1) produced in consideration of the reaction temperature, but it is preferably 1 to 12 hours.
After completion of the reaction, as in the case of the compound (1c) synthesis step, post-treatment may be performed as necessary to take out the target compound (1).

The structure of compound (1), compound (1c), etc. can be confirmed by a known method such as nuclear magnetic resonance spectroscopy ( ¹ H-NMR, ¹³ C-NMR).

<Composition for organic semiconductor layer of field effect transistor>
The composition for organic semiconductor layers of a field effect transistor according to one embodiment of the present invention includes the compound (1).
As described above, compound (1) has high solubility in a solvent. Therefore, the composition for an organic semiconductor layer of the present embodiment in which the compound (1) is dissolved in a solvent can be easily prepared. By using such a composition, the organic semiconductor layer of the field effect transistor can be formed by a dipping method, a spin method, or the like. It can be formed by a simple method such as a coating method, a casting method, an ink jet method, or a printing method. The organic semiconductor layer may be formed by depositing the compound (1) by a vacuum deposition method or the like. However, the manufacturing cost of the field effect transistor can be significantly reduced by simply forming a film without using a vacuum apparatus or the like as described above. In particular, a method of forming the organic semiconductor layer by applying the composition (compound (1)) is suitable.

The composition for an organic semiconductor layer of the present embodiment preferably contains a hydrocarbon such as toluene or a halogenated hydrocarbon such as dichloromethane, chloroform, chlorobenzene, dichlorobenzene, or trichlorobenzene, or a mixture thereof as a solvent component. For example, the composition for organic semiconductor layers may contain at least one of toluene, chlorobenzene, dichlorobenzene, trichlorobenzene, dichloromethane, and chloroform as a solvent component.

Further, the composition for an organic semiconductor layer may contain only the compound (1) in addition to the solvent component, or may contain a component other than the compound (1). However, the ratio of the compound (1) to all components other than the solvent component is preferably 90% by mass or more, and more preferably 100% by mass (including only the compound (1)).

The compound (1) contained in the composition for organic semiconductor layers may be one kind or two or more kinds. In the case of two or more kinds, the combination and ratio may be appropriately set according to the purpose.
In the composition for an organic semiconductor layer, the content of the compound (1) is preferably 0.2 to 5% by mass.

<Composition for organic semiconductor layer of solar cell>
The composition for an organic semiconductor layer of a solar cell according to one embodiment of the present invention is the same as the composition for an organic semiconductor layer of the above-described field effect transistor except that it contains the compound (1) and has a different use. For example, the composition for an organic semiconductor layer of this embodiment in which the compound (1) is dissolved in a solvent can be easily prepared, and the organic semiconductor layer of a solar cell can be formed by a simple method by using such a composition. .

In addition, another embodiment of the composition for an organic semiconductor layer according to one aspect of the present invention includes a p-type semiconductor material and an n-type semiconductor material, and the p-type semiconductor material and / or the n-type semiconductor material is Compound (1) is included.
Since the composition for organic semiconductor layers of this embodiment can be easily prepared by dissolving the compound (1) in a solvent, the organic semiconductor layer for solar cells is similar to the organic semiconductor layer composition for field effect transistors described above. Can be formed by a simple method. The organic semiconductor layer of the solar cell may be formed by vapor-depositing the compound (1) by a vacuum vapor deposition method or the like, but by simply forming a film without using a vacuum device or the like, the manufacturing cost of the solar cell can be reduced. In particular, a method of forming the organic semiconductor layer by applying the composition (compound (1)) is suitable.

The p-type semiconductor material and / or the n-type semiconductor material may be composed only of the compound (1) or may contain components other than the compound (1). However, the ratio of the compound (1) to the semiconductor material is preferably 90% by mass or more, and more preferably 100% by mass (consisting only of the compound (1)).
The compound (1) contained in the semiconductor material may be one kind or two or more kinds. In the case of two or more kinds, the combination and ratio may be appropriately set according to the purpose.

Examples of the n-type semiconductor material that does not contain the compound (1) include those exemplified as the material of the n-type semiconductor layer in the solar cell described later. Specifically, fullerene; [6,6] -phenyl is preferable. Examples include fullerene derivatives such as C61 butyric acid methyl ester (PCBM); fluorinated phthalocyanines in which one or more hydrogen atoms constituting the phthalimide ring are substituted with fluorine atoms. In the fluorinated phthalocyanine, all hydrogen atoms constituting the phthalimide ring may be substituted with fluorine atoms.

The organic semiconductor layer composition preferably contains, as a solvent component, a hydrocarbon such as toluene or a halogenated hydrocarbon such as dichloromethane, chloroform, chlorobenzene, dichlorobenzene, or trichlorobenzene, or a mixture thereof. For example, the composition for organic semiconductor layers may contain at least one of toluene, chlorobenzene, dichlorobenzene, trichlorobenzene, dichloromethane, and chloroform as a solvent component.

In the composition for an organic semiconductor layer, the content of the p-type semiconductor material is preferably 0.2 to 5% by mass. Similarly, the content of the n-type semiconductor material is preferably 0.2 to 5% by mass.

<Composition for carrier transport layer>
The composition for a carrier transport layer according to one embodiment of the present invention is the same as the composition for an organic semiconductor layer of the above-described field effect transistor except that it contains the compound (1) and has a different use. For example, the carrier transport layer composition of the present embodiment in which the compound (1) is dissolved in a solvent can be easily prepared. By using such a composition, the carrier transport layer of the organic light emitting device can be formed by a simple method. it can.

<Field effect transistor>
The field effect transistor which concerns on 1 aspect of this invention is equipped with the organic-semiconductor layer containing a compound (1). And it can be set as the structure similar to the conventional field effect transistor except having provided this organic-semiconductor layer. Here, the compound (1) is mainly used as a p-type semiconductor, but functions as an n-type semiconductor when a substituent having a strong electron-withdrawing property such as a fluorine atom is introduced or depending on the selection of an electrode material. It is also possible to make it. Hereinafter, description will be given with reference to the drawings.

FIG. 1 is a schematic cross-sectional view illustrating the main part of the field effect transistor according to the first embodiment.
The field effect transistor 1 </ b> A shown here is schematically configured by laminating a gate electrode 12, a gate insulating film 13, a source electrode 14, a drain electrode 15, and an organic semiconductor layer 16 on a substrate 11. More specifically, the gate electrode 12 is provided on a part of the substrate 11. Further, a gate insulating film 13 is provided on the substrate 11 so as to cover the gate electrode 12. On the gate insulating film 13, a source electrode 14 and a drain electrode 15 are provided apart from each other. Further, an organic semiconductor layer 16 is provided on the gate insulating film 13 so as to cover the source electrode 14 and the drain electrode 15. The organic semiconductor layer 16 is provided so as to face the gate electrode 12 with the gate insulating film 13 interposed therebetween. The field effect transistor 1A has a bottom-gate / bottom-contact transistor structure.

The material of the substrate 11 can be appropriately selected according to the configuration and performance of the device. For example, glass, quartz, silicon single crystal, polycrystalline silicon, amorphous silicon; high insulation such as polyimide, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polytetrafluoroethylene Examples thereof include molecular compounds.
The substrate 11 may have a single layer structure made of one kind of material, or may have a multiple layer structure in which two or more kinds of materials are laminated.

The material of the gate electrode 12 is not particularly limited, and may be one normally used in the field. Specifically, low resistance metals such as gold, platinum, silver, copper, aluminum, tantalum, and doped silicon; 3,4-polyethylenedioxythiophene (hereinafter abbreviated as PEDOT) / polystyrene sulfonate (hereinafter, referred to as “PETOT”) Examples thereof include organic conductors such as PSS).

The material of the source electrode 14 and the drain electrode 15 is close to the highest occupied molecular orbital (HOMO) level or the lowest unoccupied molecular orbital (LUMO) level of the composition for the organic semiconductor layer. The thing can be illustrated.
Materials close to the HOMO level include metals with relatively high work functions such as gold, platinum, silver, or alloys containing one or more of these; transparent oxides such as indium tin oxide (ITO) and zinc oxide (ZnO) Physical conductors: Organic conductors such as PEDOT / PSS can be exemplified.
Examples of the material close to the LUMO level include metals having a relatively low work function such as aluminum, titanium, alkali metals, or alloys containing one or more of these. Examples of the alkali metal include lithium, sodium, and potassium.

The source electrode 14 and the drain electrode 15 may be formed on the gate insulating film 13 through an adhesion layer (not shown). Examples of the material for the adhesion layer include chromium.

The thicknesses of the gate electrode 12, the source electrode 14, and the drain electrode 15 are not particularly limited as long as they are normal transistor thicknesses, and are preferably adjusted as appropriate according to the purpose.
For example, when the material is a metal, it is preferably 30 nm to 200 nm.
These electrodes can be formed, for example, by vapor deposition, sputtering, coating, or the like depending on the material.

The material of the gate insulating film 13 is preferably a material having a high dielectric constant and hardly causing defects such as pinholes when forming a thin film. Since the dielectric constant is high, the threshold value of the field effect transistor can be further reduced. In addition, by reducing defects such as pinholes when forming a thin film, a function effect of the gate insulating film 13 is suppressed and a field effect transistor with better characteristics can be obtained.
Examples of such films include inorganic insulating films such as silicon oxide films, silicon nitride films, tantalum pentoxide films, and aluminum oxide films; organic insulating films such as polyimide films, parylene films, and polyvinylphenol films.
The film thickness of the gate insulating film 13 is preferably set so that the capacitance per unit area is increased, and the threshold voltage of the field effect transistor can be further reduced by reducing the film thickness. The film thickness of the gate insulating film 13 is preferably adjusted as appropriate according to the relative dielectric constant, insulation, etc. of the material, and is preferably 50 nm to 300 nm, for example. By doing so, the capacitance per unit area can be increased, and the threshold voltage of the field effect transistor can be reduced.
The gate insulating film 13 can be formed by, for example, vapor deposition, sputtering, coating, or the like depending on the material.

When the gate insulating film 13 is a silicon oxide film, a silicon nitride film or the like, the surface in contact with the organic semiconductor layer 16 is preferably treated with a silane coupling agent or the like. By doing in this way, the grain of the crystal | crystallization of the organic-semiconductor layer 16 which contact | connects the gate insulating film 13 can be enlarged, and the mobility of an organic-semiconductor element can be improved more.

The organic semiconductor layer 16 includes the compound (1). For example, it may be formed by applying a composition containing the compound (1), or by using the composition for an organic semiconductor layer described above, a dipping method, a casting method, a spin coating method, an inkjet method. It may be formed by a low-cost thin film forming method such as a printing method or a printing method, or may be formed by depositing the compound (1) by a vacuum vapor deposition method or the like.
As described above, the compound (1) has high oxidation resistance. Therefore, the organic semiconductor layer 16 containing the compound (1) is stable in the air atmosphere.

The organic semiconductor layer 16 is preferably provided on a hydrophilic film. By doing so, the film quality of the organic semiconductor layer 16 can be made more uniform. In particular, when the organic semiconductor layer 16 is formed by applying the composition for an organic semiconductor layer, a remarkable effect is obtained. can get. Here, the “hydrophilic film” refers to a film having a hydrophilic group on the surface.
As shown in FIG. 1, when the organic semiconductor layer 16 is formed on the gate insulating film 13, a hydrophilic film may be separately provided on the gate insulating film 13. At least the surface itself may be hydrophilic. Examples of the material of the hydrophilic film in this case include metal oxide insulators such as a silicon oxide film and an aluminum oxide film; hydrophilic polymers such as polyethylene glycol, polyacrylic acid, and polyvinyl alcohol.

In the field effect transistor 1A, a protective film may be further provided on at least the organic semiconductor layer 16. By providing the protective film, the organic semiconductor layer 16 can be protected from erosion by oxygen, moisture, or the like, so that the field effect transistor 1A exhibits more stable semiconductor characteristics.

A field effect transistor 1A ′ shown in FIG. 2 is obtained by covering the entire surface of the organic semiconductor layer 16 with a protective film 17 in the field effect transistor shown in FIG.
The protective film 17 may be either an organic film or an inorganic film.
As the material of the organic film, polyparylene (paraxylylene polymer); epoxy resin; acrylic resin; polyparaxylene; polyperfluoroolefin, polyperfluoroether, polytetrafluoroethylene, polychlorotrifluoroethylene, polydichlorodifluoroethylene, etc. Examples of the fluorine-based polymer; polyimide and the like.
Examples of the material of the inorganic film include metal nitride, metal oxide, carbon, silicon and the like. More specifically, nitrides such as SiN, AlN, and GaN; oxides such as SiO, Al ₂ O ₃ , Ta ₂ O ₅ , ZnO, and GeO; oxynitrides such as SiON; carbonitrides such as SiCN, and the like And the metal is preferably silicon.
The protective film 17 may have either a single layer structure or a multilayer structure.

[Second Embodiment]
FIG. 3 is a schematic cross-sectional view illustrating the main part of the field effect transistor according to the second embodiment. In FIG. 3, the same components as those shown in FIG. 1 are denoted by the same reference numerals as those in FIG. 1, and detailed description thereof is omitted. The same applies to the following drawings.
The field effect transistor 1B shown here is shown in FIG. 1 except that the surface modification layer 18 is provided on the surface of the source electrode 14 and the drain electrode 15 and the organic semiconductor layer 16 is in contact with the surface modification layer 18. This is the same as the field effect transistor 1A shown. The surface modification layer 18 can be formed by, for example, causing a surface modifier to act on the surfaces of the source electrode 14 and the drain electrode 15 and may be composed of either an organic molecule or an inorganic molecule.

The surface modification layer 18 is preferably a hydrophilic film. By doing so, the film quality of the organic semiconductor layer 16 can be made more uniform. In particular, when the organic semiconductor layer 16 is formed by placing the above composition for an organic semiconductor layer, a remarkable effect is obtained. It is done.

Here, an example in which a hydrophilic film is separately provided as the surface modification layer 18 on the source electrode 14 and the surface of the drain electrode 15 is shown. However, in order for the organic semiconductor layer 16 to be in contact with the hydrophilic film. For example, at least the surfaces of the source electrode 14 and the drain electrode 15 may be hydrophilic. In the present embodiment, the hydrophilic film is preferably provided separately by modifying the surfaces of the source electrode 14 and the drain electrode 15 by surface treatment.
In the present embodiment, examples of the hydrophilic group possessed by the hydrophilic film include a hydroxyl group, an amino group, a carboxyl group, a sulfonic acid group, and a phosphoric acid group.

[Third embodiment]
FIG. 4 is a schematic cross-sectional view illustrating the main part of the field effect transistor according to the third embodiment.
The field effect transistor 1 </ b> C shown here is schematically configured by laminating a gate electrode 12, a gate insulating film 13, an organic semiconductor layer 16, a source electrode 14 and a drain electrode 15 on a substrate 11. More specifically, the gate electrode 12 is provided on a part of the substrate 11. Further, a gate insulating film 13 is provided on the substrate 11 so as to cover the gate electrode 12. An organic semiconductor layer 16 is provided on the gate insulating film 13. A source electrode 14 and a drain electrode 15 are provided on the organic semiconductor layer 16 so as to be separated from each other. The organic semiconductor layer 16 is provided so as to face the gate electrode 12 with the gate insulating film 13 interposed therebetween. The field effect transistor 1C has a top contact type transistor structure.

The film quality of the organic semiconductor layer 16 may be affected by a layer (underlying layer) immediately below the organic semiconductor layer 16. For example, in the case of a bottom gate / bottom contact field effect transistor (field effect transistor 1A) as shown in FIG. 1, the organic semiconductor layer 16 is affected by the gate insulating film 13, the source electrode 14 and the drain electrode 15 in contact therewith. In response, there is a possibility that the film quality will change at the site in contact with each.
On the other hand, in the case of a field effect transistor (field effect transistor 1C) having a top contact type structure as shown in FIG. 4, since the organic semiconductor layer 16 is entirely formed on the gate insulating film 13, the organic semiconductor The film quality of the layer 16 becomes more uniform, and the field effect transistor exhibits more stable semiconductor characteristics.
Further, in the case of a field effect transistor (field effect transistor 1C) having a top contact type structure as shown in FIG. 4, since the source electrode 14 and the drain electrode 15 are formed on the organic semiconductor layer 16, for example, a gate is formed at the time of manufacture. It is possible to reduce damage to the insulating film 13 and generation of residues. As a result, the interface between the gate insulating film 13 and the organic semiconductor layer 16 can be in a better state.

The field effect transistor 1C is the same as the field effect transistor 1A except that the stacking order of the source electrode 14, the drain electrode 15, and the organic semiconductor layer 16 is different. Therefore, for example, a protective film may be provided on the organic semiconductor layer 16 so as to cover the source electrode 14 and the drain electrode 15.

[Fourth embodiment]
FIG. 5 is a schematic cross-sectional view illustrating the main part of the field effect transistor according to the fourth embodiment.
The field effect transistor 1D shown here is the same as the field effect transistor 1C shown in FIG. 4 except that a hydrophilic film 13 ′ is provided as the gate insulating film 13. That is, in the field effect transistor 1D, the organic semiconductor layer 16 is in contact with the hydrophilic film 13 ′. By doing in this way, the film quality of the organic-semiconductor layer 16 can be made more uniform similarly to the case of the field effect transistor 1A.
The hydrophilic film 13 ′ can be made of a hydrophilic polymer such as polyethylene glycol, polyacrylic acid, or polyvinyl alcohol.

[Fifth embodiment]
The field effect transistor according to one embodiment of the present invention is not limited to the one shown in FIGS. 1 to 5, and a part of these structures may be changed. For example, the following are mentioned.
(I) As illustrated in FIG. 6, the organic semiconductor layer 16 is provided on the substrate 11, and the source electrode 14 and the drain electrode 15 are provided on the organic semiconductor layer 16 so as to be separated from each other, and the source electrode 14 and the drain electrode are provided. A field effect transistor 1E in which a gate insulating film 13 and a gate electrode 12 are provided in this order on an organic semiconductor layer 16 between 15 layers.
(II) As illustrated in FIG. 7, the source electrode 14 and the drain electrode 15 are provided separately on the substrate 11, and the organic semiconductor layer 16 is formed on the substrate 11 so as to cover the source electrode 14 and the drain electrode 15. A field effect transistor 1F in which a gate insulating film 13 is provided on the organic semiconductor layer 16, and a gate electrode 12 is provided on a part of the gate insulating film 13.

In the field effect transistor according to one embodiment of the present invention, since the organic semiconductor layer is stable in an air atmosphere, the field effect transistor can operate stably for a long period of time in the air atmosphere as well.

[Sixth embodiment]
The field effect transistor according to one embodiment of the present invention can be manufactured, for example, by the following method.
First, a method for manufacturing the field effect transistor 1A shown in FIG. 1 will be described. 8A to 8E are schematic cross-sectional views for explaining a method for manufacturing the field effect transistor 1A.

A film made of the material constituting the gate electrode 12 is formed on the substrate 11, and the film is formed into a desired pattern by photolithography and etching. As shown in FIG. A gate electrode 12 is formed. An example of the film formation method is a sputtering method.

Next, as shown in FIG. 8B, a gate insulating film 13 is formed on the substrate 11 so as to cover the gate electrode 12. An example of a method for forming the gate insulating film 13 is a sputtering method.

Next, after a resist film is formed on the gate insulating film 13 by spin coating or the like, exposure and development are performed by photolithography, thereby forming a photoresist film 90 having a predetermined pattern as shown in FIG. 8C. Form. The photoresist film 90 is for forming the source electrode 14 and the drain electrode 15 and has openings corresponding to these shapes.

Next, a metal film made of the material of the source electrode 14 and the drain electrode 15 is formed on the gate insulating film 13 so as to cover the photoresist film 90, and the photoresist film 90 is removed, as shown in FIG. 8D. Then, the source electrode 14 and the drain electrode 15 are formed at predetermined positions on the gate insulating film 13. At this time, before forming the metal film, an adhesion layer (not shown) is formed on the gate insulating film 13 so as to cover the photoresist film 90, and the metal film is formed on the adhesion layer. May be. Examples of the material for the adhesion layer include metals such as chromium. An example of a method for forming the metal film and the adhesion layer is a vacuum deposition method. When the metal film formed on the photoresist film 90 and further an adhesion layer are formed by removing the photoresist film 90, the adhesion layer is also removed together with the photoresist film 90. An example of a method for removing the photoresist film 90 is a lift-off method in which the substrate 11 is immersed in an organic solvent such as acetone.

Next, as shown in FIG. 8E, an organic semiconductor layer 16 is formed on the gate insulating film 13 so as to cover the source electrode 14 and the drain electrode 15. For example, the organic semiconductor layer 16 may be formed by placing the composition for an organic semiconductor layer of the above-described field effect transistor containing the compound (1) on the gate insulating film 13 and further removing the solvent by drying as necessary. Can be formed. Examples of the method for forming the organic semiconductor layer 16 using the composition include an immersion method, a spin coating method, a casting method, an ink jet method, and a printing method. Examples of the printing method include a micro contact printing method, a reverse offset printing method, a flexographic printing method, a lithographic printing method, and an intaglio printing method. The organic semiconductor layer 16 may be formed by vapor-depositing the compound (1) by a vacuum vapor deposition method or the like.

By performing the above steps, the field effect transistor 1A shown in FIG. 1 is obtained. At this time, the protective film 17 is further formed on the organic semiconductor layer 16 to obtain the field effect transistor 1A 'shown in FIG.

Next, a manufacturing method of the field effect transistor 1B shown in FIG. 3 will be described. 9A to 9F are schematic cross-sectional views for explaining a method of manufacturing the field effect transistor 1B.
A source electrode 14 and a drain electrode 15 are formed at predetermined positions on the gate insulating film 13 by a method similar to the method described with reference to FIGS. 8A to 8D, as shown in FIGS. 9A to 9D.

Next, as shown in FIG. 9E, a surface modifying layer 18 is formed by applying a surface modifying agent to the surfaces of the source electrode 14 and the drain electrode 15.

Next, as shown in FIG. 9F, an organic semiconductor layer 16 is formed on the gate insulating film 13 so as to cover the surface-modified source electrode 14 and drain electrode 15. The formation method of the organic semiconductor layer 16 is the same as that of the field effect transistor 1A. For example, by making the surface modification layer 18 hydrophilic, the film quality of the organic semiconductor layer 16 becomes more uniform.

By performing the above steps, the field effect transistor 1B shown in FIG. 3 is obtained. At this time, a protective film may be further formed on the organic semiconductor layer 16.

Next, a method for manufacturing the field effect transistor 1C shown in FIG. 4 will be described. 10A to 10D are schematic cross-sectional views for explaining a method of manufacturing the field effect transistor 1C.
A film made of a material constituting the gate electrode 12 is formed on the substrate 11, and the film is formed into a desired pattern by photolithography and etching. As shown in FIG. A gate electrode 12 is formed. An example of the film formation method is a sputtering method.

Next, as shown in FIG. 10B, a gate insulating film 13 is formed on the substrate 11 so as to cover the gate electrode 12. An example of a method for forming the gate insulating film 13 is a sputtering method.

Next, as shown in FIG. 10C, an organic semiconductor layer 16 is formed on the gate insulating film 13. The organic semiconductor layer 16 can be formed, for example, by placing the composition for an organic semiconductor layer containing the compound (1) on the gate insulating film 13 and further removing the solvent by drying as necessary. Examples of the method for forming the organic semiconductor layer 16 using the composition include an immersion method, a spin coating method, a casting method, an ink jet method, and a printing method. Examples of the printing method are the same as those described above. The organic semiconductor layer 16 may be formed by vapor-depositing the compound (1) by a vacuum vapor deposition method or the like.

Next, as shown in FIG. 10D, the source electrode 14 and the drain electrode 15 are formed on the organic semiconductor layer 16 by a vacuum deposition method or the like through a metal mask (not shown) having a predetermined opening.

By performing the above steps, the field effect transistor 1C shown in FIG. 4 is obtained. At this time, a protective film may be further formed on the organic semiconductor layer 16 so as to cover the source electrode 14 and the drain electrode 15.

Next, a method for manufacturing the field effect transistor 1D shown in FIG. 5 will be described. 11A to 11D are schematic cross-sectional views for explaining a method for manufacturing the field effect transistor 1D.
A gate electrode 12 is formed at a predetermined position on the substrate 11 as shown in FIG. 11A by a method similar to the method described with reference to FIG. 10A.

Next, as shown in FIG. 11B, a hydrophilic film 13 ′ is formed on the substrate 11 so as to cover the gate electrode 12. As a method for forming the hydrophilic film 13 ′, a spin coating method can be exemplified.

Next, as shown in FIG. 11C, an organic semiconductor layer 16 is formed on the hydrophilic film 13 ′. The organic semiconductor layer 16 can be formed by a method similar to the method described with reference to FIG. 10C. The film quality of the organic semiconductor layer 16 becomes more uniform on the hydrophilic film 13 '.

Next, as shown in FIG. 11D, the source electrode 14 and the drain electrode 15 are formed on the organic semiconductor layer 16. The source electrode 14 and the drain electrode 15 can be formed by a method similar to the method described with reference to FIG. 10D.

By performing the above steps, the field effect transistor 1D shown in FIG. 5 is obtained. At this time, a protective film may be further formed on the organic semiconductor layer 16 so as to cover the source electrode 14 and the drain electrode 15.

<Solar cell>
The solar cell which concerns on 1 aspect of this invention is equipped with the organic-semiconductor layer containing the said compound (1). And it can be set as the structure similar to the conventional solar cell except having provided this organic-semiconductor layer. Here, the compound (1) is mainly used as a p-type semiconductor, but functions as an n-type semiconductor when a substituent having a strong electron-withdrawing property such as a fluorine atom is introduced or depending on the selection of an electrode material. It is also possible to make it. Hereinafter, description will be given with reference to the drawings.

FIG. 12 is a schematic cross-sectional view illustrating the main part of the solar cell according to the present invention.
In the solar cell 2A shown here, an anode electrode 22, a p-type semiconductor layer 24, an n-type semiconductor layer 25, and a cathode electrode 23 are laminated in this order on a glass substrate 21, and is schematically configured.
That is, a pair of electrodes including an anode electrode 22 and a cathode electrode 23 and a pn junction p-type semiconductor layer 24 and an n-type semiconductor layer 25 sandwiched between the pair of electrodes are provided on the glass substrate 21. It is what was done.

The p-type semiconductor layer 24 contains the compound (1). And, for example, it may be formed by applying a composition containing the compound (1), or by using the above-mentioned composition for p-type semiconductor layer, a dipping method, a casting method, a spin coating method, It may be formed by a low-cost thin film forming method such as an inkjet method or a printing method, or may be formed by depositing the compound (1) by a vacuum vapor deposition method or the like.
The film thickness of the p-type semiconductor layer 24 is preferably 5 nm to 500 nm.
As described above, the compound (1) has high oxidation resistance. Therefore, the p-type semiconductor layer 24 containing the compound (1) is stable in the air atmosphere.

The p-type semiconductor layer 24 is preferably provided on a hydrophilic film. That is, it is preferable that a hydrophilic film is provided on the surface of the anode electrode 22 on the p-type semiconductor layer 24 side. By doing so, the film quality of the p-type semiconductor layer 24 can be made more uniform, particularly when the p-type semiconductor layer 24 is formed by applying the p-type semiconductor layer composition. Effects can be obtained. Here, the “hydrophilic film” is the same as in the case of the above-described field effect transistor, and can be formed by the same method.

Examples of the material of the n-type semiconductor layer 25 that does not include the compound (1) include fullerenes, fullerene derivatives, and fluorinated phthalocyanines exemplified for the n-type semiconductor material.
The film thickness of the n-type semiconductor layer 25 is preferably 5 nm to 500 nm.

Examples of the material of the anode electrode 22 include ITO, which is a transparent electrode, and PEDOT / PSS, which is an organic conductor.
The film thickness of the anode electrode 22 is preferably 10 nm to 500 nm.

Examples of the material of the cathode electrode 23 include silver and aluminum.
The film thickness of the cathode electrode 23 is preferably 10 nm to 500 nm.

In addition, another embodiment of the solar cell according to the present invention includes an organic semiconductor layer including a p-type semiconductor material and an n-type semiconductor material, and the p-type semiconductor material and / or the n-type semiconductor material includes the compound ( 1). That is, it is a so-called bulk heterojunction organic thin film solar cell. FIG. 13 is a schematic cross-sectional view illustrating the main part of such a solar cell.
In the solar cell 2B shown here, an anode electrode 22, an organic semiconductor layer 26, and a cathode electrode 23 are laminated in this order on a glass substrate 21, and is roughly configured. That is, a pair of electrodes including an anode electrode 22 and a cathode electrode 23 and an organic semiconductor layer 26 sandwiched between the pair of electrodes are provided on the glass substrate 21.
The organic semiconductor layer 26 can be formed by the same method as in the case of the p-type semiconductor layer 24 in the solar cell 2A, for example, using the composition for an organic semiconductor layer of the solar cell.

In the solar cell according to the present invention, since the organic semiconductor layer is stable in the air atmosphere, the solar cell can operate stably over a long period of time in the air atmosphere as well.

The solar cell which concerns on 1 aspect of this invention can be manufactured with the following method, for example.
14A to 14D are schematic cross-sectional views for explaining a method for manufacturing the solar cell 2A.
First, as shown in FIG. 14A, the anode electrode 22 is formed on the glass substrate 21.
Examples of the method for forming the anode electrode 22 include a sputtering method.

Next, as shown in FIG. 14B, a p-type semiconductor layer 24 is formed on the anode electrode 22. The p-type semiconductor layer 24 can be formed, for example, by placing the above-mentioned composition for a p-type semiconductor layer containing the compound (1) on the anode electrode 22 and further removing the solvent by drying as necessary. . The method for forming the p-type semiconductor layer 24 using the composition is the same as the method for forming the organic semiconductor layer using the composition for organic semiconductor layer at the time of manufacturing the field effect transistor. Examples thereof include a method, a casting method, an ink jet method, and a printing method. The p-type semiconductor layer 24 may be formed by vapor-depositing the compound (1) by a vacuum vapor deposition method or the like.

Next, as shown in FIG. 14C, an n-type semiconductor layer 25 is formed on the p-type semiconductor layer 24. An example of a method for forming the n-type semiconductor layer 25 is a vacuum deposition method.

Next, as shown in FIG. 14D, the cathode electrode 23 is formed on the n-type semiconductor layer 25. An example of a method for forming the cathode electrode 23 is a vacuum vapor deposition method.
By performing the above steps, a solar cell 2A shown in FIG. 14D is obtained. At this time, a protective film may be further formed on the cathode electrode 23. This protective film may be the same as that used in the above-described field effect transistor.

<Organic light emitting device>
The organic light emitting device according to one embodiment of the present invention includes a carrier transport layer containing the compound (1). And it can be set as the structure similar to the conventional organic light emitting element except having provided this carrier transport layer. Here, the compound (1) is mainly used as a p-type semiconductor. However, depending on the introduction of a substituent having a strong electron-withdrawing property such as a fluorine atom or the selection of an electrode material, an n-type semiconductor (electron It is also possible to function as a transport layer. Hereinafter, description will be given with reference to the drawings.

FIG. 15 is a schematic cross-sectional view illustrating the main part of the organic light-emitting element according to one embodiment of the present invention.
The organic light emitting element 3A shown here is schematically configured by laminating an anode electrode 32, an organic electroluminescence (hereinafter abbreviated as organic EL) portion 34, and a cathode electrode 33 in this order on a glass substrate 31. That is, a pair of electrodes including an anode electrode 32 and a cathode electrode 33 and an organic EL portion 34 sandwiched between the pair of electrodes are provided on a glass substrate 31.

The anode electrode 32 and the cathode electrode 33 are the same as the anode electrode and the cathode electrode in the solar cell, respectively.

The organic EL section 34 is constructed by laminating a carrier injection layer 34a, a carrier transport layer 34b, a light emitting layer 34c, an electron transport layer 34d, and an electron injection layer 34e in this order from the anode electrode 32 side to the cathode electrode 33 side. Has been.
The carrier injection layer 34a, the carrier transport layer 34b, the light emitting layer 34c, the electron transport layer 34d, and the electron injection layer 34e may each have a single layer structure or a multilayer structure.

The carrier transport layer 34b contains the compound (1). For example, it may be formed by applying a composition containing the compound (1), or by using the above carrier transport layer composition, a dipping method, a casting method, a spin coating method, an inkjet method. It may be formed by a low-cost thin film forming method such as a printing method or a printing method, or may be formed by depositing the compound (1) by a vacuum vapor deposition method or the like.
The film thickness of the carrier transport layer 34b is preferably 5 nm to 500 nm.
As described above, the compound (1) has high oxidation resistance. Therefore, the carrier transport layer 34b containing the compound (1) is stable in the air atmosphere.

The carrier transport layer 34b is preferably provided on a hydrophilic film. That is, it is preferable that a hydrophilic film is provided on the surface of the carrier injection layer 34a on the carrier transport layer 34b side. By doing so, the film quality of the carrier transport layer 34b can be made more uniform. In particular, when the carrier transport layer 34b is formed by applying the above-described composition for the carrier transport layer, a remarkable effect can be obtained. can get. Here, the “hydrophilic film” is the same as in the case of the above-described field effect transistor, and can be formed by the same method.

In the carrier injection layer 34a, the carrier injection material may be a known material for organic EL or organic photoconductor. Preferred carrier injection materials include oxides such as vanadium oxide (V ₂ O ₅ ) and molybdenum oxide (MoO ₂ ) and inorganic p-type semiconductor materials; polyaniline (PANI), polyaniline-camphor sulfonic acid (PANI-CSA), 3 , 4-polyethylenedioxythiophene / polystyrene sulfonate (PEDOT / PSS), poly (triphenylamine) derivative (Poly-TPD), polyvinylcarbazole (PVCz), poly (p-phenylene vinylene) (PPV), poly ( Examples thereof include polymer materials such as p-naphthalene vinylene) (PNV).
The material applied to the carrier injection layer 34a is the highest occupied molecular orbital (HOMO) than the carrier injection / transport material applied to the carrier transport layer 34b from the viewpoint of more efficiently injecting and transporting carriers from the anode. A material having a low energy level is preferred.
The thickness of the carrier injection layer 34a is preferably 1 nm to 500 nm.

The material of the light emitting layer 34c may be a known material for organic EL, and can be classified into, for example, a low molecular light emitting material and a polymer light emitting material.
Preferred examples of the low-molecular light-emitting material include aromatic dimethylidene compounds such as 4,4′-bis (2,2′-diphenylvinyl) -biphenyl (DPVBi); 5-methyl-2- [2- [4- Oxadiazole compounds such as (5-methyl-2-benzoxazolyl) phenyl] vinyl] benzoxazole; 3- (4-biphenylyl) -4-phenyl-5-tert-butylphenyl-1,2,4 -Triazole derivatives such as triazole (TAZ); styrylbenzene compounds such as 1,4-bis (2-methylstyryl) benzene; fluorescent organic materials such as fluorenone derivatives.
Preferred examples of the polymer light-emitting material include polyphenylene vinylene derivatives such as poly (2-decyloxy-1,4-phenylene) (DO-PPP); polyspiro derivatives such as poly (9,9-dioctylfluorene) (PDAF). Etc. can be illustrated.
The thickness of the light emitting layer 34c is preferably 5 nm to 500 nm.

In the electron transport layer 34d and the electron injection layer 34e, the electron injection / transport material may be a known material for organic EL or organic photoconductor. Preferred electron injecting and transporting materials include inorganic materials that are n-type semiconductors, oxadiazole derivatives, triazole derivatives, thiopyrazine dioxide derivatives, benzoquinone derivatives, naphthoquinone derivatives, anthraquinone derivatives, diphenoquinone derivatives, fluorenone derivatives, benzodifuran derivatives, and the like. Molecular materials: Polymer materials such as poly (oxadiazole) (Poly-OXZ) and polystyrene derivatives (PSS) can be exemplified. In particular, examples of the electron injection material include fluorides such as lithium fluoride (LiF) and barium fluoride (BaF ₂ ); oxides such as lithium oxide (Li ₂ O) and the like.
In addition, as a material applied to the electron injection layer 34e, the lowest unoccupied molecular orbital (LUMO) is used as compared with the electron injection / transport material applied to the electron transport layer 34d from the viewpoint of more efficiently injecting and transporting electrons from the cathode. A material having a high energy level is preferred. The material applied to the electron transport layer 34d is preferably a material having higher electron mobility than the electron injection transport material applied to the electron injection layer 34e.
The film thickness of the electron transport layer 34d is preferably 5 nm to 500 nm. The film thickness of the electron injection layer 34e is preferably 0.1 nm to 100 nm.

The organic light emitting device according to one embodiment of the present invention is not limited to the one shown in FIG. 15, and a part of the configuration may be changed. For example, the structure of the organic EL unit 34 as follows can be given.
(I) An organic EL part in which a carrier transport layer, a light emitting layer, and an electron transport layer are laminated in this order from the anode electrode 32 side to the cathode electrode 33 side.
(Ii) An organic EL part in which a carrier injection layer, a carrier transport layer, a light emitting layer, and an electron transport layer are laminated in this order from the anode electrode 32 side to the cathode electrode 33 side.
(Iii) An organic EL part in which a carrier injection layer, a carrier transport layer, a light emitting layer, a carrier prevention layer, and an electron transport layer are laminated in this order from the anode electrode 32 side to the cathode electrode 33 side.
(Iv) An organic EL portion in which a carrier injection layer, a carrier transport layer, a light emitting layer, a carrier prevention layer, an electron transport layer, and an electron injection layer are laminated in this order from the anode electrode 32 side to the cathode electrode 33 side.
(V) An organic EL in which a carrier injection layer, a carrier transport layer, an electron blocking layer, a light emitting layer, a carrier blocking layer, an electron transport layer, and an electron injection layer are laminated in this order from the anode electrode 32 side to the cathode electrode 33 side. Department.

The carrier prevention layer and the electron prevention layer may be known for organic EL.

The organic light-emitting device according to one embodiment of the present invention can operate stably over a long period of time in the air atmosphere because the carrier transport layer is stable in the air atmosphere.

The organic light emitting device according to one embodiment of the present invention can be manufactured, for example, by the following method.
16A to 16G are schematic cross-sectional views for explaining a method for manufacturing the organic light emitting device 3A.
First, as shown in FIG. 16A, the anode electrode 32 is formed on the glass substrate 31.
An example of a method for forming the anode electrode 32 is a sputtering method.

Next, as shown in FIG. 16B, a carrier injection layer 34 a is formed on the anode electrode 32. As a method for forming the carrier injection layer 34a, a spin coating method can be exemplified.

Next, as shown in FIG. 16C, a carrier transport layer 34b is formed on the carrier injection layer 34a. The carrier transport layer 34b can be formed, for example, by placing the above-mentioned composition for carrier transport layer containing the compound (1) on the carrier injection layer 34a and further removing the solvent by drying as necessary. The method for forming the carrier transport layer 34b using the composition for the carrier transport layer is the same as the method for forming the organic semiconductor layer using the composition for the organic semiconductor layer during the production of the field effect transistor. Examples thereof include a spin coating method, a casting method, an ink jet method, and a printing method. The carrier transport layer 34b may be formed by depositing the compound (1) by a vacuum deposition method or the like.

Next, as shown in FIG. 16D, a light emitting layer 34c is formed on the carrier transport layer 34b. An example of a method for forming the light emitting layer 34c is a vacuum deposition method.

Next, as shown in FIG. 16E, an electron transport layer 34d is formed on the light emitting layer 34c.
An example of a method for forming the electron transport layer 34d is a vacuum deposition method.

Next, as shown in FIG. 16F, an electron injection layer 34e is formed on the electron transport layer 34d. As a method for forming the electron injection layer 34e, a vacuum deposition method can be exemplified.

Next, as shown in FIG. 16G, the cathode electrode 33 is formed on the electron injection layer 34e. As a method for forming the cathode electrode 33, a vacuum deposition method can be exemplified.
By performing the above steps, an organic light emitting device 3A shown in FIG. 15 is obtained.

Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the following examples.

<Production of Compound (1)>
[Example 1]
According to the following procedure, a compound represented by the following general formula (1-1) was synthesized as a synthetic intermediate using a compound represented by the following general formula (1c-1) (hereinafter abbreviated as compound (1c-1)) ( Hereinafter, the compound (1-1) was abbreviated.

(Compound (1c-1) synthesis step)
3-amino-2-naphthol (250 mg, 1.57 mmol) and 2,3-dihydroxynaphthalene (250 mg, 1.56 mmol) are mixed well and heated at 230 ° C. for 3 hours in a nitrogen atmosphere for dehydration condensation. It was.
Then, after completion of the reaction, the product was recrystallized using N, N-dimethylformamide (DMF) to obtain 292 mg of compound (1c-1) (dibenzophenoxazine) (yield 66%). .

(Compound (1-1) Synthesis Step)
To a solution of compound (1c-1) (257 mg, 1.1 mmol) in anhydrous DMF (10 mL), sodium hydride (60%, 60 mg, 1.5 mmol) was added little by little and left at room temperature for 2 hours. 1-Bromohexane (0.25 g, 1.5 mmol) was added and further stirred for 2 hours.
Then, the solvent was distilled off under reduced pressure, the residue was extracted with methylene chloride, and 0.28 g (yield 45%) of compound (1-1) was obtained from the residue after the solvent was distilled off by silica gel column chromatography. It was. The compound (1-1) was a colorless crystal, was not hygroscopic, did not decompose in air, and was stable. As described above, compound (1-1) was easily synthesized using commercially available materials.

The structure of compound (1-1) was confirmed by ¹ H-NMR spectrum.
¹ H-NMR (400 MHz, CDCl ₃ ): 0.97 (t, J = 7.12 Hz, 3H), 1.38-1.62 (m, 6H), 1.81-1.90 (m, 2H), 3.82 (t, J = 8.13, 2H ), 6.84 (s, 2H), 7.13 (s, 2H), 7.19-7.29 (m, 4H), 7.53-7.59 (m, 4H).

[Example 2]
According to the following procedure, a compound represented by the following general formula (1-2) was synthesized as a synthetic intermediate using a compound represented by the following general formula (1c-2) (hereinafter abbreviated as compound (1c-2)) Hereinafter, compound (1-2) was prepared.

(Compound (1c-2) synthesis step)
3-Amino-6,7-dichloro-2-naphthol (250 mg, 1.10 mmol) and 6,7-dichloro-2,3-dihydroxynaphthalene (250 mg, 1.09 mmol) were mixed well under a nitrogen atmosphere. The mixture was heated at 230 ° C. for 3 hours for dehydration condensation.
Then, after completion of the reaction, the product was recrystallized using DMF to obtain 275 mg of compound (1c-2) (yield 60%).

(Compound (1-2) Synthesis Step)
To a solution of compound (1c-2) (200 mg, 0.47 mmol) in anhydrous DMF (10 mL) was added sodium hydride (60%, 40 mg, 1.0 mmol) little by little, and the mixture was allowed to stand at room temperature for 2 hours. 1-Bromohexane (0.17 g, 1.0 mmol) was added, and the mixture was further stirred for 2 hours.
Then, the solvent was distilled off under reduced pressure, the residue was extracted with methylene chloride, and 0.12 g (yield 49%) of compound (1-2) was obtained from the residue after evaporation of the solvent by silica gel column chromatography. It was. The compound (1-2) was a colorless crystal, was not hygroscopic, did not decompose in air, and was stable. As described above, compound (1-2) was easily synthesized using commercially available materials.

<Evaluation of physical properties of compound (1)>
The absorption spectrum (λmax in CH ₂ Cl ₂ ) of the compound (1-1) was measured, and the ionization potential (HOMO level) by atmospheric photoelectron spectroscopy (AC-2) was measured. These results are shown in Table 1 together with the following pentacene results. The absorption spectrum of pentacene is cited from Reference 1 “J. Am. Chem. Soc., 2007, 129, 2225.” and the ionization potential is Reference 2 “Jpn. J. Appl. Phys. 2005, 44, 561”. Quoted from "."

As shown in Table 1, the compound (1-1) had a larger ionization potential than pentacene. This indicated that the compound (1-1) had a lower HOMO level than pentacene.

On the other hand, for the compound (1-1) and pentacene, first-principles calculation was performed by the DFT method (B3LYP6-31G ^* ), and the levels of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) were calculated. . The results are shown in Table 2.

As shown in Table 2, as a result of the first principle calculation, the compound (1-1) has a lower HOMO level than pentacene and has a large ionization potential, that is, the compound (1-1) is more resistant to oxidation than pentacene. It showed that the nature is high.
In the case of the HOMO level such as the compound (1-1), for example, when used as an organic semiconductor layer of a field effect transistor in which the source electrode and the gate electrode are gold (work function is about 5 eV), holes (carriers) ) It was expected that injection would be easier.
As described above, the measurement results shown in Table 1 and the results of the first principle calculation shown in Table 2 were in good agreement.

Next, the stability of the compound (1-1) against air oxidation was evaluated.
That is, a solution of compound (1-1) was prepared using methylene chloride in an air-saturated state as a solvent and allowed to stand in the dark. Then, from the time immediately after preparation of the solution to one month after standing, the absorption spectrum of ultraviolet-visible (UV-Vis) spectroscopy was measured, and the change in absorption intensity with time was traced for the solution of compound (1-1). At this time, Reference 1 described above was referred to. FIG. 17 shows the measurement results of the absorption intensity immediately after preparation of the solution and after one month of standing in the dark.
As shown in FIG. 17, there was no difference in the absorption intensity of the solution of the compound (1-1) between immediately after preparation and after one month of standing in the dark. In addition, it is reported by literature 1 that the absorption intensity | strength of the solution will become almost zero about pentacene when it is left still for 24 hours on such conditions. Therefore, it was confirmed that the compound (1-1) had higher stability against air oxidation than pentacene.

As described above, it was confirmed that the compound (1-1) had higher oxidation resistance than pentacene, which is a typical organic semiconductor material, and was stable even in the air atmosphere. By using the compound (1-1) as a semiconductor material, a semiconductor device having stable electrical characteristics can be provided.

<Manufacture of field effect transistors>
[Example 3]
The field effect transistor 1A shown in FIG. 1 was manufactured by the manufacturing method described with reference to FIGS. 8A to 8E. More specifically, it is as follows.
As the substrate 11, a glass substrate (Corning, Eagle 2000, thickness: 0.5 mm) was used.
The material of the gate electrode 12 was an AlSi alloy in which 10% silicon (Si) was added to aluminum (Al). Then, a 40 nm thick metal film made of an AlSi alloy was formed on the substrate 11 by sputtering using a metal target made of this AlSi alloy. The patterning of the metal film was performed by photolithography and etching.
The material of the gate insulating film 13 was silicon oxide (SiO ₂ ), and a silicon oxide film having a thickness of 300 nm was formed by a sputtering method.
The photoresist film 90 was formed by spin coating using a negative photoresist (ZPN 1150, manufactured by Nippon Zeon Co., Ltd.) for lift-off process, and then by photolithography.
A lift-off method in which an adhesion layer made of chromium (Cr) with a thickness of 2 nm and a metal film made of gold (Au) with a thickness of 40 nm are sequentially formed by vacuum deposition, and the substrate 11 is immersed in an organic solvent such as acetone. The photoresist film 7 and unnecessary Au film / Cr film formed thereon were removed by the method to form the source electrode 14 and the drain electrode 15. At this time, the distance (channel length) between the source electrode 14 and the drain electrode 15 was 20 μm, and the length of the opposing electrode (channel width) was 1000 μm.
The organic semiconductor layer 16 was formed using the composition for organic semiconductor layers containing the compound (1-1) produced in Example 1. This organic semiconductor layer composition was prepared using chloroform as a solvent so that the concentration of the compound (1-1) was 0.5 mass%. The organic semiconductor layer 16 having a film thickness of about 40 nm was formed by a cast method in which the composition for an organic semiconductor layer was placed on a predetermined portion by a spin coating method (rotation number: 1500 rpm) and gently dried in a saturated chloroform atmosphere.

With respect to the field effect transistor 1A manufactured through the above steps, the gate voltage (Vg) -drain current (Id) characteristics were measured. The results are shown in FIG. In FIG. 18, “ABS (Id) [A]” is the absolute value of the drain current (see the vertical axis on the left side of the graph), and “SQRT (Id)” is the square root of the drain current (see the vertical axis on the right side of the graph). Show.
As shown in FIG. 18, the obtained field effect transistor showed good characteristics. The field effect mobility at this time was 3.1 × 10 ⁻⁶ cm ² / Vs. Further, this transistor operated stably even in an air atmosphere, and no significant deterioration in the characteristics was observed even in the measurement one month after being placed in the air.

[Example 4]
The field effect transistor 1B shown in FIG. 3 was manufactured by the manufacturing method described with reference to FIGS. 9A to 9F. More specifically, it is as follows.
As the substrate 11, a glass substrate (Corning, Eagle 2000, thickness: 0.5 mm) was used.
The material of the gate electrode 12 was an AlSi alloy in which 10% silicon (Si) was added to aluminum (Al). Then, a 40 nm thick metal film made of an AlSi alloy was formed on the substrate 11 by sputtering using a metal target made of this AlSi alloy. The patterning of the metal film was performed by photolithography and etching.
The material of the gate insulating film 13 was silicon oxide (SiO ₂ ), and a silicon oxide film having a thickness of 300 nm was formed by a sputtering method.
The photoresist film 90 was formed by spin coating using a negative photoresist (ZPN 1150, manufactured by Nippon Zeon Co., Ltd.) for lift-off process, and then by photolithography.
A lift-off method in which an adhesion layer made of chromium (Cr) with a thickness of 2 nm and a metal film made of gold (Au) with a thickness of 40 nm are sequentially formed by vacuum deposition, and the substrate 11 is immersed in an organic solvent such as acetone. The photoresist film 7 and unnecessary Au film / Cr film formed thereon were removed by the method to form the source electrode 14 and the drain electrode 15. At this time, the distance (channel length) between the source electrode 14 and the drain electrode 15 was 20 μm, and the length of the opposing electrode (channel width) was 1000 μm.
The surface modification layer 18 is obtained by immersing the substrate 11 on which the source electrode 14 and the drain electrode 15 are formed in an ethanol solution of 2-aminoethanethiol (10 mg / mL) for 5 hours, and then washing with isopropyl alcohol and drying. It was formed by drying under a nitrogen stream.
The surface modification layer 18 is a hydrophilic film.
The organic semiconductor layer 16 was formed using the composition for organic semiconductor layers containing the compound (1-1) produced in Example 1. This organic semiconductor layer composition was prepared using toluene as a solvent so that the concentration of the compound (1-1) was 0.5% by mass. The organic semiconductor layer 16 having a film thickness of about 40 nm was formed by a casting method in which the composition for an organic semiconductor layer was placed on a predetermined portion using a dispenser and gently dried in a saturated chloroform atmosphere.

The field effect transistor 1B manufactured through the above steps operates stably even in the atmosphere as in the transistor of Example 3, and no significant deterioration in characteristics is observed even after one month after being placed in the atmosphere. It was.

[Example 5]
The field effect transistor 1C shown in FIG. 4 was manufactured by the manufacturing method described with reference to FIG. More specifically, it is as follows.
As the substrate 11, a glass substrate (Corning, Eagle 2000, thickness: 0.5 mm) was used.
The material of the gate electrode 12 was an AlSi alloy in which 10% silicon (Si) was added to aluminum (Al). Then, a 40 nm thick metal film made of an AlSi alloy was formed on the substrate 11 by sputtering using a metal target made of this AlSi alloy. The patterning of the metal film was performed by photolithography and etching.
The material of the gate insulating film 13 was silicon oxide (SiO ₂ ), and a silicon oxide film having a thickness of 300 nm was formed by a sputtering method.
The organic semiconductor layer 16 was formed using the composition for organic semiconductor layers containing the compound (1-1) produced in Example 1. This organic semiconductor layer composition was prepared using toluene as a solvent so that the concentration of the compound (1-1) was 0.5% by mass. This composition for organic semiconductor layers was placed on a predetermined location by spin coating (rotation speed: 1500 rpm) to form an organic semiconductor layer 16 having a film thickness of about 40 nm.
The source electrode 14 and the drain electrode 15 were made of gold (Au), and an Au film having a film thickness of 40 nm was formed by a vacuum deposition method through a metal mask. At this time, the distance (channel length) between the source electrode 14 and the drain electrode 15 was 50 μm, and the length of the opposing electrode (channel width) was 1000 μm.

The field effect transistor 1C manufactured through the above steps operates stably in an air atmosphere as in the transistor of Example 3, and no significant deterioration in characteristics is observed even after one month after being placed in the air. It was.

[Example 6]
The field effect transistor 1D shown in FIG. 5 was manufactured by the manufacturing method described with reference to FIGS. 11A to 11D. More specifically, it is as follows.
As the substrate 11, a glass substrate (Corning, Eagle 2000, thickness: 0.5 mm) was used.
The material of the gate electrode 12 was an AlSi alloy in which 10% silicon (Si) was added to aluminum (Al). Then, a 40 nm thick metal film made of an AlSi alloy was formed on the substrate 11 by sputtering using a metal target made of this AlSi alloy. The patterning of the metal film was performed by photolithography and etching.
The hydrophilic film 13 ′ is a hydrophilic polymer layer having a thickness of 100 nm, and was formed by spin coating using an aqueous solution having a concentration of 10% by mass of polyvinyl alcohol, which is a hydrophilic polymer.
The organic semiconductor layer 16 was formed using the composition for organic semiconductor layers containing the compound (1-1) produced in Example 1. This organic semiconductor layer composition was prepared using toluene as a solvent so that the concentration of the compound (1-1) was 0.5% by mass. This composition for organic semiconductor layers was placed on a predetermined location by spin coating (rotation speed: 1500 rpm) to form an organic semiconductor layer 16 having a film thickness of about 40 nm.
The source electrode 14 and the drain electrode 15 were made of gold (Au), and an Au film having a film thickness of 40 nm was formed by a vacuum deposition method through a metal mask. At this time, the distance (channel length) between the source electrode 14 and the drain electrode 15 was 50 μm, and the length of the opposing electrode (channel width) was 1000 μm.

The field effect transistor 1D manufactured through the above steps operates stably even in the air atmosphere as in the transistor of Example 3, and no significant deterioration in the characteristics is observed even after one month after being placed in the air. It was.

[Example 7]
The organic semiconductor layer 16 was formed by an evaporation method in which the compound (1-1) was evaporated instead of forming the organic semiconductor layer 16 by a spin coating method using the composition for an organic semiconductor layer containing the compound (1-1). A field effect transistor 1A was produced in the same manner as in Example 3.
The obtained field effect transistor 1A, like the transistor of Example 3, operated stably even in the air atmosphere, and no significant deterioration in the characteristics was observed even after one month after being placed in the air.

[Example 8]
The field effect transistor 1A ′ shown in FIG. 2 was manufactured by the manufacturing method described with reference to FIGS. 8A to 8E. That is, after forming the organic semiconductor layer 16 in the same manner as in Example 3, a Parylene C film having a film thickness of 500 nm is further formed as the protective film 17 by using a lab coater PDS2010 (trade name, manufactured by Japan Parylene). Forming on the layer 16 produced the field effect transistor 1A ′.
The obtained field effect transistor 1A ′, like the transistor of Example 3, operated stably even in the air atmosphere, and no significant deterioration in the characteristics was observed even after one month after being placed in the air.

<Manufacture of solar cells>
[Example 9]
The solar cell 2A shown in FIG. 12 was manufactured by the manufacturing method described with reference to FIG. More specifically, it is as follows.
As the anode electrode 22, an ITO film having a thickness of 150 nm was formed by a sputtering method.
The p-type semiconductor layer 24 was formed using the p-type semiconductor layer composition containing the compound (1-1) produced in Example 1. This p-type semiconductor layer composition was prepared using chloroform as a solvent so that the concentration of the compound (1-1) was 0.5% by mass. This p-type semiconductor layer composition was placed on the anode electrode 22 by spin coating (rotation speed: 1500 rpm) to form a p-type semiconductor layer 24 having a thickness of about 40 nm.
As the n-type semiconductor layer 25, a film made of perfluorophthalocyanine having a film thickness of 50 nm was formed by a vacuum deposition method.
As the cathode electrode 23, an Al film having a thickness of 100 nm was formed by a vacuum deposition method.
The obtained solar cell 2A operated stably even in an air atmosphere, and no significant deterioration in the characteristics was observed even after one month after being placed in the air.

<Manufacture of organic light emitting devices>
[Example 10]
The organic light emitting device 3A shown in FIG. 15 was manufactured by the manufacturing method described with reference to FIGS. 16A to 16G. More specifically, it is as follows.
As the anode electrode 32, an ITO film having a film thickness of 150 nm was formed by a sputtering method.
The carrier injection layer 34a was formed by placing PEDOT / PSS (Bytron-P, manufactured by Bayer) on the anode electrode 32 by spin coating (rotation speed: 1500 rpm), and the film thickness was about 50 nm.
The carrier transport layer 34b was formed using the composition for the carrier transport layer containing the compound (1-1) produced in Example 1. This carrier transport layer composition was prepared using chloroform as a solvent so that the concentration of the compound (1-1) was 0.5% by mass. The carrier transport layer composition was placed on the carrier injection layer 34a by spin coating (rotation speed 1500 rpm) to form a carrier transport layer 34b having a thickness of about 40 nm.
The light-emitting layer 34c is formed by using 4,4′-N, N′-dicarbazol-biphenyl (CBP) and tris (2-phenylpyridine) iridium (Ir (PPY) ₃ ) on the carrier transport layer 34b. It was formed by a vacuum vapor deposition method in which co-evaporation was performed. The concentration of Ir (PPY) _{3 in} the formed light emitting layer 34c was 6.5% by mass. The film thickness was 40 nm.
The electron transport layer 34d was formed by vacuum-depositing tris (8-hydroxyquinoline aluminum) (A1q ₃ ) on the light emitting layer 34c, and the film thickness was 40 nm.
The electron injection layer 34e was formed by vacuum-depositing lithium oxide (Li ₂ O) on the electron transport layer 34d, and the film thickness was 0.5 nm.
The cathode electrode 33 was formed by vacuum-depositing aluminum (Al) on the electron injection layer 34e, and the film thickness was 150 nm.
In the obtained organic light emitting device 3A, light emission from Ir (PPY) ₃ was observed. Further, it stably operated even in an air atmosphere, and no significant deterioration in the characteristics was observed even after one month after being placed in the air.

The embodiment of the present invention can be used for semiconductor devices such as field effect transistors, solar cells, and organic light emitting elements.

1A, 1B, 1C, 1D, 1E, 1F ... field effect transistor, 11 ... substrate, 12 ... gate electrode, 13 ... gate insulating film, 13 '... hydrophilic film, 14 ... Source electrode, 15 ... Drain electrode, 16 ... Organic semiconductor layer, 2A, 2B ... Solar cell, 24 ... P-type semiconductor layer, 26 ... Organic semiconductor layer, 3A ... .Organic light emitting device, 34b ... carrier transport layer

Claims

A compound represented by the following general formula (1).

(Wherein R 1 is an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms; R 2 to R 13 each independently has a hydrogen atom, a halogen atom or a substituent. An aromatic group which may be substituted or an aliphatic hydrocarbon group having 1 to 20 carbon atoms.)
The compound according to claim 1, wherein R 1 is an alkyl group having 1 to 15 carbon atoms, and R 2 to R 13 are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms.
R 1 is a linear, branched or cyclic alkyl group having 5 to 9 carbon atoms, and R 2 to R 13 are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 5 carbon atoms. A compound according to claim 2.
A field effect transistor comprising an organic semiconductor layer containing the compound according to claim 1.
The field effect transistor according to claim 4, further comprising a hydrophilic film, wherein the organic semiconductor layer is provided on the hydrophilic film.
Furthermore, a gate electrode, a gate insulating film, a source electrode and a drain electrode are provided,
The organic semiconductor layer is provided so as to face the gate electrode through the gate insulating film,
The field effect transistor according to claim 4, wherein the source electrode and the drain electrode are provided in contact with the organic semiconductor layer.
Furthermore, a gate electrode, a gate insulating film, a source electrode and a drain electrode are provided,
The organic semiconductor layer is provided so as to face the gate electrode through the gate insulating film,
The field effect transistor according to claim 4, wherein the organic semiconductor layer is provided so as to cover the source electrode and the drain electrode.
The field effect transistor according to claim 4, wherein the organic semiconductor layer is formed by applying the compound.
The field effect transistor according to claim 4, wherein the organic semiconductor layer is formed by depositing the compound.
A method for producing a field effect transistor comprising an organic semiconductor layer comprising the compound according to claim 1,
Using the composition containing the compound, the organic semiconductor layer is formed by any one of a dipping method, a spin coating method, a casting method, an inkjet method, and a printing method,
The method of manufacturing a field effect transistor, wherein the composition includes at least one selected from the group consisting of toluene, chlorobenzene, dichlorobenzene, trichlorobenzene, dichloromethane, and chloroform.
A solar cell provided with the organic-semiconductor layer containing the compound of Claim 1.
The solar cell according to claim 11, further comprising a hydrophilic film, wherein the organic semiconductor layer is provided on the hydrophilic film.
The solar cell according to claim 11, wherein the organic semiconductor layer is formed by applying the compound.
The solar cell according to claim 11, wherein the organic semiconductor layer is formed by vapor deposition of the compound.
It is a manufacturing method of the solar cell provided with the organic-semiconductor layer containing the compound of Claim 1, Comprising:
Using the composition containing the compound, the organic semiconductor layer is formed by any one of a dipping method, a spin coating method, a casting method, an inkjet method, and a printing method,
The said composition is a manufacturing method of the solar cell containing at least 1 type selected from the group which consists of toluene, chlorobenzene, dichlorobenzene, trichlorobenzene, dichloromethane, and chloroform.
an organic semiconductor layer including a p-type semiconductor material and an n-type semiconductor material;
The solar cell in which at least one of the p-type semiconductor material and the n-type semiconductor material contains the compound according to claim 1.
An organic light-emitting device comprising a carrier transport layer containing the compound according to claim 1.
The organic light-emitting device according to claim 17, further comprising a hydrophilic film, wherein the carrier transport layer is provided on the hydrophilic film.
The organic light-emitting device according to claim 17, wherein the carrier transport layer is formed by applying the compound.
The organic light-emitting device according to claim 17, wherein the carrier transport layer is formed by vapor deposition of the compound.
A method for producing an organic light emitting device comprising a carrier transport layer comprising the compound according to claim 1,
The carrier transport layer is formed by a dipping method, a spin coating method, a casting method, an ink jet method or a printing method using a composition containing the compound,
The method for manufacturing an organic light emitting device, wherein the composition includes at least one selected from the group consisting of toluene, chlorobenzene, dichlorobenzene, trichlorobenzene, dichloromethane, and chloroform.
A composition for an organic semiconductor layer of a field effect transistor comprising the compound according to claim 1.
The composition for organic-semiconductor layers of the solar cell containing the compound of Claim 1.
including a p-type semiconductor material and an n-type semiconductor material,
The composition for an organic semiconductor layer of a solar cell, wherein at least one of the p-type semiconductor material and the n-type semiconductor material contains the compound according to claim 1.
A composition for a carrier transport layer of an organic light-emitting device comprising the compound according to claim 1.