JP2015151372A - Tetraamine derivative, method for producing the same, and organic electronic device using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a tetraamine derivative having naphthalene or perylene as a skeleton with cyclic urea bonds, which can be used as a coating-type organic semiconductor material such as an organic thin film transistor (organic TFT), an organic electroluminescent element (organic EL element), and an organic thin film solar cell, and a method for synthesizing the same.SOLUTION: There is provided as a coating-type semiconductor material, for example, a tetraamine derivative having a naphthalene skeleton with cyclic urea bonds, which can be obtained according to the following reaction formula.

Description

  The present invention relates to various tetraamine derivatives having a cyclic urea bond having naphthalene or perylene as a skeleton, and methods for synthesizing the same, as well as organic thin-film transistors (organic TFTs), organic electroluminescence elements (organic EL elements), and organic compounds using the tetraamine derivatives. The present invention relates to organic electronic devices such as thin film solar cells.

  Conventionally, condensed polycyclic aromatic structures have attracted attention as organic compounds for organic electronics devices such as organic TFTs, organic EL elements, and organic thin-film solar cells. For example, a naphthalene derivative modified with a predetermined substituent is known to exhibit high hole mobility, and research and development of various derivatives have been actively conducted.

  On the other hand, tetraaminobenzene, tetraaminonaphthalene, and the like containing a large amount of amine, which is a strong electron donating group, have an unstable skeleton, but the skeleton can be stabilized by modifying the substituent. Although not used for organic semiconductors, for example, Non-Patent Documents 1 and 2 describe stabilization of tetraaminoperylene with a carbonyl group or boron.

  Non-patent document 3 suggests that tetraaminonaphthalene having a cyclic urea bond has strong donor properties. Non-Patent Document 3 also discloses a method for synthesizing the compound.

Angew. Chem. Int. Ed. 2003, 42, p.2677-2681 Chem. Commun. 2008, p.5348-5350 J. Org. Chem. 1995, 60, p.5401-5406

  However, the non-patent document 3 does not suggest that tetraaminonaphthalene having a cyclic urea bond is used for organic semiconductors, and the synthesis method thereof is a pyrolysis reaction at an extremely high temperature as organic synthesis. It has a problem that the yield is low.

In addition, condensed polycyclic aromatic compounds such as pentacene are generally low in solubility in organic solvents, and it is difficult to apply a coating method that is industrially advantageous in the formation of thin films in the production of organic electronics devices. is there.
On the other hand, when the number of condensed rings is small like naphthalene derivatives, solubility is improved, but substituent modification is necessary to obtain sufficient charge mobility. Further, a compound having a tetraamine structure having a cyclic urea bond is expected to be applied to an organic semiconductor because it exhibits a strong donor property due to an amino group and a high solubility due to an alkyl group or the like.

  As a result of repeated studies in view of the above-described conventional technology and its problems, the present inventors have found that a tetraaminonaphthalene derivative having a predetermined cyclic urea bond containing a novel compound is useful for organic semiconductor applications, Moreover, the method which can manufacture the said derivative | guide_body efficiently was discovered.

  That is, the present invention provides a tetraamine derivative having a cyclic urea bond having naphthalene or perylene as a skeleton as a novel compound that can be used as a coating type organic semiconductor material, and a method for synthesizing the tetraamine derivative. An object of the present invention is to provide a used organic electronic device.

  The tetraamine derivative according to the present invention has a cyclic urea bond having a skeleton of naphthalene or perylene represented by the following general formula (1).

In the formula (1), R ₁ and R ₂ are each independently a hydrogen atom, a linear or branched alkyl group, an alkyl group containing at least one fluorine atom, an aryl group, a heterocyclic group, or the following Any of the groups shown in (Chemical Formula 2) may be the same or different. However, when n = 0, the case where both R ₁ and R ₂ are methyl groups is excluded.

  In the above (Chemical Formula 2), R is a linear or branched alkyl group.

  The tetraamine derivatives as described above are novel compounds useful in organic semiconductor applications.

In the tetraamine derivative, R ₁ is preferably a methyl group, R ₂ is an alkyl group having 2 or more carbon atoms, R ₁ and R ₂ are both alkyl groups having 2 or more carbon atoms, or both are hydrogen atoms.
In particular, a tetraamine derivative having such a substituent can be suitably used as a coating type organic semiconductor material.

  The tetraamine derivative is preferably soluble in water or an organic solvent when used as a coating type organic semiconductor material.

  In addition, the method for synthesizing a tetraamine derivative according to the present invention uses urea as a reaction reagent in the method for synthesizing a tetraamine derivative having a cyclic urea bond having a skeleton of naphthalene or perylene represented by the following general formula (1). It is characterized by forming a cyclic urea bond.

In the formula (1), R ₁ and R ₂ are each independently a hydrogen atom, a linear or branched alkyl group, an alkyl group containing at least one fluorine atom, an aryl group, a heterocyclic group, or the following Any of the groups shown in (Chemical Formula 4) may be the same or different.

  In the above formula, R is a linear or branched alkyl group.

  According to such a synthesis method, the yield of the tetraamine derivative can be improved without undergoing thermal decomposition at high temperature.

The organic semiconductor ink according to the present invention includes a tetraamine derivative having a cyclic urea bond having a skeleton of naphthalene or perylene represented by the general formula (1) shown in the above (Chemical Formula 3).
According to such an organic semiconductor ink, it is possible to coat and form a semiconductor material containing the tetraamine derivative.

Moreover, the organic electronic device according to the present invention includes an organic layer containing a tetraamine derivative having a cyclic urea bond having a skeleton of naphthalene or perylene represented by the general formula (1) shown in the above (Chemical Formula 3). It is characterized by.
The tetraamine derivative can be suitably applied as an organic semiconductor material in an organic layer constituting an organic electronic device.

  Specifically, the organic electronic device includes a gate electrode, a gate insulating layer, an organic semiconductor layer, a source electrode, and a drain electrode on a substrate, and the organic semiconductor layer includes the tetraamine derivative. An organic TFT comprising an organic layer comprising: an anode, a light emitting layer, a hole transport layer and / or an electron transport layer, and a cathode on a substrate, the hole transport layer and / or the electron An organic EL device characterized in that the transport layer is an organic layer containing the tetraamine derivative; the photoelectric conversion layer comprising an electrode and a photoelectric conversion layer containing a hole transport material and an electron transport material on a substrate; An organic thin-film solar cell, which is an organic layer containing the tetraamine derivative, comprising an electrode, a hole transport layer and / or an electron transport layer, and a photoelectric conversion layer on a substrate, and the hole transport layer and / or Electronic Feeding layer, and an organic thin film solar cell, characterized in that an organic layer including the tetraamine derivatives.

According to the present invention, a novel tetraamine derivative having a cyclic urea bond having naphthalene or perylene as a skeleton is provided. In addition, according to the synthesis method of the present invention, the tetraamine derivative can be obtained efficiently, and the yield can be improved.
Furthermore, the tetraamine derivative according to the present invention can constitute an organic semiconductor ink, can be formed into a coating film, and exhibits excellent charge mobility. Therefore, an organic TFT, an organic EL element, an organic thin film solar The present invention can be suitably applied to batteries and the like, and can also be applied to various organic electronic devices such as lighting, display devices, and displays.

It is sectional drawing which showed the layer structure of an example of organic TFT. It is sectional drawing which showed the layer structure of an example of the organic EL element. It is sectional drawing which showed the layer structure of an example of the organic thin film solar cell. It is sectional drawing which showed the layer structure of an example of a display device. 6 is a graph showing the electrical characteristics of the organic TFT of Example 5.

Hereinafter, the present invention will be described in more detail.
The tetraamine derivative according to the present invention has a cyclic urea bond having naphthalene or perylene as a skeleton, and is a novel compound represented by the above general formula (1).
Such a compound is an excellent organic semiconductor because two carbonyl groups bring about stabilization of the tetraamine structure, can be isolated as a thermally and chemically stable compound, and has a strong donor property.

In the formula (1), R ₁ and R ₂ are each independently a hydrogen atom, a linear or branched alkyl group, an alkyl group containing at least one fluorine atom, an aryl group, a heterocyclic group, or the above One of the groups shown in (Chemical Formula 2).
The two R ₁ and the two R ₂ may be the same or different, but are usually preferably the same.
However, the novel tetraamine derivatives exclude those in which both of R ₁ and R ₂ are methyl groups when n = 0.

The alkyl group or the alkyl group containing at least one fluorine atom preferably has 1 to 30 carbon atoms, and more preferably 1 to 20 carbon atoms. These alkyl groups may be linear or branched.
Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl. Group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group and the like.
Examples of the alkyl group substituted with at least one fluorine atom include, for example, a trifluoromethyl group, a difluoromethyl group, a monofluoromethyl group, a pentafluoroethyl group, a tetrafluoroethyl group, a trifluoroethyl group, and a difluoroethyl group. , Monofluoroethyl group, heptafluoropropyl group, hexafluoropropyl group, pentafluoropropyl group, tetrafluoropropyl group, trifluoropropyl group, difluoropropyl group, monofluoropropyl group, nonafluorobutyl group, octafluorobutyl group, Heptafluorobutyl group, hexafluorobutyl group, pentafluorobutyl group, tetrafluorobutyl group, trifluorobutyl group, difluorobutyl group, monofluorobutyl group, undecafluoropentyl group, decafluoro Examples include pentyl group, nonafluoropentyl group, octafluoropentyl group, heptafluoropentyl group, hexafluoropentyl group, pentafluoropentyl group, tetrafluoropentyl group, trifluoropentyl group, difluoropentyl group, monofluoropentyl group and the like. .

  The tetraamine derivative is usually water or alcohols such as methanol, ethanol, propanol and ethylene glycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; methyl acetate, ethyl acetate, butyl acetate and methyl benzoate. Esters such as N; N-dimethylformamide, N, N-dimethylacetamide, amides such as N-methylpyrrolidone; 1,3-dimethyl-2-imidazolidinone, 1,3-dimethylimidazolidine-2, Ureas such as 4-dione; sulfoxides such as dimethyl sulfoxide and diethyl sulfoxide; sulfones such as sulfolane; nitriles such as acetonitrile and propionitrile; diethyl ether, diisopropyl ether, tetrahydrofuran and dioxane Ethers such as: benzene, toluene, xylene, mesitylene, tetralin, nitrobenzene, aniline, benzonitrile and other aromatic hydrocarbons; monochlorobenzene, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, bromobenzene, Halogenated aromatic hydrocarbons such as 1,2-dibromobenzene; Complex structure hydrocarbons such as pyridine, quinoline and thiophene; Aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane; Dichloromethane, chloroform and the like Dissolves in various organic solvents such as halogenated aliphatic hydrocarbons.

Among them, R ₁ and R _{2 in} the general formula (1) are both alkyl groups, especially R ₁ is a methyl group, R ₂ is an alkyl group having 2 or more carbon atoms, or R ₁ and R ₂ are both carbon. The tetraamine derivative which is an alkyl group having a number of 2 or more preferably uses a halogenated aromatic hydrocarbon, an aromatic hydrocarbon, a halogenated aliphatic hydrocarbon, or an aliphatic hydrocarbon as a soluble solvent. it can.
Moreover, water (basic) and a sulfoxide polar solvent can be used suitably as a soluble solvent for the tetraamine derivative in which R ₁ and R _{2 in} the general formula (1) are both hydrogen atoms.
A tetraamine derivative having such a substituent can be suitably used as a coating type organic semiconductor material.
In addition, the said various solvent may be used independently, and 2 or more types may be mixed and used for it.

In addition, the tetraamine derivative (in the above general formula (1), when n = 0, both R ₁ and R ₂ are methyl groups) are synthesized according to the following synthesis schemes. Can do. This synthesis method is a method that undergoes a step of forming a cyclic urea bond by using urea as a reaction reagent (see, for example, Aust. J. Chem. 1982, 35, 775, etc.).
First, a synthesis scheme of a tetraamine derivative having naphthalene as a skeleton is shown.

  According to this scheme, it can be performed with fewer steps than Scheme A.

  Next, a synthesis scheme of a tetraamine derivative having a perylene skeleton is shown.

In the above formulas (Chemical formula 5) to (Chemical formula 8), R ₁ and R ₂ have the same meaning as in the general formula (1), X is a halogen atom, and preferably a bromine atom or an iodine atom. The base is an inorganic base, preferably potassium hydroxide or sodium hydroxide.

In the method for synthesizing the tetraamine derivative according to the present invention, the synthesis is preferably performed according to any one of the above-described schemes AD.
All of the synthesis schemes are efficient and have a lower yield than the synthesis method described in Non-Patent Document 3 above, with fewer steps and without requiring a high temperature of 700 ° C. for thermal decomposition. Improvement is also achieved.

  The tetraamine derivative is subjected to general operations such as filtration, concentration, extraction, distillation, sublimation, recrystallization, column chromatography, and Soxhlet extraction after completion of the synthesis reaction according to each of the above schemes. Can be isolated and purified.

Further, since the tetraamine derivative is soluble in the above-described solvent, the obtained solution can be used as an organic semiconductor ink.
According to such an organic semiconductor ink, a layer or thin film of a semiconductor material containing the tetraamine derivative can be formed by applying or printing the ink.
In addition, by forming a heat conversion solubilization unit by protecting a substituent with N-tertiarybutoxycarbonyl (N-Boc) or the like, a film is formed using various solvents as described above via the precursor structure. You can also.
The organic semiconductor ink includes at least one of the tetraamine derivatives, and may further include a compound such as another organic semiconductor or an insulating polymer compound. Moreover, the solvent used for constituting the ink may be a single solvent or a mixture of two or more solvents. Furthermore, an additive for controlling the physical properties of the ink, such as adjustment of the viscosity of the ink and control of hydrophilicity or water repellency, may be included.
Further, the content of the tetraamine derivative in the ink can be appropriately set, and is usually about 0.001 to 10 wt%, and from the viewpoint of film formability, about 0.01 to 1 wt%. preferable.

Examples of organic semiconductors other than the tetraamine derivative contained in the ink include high molecular compounds exhibiting semiconductivity, specifically, polyacetylene polymers, polydiacetylene polymers, polyparaphenylene polymers, and the like. Copolymerization of molecule, polyaniline polymer, polytriphenylamine polymer, polythiophene polymer, polypyrrole polymer, polyparaphenylene vinylene polymer, polyethylenedioxythiophene polymer, naphthalene diimide Polymer, Copolymer polymer containing perylene diimide as one component, Copolymer polymer containing diketopyrrolopyrrole as one component, Copolymer polymer containing benzobisthiadiazole as one component, Copolymer containing thienothiophene as one component Polymerized polymer, copolymer polymer containing thiazolothiazole as one component It is.
In addition, the other organic semiconductor may be, for example, a low molecular compound exhibiting semiconductivity, and specifically includes an acene derivative, a phenylene vinylene derivative, a triphenylamine derivative, a fluorene derivative, an azaacene derivative, a thienoacene derivative, a thiophene derivative. , Benzothiophene derivatives, thienothiophene derivatives, thiazole derivatives, thiazolothiazole derivatives, tetrathiafulvalene derivatives, phthalocyanine derivatives, porphyrin derivatives, naphthalene diimide derivatives, perylene diimide derivatives, benzothiadiazole derivatives, naphthobithiadiazole derivatives, diketopyrrolopyrrole derivatives And fullerene derivatives.
In addition, for example, organic semiconductors described in Chem. Rev. 112, 2012, p.2208-2267 can also be used.

The insulating polymer compound contained in the ink includes synthetic resin, plastic, synthetic rubber, and the like. Specifically, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyester, phenol resin, acrylic resin, Examples include amide resin, nylon, vinylon, polyisoprene, polybutadiene, acrylic rubber, acrylonitrile rubber, and urethane rubber.
By adding these, effects such as controlling the crystallinity of the organic semiconductor layer containing the tetraamine derivative, optimizing the viscosity of the ink, and improving the film forming property are obtained.

Furthermore, the organic semiconductor ink may contain a conductive polymer compound as necessary. Specifically, polyacetylene polymer, polydiacetylene polymer, polyparaphenylene polymer, polyaniline polymer, polytriphenylamine polymer, polythiophene polymer, polypyrrole polymer, polyparaphenylene vinylene And a mixture of polyethylene dioxythiophene and polyethylene dioxythiophene / polystyrene sulfonic acid (PEDOT: PSS).
By adding these, in addition to controlling the crystallinity of the organic semiconductor layer containing the tetraamine derivative, optimizing the viscosity of the ink, and improving the film forming property, effects such as an improvement in charge mobility can be obtained.

  The organic semiconductor ink can be applied by a known method such as spin coating, drop casting, casting, Langmuir-Blodgett, or the like. Also, a known method can be used as a printing technique. For example, printing can be performed by an inkjet method, a screen printing method, an offset printing method, a gravure method, a flexo method, a microcontact method, or the like.

After the organic semiconductor ink is applied or printed on the substrate by the method as described above, the solvent component is removed to obtain a layer or thin film containing the tetraamine derivative. The removal condition of the solvent component is appropriately selected. be able to.
Preferably, it is air-dried or air-dried at room temperature, but when the solvent has a high boiling point and is difficult to remove, a vacuum treatment near room temperature or a heat treatment at about 50 to 200 ° C., or these treatments are used in combination. The heat treatment may be performed under reduced pressure.

  Further, the layer or thin film containing the tetraamine derivative may be heat-treated for the purpose of improving semiconductor characteristics. The heat treatment conditions can be appropriately set. For example, the heat treatment is performed at about 50 to 250 ° C. for 0.1 to 24 hours. This treatment may also serve as the solvent component removal treatment.

Alternatively, for the same purpose, the layer or thin film containing the tetraamine derivative may be exposed to solvent vapor. This treatment can be performed, for example, by allowing the layer or thin film containing the tetraamine derivative and the solvent to stand in an airtight space while preventing direct contact with the solvent. In order to increase the amount of the solvent vapor, the solvent may be heated to about 40 to 150 ° C. After this process, the process after the removal process of the solvent component may be appropriately performed.
Solvents used in this treatment include alcohols such as methanol, ethanol, propanol, and ethylene glycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; methyl acetate, ethyl acetate, butyl acetate, methyl benzoate, and the like Esters; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone; 1,3-dimethyl-2-imidazolidinone, 1,3-dimethylimidazolidine-2,4- Ureas such as dione; Sulfoxides such as dimethyl sulfoxide and diethyl sulfoxide; Sulfones such as sulfolane; Nitriles such as acetonitrile and propionitrile; Acetates such as diethyl ether, diisopropyl ether, tetrahydrofuran and dioxane Aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, tetralin, nitrobenzene, aniline, benzonitrile; monochlorobenzene, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, bromobenzene, 1 Halogenated aromatic hydrocarbons such as 1,2-dibromobenzene; Complex structure hydrocarbons such as pyridine, quinoline and thiophene; Aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane; Halogens such as dichloromethane and chloroform Examples include various organic solvents such as activated aliphatic hydrocarbons. These solvents may be used alone or in combination of two or more.

Since the tetraamine derivative according to the present invention is chemically stable and has good semiconductor properties, for example, organic TFTs, organic EL elements, organic thin-film solar cells, other lighting, display devices, displays, etc. It can be suitably applied to organic electronic devices. Furthermore, it is expected to be applied in various applications such as backlight, optical communication, electrophotography, illumination light source, exposure light source, reading light source, sign, signboard, and interior.
Hereinafter, some specific examples of these organic electronic devices will be described.

(Organic TFT)
FIG. 1 shows an example of the layer structure of the organic TFT. The organic TFT shown in FIG. 1 has a bottom gate-top contact structure. A gate electrode 12, a gate insulating layer 13, an organic semiconductor layer 16, a drain electrode 14, and a source electrode 15 are arranged on a substrate 11 in this order. And are laminated. The organic semiconductor layer 16 is an organic layer containing at least one tetraamine derivative according to the present invention. In addition, this organic layer may contain other organic compounds.
Thereby, the orientation direction of molecules in the organic layer can be easily aligned, and high hole and electron mobility (field effect mobility) characteristics can be obtained.
In addition to the organic layer, known structures and materials can be applied.

The film thickness of the organic semiconductor layer 16 is preferably thin as long as necessary functions are not impaired. Usually, it is 1 nm to 10 μm, preferably 5 nm to 5 μm, more preferably 10 nm to 1 μm.
The organic semiconductor layer 16 can be formed by, for example, a known film forming method such as a vacuum deposition method or spin coating. In particular, since the tetraamine derivative according to the present invention is soluble in an organic solvent, the organic semiconductor layer 16 can be formed by a coating (printing) method.

For the substrate 11, for example, an inorganic material such as glass, quartz, silicon, or ceramics, or a plastic material can be used.
For the gate electrode 12, the drain electrode 14, and the source electrode 15, for example, a metal such as gold, platinum, chromium, tungsten, tantalum, nickel, copper, aluminum, silver, magnesium or calcium, or an alloy thereof, or polysilicon Materials such as amorphous silicon, graphite, tin-doped indium oxide (ITO), zinc oxide, conductive polymer, and organic metal can be used, and well-known methods such as vacuum deposition, electron beam deposition, RF sputtering, and printing It can be formed by a film forming method.
The gate insulating layer 13, for _{example, SiO 2, Si 3 N 4} , SiON, Al 2 O 3, Ta 2 O 5, amorphous silicon, polyimide resin, polyvinyl phenol resins, polyparaxylylene resins, polystyrene resins, polymethyl Materials such as methacrylate resin, polyfluorocarbon resin, divinyltetramethylsiloxane benzocyclobutene resin, and the like can be used, and can be formed by a known film forming method similar to that for the gate electrode 12.

(Organic EL device)
An organic EL element is an element in which at least one organic compound layer including a light emitting layer is formed between an anode and a cathode. Typical element structures include (anode / hole transport layer / light emitting layer / cathode), (anode / light emitting layer / electron transport layer / cathode), (anode / hole transport layer / light emitting layer / electron transport layer / Cathode). When a predetermined DC voltage is applied between the anode and the cathode, light emission with high luminance can be obtained from the light emitting layer.

FIG. 2 shows an example of the layer structure of the organic EL element. The organic EL element shown in FIG. 2 is formed by laminating an anode 22, a hole transport layer 23, a light emitting layer 24, an electron transport layer 25, and a cathode 26 in this order on a substrate 21. The hole transport layer 23 and the electron transport layer 25 are organic layers including at least one tetraamine derivative according to the present invention. In addition, this organic layer may contain other organic compounds.
By applying the tetraamine derivative according to the present invention having excellent hole and electron (charge) transportability to the hole transport layer and the electron transport layer in this way, holes and electrons can be efficiently injected into the light emitting layer. And the luminous efficiency can be increased.

  The hole transport layer 23 and the electron transport layer 25 can be formed, for example, by a known film forming method such as a vacuum deposition method or spin coating. In particular, since the tetraamine derivative according to the present invention is soluble in an organic solvent, the hole transport layer 23 and the electron transport layer 25 can be formed by a coating (printing) method.

  In the case where the tetraamine derivative according to the present invention is not used for the hole transport layer 23 or the electron transport layer 25, as the hole transport layer 23, for example, N, N′-bis (3-methylphenyl) -N, N '-Bis (phenyl) -benzidine (TPD), N, N'-bis (naphthalen-1-yl) -N, N'-bis (phenyl) -2,2'-dimethylbenzidine (α-NPD), 2 , 2-bis (3- (N, N-di-p-triamino) phenyl) biphenyl (3DTAPBP) can be used. Examples of the electron transport layer 25 include 2- (4-biphenyl) -5- (4-tert-butylphenyl) -1,3,4-oxazole (PBD), 1,3-bis [2- ( 4-tert-butylphenyl) -1,3,4-oxadiazo-5-yl] benzene (OXD-7), 2,2 ′, 2 ″-(1,3,5-benzentriyl) -tris ( A material such as 1-phenyl-1-H-benzimidazole (TPBi) can be used.

  The light emitting layer 24 is preferably formed by adding a host material such as a quinolinol complex or an aromatic amine to a coloring material such as a coumarin derivative or DCM, quinacridone, or rubrene (doping). May be. Moreover, what doped the iridium metal complex may be used. Further, delayed fluorescence or room temperature phosphorescent material may be doped. The light emitting layer 24 can be formed by a known film forming method similar to the hole transport layer 23 and the electron transport layer 25.

For the substrate 21, for example, a transparent material such as glass or plastic can be used.
A material that transmits light is usually used for the anode 22. Specifically, tin-doped indium oxide (ITO), indium oxide, tin oxide, indium oxide, or zinc oxide alloy is preferable. A thin film of metal such as gold, platinum, silver or magnesium alloy can also be used. Organic materials such as polyaniline, polythiophene, polypyrrole or derivatives thereof can also be used.
The cathode 26 is preferably made of an alkaline metal such as Li, K, or Na or an alkaline earth metal such as Mg or Ca that has a low work function from the viewpoint of electron injection. It is also preferable to use stable Al or the like. In order to achieve both stability and electron injection property, a layer including two or more materials may be used.
The anode 22 and the cathode 26 can be formed by a known film forming method such as a vacuum evaporation method, an electron beam evaporation method, an RF sputtering method, or a coating (printing) method.

  In addition to the above layers, an electron injection layer, a hole injection layer, an electron block layer, a hole block layer, a protective layer, and the like may be provided. These layers can also be formed by a known film forming method similar to that for the hole transport layer 23 and the electron transport layer 25.

(Organic thin film solar cell)
An organic thin film solar cell is an element in which at least one organic compound layer including a photoelectric conversion layer is formed between an anode and a cathode. Typical element structures include (anode / photoelectric conversion layer / cathode), (anode / photoelectric conversion layer / electron transport layer / cathode), (anode / hole transport layer / photoelectric conversion layer / electron transport layer / cathode). Etc. When light is irradiated, holes and electrons are generated in the photoelectric conversion layer 33, and current can be taken out by connecting the anode 32 and the cathode 34.

In FIG. 3, the layer structure of an example of an organic thin film solar cell is shown. The organic thin film solar cell shown in FIG. 3 is formed by laminating an anode 32, a photoelectric conversion layer 33, and a cathode 34 in this order on a substrate 31. The photoelectric conversion layer 33 is an organic layer containing at least one tetraamine derivative according to the present invention. In addition, this organic layer may contain other organic compounds.
By applying the tetraamine derivative according to the present invention having excellent hole and electron (charge) transportability to a photoelectric conversion layer containing a hole transport material and an electron transport material, holes and electrons can be efficiently removed from the photoelectric conversion layer 33. And the photoelectric conversion efficiency can be increased.
In addition to the organic layer, known structures and materials can be applied.

  Examples of the material constituting the photoelectric conversion layer 33 together with the tetraamine derivative include poly (3-hexylthiophene-2,5-diyl) (P3HT) and poly [2-methoxy-5- (2) as a hole transport material. -Ethylhexyloxy) -1,4-phenylene vinylene] (MEH-PPV) and the like. Moreover, as an electron transport material, fullerene C60, (6,6) -phenyl-C61 butyric acid methyl ester (C61-PCBM), fullerene C70, (6,6) -phenyl-C71 butyric acid methyl ester (C71-PCBM) ) And the like.

  The photoelectric conversion layer 33 can be formed by, for example, a known film forming method such as a vacuum deposition method or spin coating. In particular, since the tetraamine derivative according to the present invention is soluble in an organic solvent, the photoelectric conversion layer 33 can be formed by a coating (printing) method.

The organic thin film solar cell may further be provided with a hole transport layer and / or an electron transport layer. In this case, at least one of the photoelectric conversion layer, the hole transport layer, and the electron transport layer is an organic layer containing at least one tetraamine derivative according to the present invention. In addition, this organic layer may contain other organic compounds.
By applying the tetraamine derivative according to the present invention excellent in hole and electron (charge) transportability to the hole transport layer, the hole is applied to the anode, or the electron is applied to the electron transport layer, to the cathode. Each can be efficiently transported and the photoelectric conversion efficiency can be increased.

  When the tetraamine derivative according to the present invention is not used for the hole transport layer or the electron transport layer, examples of the hole transport layer include poly (3,4-ethylenedioxythiophene) poly (styrene sulfonate) (PEDOT: A material such as PSS) can be used, and as the electron transport layer, for example, a material such as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) can be used. The hole transport layer and the electron transport layer can be formed by a known film forming method similar to that for the photoelectric conversion layer 33.

For the substrate 31, for example, a transparent material such as glass or plastic can be used.
For the anode 32, a light transmitting material is usually used. Specifically, tin-doped indium oxide (ITO), indium oxide, tin oxide, indium oxide, or zinc oxide alloy is preferable. A thin film of metal such as gold, platinum, silver or magnesium alloy can also be used. Organic materials such as polyaniline, polythiophene, polypyrrole or derivatives thereof can also be used.
For the cathode 34, it is preferable to use an alkali metal such as Li, K, or Na or an alkaline earth metal such as Mg or Ca that has a small work function from the viewpoint of electron extraction. It is also preferable to use stable Al or the like. In order to achieve both stability and electron extraction property, a layer including two or more materials may be used.
The anode 32 and the cathode 34 can be formed by a known film forming method such as a vacuum evaporation method, an electron beam evaporation method, an RF sputtering method, or a coating (printing) method.

(Display device)
Further, a display device in which the organic TFT and the organic EL element are combined will be described. FIG. 4 shows an example of a layer structure of the display device. The display device shown in FIG. 4 includes an organic EL element 120 composed of an anode 107, a hole transport layer 108, a light emitting layer 109, an electron transport layer 110, and a cathode 111 on a substrate 101 with a barrier layer 112 interposed therebetween, and a gate. An organic TFT element 121 including an electrode 102, a gate insulating film 103, a drain electrode 104, a source electrode 105, and an organic semiconductor layer 106 is provided. The upper part of these layer structures is covered with a protective film 113.
This display device has a structure in which the anode 107 of the organic EL element 120 and the drain electrode 104 of the organic TFT element 121 are electrically connected. Therefore, when a voltage is applied to the gate electrode 102, a current flows between the source / drain electrodes 104 and 105, and the organic EL element 120 emits light. Thus, driving and lighting of the organic EL element are controlled by the organic TFT element.
The tetraamine derivative according to the present invention as described above is applied to at least one of the organic TFT element and the organic EL element, preferably both.
By arranging display device elements (pixels) combining such organic TFT elements for switching and organic EL elements in a matrix, an active matrix type organic EL display excellent in luminous efficiency and responsiveness is configured. be able to.
The organic TFT element and the organic EL element can be applied with known structures and materials except that the tetraamine derivative is applied as described above, and can be manufactured by a known method.

  The display device may have a structure in which the cathode and the drain electrode of the organic TFT element are electrically connected instead of the anode of the organic EL element. Moreover, it can also be set as the structure which provided two organic TFT elements with respect to one organic EL element.

As the substrate 101, it is preferable to use a plastic substrate excellent in heat resistance, dimensional stability, solvent resistance, electrical insulation, workability, low air permeability and low moisture absorption. Examples thereof include polyethylene terephthalate, polyethylene naphthalate, polystyrene, polycarbonate, polyacrylate, polyimide, and the like.
In this case, it is preferable to provide a moisture permeation preventing layer (gas barrier layer) on one or both surfaces of the substrate. The moisture permeation preventive layer is preferably composed of an inorganic material such as silicon nitride or silicon oxide, and can be formed by a known film forming method such as an RF sputtering method.
Furthermore, you may provide a hard-coat layer and an undercoat layer as needed.

EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not restrict | limited by the following Example.
Example 1 Synthesis of Tetraamine Derivative According to Scheme A above, compound (C1) (1,3,6,8-tetramethyl-6,8-dihydropyrimido [4,5,6-gh] perimidine-2, 7 (1H, 3H) -dione) was synthesized.

(1-1) Synthesis of compound (C1a)

1,8-Diaminonaphthalene (6.01 g, 38.0 mmol) was finely powdered using a mortar and pestle and placed in a 100 mL glass container. Then, 9.50 mL of 10M hydrochloric acid was added, and after stirring, water was removed under reduced pressure and dried. 2.31 g (38.5 mmol) of urea was added and reacted at 130 ° C. for 6 hours.
After cooling to room temperature, the reaction solid was washed with water and ethanol and filtered to obtain 8.50 g of a crude product. The crude product was purified by sublimation to obtain 4.19 g of compound (C1a) as a pale red solid.

The physical property values of the compound (C1a) were as follows. Hereinafter, the measurement was performed at room temperature unless otherwise specified.
¹ H-NMR: δ / ppm (500 MHz, DMSO-d ₆ ) = 10.09 (s, 2H); 7.20 (dd, 2H); 7.09 (d, 2H); 6.51 (d, 2H).
¹³ C-NMR: δ / ppm (125 MHz, DMSO-d ₆ ) = 150.1; 137.6; 134.1; 128.0; 117.6; 113.6; 104.0.

(1-2) Synthesis of compound (C1b)

A 100 mL glass reaction vessel equipped with a stirrer was charged with 2.14 g (11.6 mmol) of compound (C1a) and 85 mL of dimethyl sulfoxide, and stirred for 10 minutes until completely dissolved. At room temperature, 70 mL of an aqueous solution of 1.97 g (35.1 mmol) of potassium hydroxide was added and stirred for 15 minutes. Subsequently, 13.6 g (95.6 mmol) of iodomethane was added dropwise and stirred at room temperature for 12 hours.
The reaction solution was neutralized with hydrochloric acid, extracted with ethyl acetate, dried over sodium sulfate, and the solvent was evaporated. The obtained crude product was purified by silica gel chromatography to obtain 1.94 g of compound (C1b) as a pale yellow solid.

The physical property values of the compound (C1b) were as follows.
¹ H-NMR: δ / ppm (500 MHz, CDCl ₃ ) = 7.37 (dd, 2H); 7.29 (d, 2H); 6.57 (d, 2H); 3.44 (s, 6H) .
¹³ C-NMR: δ / ppm (125 MHz, CDCl ₃ ) = 151.0; 137.8; 134.3; 127.8; 119.2; 114.8; 104.0;

(1-3) Synthesis of compound (C1c)

In a 300 mL glass reaction vessel equipped with a stirrer, 2.03 g (9.56 mmol) of compound (C1b) and 200 mL of glacial acetic acid were added, and 1.5 mL of concentrated nitric acid (70%) and ice were kept at 30 ° C. or lower. 50 mL of acetic acid was added dropwise over 10 minutes and refluxed for 1 hour.
After cooling to room temperature, the resulting reaction solid was filtered, washed with acetic acid and dried to give 1.50 g of a crude product. The crude product was recrystallized from chloroform to obtain 1.47 g of compound (C1c) as a yellow solid.

The physical property values of the compound (C1c) were as follows.
¹ H-NMR: δ / ppm (500 MHz, CDCl ₃ ) = 8.38 (d, 2H); 6.89 (d, 2H); 3.65 (s, 6H).
¹³ C-NMR: δ / ppm (125 MHz, CDCl ₃ ) = 142.1; 130.0; 104.8; 32.1.

(1-4) Synthesis of compound (C1d)

A 100 mL glass reaction vessel equipped with a stirrer was charged with 0.44 g (1.47 mmol) of compound (C1c), 0.054 g of 5% palladium carbon and 40 mL of dimethylformamide, the reaction vessel was replaced with hydrogen gas, And stirred overnight.
The reaction solution was warmed to 50 ° C. and filtered. The filtrate was concentrated at room temperature to obtain 0.30 g of compound (C1d) as a brown solid.

The physical property values of the compound (C1d) were as follows.
¹ H-NMR: δ / ppm (500 MHz, DMSO-d ₆ ) = 6.58 (d, 2H); 6.41 (d, 2H); 5.15 (s, 4H); 3.21 (s, 6H).
¹³ C-NMR: δ / ppm (125 MHz, DMSO-d ₆ ) = 150.3; 139.4; 129.5; 117.2; 116.9; 112.7; 105.9;

(1-5) Synthesis of Compound (C1e)

In a glass container with a capacity of 30 mL, 0.80 g (3.31 mmol) of the compound (C1d) and 0.85 mL of 10M hydrochloric acid were added, and after stirring, water was removed under reduced pressure and dried. 0.40 g (6.61 mmol) of urea was added and reacted at 130 ° C. for 6 hours.
After cooling to room temperature, the reaction solid was washed with water and ethanol and filtered to obtain 0.83 g of compound (C1e) as a red solid.

The physical property values of the compound (C1e) were as follows.
¹ H-NMR: δ / ppm (500 MHz, DMSO-d ₆ ) = 9.54 (s, 2H); 6.37 (d, 2H); 6.35 (d, 2H); 3.16 (s, 6H).

(1-6) Synthesis of compound (C1)

A 20 mL glass reaction vessel equipped with a stirrer was charged with 0.13 g (0.50 mmol) of compound (C1e) and 8 mL of dimethyl sulfoxide, and stirred for 10 minutes until completely dissolved. At room temperature, 3.5 mL of an aqueous solution of 0.085 g (1.50 mmol) of potassium hydroxide was added and stirred for 15 minutes. Subsequently, 0.28 g (2.00 mmol) of iodomethane was added dropwise and stirred at room temperature for 4 hours.
The reaction solution was neutralized with hydrochloric acid, extracted with ethyl acetate, dried over sodium sulfate, and the solvent was evaporated. The resulting crude product was purified by sublimation to obtain 0.075 g of compound (C1) as a yellow solid.

The physical property values of the compound (C1) were as follows.
¹ H-NMR: δ / ppm (500 MHz, CDCl ₃ ) = 6.42 (s, 4H); 3.33 (s, 12H).
¹³ C-NMR: δ / ppm (125 MHz, CDCl ₃ ) = 151.0; 131.6; 115.5; 105.6; 30.4.
When the crystal structure analysis of the compound (C1) was conducted, a preferable crystal structure of a π-π stack type was shown. When the solubility was evaluated, 0.5 wt% of the compound (C1) was completely dissolved in chloroform at 60 ° C.

Comparative Example 1 Synthesis of Tetraamine Derivative Compound (C1) was synthesized through the steps shown below using compound (C1d) obtained in the step (1-4) of Example 1 (above Non-Patent Document 3).

(RC1-1) Synthesis of Compound (RC1a)

In a glass container having a capacity of 50 mL, 0.80 g (3.31 mmol) of the compound (C1d), 4.41 ml (30.0 mmol) of diethyl carbonate and 20 ml of dimethylformamide were reacted at 80 ° C. for 3 hours.
After cooling to room temperature, dichloromethane was added and the reaction solid was filtered. The obtained crude product was recrystallized from dimethylformamide to obtain 1.08 g of compound (RC1a) as a colorless solid.

The physical property values of the compound (RC1a) were as follows.
¹ H-NMR: δ / ppm (500 MHz, CDCl ₃ ) = 8.73 (s, 2H); 7.37 (d, 2H); 6.75 (d, 2H); 4.05 (q, 4H) 3.36 (s, 6H); 1.21 (t, 6H).

(RC1-2) Synthesis of Compound (RC1b)

In a glass container with a capacity of 200 mL, 1.08 g (2.81 mmol) of the compound (RC1a), 10 mL (0.16 mol) of iodomethane, 0.5 mL of water, 10 g of barium oxide and 130 mL of dimethylformamide are allowed to react at room temperature for 12 hours. It was.
After removing the inorganic salt by centrifugation, the solid was washed with dichloromethane. The obtained solutions were combined, washed with 2M hydrochloric acid and water, dried over sodium sulfate, and the solvent was distilled off. The resulting crude product was purified by silica gel chromatography to obtain 0.48 g of compound (RC1b) as a colorless solid.

The physical property values of the compound (RC1b) were as follows.
¹ H-NMR: δ / ppm (500 MHz, CDCl ₃ ) = 7.35-7.40 (m, 2H); 6.82 (d, 2H); 3.89-4.12 (m, 4H); 3.39 (s, 6H); 2.98-3.10 (m, 6H); 0.95-1.30 (m, 6H).

(RC1-3) Synthesis of Compound (C1)

In a glass tube, 0.48 g (1.18 mmol) of the compound (RC1b) was put and pyrolyzed at 700 ° C. The pyrolyzate was dissolved in dichloromethane and purified by silica gel chromatography to obtain 0.035 g of compound (C1) as a yellow solid.
The total yield was 1/10 or less compared to Example 1.

Example 2 Synthesis of Tetraamine Derivative According to Scheme B above, compound (C2) (6,8-dihydropyrimido [4,5,6-gh] perimidine-2,7 (1H, 3H) -dione) was synthesized. did.

(2-1) Synthesis of compound (C2a)

A 200 mL glass reaction vessel equipped with a stirrer is charged with 50 mL of concentrated sulfuric acid and 56 mL of fuming nitric acid (d = 1.51), followed by 19.6 g (90.0 mmol) of 1,5-dinitronaphthalene, Stirring was carried out at 80 ° C. for 2.5 hours.
The reaction solid obtained was cooled to room temperature and filtered. After washing with 200 mL of hot ethanol, it was washed twice with 75 mL of acetone and dried to obtain 4.03 g of compound (C2a) as a colorless solid.

The physical property values of the compound (C2a) were as follows.
¹ H-NMR: δ / ppm (500 MHz, DMSO-d ₆ ) = 8.83 (s, 4H).

(2-2) Synthesis of compound (C2)

To a 200 mL glass reaction vessel equipped with a stirrer, 20.4 g (90.2 mmol) of tin chloride dihydrate and 90 mL of concentrated hydrochloric acid were added and heated to 40 ° C. Subsequently, 1.86 g (6.03 mmol) of compound (C2a) and 40 mL of ethanol were added dropwise and stirred for 3 hours.
The reaction solid obtained was cooled to room temperature and filtered. After washing with ethanol and drying, 1.80 g of a reduced form of compound (C2a) was obtained.

Next, 1.80 g of the obtained solid and 0.98 g (16.2 mmol) of urea were placed in a 20 mL glass reaction vessel equipped with a stirrer, and reacted at 130 ° C. for 6 hours.
After cooling to room temperature, the reaction solid was washed with warm water and filtered to obtain 0.97 g of a crude product. The crude product was washed with warm water using a Soxhlet extractor to obtain 0.89 g of compound (C2) as a dark red solid.

The physical property values of the compound (C2) were as follows.
¹ H-NMR: δ / ppm (500 MHz, DMSO-d ₆ ) = 9.39 (s, 4H); 6.15 (s, 4H).

Example 3 Synthesis of Tetraamine Derivative According to Scheme B above, compound (C1) (1,3,6,8-tetramethyl-6,8-dihydropyrimido [4,5,6-gh] perimidine-2, 7 (1H, 3H) -dione) was synthesized.

In a 50 mL glass reaction vessel equipped with a stirrer, 0.048 g (2.00 mmol) of sodium hydride washed with hexane and dried and 30 ml of dimethylformamide were added and stirred. At room temperature, 0.13 g (0.53 mmol) of compound (C2) was added and stirred for 10 minutes. Subsequently, 0.76 ml (8.00 mmol) of iodomethane was added dropwise and stirred at room temperature for 20 hours.
Pure water was added, and the resulting crude product was filtered and purified by sublimation to obtain 0.035 g of compound (C1) as a yellow solid.

The physical property values of the compound (C1) were as follows.
¹ H-NMR: δ / ppm (500 MHz, CDCl ₃ ) = 6.42 (s, 4H); 3.33 (s, 12H).

[Example 4]
According to Scheme A above, compound (C4) (1,3,6,8-tetrahexyl-6,8-dihydropyrimido [4,5,6-gh] perimidine-2,7 (1H, 3H) -dione) Was synthesized.

(4-1) Synthesis of compound (C4a)

To a 100 mL glass reaction vessel equipped with a stirrer is added 1.12 g (6.08 mmol) of the compound (C1a) obtained in the step (1-1) of Example 1 and 35 mL of dimethyl sulfoxide, and completely dissolved. Stir for 10 minutes. Then, 18 mL of an aqueous solution of 1.38 g (24.6 mmol) of potassium hydroxide was added at room temperature and stirred for 15 minutes. Subsequently, 3.40 mL (24.2 mmol) of bromohexane was added dropwise and stirred at 90 ° C. for 20 hours.
The reaction solution was neutralized with hydrochloric acid, extracted with ethyl acetate, dried over sodium sulfate, and the solvent was evaporated. The resulting crude product was purified by silica gel chromatography to obtain 1.58 g of compound (C4a) as a pale yellow solid.

The physical property values of the compound (C4a) were as follows.
¹ H-NMR: δ / ppm (500 MHz, CDCl ₃ ) = 7.32 (dd, 2H); 7.23 (d, 2H); 6.55 (d, 2H); 3.98 (t, 4H) 1.73 (m, 4H); 1.43 (m, 4H); 1.35 (m, 8H); 0.90 (t, 6H).

(4-2) Synthesis of compound (C4b)

To a 100 mL glass reaction vessel equipped with a stirrer, 1.07 g (3.04 mmol) of compound (C4a) and 50 mL of glacial acetic acid are added, and 0.34 mL of concentrated nitric acid (70%) and ice are kept at 30 ° C. or lower. 3 mL of acetic acid was combined, added dropwise over 10 minutes, and refluxed for 1 hour.
After cooling to room temperature, the obtained reaction solid was filtered, washed with acetic acid and dried to obtain 0.46 g of compound (C4b) as a yellow solid.

The physical property values of the compound (C4b) were as follows.
¹ H-NMR: δ / ppm (500 MHz, CDCl ₃ ) = 8.35 (d, 2H); 6.84 (d, 2H); 4.14 (t, 4H); 1.76 (m, 4H) 1.46 (m, 4H); 1.37 (m, 8H); 0.91 (t, 6H).

(4-3) Synthesis of compound (C4c)

A 200 mL glass reaction vessel equipped with a stirrer was charged with 0.79 g (1.79 mmol) of compound (C4b), 0.094 g of 5% palladium carbon and 75 mL of dimethylformamide, and the reaction vessel was replaced with hydrogen gas. And stirred overnight.
The reaction solution was filtered, and the filtrate was concentrated at room temperature. The obtained solid was dissolved in ethyl acetate and washed with water, and then the solvent was distilled off to obtain 0.65 g of compound (C4c) as a brown solid.

The physical property values of the compound (C4c) were as follows.
¹ H-NMR: δ / ppm (500 MHz, CDCl ₃ ) = 6.52 (d, 2H); 6.33 (d, 2H); 4.32 (s, 4H); 3.87 (t, 4H) 1.67 (m, 4H); 1.40 (m, 4H); 1.33 (m, 8H); 0.89 (t, 6H).

(4-4) Synthesis of compound (C4d)

In a glass container with a capacity of 30 mL, 0.36 g (0.94 mmol) of compound (C4c) and 0.5 mL of 10M hydrochloric acid were added, and after stirring, water was removed under reduced pressure and dried. 0.24 g (4.00 mmol) of urea was added and reacted at 130 ° C. for 20 hours.
After cooling to room temperature, the reaction solid was washed with water. After dissolving in chloroform, the mixture was filtered and the solvent was distilled off to obtain 0.16 g of compound (C4d) as a brown solid.

The physical property values of the compound (C4d) were as follows.
¹ H-NMR: δ / ppm (500 MHz, DMSO-d ₆ ) = 9.45 (s, 2H); 6.32 (d, 2H); 6.26 (d, 2H); 3.67 (t, 4H); 1.47 (m, 4H); 1.35-1.15 (m, 12H); 0.80 (t, 6H).

(4-5) Synthesis of compound (C4)

In a 20 mL glass reaction vessel equipped with a stirrer, 0.10 g (0.25 mmol) of the compound (C4d) and 10 mL of dimethyl sulfoxide were added and stirred for 10 minutes until completely dissolved. At room temperature, 5 mL of an aqueous solution of 0.056 g (1.00 mmol) of potassium hydroxide was added and stirred for 15 minutes. Subsequently, 0.14 ml (1.00 mmol) of 1-bromohexane was added dropwise and stirred at 90 ° C. for 1 hour.
Pure water was added and filtered, and the resulting solid was dissolved in ethyl acetate, washed with water and dried over sodium sulfate, and the solvent was distilled off. The resulting crude product was purified by silica gel chromatography to obtain 0.067 g of compound (C4) as a yellow solid.

The physical property values of the compound (C4) were as follows.
¹ H-NMR: δ / ppm (500 MHz, CDCl ₃ ) = 6.34 (s, 4H); 3.83 (t, 8H); 1.66 (m, 8H); 1.39 (m, 8H) 1.33 (m, 16H); 0.89 (t, 12H).
¹³ C-NMR: δ / ppm (125 MHz, CDCl ₃ ) = 150.7; 130.6; 116.9; 105.5; 43.3; 31.7; 26.7; 25.9; ; 14.1.

Example 5 Production of Organic TFT Using the compound (C1) obtained in Example 1, an organic semiconductor layer was produced by spin coating to produce an organic TFT and evaluated.

(Production of substrate)
A commercially available low-resistance silicon wafer having a surface formed with 200 nm thick thermally oxidized silicon was used. This was made to function as the gate electrode of organic TFT. A silicon oxide film was used as the gate insulating film.
The silicon wafer was washed with a mixed solution of hydrogen peroxide and sulfuric acid, and the surface was cleaned by UV ozone treatment immediately before being used in the next step to obtain a bare substrate.

(Substrate surface modification)
The bare substrate was immersed in commercially available hexamethyldisilazane and allowed to stand for 10 hours or more to modify the substrate surface to obtain an HMDS treated substrate.

(Formation of organic semiconductor layer)
Compound (C1) is added to chloroform so that the concentration becomes 0.5 wt%, and 0.2 mL of a solution prepared by heating at 60 ° C. is dropped on the HMDS-treated substrate and spin-coated at 2000 rpm for 1 minute in a nitrogen atmosphere. An organic semiconductor layer having a thickness of about 20 nm was formed. And it heated at 100 degreeC for 30 minutes in nitrogen atmosphere.
When the appearance of the film was visually observed, it was confirmed that a uniform thin film was formed and the film could be formed satisfactorily.

(Production of source / drain electrodes)
On the organic semiconductor layer, using a metal mask, gold was deposited by a vacuum deposition method to form source / drain electrodes. The channel width was 1000 μm, the channel length was 70 μm, and the electrode layer thickness was 50 nm.

(Evaluation of organic TFT)
When the transfer characteristics of the fabricated organic TFT were measured under the condition of a drain voltage of 100 V using a semiconductor characteristic evaluation system 4200-SCS type (KEITHLEY), p-type semiconductor characteristics were shown.
FIG. 5 shows the obtained electrical characteristics. In the graph of FIG. 5, the horizontal axis indicates the gate voltage (V), and the vertical axis indicates the drain current (A).

Further, the field effect mobility μ was calculated from the threshold voltage and the drain current value at a predetermined gate voltage obtained from the measurement result of the transfer characteristics according to the following formula, and 10 ⁻⁴ cm ² / Vs.
Id = (W / 2L) μCi (Vg−Vt) ²
Here, Id is a drain current, W is a channel width, L is a channel length, Ci is a capacitance per unit area of the insulating layer, Vg is a gate voltage, and Vt is a threshold voltage.

  From the above results, it can be said that the compound (C1) has both solution process (application) adaptability and good semiconductor properties.

[Comparative Example 1] Production of organic TFT Using tetrathiafulvalene (TTF) having a donor property equivalent to that of compound (C1), an organic semiconductor layer was spin-coated on a HMDS-treated substrate in the same manner as in Example 5. An organic TFT was fabricated and evaluated.

(Formation of organic semiconductor layer)
0.2 mL of a solution prepared by adding TTF to chloroform to 0.5 wt% was dropped on the HMDS-treated substrate, and spin coating was performed at 2000 rpm for 1 minute in a nitrogen atmosphere.
When the appearance of the film was visually observed, it was not formed uniformly.

(Evaluation of organic TFT)
When the transfer characteristics of the produced organic TFT were measured under the condition of a drain voltage of 100 V, the organic TFT did not show transistor characteristics.

11, 21, 31, 101 Substrate 12, 102 Gate electrode 13, 103 Gate insulating film 14, 104 Drain electrode 15, 105 Source electrode 16, 106 Organic semiconductor layer 22, 32, 107 Anode 23, 108 Hole transport layer 24, 109 Light-Emitting Layer 33 Photoelectric Conversion Layer 25, 110 Electron Transport Layer 26, 34, 111 Cathode 112 Barrier Layer 113 Protection Layer 120 Organic EL Element 121 Organic TFT

Claims (12)

A tetraamine derivative having a cyclic urea bond having a skeleton of naphthalene or perylene represented by the following general formula (1).

(Wherein R ₁ and R ₂ are each independently a hydrogen atom, a linear or branched alkyl group, an alkyl group containing at least one fluorine atom, an aryl group, a heterocyclic group, or And any of these may be the same or different, except that when n = 0, both R ₁ and R ₂ are methyl groups.)

(In the formula, R is a linear or branched alkyl group.) The tetraamine derivative according to claim 1, wherein R ₁ is a methyl group and R ₂ is an alkyl group having 2 or more carbon atoms. The tetraamine derivative according to claim _1, wherein R ₁ and R ₂ are both alkyl groups having 2 or more carbon atoms. The tetraamine derivative according to claim _1, wherein R ₁ and R ₂ are both hydrogen atoms.   The tetraamine derivative according to any one of claims 1 to 4, which is soluble in water or an organic solvent. A tetraamine derivative characterized in that in the method for synthesizing a tetraamine derivative having a cyclic urea bond having naphthalene or perylene as a skeleton represented by the following general formula (1), a cyclic urea bond is formed by using urea as a reaction reagent. Synthesis method.

(Wherein R ₁ and R ₂ are each independently a hydrogen atom, a linear or branched alkyl group, an alkyl group containing at least one fluorine atom, an aryl group, a heterocyclic group, or ), And any of them may be the same or different.)

(In the formula, R is a linear or branched alkyl group.) An organic semiconductor ink comprising a tetraamine derivative having a cyclic urea bond having a skeleton of naphthalene or perylene represented by the following general formula (1):

(Wherein R ₁ and R ₂ are each independently a hydrogen atom, a linear or branched alkyl group, an alkyl group containing at least one fluorine atom, an aryl group, a heterocyclic group, or ), And any of them may be the same or different.)

(In the formula, R is a linear or branched alkyl group.) An organic electronic device comprising an organic layer containing a tetraamine derivative having a cyclic urea bond having naphthalene or perylene represented by the following general formula (1) as a skeleton.

(Wherein R ₁ and R ₂ are each independently a hydrogen atom, a linear or branched alkyl group, an alkyl group containing at least one fluorine atom, an aryl group, a heterocyclic group, or ), And any of them may be the same or different.)

(In the formula, R is a linear or branched alkyl group.)   The organic electronic device is an organic thin film transistor including a gate electrode, a gate insulating layer, an organic semiconductor layer, a source electrode, and a drain electrode on a substrate, and the organic semiconductor layer includes the tetraamine derivative. The organic electronic device according to claim 8, wherein the organic electronic device is an organic layer.   The organic electronic device is an organic electroluminescent device comprising an anode, a light emitting layer, a hole transport layer and / or an electron transport layer, and a cathode on a substrate, and the hole transport layer and / or the electron 9. The organic electronic device according to claim 8, wherein the transport layer is an organic layer containing the tetraamine derivative.   The organic electronic device is an organic thin-film solar cell including an electrode and a photoelectric conversion layer including a hole transport material and an electron transport material on a substrate, and the photoelectric conversion layer includes an organic layer including the tetraamine derivative. The organic electronic device according to claim 8, wherein:   The organic electronic device is an organic thin-film solar cell including an electrode, a hole transport layer and / or an electron transport layer, and a photoelectric conversion layer on a substrate, and the hole transport layer and / or the electron transport layer. Is an organic layer containing the tetraamine derivative.

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