JP2020120031A - Perylene derivative compound, composition for organic semiconductor arranged by use of the compound, and organic thin film transistor arranged by use of the composition for organic semiconductor - Google Patents

Abstract

To provide: an n-type organic semiconductor material having high dissolubility adaptive to a solution process; an organic semiconductor element of high electron mobility, in which the n-type organic semiconductor material is used as a composition for an organic semiconductor; and an organic thin film transistor.SOLUTION: A composition for an organic semiconductor comprises a perylene derivative compound represented by the formula (1) below. An organic thin film transistor comprises an organic semiconductor element of 10cm/Vs or more in mobility, which is arranged by use of the composition for an organic semiconductor.SELECTED DRAWING: None

Description

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

Conventionally, thin film transistors using a silicon-based inorganic material as an inorganic semiconductor material have been widely used, but since these film formations are performed at a high temperature, they are lightweight and flexible as a substrate compatible with thin display. Plastic materials have the drawback that they cannot be used due to their poor heat resistance. Therefore, in recent years, in place of the silicon-based inorganic material, an organic thin film transistor using an organic compound having a property as a semiconductor as an organic semiconductor material has been actively developed.

In the formation of the organic semiconductor layer containing the organic semiconductor material in the organic thin film transistor, as compared with the vacuum deposition process which is produced under high temperature in vacuum, the solution process which is produced in the atmosphere by the solution process of the organic thin film transistor element while suppressing the production cost. It becomes easy to upsize. Further, the temperature required for film formation can be lowered, and a plastic material or the like can be used for the substrate. Therefore, an organic semiconductor material that is compatible with a solution process that can be applied to a flexible element is desired.

The organic semiconductor forming the organic semiconductor layer is classified into a p-type organic semiconductor material in which holes flow as carriers and an n-type organic semiconductor material in which electrons flow as carriers. Many p-type organic semiconductor materials have been reported so far.

On the other hand, as the n-type organic semiconductor material, materials such as perylene derivative and fullerene are being developed, but their solubility in a solvent is low and compatibility with a solution process is low.

Further, a high-performance n-type organic semiconductor material is necessary for constructing a pn junction or an integrated circuit, but the electron current is more susceptible to external factors such as the atmosphere and impurities than the hole current, Its electron mobility is still lower than that of p-type organic semiconductor materials.

As described above, it is desired to develop an organic semiconductor material that has both high solubility in a solvent compatible with a solution process and high carrier mobility.

Special table 2007-527114 Special table 2008-524846 Special table 2017-52139 Japanese Unexamined Patent Publication No. 2015-115490

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

The problem to be solved by the present invention is to provide an n-type organic semiconductor material having a high solubility corresponding to a solution process, and to use the n-type organic semiconductor material as a composition for an organic semiconductor, which has a high electron mobility. An organic semiconductor device and an organic thin film transistor are provided.

In order to solve the above-mentioned problems, the inventors diligently studied an n-type organic semiconductor material having solubility corresponding to a solution process, and an organic thin-film transistor having excellent electron mobility, and as a result, have a specific structure It was found that an organic thin film transistor with high mobility can be obtained by using a compound having improved properties as an n-type organic semiconductor material and further incorporating the compound in the organic semiconductor layer. That is, the present invention is summarized below.

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

[Wherein R ¹ and R ¹⁰ are different from each other,
Hydrogen atom, halogen atom,
A linear or branched alkyl group having 1 to 20 carbon atoms, which may have a substituent,
A linear or branched alkenyl group having 1 to 20 carbon atoms which may have a substituent,
An aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent,
Alternatively, it represents a heterocyclic group having 2 to 36 carbon atoms, which may have a substituent.
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,
A linear or branched alkyl group having 1 to 20 carbon atoms, which may have a substituent,
Or represents a linear or branched alkenyl group having 1 to 20 carbon atoms which may have a substituent,
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 , and R ⁸ and R ⁹ may be bonded to each other to form a ring. ]

2. In the general formula (1), R ¹ or R ¹⁰ 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 each represents a hydrogen atom, a halogen atom,
A linear or branched alkyl group having 1 to 20 carbon atoms, which may have a substituent,
A linear or branched alkenyl group having 1 to 20 carbon atoms which may have a substituent,
Alternatively, it 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 formula, n represents the integer of 0-5 and m represents the integer of 0-10. ]

4. In the general formula (1), R ^{1 to} R ¹⁰ are compounds having at least one fluorine atom.

5. In the general formula (1), R ³ , R ⁴ , R ⁷ , and R ⁸ are at least one cyano group, or a linear or branched C1 to C4 optionally substituted group. A compound which is an alkyl group of.

The compound as described above, which has a solubility of 0.02 to 5% by mass in an aromatic organic solvent or a halogen organic solvent at 6.25±2°C.

7. An organic semiconductor composition containing the compound.

8. An organic semiconductor device using the composition for organic semiconductors.

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.

INDUSTRIAL APPLICABILITY The perylene derivative compound according to the present invention can provide an n-type organic semiconductor material having solubility in an organic solvent compatible with a solution process, and further uses a composition for an organic semiconductor containing the organic semiconductor material. This makes it possible to obtain an organic thin film transistor having excellent electron mobility.

It is a schematic sectional drawing showing the structure of the bottom gate/bottom contact type organic thin-film transistor which concerns on one Embodiment of this 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 further 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 compound represented by formula (1) is specifically described below, but the invention is not limited thereto. In the specification of the application, a numerical range represented by “to” means a range including the numerical values before and after “to” as the lower limit value and the upper limit value.

In the present invention, examples of the “halogen atom” include fluorine, chlorine, bromine and iodine.

In the general formula (1), "1 to 1 carbon atoms in the "linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent" represented by R ¹ or R ¹⁰ " Examples of the “20 linear or branched alkyl group” specifically include methyl group, ethyl group, n-propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, 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), “C ^{1 to} C ^{1 in} “a linear or branched alkenyl group having 1 to 20 carbon atoms which may have a substituent” represented by R ¹ or R ¹⁰ As the “20 linear or branched alkenyl group”, specifically, a vinyl group, a 1-propenyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, a 1-pentenyl group, a 1-hexenyl group, Examples thereof include an isopropenyl group, an isobutenyl group, and 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 group having 6 to 36 carbon atoms” in the “aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent” represented by R ¹ or R ^10. Specific examples of the “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 group. Examples thereof include a tenyl 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), "heterocyclic group having 2 to 36 carbon atoms" in "heterocyclic group having 2 to 36 carbon atoms which may have a substituent" represented by R ¹ or R ^10. Specific examples thereof include a pyridyl group, a pyrimidinyl group, a triazinyl group, a thienyl group, a furyl group (furanyl group), a pyrrolyl group, an imidazolyl group, a pyrazolyl group, a triazolyl group, a quinolyl group, an isoquinolyl group, a naphthyldinyl group, an acridinyl group, and fe Nantrolinyl 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 , Carbonylyl group and the like.

In the general formula (1), “a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent” represented by R ¹ or R ¹⁰ and “having a substituent An optionally substituted straight-chain or branched alkenyl group having 1 to 20 carbon atoms, "an optionally substituted aromatic hydrocarbon group having 6 to 36 carbon atoms" or "a substituent" As the "substituent" in the "heterocyclic group having 2 to 36 carbon atoms which may have", specifically, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a cyano group; a hydroxyl group; Nitro group; Nitroso group; Carboxyl group;
Carboxylic acid ester groups such as methyl ester group and 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, A linear or branched alkyl group having 1 to 18 carbon atoms such as a heptyl group, an octyl group, an isooctyl group, a nonyl group and a decyl group;
Vinyl group, 1-propenyl group, allyl group, 1-butenyl group, 2-butenyl group, 1-pentenyl group, 1-hexenyl group, isopropenyl group, isobutenyl group, etc., linear or branched having 2 to 20 carbon atoms Alkenyl group;
A linear or branched alkoxy group having 1 to 18 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, a t-butoxy group, a pentyloxy group, a hexyloxy group;
Aromatic hydrocarbon group having 6 to 30 carbon atoms such as phenyl group, naphthyl group, anthryl group, phenanthryl group, and pyrenyl group;
Pyridyl group, pyrimidinyl 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 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, carbonylyl group, etc. A heterocyclic group having 2 to 30 atoms;
A linear 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 mono- or di-substituted amino group having 0 to 18 carbon atoms having a substituent selected from an aromatic hydrocarbon group having 6 to 18 atoms;
A thio group having 1 to 18 carbon atoms such as methylthio group, ethanethio group, propylthio group, di-t-butylthio group, hexa-5-ene-3-thio group, phenylthio group, biphenylthio group;
And so on. Only one of these "substituents" may be contained, or a plurality of them may be contained, and when a plurality of "substituents" are contained, they may be the same or different from each other. Further, these “substituents” may further have the substituents exemplified above. Only one of these "substituents" may be contained, or a plurality of them may be contained, and when a plurality of "substituents" are contained, they may be the same or different from each other. Further, it may contain at least one or more fluorine atoms.

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

In the general formula (1), R ^{2 to} R ⁹ are each a “direct group having 1 to 20 carbon atoms” in the “linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent”. The "chain or branched alkyl group" is represented by R ¹ or R ¹⁰ in the general formula (1), which may be a straight chain or branched chain having 1 to 20 carbon atoms and optionally having a substituent. Same as the "like alkyl group".

In the general formula (1), R ^{2 to} R ⁹ are each a “direct group having 1 to 20 carbon atoms” in the “linear or branched alkenyl group having 1 to 20 carbon atoms which may have a substituent”. The "chained or branched alkenyl group" is represented by R ¹ or R ¹⁰ in the general formula (1), which may be a linear or branched chain having 1 to 20 carbon atoms which may have a substituent. The same as the "like alkenyl group".

In the general formula (1), “a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent” represented by R ^{2 to} R ⁹ or “having a substituent” As the "substituent" of the linear or branched alkenyl group having 1 to 20 carbon atoms which may be present, a "substituent represented by R ¹ or R ¹⁰ in the general formula (1) is represented by "A linear or branched alkyl group having 1 to 20 carbon atoms which may have", "a linear or branched alkenyl group having 1 to 20 carbon atoms which may have a substituent"","Substituted" in "Aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent" or "heterocyclic group having 2 to 36 carbon atoms which may have a substituent" The same as "group" can be mentioned. Further, it may contain at least one or more fluorine atoms.

In the general formula (1), R ^{2 to} R ⁹ represent the 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 and R ⁸ and R ⁹ may be bonded to each other by a single bond, a bond through a sulfur atom or a bond through a nitrogen atom to form a ring.

In the general formula (1), R ^{2 to} R ⁹ may be the same or different and each is a hydrogen atom, a cyano group, or a linear alkyl group having 1 to 5 carbon atoms which may have a substituent. Is preferred.

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

In the general formula (2), “C 1 to C 1 in the “linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent” represented by R ^{11 to} R ¹⁵ ” The “20 linear or branched alkyl group” has 1 to 20 carbon atoms which may have a substituent represented by R ¹ or R ¹⁰ in the general formula (1). The same thing as the "linear or branched alkyl group" can be mentioned.

In the general formula (2), “C 1 to C 1 in “a linear or branched alkenyl group having 1 to 20 carbon atoms which may have a substituent” represented by R ^{11 to} R ¹⁵ ” The "20 linear or branched alkenyl group" 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(s)." The same as the "standard or branched alkenyl group".

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

In the general formula (2), R ^{11 to} R ¹⁵ are preferably a hydrogen atom, a fluorine atom, and a linear alkyl group having 1 to 5 carbon atoms which may have a substituent, and a substituent. The 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 to 3.

In the general formula (2), the monovalent group represented by the general formulas (3) and (4) is preferable.

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

Specific examples of the compound of the present invention represented by the general formula (1) are shown below, but the present invention is not limited thereto. Further, the following exemplary compounds are described with a part of hydrogen atoms, carbon atoms and the like omitted, and show one example of isomers that may exist, and include all other isomers. To do. Further, it may be a mixture of two or more isomers.

The perylene derivative compound of the present invention represented by the general formula (1) is described in J. Org. Chem. 2014, 79, P.I. It can be synthesized by a known method such as 6655-6662 (Non-Patent Document 2). Perylene tetracarboxylic acid dianhydride is esterified on one side only and reacted with the corresponding amines, then the ester portion is closed and again reacted with the corresponding amines to obtain the compound represented by the general formula (1). Can be obtained.

As a method for purifying the perylene derivative compound represented by the general formula (1), purification by column chromatography, adsorption purification by silica gel, activated carbon, activated clay or the like, recrystallization by a solvent, crystallization and the like can be performed. Alternatively, it is effective to use a compound with increased purity by combining these methods.
Further, the identification of these compounds can be performed by nuclear magnetic resonance analysis (NMR).

The compound represented by the general formula (1) in the present invention tends to have improved solubility in a solvent. The solubility of the compound represented by the general formula (1) according to the present invention is measured in a transparent sample tube, and a toluene or chloroform solvent is added so that the concentration becomes 0.1% by mass, and the room temperature (20- After stirring at 27° C. for several hours, the solubility (or saturated solubility) is visually evaluated. The solubility is preferably 0.01 to 10 mass% concentration, and more preferably 0.02 to 5 mass% concentration.

The perylene derivative compound of the present invention can be used as an organic semiconductor material. In the present invention, a composition containing the organic semiconductor material and a solvent is referred to as an organic semiconductor composition. The composition for 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 dissolved in a solvent or a dispersion liquid in which the organic semiconductor material is dispersed, and a state in which the organic semiconductor material partially remains in the dispersion liquid is also included. The composition for organic semiconductor of the present invention is preferably a solution.

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

Although the thin film containing the 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, a stable and uniform thin film can be formed by a solution process. The film formation by the solution process in the present invention refers to a method of forming a film by using the composition for organic semiconductor which comprises the above organic semiconductor and a solvent. Specifically, drop casting method, dip coating method, die coater method, roll coater method, bar coater method, spin coat method and other coating methods, ink jet method, screen printing method, gravure printing method, flexographic printing method, offset Various printing methods such as a printing method and a microcontact printing method, and a method such as a Langmuir-Blodgett (LB) method. After forming the film as described above, the thin film can also be formed by heating to remove the solvent. The organic semiconductor thin film of the present invention is preferably formed by a drop casting method, a spin coating method, or an inkjet method.

In the present invention, the solvent used in the composition for organic semiconductors is an aromatic organic solvent such as benzene, toluene, xylene, mesitylene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene or nitrobenzene; Halogen-based organic solvents such as dichloromethane, chloroform, 1,2-dichloroethane, 1,1,2-trichloroethane, dichloromethane; nitrile-based solvents such as benzonitrile and acetonitrile; ketone-based solvents such as 2-butanone; tetrahydrofuran, dioxane, diisopropyl Ether-based solvents such as ether, c-propyl methyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether and propylene glycol monomethyl ether; ester-based 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, 2-n-butoxyethanol; aprotic substances such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, etc. Examples thereof include polar solvents, but are not limited thereto. The above solvents may be used alone or in combination of two or more. In particular, it is preferable to use an aromatic organic solvent and a halogen organic solvent.

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

An organic thin film transistor will be described as an example of the organic semiconductor element of the present invention.
An organic thin film transistor generally includes a substrate, an organic semiconductor layer, a gate electrode stacked on the organic semiconductor layer via a gate insulating layer, and a source electrode and a drain electrode arranged to face each other via the organic semiconductor layer. Is configured. In the present invention, an organic semiconductor thin film containing the 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 of bottom gate/bottom contact type, bottom gate/top contact type, top gate/bottom contact type, 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 described 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 formed on the gate insulating film 3 at predetermined intervals. 4 is formed, and the organic semiconductor layer 5 is further 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.

The mobility refers to the ease with which carriers of electrons or holes move in the device of the present invention, and the electron mobility refers to the amount indicating the ease with which electrons in a solid substance move. 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). Since mobility is inversely proportional to resistivity in semiconductors, mobility is an important parameter that determines the electrical properties of materials.

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 that the electron mobility has a large value such that a large current can be obtained in the organic thin film transistor. The electron mobility is preferably 0.001 cm ² /V·s or more.

In the present invention, when the organic semiconductor layer is formed by a solution process, the above composition for organic semiconductor is used. After forming the organic semiconductor layer by a solution process, it may be preferable to perform heat treatment with a hot plate, an oven, or the like. The heat treatment temperature is not particularly limited, but is performed 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 generally glass, quartz, silicon, polyimide, polyester, polyethylene, polystyrene, polypropylene and a plastic substrate such as polycarbonate and the like. Can be used.

<electrode>
As a material used for the electrodes of the organic thin film transistor, any conductive material can be used. A material having a small electron injection barrier to the organic semiconductor material is preferable.

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

Although the film thickness of the source and drain electrodes is not particularly limited, it is preferably set in the range of several nm to several μm. The distance between the source and drain electrodes is preferably set in the range of several hundred nm to several hundred μm.

<Gate electrode>
Examples of the material forming the gate electrode include 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 aluminum is preferably used in the present invention.

<Insulation layer>
Examples of the material forming the gate insulating layer include inorganic compounds such as silicon oxide, silicon nitride, aluminum oxide, aluminum nitride, and tantalum oxide, polyvinyl alcohol, polyvinyl phenol, polymethyl methacrylate, cyanoethyl pullulan, parylene (Nippon Parylene LLC). Organic polymer compounds such as registered trademark) can be used.

The thickness of the gate insulating film is not particularly limited, but it is preferably set in the range of several nm to several μm.

<Source electrode, drain electrode>
Examples of the material forming the source electrode and the drain electrode include gold, silver, platinum, chromium, aluminum, indium, alkali metals (Li, Na, K, Rb, Cs), alkaline earth metals (Mg, Ca, Sr, Ba) and the like. In the present invention, it is preferable to use gold.

<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 derivative, or naphthalene, naphthalenediimide, anthracene, tetracene, perylene, pentacene, pyrene substituted with an electron withdrawing group such as fluorine or nitrile. , Polycyclic aromatic molecules such as coronene, chrysene, decacyclene, and violanthrene, and their derivatives, triphenylene, thiophene oligomers, aromatic ring oligomers such as polythiophene, polymers and their derivatives, phthalocyanine, tetrathiafulvalene, tetrathiotetracene and their derivatives An electron-deficient organic semiconductor material such as a derivative may be used together in an appropriate amount. Further, a polymer material such as polystyrene or polyvinylphenol may be added in an appropriate amount.

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

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 the synthesis examples were identified by ¹ H-NMR (Nuclear Magnetic Resonance Device, JNM-ECA-600 manufactured by JEOL Ltd.).

[Synthesis Example 1] Synthesis of compound (A-1) The synthesis of 1,7-dibromoperylene-3,4,9,10-tetracarboxylic acid dibutyl ester monoanhydride was performed according to the method described in J. Org. Chem. 2014, 79, P.I. By the method described in 6655-6662, 10 g of 1,7-dibromoperylene-3,4,9,10-tetracarboxylic acid dibutyl ester monoanhydride represented by the following formula (5) was obtained. (Process 1)

In a reaction vessel purged with nitrogen, 1,7-dibromoperylene-3,4,9,10-tetracarboxylic acid dibutyl ester monoanhydride (7.0 g) represented by the above formula (5) and heptafluorobutylamine (4. 5 g) and an N-methyl-2-pyrrolidone solution (45 mL) of acetic acid (3.4 g) were stirred at 60° C. for 5 hours under a nitrogen stream. The reaction solution was cooled to room temperature, poured into water (250 mL), stirred for 30 minutes and then filtered to obtain a crude product. The crude product is purified by column chromatography (carrier: silica gel, developing solution: toluene) and then dried under reduced pressure to give 1,7-dibromoperylene-3,4,9,10- represented by the following formula (6). Tetracarboxylic acid dibutyl ester monoimide (yield: 3.5 g, yield: 50%) was obtained. (Process 2)

In a reaction vessel purged with nitrogen, 1,7-dibromoperylene-3,4,9,10-tetracarboxylic acid dibutyl ester monoimide (3.5 g) represented by the above formula (6) and p-toluenesulfonic acid monohydrate were added. A toluene solution (140 mL) of the solvate (3.5 g) was stirred at 90° C. for 20 hours under a nitrogen stream. The reaction solution was cooled to room temperature and filtered to obtain a crude product, which was washed with toluene and water. Then, it is dried under reduced pressure to obtain 1,7-dibromoperylene-3,4,9,10-tetracarboxylic acid monoanhydride monoimide represented by the following formula (7) (yield: 2.4 g, yield: 83%). Obtained. (Process 3)

In a reaction vessel purged with nitrogen, 1,7-dibromoperylene-3,4,9,10-tetracarboxylic acid monoanhydride monoimide (1.0 g) represented by the above formula (7), pentafluoroaniline (750 mg), A solution of acetic acid (431 μL) in N-methyl-2-pyrrolidone (6 mL) was stirred at 120° C. for 18 hours under a nitrogen stream. The reaction solution was cooled to room temperature, poured into 2N hydrochloric acid water (100 mL), stirred for 30 minutes and then filtered to obtain a crude product. Chloroform-dissolved components were purified by column chromatography (carrier: silica gel, developing solution: toluene) and then dried under reduced pressure to give 1,7-dibromoperylene-3,4,9,10- represented by the following formula (8). Tetracarboxylic acid diimide (yield: 165 mg, yield: 14%) was obtained. (Process 4)

In a reaction vessel purged with nitrogen, 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 was used. The formamide solution (10 mL) was stirred under a nitrogen stream at 90°C for 8 hours. After cooling to room temperature, the reaction solution was poured into water (200 mL), stirred for 30 minutes and then filtered to obtain a crude product. The crude product was added to chloroform, and the dissolved component was purified by column chromatography (carrier: silica gel, developing solution: chloroform) and dried under reduced pressure to give the target compound as a reddish purple solid (yield: 130 mg, yield: 74). %). (Process 5)

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

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

[Synthesis Example 2] Synthesis of compound (A-2) Synthesis was performed in the same manner as in Synthesis Example 1 except that pentafluorophenethylamine was used instead of pentafluoroaniline in Synthesis Example 1, and the target compound was reddish purple. Obtained as a solid (230 mg, yield 31%).

NMR analysis of the obtained reddish purple solid was performed, the following 12 hydrogen signals were detected, and the structure was identified as (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 0.06 (4H), 9.71-9.75 (2H).

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

NMR analysis of the obtained reddish-purple solid was performed, the following 12 hydrogen signals were detected, and the structure was identified as (A-3).

¹ H-NMR (600 MHz, CDCl ₃ ): δ (ppm)=5.03 to 5.08 (2H), 7.28 to 7.34 (4H), 9.00 to 9.02 (2H), 9 0.04 (1H), 9.06 (1H), 9.75-9.77 (2H).

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

NMR analysis of the obtained reddish purple solid was performed, and the following 12 hydrogen signals were detected, and the structure was identified as (A-4).

¹ H-NMR (600 MHz, CDCl ₃ ): δ (ppm)=5.03 to 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 in place of pentafluoroaniline in Synthesis Example 1, The target compound was obtained as a reddish purple solid (590 mg, yield 80%).

NMR analysis of the obtained reddish purple solid was performed, and the following 14 hydrogen signals were detected, and the structure was identified as (A-5).

¹ H-NMR (600 MHz, CDCl ₃ ): δ (ppm)=5.02 to 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 performed 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, yield 69%).

NMR analysis of the obtained reddish purple solid was performed, and the following eight hydrogen signals were detected, and the structure was identified as (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 that pentadecafluorooctylamine was used instead of heptafluorobutylamine and 4-(nonafluorobutyl)aniline was used instead of pentafluoroaniline in Synthesis Example 1. Was synthesized in the same manner as in Synthesis Example 1 to obtain the target compound as a reddish purple solid (170 mg, yield 65%).

NMR analysis of the obtained reddish-purple solid was performed, the following 12 hydrogen signals were detected, and the structure was identified as (A-11).

¹ H-NMR (600 MHz, CDCl ₃ ): δ (ppm)=5.04 to 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) Similar to Synthesis Example 7 except that 4-(tridecafluorohexyl)aniline was used in place of 4-(nonafluorobutyl)aniline in Synthesis Example 7. The target compound was synthesized and obtained as a reddish purple solid (120 mg, yield 66%).

NMR analysis of the obtained reddish purple solid was performed, and the following 12 hydrogen signals were detected, and the structure was identified as the structure represented by formula A-12).

¹ H-NMR (600 MHz, CDCl ₃ ): δ (ppm) = 5.06 (2H), 7.51 to 7.55 (2H), 7.83 to 7.86 (2H), 8.99-9. 0.00 (2H),
9.02-9.06 (2H), 9.75-9.78 (2H).

[Synthesis Example 9] Synthesis of (A-17) The 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-tetramethyl of the following formula (9) was used. 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. 69 mmol) and a solution of 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 filtered, and then water was added to the filtrate for liquid separation. 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, the dissolved content was purified by column chromatography (carrier: silica gel, developing solution: toluene), and then dried under reduced pressure to give the target compound as a reddish purple solid (yield: 250 mg, yield: 17). %).

NMR analysis of the obtained reddish purple solid was performed, and the following 12 hydrogen signals were detected, and the structure was identified as the structure 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. The method described in 2004, 43, 6363-6366 was performed 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 in a transparent sample tube and added to a toluene or chloroform solvent so that the concentration was 0.1% by mass, and the mixture was allowed to stand at room temperature (25 After stirring for several hours at (±2° C.), the solubility was visually evaluated. The results are shown in Table 1. The judgment conditions are indicated by ◯ for complete dissolution (25±2° C.), Δ for turbidity remaining (25±2° C.), and x for insoluble (25±2° C.).

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

[Comparative Example 1]
Solubility was measured in the same manner as in Example 1 except that the comparative compound (B-1) was used instead of the compound (A-1). The results are shown in Table 1.

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

* Judgment condition ○: Complete dissolution (25±2°C)
△: Remains cloudy (25±2°C)
X: Insoluble (25±2°C)

From Table 1, it is clear that the compounds shown in Examples have solubility in chloroform and toluene that is equal to or higher than that of Comparative Examples.

[Example 10] Measurement of transfer characteristic of organic thin film transistor After ultrasonic cleaning of a glass substrate with a neutral detergent for 10 minutes, water for 10 minutes, acetone for 10 minutes and isopropyl alcohol for 10 minutes, an oven at 100°C was used. It was dried for 1 hour. Aluminum serving as a gate electrode was vapor-deposited on the surface of the substrate to a thickness of 50 nm using a metal mask. Then, a mixed solution of polyvinylphenol and melamine was applied by a spin coating method 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 to be source and drain electrodes was evaporated to a thickness of 50 nm on the insulating layer, and a source and drain electrode having a channel width of 500 μm and a channel length of 5 μm was formed by photolithography.

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

The produced organic thin film transistor was subjected to measurement of transfer characteristics of the organic thin film transistor using a semiconductor analyzer (4200-SCS type, manufactured by Keithley Co., Ltd.) under a light shield in the air at a gate voltage of -40V to 80V.

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 results of the mobility 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 transistor Instead of the synthetic compound (A-1), (A-2), (A-3), (A-4), (A-6), The transfer characteristics of the organic thin film transistor manufactured in the same manner as in Example 10 using (A-11) and (A-12) were measured. Table 2 shows the results of the mobility obtained from this measurement.

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

From Table 2, it is clear that the organic thin film transistor using the compound represented by the example in the organic semiconductor layer has higher electron mobility than the comparative example.

The perylene derivative compound according to the present invention can provide an n-type organic semiconductor material having solubility corresponding to a solution process. Further, by using the composition for organic semiconductor containing the organic semiconductor material, it is possible to provide an organic thin film transistor having an excellent electron transporting property.

1: Substrate 2: Gate electrode 3: Gate insulating layer 4: Drain electrode 5: Organic semiconductor layer 6: Source electrode

Claims (10)

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

[Wherein R ¹ and R ¹⁰ are different from each other,
Hydrogen atom, halogen atom,
A linear or branched alkyl group having 1 to 20 carbon atoms, which may have a substituent,
A linear or branched alkenyl group having 1 to 20 carbon atoms which may have a substituent,
An aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent,
Alternatively, it represents a heterocyclic group having 2 to 36 carbon atoms, which may have a substituent.
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,
A linear or branched alkyl group having 1 to 20 carbon atoms, which may have a substituent,
Or represents a linear or branched alkenyl group having 1 to 20 carbon atoms which may have a substituent,
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 , and R ⁸ and R ⁹ may be bonded to each other to form a ring. ] The compound according to claim 1, wherein in the general formula (1), R ¹ or R ¹⁰ 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 each represents a hydrogen atom, a halogen atom,
A linear or branched alkyl group having 1 to 20 carbon atoms, which may have a substituent,
A linear or branched alkenyl group having 1 to 20 carbon atoms which may have a substituent,
Alternatively, it 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. ] The compound according to claim 2, which is a monovalent group represented by the following general formula (3) or (4) in the general formula (2).

[In formula, n represents the integer of 0-5 and m represents the integer of 0-10. ] The compound according to any one of claims 1 to 3, wherein in the general formula (1), R ^{1 to} R ¹⁰ each contain at least one fluorine atom. In the general formula (1), R ³ , R ⁴ , R ⁷ , and R ⁸ are at least one cyano group, or a linear or branched C1 to C4 optionally substituted group. The compound according to any one of claims 1 to 4, which is an alkyl group of. The compound according to claim 1, wherein the solubility in an aromatic organic solvent or a halogen organic solvent at 25±2° C. is 0.02 to 5 mass% concentration. A composition for an organic semiconductor, which comprises the compound according to any one of claims 1 to 6. An organic semiconductor device using the composition for organic semiconductor according to claim 7. The organic semiconductor device according to claim 8, which has a mobility of 10 ⁻³ cm ² /Vs or more. An organic thin film transistor using the organic semiconductor element according to claim 9.

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