JP7290948B2 - Perylene derivative compound, composition for organic semiconductor using said compound, organic thin film transistor using said composition for organic semiconductor - Google Patents

Description

The present invention relates to a perylene derivative compound, an organic semiconductor composition using the compound, an organic semiconductor device and an organic thin film transistor using the organic semiconductor composition.

Conventionally, thin-film transistors using silicon-based inorganic materials as inorganic semiconductor materials have been widely used, but since these films are formed at high temperatures, they are lightweight and flexible as substrates for thin displays. Plastic materials have the disadvantage that they cannot be used due to their poor heat resistance. Therefore, in recent years, in place of silicon-based inorganic materials, organic thin-film transistors using organic compounds exhibiting properties as semiconductors have been actively developed as organic semiconductor materials.

In the formation of an organic semiconductor layer containing an organic semiconductor material in an organic thin film transistor, a solution process that is produced in the air compared to a vacuum vapor deposition process that is produced under high temperature in a vacuum can reduce the production cost of the organic thin film transistor element. It becomes easy to increase the size. Furthermore, the temperature required for film formation can be lowered, making it possible to use a plastic material or the like for the substrate. Therefore, there is a demand for an organic semiconductor material that can be applied to a flexible device and that can be applied to a solution process.

Organic semiconductors forming the organic semiconductor layer are classified into p-type organic semiconductor materials in which holes flow as carriers and n-type organic semiconductor materials in which electrons flow as carriers. Many p-type organic semiconductor materials have been reported so far.

On the other hand, materials such as perylene derivatives and fullerenes are being developed as n-type organic semiconductor materials, but they have low solubility in solvents and low compatibility with solution processes.

In addition, high-performance n-type organic semiconductor materials are necessary for the construction of pn junctions and integrated circuits. Its electron mobility is still low compared to p-type organic semiconductor materials.

As described above, there is a demand for the development of organic semiconductor materials that have both high solubility in solvents suitable for solution processes and high carrier mobility.

Special table 2007-527114 Special table 2008-524846 Special table 2017-52139 JP 2015-115490

Angew. Chem. Int. Ed. 2004, 43, p. 6363-6366 J. Org. Chem. 2014, 79, p. 6655-6662

The problem to be solved by the present invention is to provide an n-type organic semiconductor material having high solubility corresponding to a solution process, and further to provide a high electron mobility composition using the n-type organic semiconductor material as an organic semiconductor composition. An object of the present invention is to provide an organic semiconductor device and an organic thin film transistor.

In order to solve the above problems, the inventors have made intensive studies on n-type organic semiconductor materials with solubility suitable for solution processes and organic thin-film transistors with excellent electron mobility. It has been found that an organic thin film transistor with high mobility can be obtained by using a compound with improved properties as an n-type organic semiconductor material and by incorporating the compound into the organic semiconductor layer. That is, the gist of the present invention is as follows.

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

[In the formula, R ¹ and R ¹⁰ are different from each other,
hydrogen atom, halogen atom,
an optionally substituted linear or branched alkyl group having 1 to 20 carbon atoms,
an optionally substituted linear or branched alkenyl group having 1 to 20 carbon atoms,
an aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent,
or represents an optionally substituted heterocyclic group having 2 to 36 carbon atoms.
R ² to R ⁹ may be the same or different,
hydrogen atom, halogen atom, cyano group, hydroxyl group, nitro group, nitroso group, thio group, amino group,
an optionally substituted linear or branched alkyl group having 1 to 20 carbon atoms,
or an optionally substituted linear or branched alkenyl group having 1 to 20 carbon atoms,
R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁸ and R ⁹ may combine with each other to form a ring. ]

2. A compound in which R ¹ or R ¹⁰ in the general formula (1) is a monovalent group represented by the following general formula (2).

[In the formula, R ¹¹ to R ¹⁵ may be the same or different, and are hydrogen atoms, halogen atoms,
an optionally substituted linear or branched alkyl group having 1 to 20 carbon atoms,
an optionally substituted linear or branched alkenyl group having 1 to 20 carbon atoms,
or represents an aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent.
n represents an integer of 0 to 5;
At least one of R ¹¹ to R ¹⁵ may be substituted with a fluorine atom. ]

3. A compound which is a monovalent group represented by the following general formula (3) or (4) in the general formula (2).

[In the formula, n represents an integer of 0 to 5, and m represents an integer of 0 to 10. ]

4. A compound in which R ¹ to R ¹⁰ contain at least one fluorine atom in the general formula (1).

5. In the general formula (1), R ³ , R ⁴ , R ⁷ and R ⁸ are at least one cyano group, or an optionally substituted linear or branched chain having 1 to 4 carbon atoms. A compound that is an alkyl group of

6. The compound described above, which has a solubility of 0.02 to 5% by mass in an aromatic organic solvent or a halogenated organic solvent at 25±2°C.

7. A composition for an organic semiconductor containing the above compound.

8. An organic semiconductor element using the composition for an organic semiconductor.

9. The organic semiconductor device as described above, which has a mobility of 10 ⁻³ cm ² /Vs or more.

10. An organic thin film transistor using the organic semiconductor element.

The perylene derivative compound according to the present invention can provide an n-type organic semiconductor material having solubility in an organic solvent suitable for a solution process, and furthermore, a composition for an organic semiconductor containing the organic semiconductor material can be used. Thus, an organic thin film transistor having excellent electron mobility can be obtained.

1 is a schematic cross-sectional view showing the configuration of a bottom-gate/bottom-contact organic thin film transistor according to an embodiment of the present invention; FIG.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail. The compound represented by the general formula (1) of the present invention is dissolved in a solvent, an organic semiconductor layer is formed using a composition for an organic semiconductor containing the compound, and the layer is used as an organic semiconductor element. In the specification of the present application, the organic semiconductor composition and the organic semiconductor layer contain at least one compound represented by the general formula (1), and optionally other semiconductor materials not belonging to the present invention. and the like.

The compounds represented by formula (1) are specifically described below, but the present invention is not limited thereto. In the specification of the present application, a numerical range represented by "-" means a range including the numerical values described before and after "-" as lower and upper limits.

In the present invention, the "halogen atom" includes fluorine, chlorine, bromine and iodine.

In the general formula (1), the "linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted" represented by R ¹ or R ¹⁰ 20 linear or branched alkyl groups" specifically include methyl group, ethyl group, n-propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group. , isopropyl group, isobutyl group, s-butyl group, t-butyl group, isooctyl group, t-octyl group and the like.

In the general formula (1), in the "linear or branched alkenyl group optionally having 1 to 20 carbon atoms" represented by R ¹ or R ¹⁰ , "1 to 1 carbon atoms 20 linear or branched alkenyl group" specifically includes vinyl group, 1-propenyl group, allyl group, 1-butenyl group, 2-butenyl group, 1-pentenyl group, 1-hexenyl group, Examples include an isopropenyl group, an isobutenyl group, or a linear or branched alkenyl group having 2 to 18 carbon atoms in which a plurality of these alkenyl groups are bonded.

In the general formula (1), the "aromatic hydrocarbon group having 6 to 36 carbon atoms which may be substituted" represented by R ¹ or R ¹⁰ Specific examples of "hydrocarbon group" include phenyl group, biphenyl group, terphenyl group, naphthyl group, biphenyl group, anthracenyl group (anthryl group), phenanthryl group, fluorenyl group, indenyl group, pyrenyl group, perylenyl group, fluorane Examples include a thenyl group and a triphenylenyl group. In the present invention, the aromatic hydrocarbon group includes "condensed polycyclic aromatic group" and "aryl group".

In the general formula (1), the "heterocyclic group having 2 to 36 carbon atoms" in the "heterocyclic group having 2 to 36 carbon atoms which may be substituted" represented by R ¹ or R ¹⁰ Specifically, pyridyl group, pyrimidylinyl group, triazinyl group, thienyl group, furyl group (furanyl group), pyrrolyl group, imidazolyl group, pyrazolyl group, triazolyl group, quinolyl group, isoquinolyl group, naphthyldinyl group, acridinyl group, phenyl nantholinyl group, benzofuranyl group, benzothienyl group, oxazolyl group, indolyl group, carbazolyl group, benzoxazolyl group, thiazolyl group, benzothiazolyl group, quinoxalinyl group, benzimidazolyl group, pyrazolyl group, dibenzofuranyl group, dibenzothienyl group , a carbonylyl group, and the like.

In the general formula (1), represented by R ¹ or R ¹⁰ is "a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent", "a A linear or branched alkenyl group having 1 to 20 carbon atoms which may be substituted", "an aromatic hydrocarbon group having 6 to 36 carbon atoms which may have Specific examples of the "substituent" in the heterocyclic group optionally having 2 to 36 carbon atoms include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; a cyano group; a hydroxyl group; nitro group; nitroso group; carboxyl group;
carboxylic acid ester groups such as a methyl ester group and an ethyl ester group;
methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-pentyl group, isopentyl group, n-hexyl group, 2-ethylhexyl group, linear or branched alkyl groups having 1 to 18 carbon atoms such as heptyl group, octyl group, isooctyl group, nonyl group and decyl group;
Linear or branched chain having 2 to 20 carbon atoms such as vinyl group, 1-propenyl group, allyl group, 1-butenyl group, 2-butenyl group, 1-pentenyl group, 1-hexenyl group, isopropenyl group, isobutenyl group, etc. -shaped alkenyl group;
linear or branched alkoxy groups having 1 to 18 carbon atoms such as methoxy, ethoxy, propoxy, t-butoxy, pentyloxy and hexyloxy;
aromatic hydrocarbon groups having 6 to 30 carbon atoms such as phenyl group, naphthyl group, anthryl group, phenanthryl group and pyrenyl group;
pyridyl group, pyrimidylinyl group, triazinyl group, thienyl group, furyl group (furanyl group), pyrrolyl group, imidazolyl group, pyrazolyl group, triazolyl group, quinolyl group, isoquinolyl group, naphthyldinyl group, acridinyl group, phenanthrolinyl group, benzofuranyl benzothienyl group, oxazolyl group, indolyl group, carbazolyl group, benzoxazolyl group, thiazolyl group, benzothiazolyl group, quinoxalinyl group, benzimidazolyl group, pyrazolyl group, dibenzofuranyl group, dibenzothienyl group, carbonylyl group, etc. a heterocyclic group having 2 to 30 atoms;
A straight or branched alkyl group having 1 to 18 carbon atoms, such as dimethylamino group, diethylamino group, ethylmethylamino group, methylpropylamino group, di-t-butylamino group, diphenylamino group, or carbon a monosubstituted or disubstituted amino group having 0 to 18 carbon atoms and having a substituent selected from aromatic hydrocarbon groups having 6 to 18 atoms;
a thio group having 1 to 18 carbon atoms such as a methylthio group, an ethanethio group, a propylthio group, a di-t-butylthio group, a hex-5-ene-3-thio group, a phenylthio group and a biphenylthio group;
etc. can be given. Only one of these "substituents" may be included, or a plurality of them may be included, and when a plurality of "substituents" are included, they may be the same or different. Moreover, these "substituents" may further have the substituents exemplified above. Only one of these "substituents" may be included, or a plurality of them may be included, and when a plurality of "substituents" are included, they may be the same or different. Moreover, at least one or more fluorine atoms may be contained.

In general formula (1), R ¹ and R ¹⁰ are different from each other, and may have a linear or branched alkyl group having 1 to 4 carbon atoms which may have a substituent, or a substituent. It is preferably an aromatic hydrocarbon group having 6 to 18 carbon atoms and containing at least one fluorine atom.

In the general formula (1), R ² to R ⁹ are the “linear or branched alkyl groups having 1 to 20 carbon atoms which may be substituted”. The “chain or branched alkyl group” includes “an optionally substituted linear or branched alkyl group having 1 to 20 carbon atoms represented by R ¹ or R ¹⁰ in the general formula (1). and the same as the "alkyl group having a shape" can be mentioned.

In the general formula (1), R ² to R ⁹ are the “linear or branched alkenyl groups having 1 to 20 carbon atoms which may be substituted”. The “chain or branched alkenyl group” includes “an optionally substituted linear or branched alkenyl group having 1 to 20 carbon atoms represented by R ¹ or R ¹⁰ in the general formula (1). and the same as the "alkenyl group in the form of a

In the general formula (1), represented by R ² to R ⁹ "a linear or branched alkyl group having 1 to 20 carbon atoms optionally having a substituent" or "having a substituent As the “substituent” of the linear or branched alkenyl group having ¹ to ²⁰ carbon atoms which may be Linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted", "Linear or branched alkenyl group having 1 to 20 carbon atoms which may be substituted ", "optionally substituted aromatic hydrocarbon group having 6 to 36 carbon atoms" or "heterocyclic group having 2 to 36 carbon atoms optionally having substituents""substitution You can give the same thing as "base". Moreover, at least one or more fluorine atoms may be contained.

In general formula (1), R ² to R ⁹ represent substituents as described above, but R ² and R ³ , R ³ and R 4 , R ⁴ and R ⁵ , R ⁶ and ^{R 7 ,} R ⁷ and R ⁸ , R ⁸ and R ⁹ may be bonded to each other via a single bond, a bond via a sulfur atom or a bond via a nitrogen atom to form a ring.

In general formula (1), R ² to R ⁹ may be the same or different, and may be a hydrogen atom, a cyano group, or an optionally substituted linear alkyl group having 1 to 5 carbon atoms. is preferred.

In general formula (1), R ¹ or R ¹⁰ is preferably represented by general formula (2).

In the general formula (2), in the "linear or branched alkyl group optionally having 1 to 20 carbon atoms" represented by R ¹¹ to R ¹⁵ , The straight-chain or branched alkyl group for 20" is represented by R ¹ or R ¹⁰ in the general formula (1), which is a group having 1 to 20 carbon atoms which may be substituted. The same groups as those mentioned in the "linear or branched alkyl group" can be mentioned.

In the general formula (2), the "linear or branched alkenyl group optionally having 1 to 20 carbon atoms" represented by R ¹¹ to R ¹⁵ The linear or branched alkenyl group of 20" is represented by R ¹ or R ¹⁰ in the general formula (1), "a straight chain having 1 to 20 carbon atoms which may have a substituent and the same groups as those described in "a linear or branched alkenyl group" can be mentioned.

In the general formula (2), the “aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent” represented by R ¹¹ to R ¹⁵ The "hydrocarbon group" is the same as the "optionally substituted aromatic hydrocarbon group having 6 to 36 carbon atoms" represented by R ¹ or R ¹⁰ in general formula (1). I can give

In general formula (2), R ¹¹ to R ¹⁵ are preferably a hydrogen atom, a fluorine atom, or an optionally substituted linear alkyl group having 1 to 5 carbon atoms, and substituted A linear alkyl group having 1 to 5 carbon atoms which may have a group preferably contains at least one fluorine atom. Further, n is preferably an integer of 0-3.

In general formula (2), it is preferably a monovalent group represented by general formulas (3) and (4).

In formulas (3) and (4), n is preferably an integer of 0-3, and m is preferably an integer of 0-6.

Specific examples of the compound of the present invention represented by formula (1) are shown below, but the present invention is not limited thereto. In addition, the following exemplified compounds are described with some hydrogen atoms, carbon atoms, etc. omitted, and are examples of possible isomers, and include all other isomers. do. A mixture of two or more isomers may also be used.

The perylene derivative compound of the present invention represented by the general formula (1) is described in J. Am. Org. Chem. 2014, 79, p. 6655-6662 (Non-Patent Document 2) and other known methods. Perylene tetracarboxylic acid dianhydride is esterified only on one side, reacted with corresponding amines, then ring-closed at the ester portion, and reacted again with corresponding amines to obtain the compound represented by the general formula (1). perylene derivatives can be obtained.

The perylene derivative compound represented by the general formula (1) can be purified by column chromatography, adsorption purification using silica gel, activated carbon, activated clay, or the like, recrystallization or crystallization using a solvent, or the like. Alternatively, it is effective to use these methods in combination to use a compound with increased purity.
Also, identification of these compounds can be performed by nuclear magnetic resonance spectroscopy (NMR).

The compound represented by the general formula (1) in the present invention tends to have improved solubility in solvents. The solubility of the compound represented by the general formula (1) according to the present invention was evaluated by weighing it in a transparent sample tube, adding toluene or chloroform solvent so that the concentration was 0.1% by mass, and After stirring for several hours at 27° C.), the solubility (or saturated solubility) is visually evaluated. The solubility is preferably 0.01 to 10% by mass, more preferably 0.02 to 5% by mass.

The perylene derivative compound of the present invention can be used as an organic semiconductor material. In the present invention, a composition containing the above organic semiconductor material and a solvent is referred to as a composition for organic semiconductor. The composition for an organic semiconductor contains one or more compounds represented by the general formula (1), and may optionally contain other compounds not belonging to the present invention. Further, it may be a solution in which the organic semiconductor material is dissolved in a solvent, or a dispersion liquid in which the organic semiconductor material is dispersed, and includes a state in which the organic semiconductor material partially remains in the dispersion liquid. The composition for an organic semiconductor of the present invention is preferably a solution.

The perylene derivative compound of the present invention described above can be thinned, for example, to form an organic semiconductor layer of an organic semiconductor element such as a field effect transistor, a diode such as a light emitting diode, a photoelectric conversion element, an organic thin film solar cell, or the like. It can be suitably used as a semiconductor material. In the present invention, it is preferably used as an organic thin film transistor.

A thin film containing an organic semiconductor material of the perylene derivative compound of the present invention can be formed by a dry process such as a vacuum deposition method, but a stable and uniform thin film can also be formed by a solution process. Film formation by a solution process in the present invention refers to a method of forming a film using a composition for an organic semiconductor comprising the above organic semiconductor and a solvent. Specifically, coating methods such as drop casting, dip coating, die coating, roll coating, bar coating, spin coating, ink jet, screen printing, gravure printing, flexographic printing, offset Various printing methods such as a printing method, a microcontact printing method, and a method such as the Langmuir-Blodgett (LB) method. A thin film can also be formed by removing the solvent by heating after forming the film as described above. The organic semiconductor thin film of the present invention is preferably formed by a drop casting method, a spin coating method, or an ink jet method.

In the present invention, the solvent used in the composition for organic semiconductors includes aromatic organic solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, and nitrobenzene; Halogen organic solvents such as dichloromethane, chloroform, 1,2-dichloroethane, 1,1,2-trichloroethane, and dichloromethane; nitrile solvents such as benzonitrile and acetonitrile; ketone solvents such as 2-butanone; tetrahydrofuran, dioxane, diisopropyl Ether solvents such as ether, c-propyl methyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and propylene glycol monomethyl ether; Ester solvents such as ethyl acetate and propylene glycol monomethyl ether acetate; Methanol, isopropanol, n-butanol, propylene alcoholic solvents such as glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, cyclohexanol and 2-n-butoxyethanol; aprotons such as dimethylformamide, dimethylacetamide and dimethylsulfoxide; Examples include, but are not limited to, polar solvents and the like. Moreover, the above solvents may be used alone or in combination of two or more. In particular, it is preferable to use aromatic organic solvents and halogen-based organic solvents.

In the present invention, the content of the compound represented by the general formula (1) in the composition for an organic semiconductor is not particularly limited, but the concentration is preferably 0.01 to 20% by mass. A concentration of 02 to 10% by mass is more preferable.

An organic thin film transistor will be described as an example of the organic semiconductor device of the present invention.
An organic thin film transistor generally includes a substrate, an organic semiconductor layer, a gate electrode laminated on the organic semiconductor layer with a gate insulating layer interposed therebetween, and a source electrode and a drain electrode arranged opposite to each other with the organic semiconductor layer interposed therebetween. is configured with In the present invention, an organic semiconductor thin film containing a perylene derivative compound represented by the general formula (1) is used as the organic semiconductor layer. The form of the organic thin film transistor is not particularly limited, and any form of bottom gate/bottom contact type, bottom gate/top contact type, top gate/bottom contact type, and top gate/top contact type may be used, The gate electrode, the gate insulating layer, the source electrode, the drain electrode, and the organic semiconductor layer may be appropriately arranged according to each form.

The form of the organic thin film transistor of the present invention will be explained with reference to the drawings.
FIG. 1 is a schematic cross-sectional view showing one form of an organic thin film transistor, which has a bottom-gate/bottom-contact structure. In the form of this organic thin film transistor, a gate electrode 2 is provided on a substrate 1, a gate insulating film 3 is laminated on the gate electrode, and a source electrode 6 and a drain electrode are formed thereon at a predetermined interval. 4 is formed, and an organic semiconductor layer 5 is laminated thereon.

In the element of the organic thin film transistor having the above structure, the organic semiconductor layer forms the channel region, and the current flowing between the source electrode and the drain electrode is controlled by the voltage of the gate electrode to perform ON/OFF operation.

In the element of the present invention, the mobility indicates the easiness of movement of electron or hole carriers, and the electron mobility is a quantity indicating the easiness of movement of electrons in a solid substance. The carrier velocity v in the electric field E is represented by the following formula (a-1),
v=μE (a−1)
The proportionality coefficient μ is the mobility (cm ² /V·s). In semiconductors, the mobility is inversely proportional to the resistivity, so the mobility is an important parameter that determines the electrical properties of the material.

The transfer characteristics of the organic semiconductor element or organic thin film transistor of the present invention can be evaluated by electron mobility. It is important for the electron mobility to be a large value in an organic thin film transistor, such as to obtain a large current. The electron mobility is desirably 0.001 cm ² /V·s or more.

In the present invention, when the organic semiconductor layer is formed by a solution process, the composition for an organic semiconductor is used. After forming the organic semiconductor layer by a solution process, it may be preferable to perform heat treatment using a hot plate, an oven, or the like. The heat treatment temperature is not particularly limited, but the heat treatment is carried out at room temperature (20 to 27°C) to about 200°C.

<substrate>
The substrate used for the organic semiconductor element such as the organic thin film transistor of the present invention is not particularly limited, but in general, plastic substrates such as glass, quartz, silicon, polyimide, polyester, polyethylene, polystyrene, polypropylene and polycarbonate are used. can be used.

<electrode>
As the material used for the electrode of the organic thin film transistor, any conductive material can be used. Preferably, a material having a low electron injection barrier to the organic semiconductor material is desirable.

The method for forming each electrode is not particularly limited, but it can be formed using a dry film formation method such as vapor deposition or sputtering, or a method by printing. It can be patterned into a desired shape, and can also be patterned using a metal mask.

The film thickness of the source and drain electrodes is not particularly limited, but is preferably set within the range of several nanometers to several micrometers. Note that the distance between the source and drain electrodes is preferably set in the range of several hundred nanometers to several hundred micrometers.

<Gate electrode>
Materials constituting the gate electrode include, for example, p-doped silicon, n-doped silicon, indium-tin oxide (ITO), conductive polymers such as doped polythiophene and polyaniline, gold, silver, platinum, aluminum, and chromium. and the like, and in the present invention, it is preferable to use aluminum.

<Insulating layer>
Materials constituting the gate insulating layer include, for example, inorganic compounds such as silicon oxide, silicon nitride, aluminum oxide, aluminum nitride, and tantalum oxide, polyvinyl alcohol, polyvinyl phenol, polymethyl methacrylate, cyanoethyl pullulan, and parylene (Nippon Parylene LLC. (registered trademark) can be used.

Although the film thickness of the gate insulating film is not particularly limited, it is preferably set in the range of several nanometers to several micrometers.

<Source electrode, drain electrode>
Materials constituting the source electrode and drain electrode include, for example, gold, silver, platinum, chromium, aluminum, indium, alkali metals (Li, Na, K, Rb, Cs), alkaline earth metals (Mg, Ca, Sr, Ba) and the like. It is preferred to use gold in the present invention.

<Organic semiconductor layer>
The organic thin film transistor of the present invention comprises an organic semiconductor layer containing the compound represented by the general formula (1).
In the organic semiconductor layer, in addition to the perylene derivative compound of the present invention, for example, fullerene and its derivatives, and naphthalene, naphthalene diimide, anthracene, tetracene, perylene, pentacene, pyrene substituted with electron-withdrawing groups such as fluorine and nitrile. , coronene, chrysene, decacyclene, violansthrene and other polycyclic aromatic molecules and their derivatives, triphenylene, thiophene oligomers, polythiophene and other aromatic ring oligomers, polymers and their derivatives, phthalocyanine, tetrathiafulvalene, tetrathiotetracene and these An appropriate amount of an electron-deficient organic semiconductor material such as a derivative may also be used. Also, a suitable amount of polymer material such as polystyrene or polyvinylphenol may be added.

<Sealing>
The organic thin film transistor of the present invention can be provided with a gas barrier layer on the whole or part of the outer peripheral surface of the organic thin film transistor for the purpose of reducing the influence of oxygen, moisture, etc. in the atmosphere. Materials for forming the gas barrier layer include polyvinyl alcohol, ethylene-vinyl alcohol, copolymers, polyvinyl chloride, and polytetrafluoroethylene.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to the following examples. The compounds obtained in Synthesis Examples were identified by ¹ H-NMR (Nuclear magnetic resonance apparatus, JNM-ECA-600, manufactured by JEOL Ltd.).

[Synthetic Example 1] Synthesis of compound (A-1) Synthesis of 1,7-dibromoperylene-3,4,9,10-tetracarboxylic acid dibutyl ester monoanhydride was carried out according to J. Am. Org. Chem. 2014, 79, p. 6655-6662 to obtain 10 g of 1,7-dibromoperylene-3,4,9,10-tetracarboxylic acid dibutyl ester monoanhydride represented by the following formula (5). (Step 1)

1,7-Dibromoperylene-3,4,9,10-tetracarboxylic acid dibutyl ester monoanhydride (7.0 g) represented by the above formula (5), heptafluorobutylamine (4. 5 g) and acetic acid (3.4 g) in N-methyl-2-pyrrolidone (45 mL) were stirred at 60° C. for 5 hours under a nitrogen stream. After cooling the reaction mixture to room temperature, it was poured into water (250 mL), stirred for 30 minutes, and filtered to obtain a crude product. After purifying the crude product by column chromatography (carrier: silica gel, developing solution: toluene), it is dried under reduced pressure to obtain 1,7-dibromoperylene-3,4,9,10- A tetracarboxylic acid dibutyl ester monoimide (yield: 3.5 g, yield: 50%) was obtained. (Step 2)

1,7-Dibromoperylene-3,4,9,10-tetracarboxylic acid dibutyl ester monoimide (3.5 g) represented by the above formula (6), p-toluenesulfonic acid monohydrate were placed in a nitrogen-purged reaction vessel. A toluene solution (140 mL) of the soda (3.5 g) was stirred at 90° C. for 20 hours under a nitrogen stream. After cooling the reaction solution to room temperature, the crude product obtained by filtration was washed with toluene and water. After drying under reduced pressure, 1,7-dibromoperylene-3,4,9,10-tetracarboxylic acid monoanhydride monoimide represented by the following formula (7) (yield: 2.4 g, yield: 83%) was obtained. Obtained. (Step 3)

1,7-Dibromoperylene-3,4,9,10-tetracarboxylic acid monoanhydride monoimide (1.0 g) represented by the above formula (7), pentafluoroaniline (750 mg), An N-methyl-2-pyrrolidone solution (6 mL) of acetic acid (431 μL) was stirred at 120° C. for 18 hours under a nitrogen stream. After cooling the reaction mixture to room temperature, it was poured into 2N aqueous hydrochloric acid (100 mL), stirred for 30 minutes, and filtered to obtain a crude product. After purifying the portion dissolved in chloroform by column chromatography (carrier: silica gel, developing solution: toluene), it is dried under reduced pressure to obtain 1,7-dibromoperylene-3,4,9,10- represented by the following formula (8). A tetracarboxylic acid diimide (yield: 165 mg, yield: 14%) was obtained. (Step 4)

1,7-dibromoperylene-3,4,9,10-tetracarboxylic acid diimide represented by the above formula (8) (200 mg), copper cyanide (359 mg), N,N-dimethyl A formamide solution (10 mL) was stirred at 90° C. for 8 hours under a nitrogen stream. After cooling to room temperature, the reaction solution was poured into water (200 mL), stirred for 30 minutes, and filtered to obtain a crude product. The crude product was added to chloroform, and the dissolved portion was purified by column chromatography (carrier: silica gel, developing solution: chloroform) and dried under reduced pressure to obtain the desired compound as a reddish purple solid (yield: 130 mg, yield: 74). %). (Step 5)

The resulting reddish-purple solid was subjected to NMR analysis, the following eight hydrogen signals were detected, and the structure was identified as represented by (A-1).

¹ H-NMR (600 MHz, CDCl ₃ ): δ (ppm) = 5.03-5.08 (2H), 9.01-9.04 (2H), 9.07 (1H), 9.08 (1H ), 9.75-9.77 (2H).

[Synthesis Example 2] Synthesis of Compound (A-2) Instead of pentafluoroaniline in Synthesis Example 1, pentafluorophenethylamine was synthesized in the same manner as in Synthesis Example 1, and the target compound was obtained in reddish purple. Obtained as a solid (230 mg, 31% yield).

The resulting reddish-purple solid was subjected to NMR analysis, the following 12 hydrogen signals were detected, and the structure was identified as represented by (A-2).

¹ H-NMR (600 MHz, CDCl ₃ ): δ (ppm) = 3.26 (2H), 4.52-4.55 (2H), 5.02-5.07 (2H), 8.91-9 .06 (4H), 9.71-9.75 (2H).

[Synthesis Example 3] Synthesis of compound (A-3) Synthesis was carried out in the same manner as in Synthesis Example 1 except that 4-fluoroaniline was used in place of pentafluoroaniline in Synthesis Example 1, and the desired compound was obtained in red. Obtained as a purple solid (140 g, 81% yield).

The resulting reddish-purple solid was subjected to NMR analysis, the following 12 hydrogen signals were detected, and the structure was identified as represented by (A-3).

¹ H-NMR (600 MHz, CDCl ₃ ): δ (ppm) = 5.03-5.08 (2H), 7.28-7.34 (4H), 9.00-9·02 (2H), 9 .04 (1H), 9.06 (1H), 9.75-9.77 (2H).

[Synthesis Example 4] Synthesis of compound (A-4) Synthesis was carried out in the same manner as in Synthesis Example 1, except that 4-(nonafluorobutyl)aniline was used instead of pentafluoroaniline in Synthesis Example 1, and the desired product was obtained. The compound was obtained as a magenta solid (741 mg, 98% yield).

The resulting reddish-purple solid was subjected to NMR analysis, the following 12 hydrogen signals were detected, and the structure represented by (A-4) was identified.

¹ H-NMR (600 MHz, CDCl ₃ ): δ (ppm) = 5.03-5.08 (2H),
7.52-7.54 (2H), 7.84-7.85 (2H), 9.00-9.06 (4H), 9.76-9.78 (2H).

[Synthesis Example 5] Synthesis of Compound (A-5) Synthesis was performed in the same manner as in Synthesis Example 1 except that 4-(trifluoromethyl)benzylamine was used instead of pentafluoroaniline in Synthesis Example 1, The desired compound was obtained as a reddish purple solid (590 mg, 80% yield).

The resulting reddish-purple solid was subjected to NMR analysis, the following 14 hydrogen signals were detected, and the structure was identified as represented by (A-5).

¹ H-NMR (600 MHz, CDCl ₃ ): δ (ppm) = 5.02-5.07 (2H),
5.46-5.48 (2H), 7.60-7.61 (2H), 7.68-7.70 (2H), 8.90-9.09 (4H), 9.71-9. 74 (2H).

[Synthesis Example 6] Synthesis of (A-6) Synthesis was carried out in the same manner as in Synthesis Example 1, except that undecafluorohexylamine was used instead of heptafluorobutylamine in Synthesis Example 1, and the target compound was reddish purple. Obtained as a solid (723 mg, 69% yield).

The resulting reddish-purple solid was subjected to NMR analysis, the following eight hydrogen signals were detected, and the structure was identified as represented by (A-6).

¹ H-NMR (600 MHz, CDCl ₃ ): δ (ppm) = 5.01-5.12 (2H),
9.01-9.08 (4H), 9.74-9.78 (2H).

[Synthesis Example 7] Synthesis of (A-11) Except for using pentadecafluorooctylamine instead of heptafluorobutylamine in Synthesis Example 1 and using 4-(nonafluorobutyl)aniline instead of pentafluoroaniline. was synthesized in the same manner as in Synthesis Example 1 to obtain the desired compound as a reddish purple solid (170 mg, yield 65%).

The resulting reddish-purple solid was subjected to NMR analysis, the following 12 hydrogen signals were detected, and the structure was identified as represented by (A-11).

¹ H-NMR (600 MHz, CDCl ₃ ): δ (ppm) = 5.04-5.09 (2H),
7.52-7.54 (2H), 7.84-7.85 (2H), 9.00-9.06 (4H), 9.76-9.78 (2H).

[Synthesis Example 8] Synthesis of (A-12) In the same manner as in Synthesis Example 7 except that 4-(tridecafluorohexyl)aniline was used instead of 4-(nonafluorobutyl)aniline in Synthesis Example 7. Synthesized to obtain the desired compound as a reddish purple solid (120 mg, yield 66%).

The resulting reddish-purple solid was subjected to NMR analysis, the following 12 hydrogen signals were detected, and the structure was identified as represented by formula A-12).

¹ H-NMR (600 MHz, CDCl ₃ ): δ (ppm) = 5.06 (2H), 7.51-7.55 (2H), 7.83-7.86 (2H), 8.99-9 .00 (2H),
9.02-9.06 (2H), 9.75-9.78 (2H).

[Synthesis Example 9] Synthesis of (A-17) Synthesis up to Step 4 was carried out in the same manner as in Synthesis Example 1, and 1,7-dibromoperylene-3,4,9,10-tetra A carboxylic acid diimide was obtained.

1,7-dibromoperylene-3,4,9,10-tetracarboxylic acid diimide (1.5 g, 1.46 mmol), copper iodide (112 mg, 0.59 mmol), phenanthroline monohydrate (116 mg, 0.59 mmol). 69 mmol) and potassium trimethoxy(trifluoromethyl)borate (1.27 g, 8.76 mmol) in dimethylsulfoxide (DMSO) were stirred at 60° C. for 4 hours under a nitrogen stream. After cooling to room temperature, ethyl acetate was added to the reaction solution, and after filtration, water was added to the filtrate to separate the layers. The solvent was removed from the organic layer by concentration under reduced pressure to obtain a crude product. The crude product was dissolved in chloroform, and the dissolved portion was purified by column chromatography (carrier: silica gel, developing solution: toluene) and dried under reduced pressure to obtain the desired compound as a reddish purple solid (yield: 250 mg, yield: 17 %).

The resulting reddish-purple solid was subjected to NMR analysis, the following 12 hydrogen signals were detected, and the structure was identified as represented by formula (A-17).

¹ H-NMR (600 MHz, CDCl ₃ ): δ (ppm) = 5.05-5.10 (2H), 7.53-7.54 (2H), 7.83-7.85 (2H), 8 .63-8.65 (2H), 8.88-8.89 (2H), 9.12-9.14 (2H).

[Comparative compound] Synthesis of compound (B-1) Angew. Chem. Int. Ed. 2004, 43, 6363-6366 to obtain 1,7-dicyanoperylene-3,4,9,10-tetracarboxylic acid diimide represented by the following formula (B-1).

[Example 1] Solubility measurement of (A-1) The compound (A-1) was weighed into a transparent sample tube, added to a toluene or chloroform solvent so that the concentration was 0.1% by mass, and at room temperature (25 After stirring for several hours at ±2°C, the solubility was visually evaluated. Table 1 shows the results. Judgment conditions were as follows: complete dissolution (25±2° C.) was indicated by ◯;

[Examples 2 to 9]
(A-2), (A-3), (A-4), (A-5), (A-6), (A-11), (A-12) instead of compound (A-1) Or the solubility was measured in the same manner as in Example 1 using (A-17). Table 1 shows the results.

[Comparative Example 1]
Solubility measurement was performed in the same manner as in Example 1 using comparative compound (B-1) instead of compound (A-1). Table 1 shows the results.

＊判定条件
○：完全溶解（２５±２℃）
△：濁り残る（２５±２℃）
×：不溶解（２５±２℃）

* Judgment conditions ○: complete dissolution (25 ± 2 ° C)
△: remains cloudy (25 ± 2 ° C)
×: insoluble (25 ± 2 ° C.)

From Table 1, it is clear that the compounds represented by the examples have solubility in chloroform and toluene equal to or greater than those of the comparative examples.

[Example 10] Measurement of transfer characteristics of an organic thin film transistor A glass substrate was ultrasonically cleaned with a neutral detergent for 10 minutes, water for 10 minutes, acetone for 10 minutes, and isopropyl alcohol for 10 minutes, and then an oven at 100°C. and dried for 1 hour. A metal mask was used to vapor-deposit aluminum to form a gate electrode on the surface of the substrate to a thickness of 50 nm. Thereafter, a mixed solution of polyvinylphenol and melamine was applied by spin coating, and heated on a hot plate at 100° C. for 10 minutes and 150° C. for 1 hour to form an insulating layer with a thickness of 400 nm. Subsequently, gold was deposited on the insulating layer to a thickness of 50 nm to form source and drain electrodes, and photolithography was used to form source and drain electrodes with a channel width of 500 μm and a channel length of 5 μm.

Chloroform was added to the compound (A-1) so that the concentration was 0.1% by mass to prepare an organic semiconductor solution. After the substrate was subjected to UV ozone treatment for 7 minutes, the organic semiconductor solution was applied onto the channels by a drop casting method and heated at 150° C. for 10 minutes on a hot plate to form an organic semiconductor layer.

Using a semiconductor analyzer (manufactured by Keithley Co., Model 4200-SCS), the transfer characteristics of the organic thin film transistor thus prepared were measured at gate voltages in the range of -40 V to 80 V in the atmosphere shielded from light.

From the measured values, the mobility μ (cm ² /Vs) was calculated using the following formulas (a-2) and (a-3). Table 2 shows the mobility results obtained from this measurement.

ｄ_ｏｘ＝絶縁膜の厚さ
ε_ｏｘ＝真空の誘電率、ε_０＝絶縁膜の誘電率
Ｗ＝チャネル幅、Ｌ＝チャネル長
Ｉｄ＝ドレイン電流、Ｖｇ＝ゲート電圧

d _ox = thickness of insulating film ε _ox = dielectric constant of vacuum, ε ₀ = dielectric constant of insulating film W = channel width, L = channel length Id = drain current, Vg = gate voltage

[Examples 11 to 16] Measurement of transfer characteristics of organic thin film transistors Instead of synthetic compound (A-1), (A-2), (A-3), (A-4), (A-6), Using (A-11) and (A-12), the transfer characteristics of an organic thin film transistor fabricated in the same manner as in Example 10 were measured. Table 2 shows the mobility results obtained from this measurement.

[Comparative Example 2]
The transmission characteristics of an organic thin film transistor fabricated in the same manner as in Example 10 were measured except that (B-1), which does not belong to the present invention, was used as the compound instead of (A-1). Table 2 shows the mobility results obtained from this measurement.

From Table 2, it is clear that the organic thin film transistors using the compounds represented by the examples in the organic semiconductor layer have higher electron mobilities than the comparative examples.

The perylene derivative compound according to the present invention can provide an n-type organic semiconductor material having solubility suitable for solution processing. Furthermore, by using a composition for an organic semiconductor containing the organic semiconductor material, an organic thin film transistor having excellent electron transport properties can be provided.

1: substrate 2: gate electrode 3: gate insulating layer 4: drain electrode 5: organic semiconductor layer 6: source electrode

Claims (8)

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

[In the formula, R ¹ and R ¹⁰ are different from each other,
R ¹ is a monovalent group represented by the following general formula (2),
R ¹⁰ is a hydrogen atom, a halogen atom,
an optionally substituted linear or branched alkyl group having 1 to 20 carbon atoms,
an optionally substituted linear or branched alkenyl group having 1 to 20 carbon atoms,
an aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent,
or represents an optionally substituted heterocyclic group having 2 to 36 carbon atoms,
The linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, the linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent An alkenyl group or an optionally substituted aromatic hydrocarbon group having 6 to 36 carbon atoms contains at least one fluorine atom.
R ² to R ⁹ may be the same or different,
hydrogen atom, halogen atom, cyano group, hydroxyl group, nitro group, nitroso group, thio group, amino group,
an optionally substituted linear or branched alkyl group having 1 to 20 carbon atoms,
or an optionally substituted linear or branched alkenyl group having 1 to 20 carbon atoms,
R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁸ and R ⁹ may combine with each other to form a ring. ]

[In the formula, R ¹¹ to R ¹⁵ may be the same or different, and are hydrogen atoms, halogen atoms,
an optionally substituted linear or branched alkyl group having 1 to 20 carbon atoms,
an optionally substituted linear or branched alkenyl group having 1 to 20 carbon atoms,
or represents an aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent.
n represents an integer of 0 to 5;
at least one of R ¹¹ to R ¹⁵ is a fluorine atom, or a linear or branched alkyl group having 1 to 20 carbon atoms containing at least one fluorine atom, or containing at least one fluorine atom is a linear or branched alkenyl group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 36 carbon atoms and containing at least one fluorine atom. ] 2. The compound according to claim 1 , wherein said general formula (2) is a monovalent group represented by the following general formula (3) or (4).

[In the formula, n represents an integer of 0 to 5, and m represents an integer of 0 to 10. ] In the general formula (1), R ³ , R ⁴ , R ⁷ and R ⁸ are at least one cyano group, or an optionally substituted linear or branched chain having 1 to 4 carbon atoms. 3. The compound of claim 1 or claim 2 , which is an alkyl group of . 4. The compound according to any one of claims 1 to 3 , having a solubility in an aromatic organic solvent or a halogenated organic solvent at 25±2°C of 0.02 to 5% by mass. A composition for an organic semiconductor containing the compound according to any one of claims 1 to 4 . An organic semiconductor device using the composition for an organic semiconductor according to claim 5 . 7. The organic semiconductor device according to claim 6 , having a mobility of 10 ⁻³ cm ² /Vs or more. An organic thin film transistor using the organic semiconductor element according to claim 7 .

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