JP2015189753A - Heteroacene derivative, organic semiconductor layer and organic thin film transistor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel heteroacene derivative which is a coating type organic semiconductor material having high carrier mobility, high thermostability and high solubility, and an organic semiconductor layer and an organic thin film transistor using the same.SOLUTION: There is provided a heteroacene derivative represented by the following general formula (1). (1), where Rand Rrepresent each independently a hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, Rand Rrepresent each independently a hydrogen atom or a hydrocarbon group containing 1 to 20 carbon atoms, Rand Rrepresent each independently a hydrogen atom, hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms and containing silicon, Tto Trepresent each independently a sulfur atom or an oxygen atom, n represents an integer of 2 to 20 and m represents an integer of 1 to 10.

Description

  The present invention relates to a novel heteroacene derivative that can be developed into an electronic material such as an organic semiconductor material, an organic semiconductor layer using the same, and an organic thin film transistor. The present invention relates to a novel heteroacene derivative that can be developed into an organic semiconductor solution for a film, an organic semiconductor layer and an organic thin film transistor using the same.

  Organic semiconductor devices typified by organic thin film transistors have been attracting attention in recent years because they have features not found in inorganic semiconductor devices such as energy saving, low cost, and flexibility. This organic semiconductor device is composed of several kinds of materials such as an organic semiconductor layer, a substrate, an insulating layer, and an electrode. Among them, the organic semiconductor layer responsible for charge carrier movement has a central role of the device. And since organic-semiconductor device performance is influenced by the carrier mobility of the organic-semiconductor material which comprises this organic-semiconductor layer, the appearance of the organic-semiconductor material which gives a high carrier mobility is desired.

As a method for producing an organic semiconductor layer, generally known are a vacuum deposition method in which an organic material is vaporized under a high temperature vacuum, and a coating method in which an organic material is dissolved in an appropriate solvent and applied. It has been. Of these, the coating method can be carried out even using a printing technique that does not require high-temperature and high-vacuum conditions, so it can be expected to greatly reduce the manufacturing cost of device fabrication, and is an economically preferable process. . In addition, organic semiconductor materials used in such a coating method include a low molecular weight type and a high molecular weight type, but a low molecular weight capable of obtaining a carrier mobility exceeding 1.0 cm ² / V · s. System materials are preferred. Furthermore, it is preferable from the viewpoint of device fabrication process that it has a solubility of 1.0% by weight or more at room temperature and also has heat resistance of 150 ° C. or more. However, there is currently no known low molecular weight organic semiconductor material that combines high carrier mobility, high solubility, and high heat resistance.

  Currently, low molecular weight materials include bis [(triisopropylsilyl) ethynyl] pentacene (see, for example, Non-Patent Document 1), dialkyl-substituted benzothienobenzothiophene (see, for example, Patent Document 1), and dihexyl dithienobenzo. Dithiophene (see, for example, Patent Document 2 and Patent Document 3) has been proposed.

However, bis [(triisopropylsilyl) ethynyl] pentacene described in Non-Patent Document 1 has a coating film mobility of 0.3 to 1.0 cm ² / Vs. There was a problem that it decreased to 0.2 cm ² / Vs. The dialkyl-substituted benzothienobenzothiophene described in Patent Document 1 also has a problem that the transistor operation is lost when heat treatment is performed at 130 ° C. Furthermore, the dihexyl dithienobenzodithiophene proposed in Patent Document 2 and Patent Document 3 shows a carrier mobility of 0.1 cm ² / V · s by a drop cast method, but has a problem of low solubility in a solvent at room temperature. was there.

Republished patent WO2008 / 047896 Special table 2011/526588 gazette JP 2012/209329 A

Journal of Polymer Science: Part B: Polymer Physics, 2006, 44, 3631-3641

  The present invention has been made in view of the above problems, and an object of the present invention is to provide a novel coating type organic semiconductor material having high carrier mobility, high heat resistance and high solubility.

  As a result of intensive studies to solve the above problems, the present inventors have found that an organic thin film transistor having high carrier mobility and high solubility and high heat resistance can be obtained by using a novel heteroacene derivative. The headline and the present invention have been completed.

  That is, the present invention relates to a heteroacene derivative represented by the following general formula (1), an organic semiconductor layer, and an organic thin film transistor using the heteroacene derivative.

(In the formula, R ¹ and R ² each independently represent a hydrocarbon group having 1 to 20 carbon atoms and an alkoxy group having 1 to 20 carbon atoms. R ³ and R ⁴ are each independently a hydrogen atom. Or a hydrocarbon group having 1 to 20 carbon atoms, R ⁵ and R ⁶ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a carbon atom having 1 to 20 carbon atoms containing silicon. T ^{1 to} T ⁴ each independently represents a sulfur atom or an oxygen atom, n represents an integer of 2 to 20, and m represents an integer of 1 to 10.
The present invention is described in detail below.

The heteroacene derivative of the present invention is a derivative represented by the above general formula (1), and the substituents R ¹ and R ² are each independently a hydrocarbon group having 1 to 20 carbon atoms or an alkoxy having 1 to 20 carbon atoms. Groups R ³ and R ⁴ are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ⁵ and R ⁶ are each independently a hydrogen atom or a carbon atom having 1 to 20 carbon atoms. A hydrogen group or a C1-C20 hydrocarbon group containing silicon is shown. T ^{1 to} T ⁴ each independently represent a sulfur atom or an oxygen atom. n represents an integer of 2 to 20, and m represents an integer of 1 to 10.

Since the heteroacene derivative of the present invention is suitable for simultaneously satisfying high carrier mobility, high solubility and high heat resistance, the following general formula (2) is preferable. Further, dithienobenzodithiophene (T ^{1 to} T ⁴ is a sulfur atom) represented by the following general formula (3) is particularly preferable for better carrier mobility.

  The heteroacene derivative of the present invention is characterized by having a side chain containing a siloxy group on the 2nd and 7th alkyl side chains of the heteroacene skeleton represented by the following general formula (4).

  The heteroacene derivative of the present invention has high solubility due to good carrier mobility and high heat resistance due to strong π-π interaction between rigid heteroacene fused polycyclic skeletons, and silicon atoms contained in the side chain. Sexual expression is possible. Improvement of the normally conflicting properties of heat resistance and solubility can be achieved by introducing a siloxy group into the side chain.

  Since the heteroacene derivative of the present invention is suitable for simultaneously satisfying high carrier mobility, high solubility and high heat resistance, the silicon atom contained in one alkyl side chain at the 2-position or 7-position of the heteroacene skeleton is 3 It is preferable that the number is less than or equal to 3 (m is equal to or less than 3), and it is more preferable that the number of silicon atoms contained in one alkyl side chain is 2 (m is 2). A derivative represented by the following general formula (5) having one silicon atom (m is 1) is particularly preferable. Further, n is preferably 12 or less, and more preferably 8 or less, because it is suitable for simultaneously satisfying high carrier mobility, high solubility, and high heat resistance. However, when n is 1, the problem that solubility falls arises.

In the heteroacene derivative of the present invention, examples of the hydrocarbon group having 1 to 20 carbon atoms in the substituents R ¹ and R ² include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t- Butyl group, isobutyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, cyclohexyl group, cyclooctyl group and other aliphatic hydrocarbon groups, phenyl group, 1- Examples thereof include aromatic hydrocarbon groups such as naphthyl group and 2-naphthyl group. Among them, hydrocarbon groups having 1 to 10 carbon atoms are preferable because of high heat resistance and high solubility, and ethyl group, n- More preferred are a propyl group, an isopropyl group, an n-butyl group, a t-butyl group, and a phenyl group.

In the heteroacene derivative of the present invention, examples of the alkoxy group having 1 to 20 carbon atoms in the substituents R ¹ and R ² include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, t- Aliphatic hydrocarbon alkoxy groups such as butyroxy group, isobutoxy group, n-pentoxy group, n-hexoxy group, n-heptoxy group, n-octoxy group, 2-ethylhexoxy group, cyclohexoxy group, cyclooctoxy group, phenoxy Group, 1-naphthoxy group, aromatic hydrocarbon-based alkoxy group such as 2-naphthoxy group, etc. Among them, since it is particularly high heat resistant and highly soluble, an alkoxy group having 1 to 10 carbon atoms is preferable, Ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, t-butoxy group, phenoxy group Rukoto is more preferable.

In the heteroacene derivative of the present invention, examples of the hydrocarbon group having 1 to 20 carbon atoms in the substituents R ³ and R ⁴ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. , N-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-dodecyl group, 2-ethylhexyl group, cyclohexyl group, cyclooctyl group, etc. Among them, hydrocarbon groups having 1 to 10 carbon atoms are preferable, among which n-butyl group, n-pentyl group, n-hexyl group, More preferably, they are an n-heptyl group and an n-octyl group.

In the heteroacene derivative of the present invention, examples of the hydrocarbon group having 1 to 20 carbon atoms in the substituents R ⁵ and R ⁶ include, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. , N-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-dodecyl group, 2-ethylhexyl group, cyclohexyl group, cyclooctyl group, etc. Among them, hydrocarbon groups having 1 to 10 carbon atoms are preferable, among which n-butyl group, n-pentyl group, n-hexyl group, More preferably, they are an n-heptyl group and an n-octyl group.

In the heteroacene derivative of the present invention, the hydrocarbon group having 1 to 20 carbon atoms including silicon in the substituents R ⁵ and R ⁶ is a (trimethylsilyl) ethynyl group, Triethylsilyl) ethynyl group, (triisopropylsilyl) ethynyl group, (tritertiarybutylsilyl) ethynyl group, (diphenyltertiarybutylsilyl) ethynyl group, (triphenylsilyl) ethynyl group, and the like are preferable. A silyl) ethynyl group and a (triisopropylsilyl) ethynyl group are more preferable.

  Specific examples of the heteroacene derivative of the present invention include the following.

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Since the heteroacene derivative of the present invention is suitable for simultaneously satisfying high carrier mobility, high solubility and high heat resistance, bis [2- (triisopropylsiloxy) ethyl] dithienobenzodithiophene, bis [3 -(Triisopropylsiloxy) n-propyl] dithienobenzodithiophene, bis [4- (triisopropylsiloxy) n-butyl] dithienobenzodithiophene, bis [5- (triisopropylsiloxy) n-pentyl] dithieno Benzodithiophene, bis [6- (triisopropylsiloxy) n-hexyl] dithienobenzodithiophene, bis [2- (triethylsiloxy) ethyl] dithienobenzodithiophene, bis [3- (triethylsiloxy) n-propyl ] Dithienobenzodithiophene, bis [4- (triethylsiloxy) n-butyl] dithi Enobenzodithiophene, bis [5- (triethylsiloxy) n-pentyl] dithienobenzodithiophene, bis [6- (triethylsiloxy) n-hexyl] dithienobenzodithiophene, bis [6- (tertiary butyldimethyl) Siloxy) n-hexyl] dithienobenzodithiophene, bis [2- (triisopropylsiloxy) ethyl] dithienobenzodifuran, bis [3- (triisopropylsiloxy) n-propyl] dithienobenzodifuran, bis [ 4- (Triisopropylsiloxy) n-butyl] dithienobenzodifuran, bis [5- (triisopropylsiloxy) n-pentyl] dithienobenzodifuran, bis [6- (triisopropylsiloxy) n-hexyl] di Thienobenzodifuran, bis [2- (triethylsiloxy) ethyl] dithienobenzodi Lan, bis [3- (triethylsiloxy) n-propyl] dithienobenzodifuran, bis [4- (triethylsiloxy) n-butyl] dithienobenzodifuran, bis [5- (triethylsiloxy) n-pentyl] Dithienobenzodifuran, bis [6- (triethylsiloxy) n-hexyl] dithienobenzodifuran, bis [6- (tertiarybutyldimethylsiloxy) n-hexyl] dithienobenzodifuran, bis [2- ( Triisopropylsiloxy) ethyl] difurobenzodifuran, bis [3- (triisopropylsiloxy) n-propyl] difurobenzodifuran, bis [4- (triisopropylsiloxy) n-butyl] difurobenzodifuran, Bis [5- (triisopropylsiloxy) n-pentyl] difurobenzodifuran, bis [6- (triisopropylsilo N) hexyl] difurobenzodifuran, bis [2- (triethylsiloxy) ethyl] difurobenzodifuran, bis [3- (triethylsiloxy) n-propyl] difurobenzodifuran, bis [4- (Triethylsiloxy) n-butyl] difurobenzodifuran, bis [5- (triethylsiloxy) n-pentyl] difurobenzodifuran, bis [6- (triethylsiloxy) n-hexyl] difurobenzodifuran, Bis [6- (tertiarybutyldimethylsiloxy) n-hexyl] difurobenzodifuran is preferred.

As a method for producing the heteroacene derivative of the present invention, any production method can be used as long as the heteroacene derivative can be produced. When producing the heteroacene derivative of the general formula (1) in which the substituents R ¹ and R ² are hydrocarbon groups having 1 to 20 carbon atoms and R ^{3 to} R ⁶ are hydrogen atoms, the following (A) to (C) It is possible to produce a heteroacene derivative by a production method through a process.

  Step (A): A diacyl derivative of heteroacene (the following general formula (7)) is produced by Friedel-Crafts acylation reaction of heteroacene (the following general formula (6)) and an acyl chloride compound in the presence of aluminum chloride as a catalyst. Process.

  Step (B): A step of producing a di (hydroxyalkyl) form of heteroacene (the following general formula (8)) by subjecting the heteroacene diacyl form (7) obtained in Step (A) to a reduction reaction.

  Step (C): In the presence of a base, the reaction of the di (hydroxyalkyl) isomer of heteroacene (8) obtained in Step (B) with silyl halide or silyltrifluoromethanesulfonate yields a heteroacene derivative (the following general formula ( 9)).

  A specific production method is shown in Reaction Scheme 1 below.

(Here, R is a hydrocarbon group having 1 to 20 carbon atoms, T ^{1 to} T ⁴ are each independently a sulfur atom or an oxygen atom, X is a halogen or trifluoromethanesulfonate, a is an integer of 0 to 18, b Represents an integer of 0 to 9.)
Here, the step (A) in Reaction Scheme 1 is a step of producing a diacyl derivative (7) of heteroacene by Friedel-Crafts acylation reaction of heteroacene (6) and an acyl chloride compound in the presence of aluminum chloride as a catalyst. It is.

  Examples of the acyl chloride compound include 2-methyloxalyl chloride, (methoxycarbonyl) acetyl chloride, 3- (methoxycarbonyl) propanoyl chloride, 4- (methoxycarbonyl) butanoyl chloride, 5- (methoxycarbonyl) pentanoyl chloride, 6 Examples include-(methoxycarbonyl) hexanoyl chloride, 7- (methoxycarbonyl) heptanoyl chloride, and 8- (methoxycarbonyl) octanoyl chloride. The Friedel-Crafts acylation reaction can be carried out in a solvent such as dichloromethane, 1,2-dichloroethane, toluene and the like. The amount of the acyl chloride compound used is preferably 2 to 10 equivalents per 1 equivalent of the heteroacene (6) because the heteroacene diacyl derivative (7) can be collected efficiently. The amount of aluminum chloride to be used is preferably 2 equivalents or more per 1 equivalent of the acyl chloride compound because the diacyl derivative (7) of heteroacene can be collected more selectively.

  Step (B) in Reaction Scheme 1 is a step for producing a di (hydroxyalkyl) isomer (8) of heteroacene by subjecting the diacyl isomer (7) of heteroacene to a reduction reaction.

  Examples of the reduction reaction of the heteroacene diacyl derivative (7) include a reaction using sodium borohydride / aluminum chloride as a reducing agent.

  In step (C) in reaction scheme 1, the heteroacene derivative is obtained by reacting the di (hydroxyalkyl) isomer of heteroacene (8) obtained in step (B) with silyl halide or silyltrifluoromethanesulfonate in the presence of a base. (9) is a process of manufacturing.

  The silyl halide or silyl trifluoromethanesulfonate is, for example, trimethylsilyl chloride, triethylsilyl chloride, triisopropylsilyl chloride, tertiary butyldimethylsilyl chloride, tertiary butyldiphenyl chloride, trimethylsilyl trifluoromethanesulfonate, triethylsilyltrifluoromethanesulfonate. , Triisopropyl trifluoromethanesulfonate, tertiary butyldimethylsilyl trifluoromethanesulfonate, tertiary butyldiphenylsilyl trifluoromethanesulfonate, and the like. Examples of the base include imidazole, 2,6-lutidine, sodium hydride, potassium hydride, n-butyllithium, lithium diisopropylamide and the like.

  Furthermore, the produced heteroacene derivative can be purified by subjecting it to column chromatography and the like, and examples of the separating agent include silica gel and alumina. Solvents include hexane, heptane, Toluene, dichloromethane, chloroform and the like can be mentioned.

  Further, the produced heteroacene derivative may be further purified by recrystallization. Purity can be improved by increasing the number of recrystallizations. Examples of the solvent used for recrystallization include hexane, heptane, octane, toluene, xylene, chloroform, chlorobenzene, dichlorobenzene, and the like, and a mixture of any ratio thereof may be used. In the recrystallization method, a heteroacene derivative solution is prepared by heating, and the solution is cooled to precipitate and isolate a heteroacene derivative crystal. In addition, when measuring purity, it can measure by analyzing by liquid chromatography.

  The heteroacene used in the step (A) for producing the heteroacene derivative of the present invention may be produced by any method. Specific examples of the method for producing heteroacene used in step (A) include the following (of heteroacene, dithienobenzothiophene (general formula (11)), dithienobenzodi Furan (general formula (14)) and difurobenzodifuran (general formula (17) production method).

Of the heteroacene compounds, T ^{1 to} T ⁴ are sulfur, that is, dithienobenzodithiophene can be produced by any production method as long as the dithienobenzodithiophene can be produced. It is. For example, when manufacturing dithienobenzodithiophene, it can manufacture with the manufacturing method which passes through the process of following (D)-(E).

  Step (D): 1,4-di (3-halothienyl) -2,5-dihalobenzene (3-halothiophene-2-zinc derivative and 1,2,4,5-tetrahalobenzene in the presence of a palladium catalyst ( A method for producing the following general formula (10).

  Step (E): Dithienobenzodi by intramolecular cyclization of 1,4-di (3-halothienyl) -2,5-dihalobenzene (10) obtained by Step (D) in the presence of an alkali metal sulfide. A step of producing thiophene (the following general formula (11)).

  A specific production method is shown in Reaction Scheme 2 below.

  Here, step (D) in Reaction Scheme 2 is carried out by cross-coupling of 3-bromothiophene-2-zinc derivative and 1,4-dibromo-2,5-difluorobenzene in the presence of a palladium catalyst. In this step, di (3-bromothienyl) -2,5-difluorobenzene (10) is produced.

  Step (E) in Reaction Scheme 2 is an intramolecular cyclization of 1,4-di (3-bromothienyl) -2,5-difluorobenzene (10) obtained by step (D) in the presence of sodium sulfide. Is a step of producing dithienobenzodithiophene (11).

Among the heteroacene compounds, T ¹ and T ⁴ are oxygen, and T ² and T ³ are sulfur. That is, as a method for producing dithienobenzodifuran, it is possible to produce the dithienobenzodifuran. Any manufacturing method can be used. For example, when manufacturing dithienobenzodifuran, it can manufacture with the manufacturing method which passes through the process of following (F)-(H).

  Step (F): 1,4-di (3-bromofuryl) -2 by palladium-catalyzed cross coupling of a 3-bromofuran-2-zinc derivative and 1,4-dibromo-2,5-dihalobenzene in the presence of a palladium catalyst. , 5-Dihalobenzene (the following general formula (12)).

  (G) Step; Bromohalomonocyclized product (described below) by monomolecular cyclization reaction using 1,4-di (3-bromofuryl) -2,5-dihalobenzene (12) obtained in Step (F) and sodium sulfide. The process of manufacturing General formula (13)).

  (H) step; dithienobenzodifuran by a method in which the bromohalomonocyclization product (13) obtained in step (G) is dilithiated with n-butyllithium / a second ring is formed with bis (phenylsulfonyl) sulfide. The process of manufacturing (following General formula (14)).

  A specific production method is shown in Reaction Scheme 3 below.

  Here, the step (F) in Reaction Scheme 3 is carried out by cross-coupling of a 3-bromofuran-2-zinc derivative and 1,4-dibromo-2,5-diiodobenzene in the presence of a palladium catalyst. In this step, di (3-bromofuryl) -2,5-dibromobenzene (12) is produced.

  Step (G) in Reaction Scheme 3 is a monomolecular cyclization reaction using 1,4-di (3-bromofuryl) -2,5-dibromobenzene (12) obtained in step (F) and sodium sulfide. Is a step for producing a dibromomonocyclized product (13).

  In step (H) in Reaction Scheme 3, the dibromomonocyclized product (13) obtained in step (G) is subjected to dilithiation with n-butyllithium / cyclization reaction with bis (phenylsulfonyl) sulfide, and dithienobenzo It is a process for producing gifrane (14).

Of the heteroacene compounds, T ^{1 to} T ⁴ are oxygen, that is, difurobenzodifuran can be produced by any production method as long as the difurobenzodifuran can be produced. It is. For example, when manufacturing difurobenzodifuran, it can manufacture with the manufacturing method which passes through the process of following (I)-(K).

  Step (I): 1,4-di (3-bromofuryl) -2,5-dimethoxybenzene with 3-bromofuran-2-zinc derivative and 1,4-dibromo-2,5-dimethoxybenzene in the presence of a palladium catalyst The process of manufacturing (the following general formula (15)).

  Step (J): 1,4-di (3-bromofuryl) -2,5-dimethoxybenzene (15) obtained by Step (I) in the presence of boron tribromide is demethylated to give 1,4- A step of producing di (3-bromofuryl) -2,5-dihydroxybenzene (the following general formula (16)).

  Step (K): Difluorobenzodifuran by intramolecular cyclization of 1,4-di (3-bromofuryl) -2,5-dihydroxybenzene (16) obtained in Step (J) in the presence of a palladium catalyst. The process of manufacturing (the following general formula (17)).

  A specific production method is shown in Reaction Scheme 4 below.

  Here, step (I) in reaction scheme 4 can be carried out under the same reaction conditions as in step (F) of reaction scheme 3 described above, and 1,4-di (3-bromofuryl) -2,5- In this step, dimethoxybenzene (15) is produced.

  Step (J) in Reaction Scheme 4 includes demethylation of 1,4-di (3-bromofuryl) -2,5-dimethoxybenzene (15) obtained in Step (I) in the presence of boron tribromide. Is a step for producing 1,4-di (3-bromofuryl) -2,5-dihydroxybenzene (16).

Step (K) in Reaction Scheme 4 is carried out by intramolecular cyclization of 1,4-di (3-bromofuryl) -2,5-dihydroxybenzene (16) obtained in Step (J) in the presence of a palladium catalyst. This is a step for producing difurobenzodifuran (17) in which the substituents R ¹ and R ² are hydrogen.

  In addition, this cyclization reaction can also be implemented, for example using the method described in Journal of Organic Chemistry (USA), 2007, 72, 5119-5128.

  The organic semiconductor layer forming solution of the present invention contains the heteroacene derivative and a solvent, and the concentration of the heteroacene derivative in the solution is suitable for film formation by a drop cast method, particularly an ink jet method or a slit coat method. Therefore, it is preferable that the solubility is 1.0% by weight or more with respect to the solvent at room temperature.

  Examples of the solvent used include toluene, xylene, mesitylene, ethylbenzene, pentylbenzene, hexylbenzene, octylbenzene, cyclohexylbenzene, indane, tetralin, anisole, 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, 1,2 -C7-14 aromatic hydrocarbon solvent such as dimethylanisole, 2,3-dimethylanisole, 3,4-dimethylanisole; C6-14 such as hexane, heptane, octane, decane, dodecane, tetradecane, etc. Aliphatic hydrocarbon solvents; o-dichlorobenzene, chlorobenzene, trichlorobenzene, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, chloroform, dichloromethane and other halogenated solvents having 1 to 7 carbon atoms; tetrahydrofuran, Ether solvents such as 1,2-dimethoxyethane and dioxane; ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, diisopropyl ketone and acetophenone; ester solvents such as ethyl acetate, γ-butyrolactone, cyclohexanol acetate and 3-methoxybutyl acetate Solvent: Amide-based solvent such as N, N-dimethylformamide, N-methyl-2-pyrrolidone; dipropylene glycol dimethyl ether, dipropylene glycol diacetate, dipropylene glycol methyl-n-propyl ether, dipropylene glycol methyl ether acetate, 1,4-butanediol diacetate, 1,3-butylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate And glycol solvents such as ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate. Among them, it is possible to obtain a high boiling point solution. Therefore, it is preferably an aromatic hydrocarbon solvent having 7 to 14 carbon atoms such as toluene, xylene, mesitylene, ethylbenzene, pentylbenzene, cyclohexylbenzene, tetralin, 3,4-dimethylanisole, and toluene, mesitylene, cyclohexyl. More preferred are benzene, tetralin, and 3,4-dimethylanisole. Here, room temperature is generally referred to as room temperature, and examples thereof include a temperature of 20 to 26 ° C.

  In the present invention, a solution for forming an organic semiconductor layer can be prepared by dissolving or dispersing the heteroacene derivative represented by the general formula (1) in a liquid medium that is the solvent mentioned above. At this time, a specific method for preparing the solution for forming an organic semiconductor includes mixing the above-mentioned solvent and the heteroacene derivative represented by the general formula (1), and heating and stirring.

  The solution can be prepared at a relatively low temperature because the heteroacene derivative itself has appropriate cohesiveness, and can be suitably applied to the production of an organic thin film by a coating method because it has oxidation resistance. That is, since it is not necessary to remove air from the atmosphere, the coating process can be simplified. Further, the solution is, for example, polystyrene, poly-α-methylstyrene, polyvinyl naphthalene, ethylene-norbornene copolymer, polymethyl methacrylate, polytriarylamine, poly (9,9-dioctylfluorene-co-dimethyltriarylamine), etc. The polymer can also be present as a binder. The concentration of these polymer binders is preferably 0.1 to 10.0% by weight for the expression of excellent carrier mobility, and since the solution has excellent coating properties, 0.5 to 50 mPa -It is preferable that the viscosity is in the range of s.

  The heteroacene derivative contained in the solution for forming an organic semiconductor layer of the present invention has excellent characteristics as an organic semiconductor material because it provides high carrier mobility, and has high solubility in a solvent. The organic semiconductor layer can be formed easily and efficiently by a method such as a drop casting method, particularly an inkjet method, using the organic semiconductor layer forming solution.

  When the organic semiconductor layer is formed using the heteroacene derivative of the present invention, for example, a drop casting method such as spin coating, cast coating, inkjet, slit coating, etc .; blade coating; dip coating; screen printing, gravure printing, flexographic printing, etc. It is possible to use a method such as a printing method, and among them, it is possible to easily and efficiently make an organic semiconductor layer, so that it is preferably a drop cast method such as spin coating, cast coating, inkjet, More preferably, it is an inkjet. Moreover, there is no restriction | limiting in the film thickness of the organic-semiconductor layer in that case, Preferably it is 1 nm-1 micrometer, More preferably, it is 10 nm-300 nm for the outstanding carrier mobility expression. In addition, a plurality of heteroacene derivatives may be mixed to form the organic semiconductor layer.

  The organic semiconductor layer containing the heteroacene derivative of the present invention can be annealed at 40 to 200 ° C. after coating and drying.

  The organic thin film transistor is obtained by laminating an organic semiconductor layer provided with a source electrode and a drain electrode on a substrate and a gate electrode through an insulating layer, and the heteroacene derivative of the present invention is used for the organic semiconductor layer. By employing an organic semiconductor layer, an organic thin film transistor can be obtained.

  FIG. 1 shows a structure of a general organic thin film transistor by a sectional shape. Here, (A) is a bottom gate-top contact type, (B) is a bottom gate-bottom contact type, (C) is a top gate-top contact type, and (D) is a top gate-bottom contact type. 1 is an organic semiconductor layer, 2 is a substrate, 3 is a gate electrode, 4 is a gate insulating layer, 5 is a source electrode, 6 is a drain electrode, and an organic semiconductor layer using the heteroacene derivative of the present invention Can be applied to any organic thin film transistor.

  Examples of the substrate include polyethylene terephthalate, polyethylene naphthalate, polymethyl methacrylate, polymethyl acrylate, polyethylene, polypropylene, polystyrene, cyclic polyolefin, polyimide, polycarbonate, polyvinyl phenol, polyvinyl alcohol, poly (diisopropyl fumarate), poly (Diethyl fumarate), poly (diisopropyl maleate), polyethersulfone, polyphenylene sulfide, cellulose triacetate and other plastic substrates; glass, quartz, aluminum oxide, silicon, highly doped silicon, silicon oxide, tantalum dioxide, tantalum pentoxide, Inorganic tin oxide and other inorganic material substrates; metal substrates such as gold, copper, chromium, titanium, and aluminum Can. When highly doped silicon is used for the substrate, the substrate can also serve as the gate electrode.

  Examples of the gate electrode include inorganic materials such as aluminum, gold, silver, copper, highly doped silicon, tin oxide, indium oxide, indium tin oxide, chromium, titanium, tantalum, chromium, graphene, and carbon nanotubes; Examples thereof include organic materials such as conductive polymers (for example, PEDOT-PSS).

  Examples of the gate insulating layer include silicon oxide, silicon nitride, aluminum oxide, aluminum nitride, titanium oxide, tantalum dioxide, tantalum pentoxide, indium tin oxide, tin oxide, vanadium oxide, barium titanate, and bismuth titanate. Inorganic material substrate: polymethyl methacrylate, polymethyl acrylate, polyimide, polycarbonate, polyvinyl phenol, polyvinyl alcohol, poly (diisopropyl fumarate), poly (diethyl fumarate), polyethylene terephthalate, polyethylene naphthalate, polyether sulfone, polycyclopentane , Polycyclohexane, polycyclohexane-ethylene copolymer, polyfluorinated cyclopentane, polyfluorinated cyclohexane, polyfluorinated cyclohexane-ethylene And a plastic material such as a copolymer. The surfaces of these gate insulating layers are, for example, octadecyltrichlorosilane, decyltrichlorosilane, decyltrimethoxysilane, octyltrichlorosilane, octadecyltrimethoxysilane, β-phenethyltrichlorosilane, β-phenethyltrimethoxysilane, phenyltrichlorosilane. Silanes such as chlorosilane and phenyltrimethoxysilane; phosphonic acids such as octadecylphosphonic acid, decylphosphonic acid and octylphosphonic acid; and those modified with silylamines such as hexamethyldisilazane can also be used. In general, the surface treatment of the gate insulating layer is preferable in order to increase the crystal grain size and molecular orientation of the organic semiconductor material, and to improve the carrier mobility and current on / off ratio, and to lower the threshold voltage. Results are obtained.

  As a material of the source electrode and the drain electrode, the same material as that of the gate electrode can be used, and the material may be the same as or different from the material of the gate electrode, or different materials may be stacked. In order to increase the carrier injection efficiency, surface treatment can be performed on these electrode materials. Examples of the surface treatment agent for performing the surface treatment include benzenethiol and pentafluorobenzenethiol.

  The heteroacene derivative of the present invention is used for an organic semiconductor layer of an electronic paper, an organic EL display, a liquid crystal display, an IC tag (RFID tag), a transistor such as a pressure sensor; an organic EL display material; an organic semiconductor laser material; Materials: Can be used for electronic materials such as photonic crystal materials.

  The novel heteroacene derivative of the present invention is a coating-type organic semiconductor material that provides high carrier mobility and high heat resistance and high solubility, and is a novel organic semiconductor material that solves the conventional problems by the present invention As a semiconductor device material typified by an organic thin film transistor, the effect is extremely high.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

¹ H-NMR spectrum (manufactured by JEOL GSX-400 (400 MHz)), mass spectrum (manufactured by Shimadzu Corporation, GCMS-QP2010 SE), and elemental analysis (manufactured by PerkinElmer Japan, 2400II) are used for product identification. It was. Moreover, the liquid chromatography (LC) (the Tosoh make, LC-8020) was used for the purity measurement of a product. Commercially available products were used for reagents such as aluminum chloride and acid chloride unless otherwise noted.

  Example 1 (Synthesis of bis [6- (triisopropylsiloxy) n-hexyl] dithienobenzodithiophene)

(Synthesis of bis [(5-methoxycarbonyl) pentanoyl] dithienobenzodithiophene (step (A)))
Under a nitrogen atmosphere, 1600 mg (12.0 mmol) of aluminum chloride and 25 ml of dichloromethane (dehydrated grade) were added to a 200 ml three-necked flask. Thereafter, 1072 mg (6.0 mmol) of 5- (methoxycarbonyl) pentanoyl chloride was added and stirred for 1 hour. To the resulting mixture, 605 mg (2.0 mmol) of dithienobenzodithiophene was added and stirred for 150 hours. The reaction was stopped by adding water to the obtained mixture, and dichloromethane was distilled off. The obtained solid was washed with water, methanol, and hexane to obtain 980 mg of bis [(5-methoxycarbonyl) pentanoyl] dithienobenzodithiophene (yield 84%).
MS m / z: 587 (M ⁺ , 100%)
(Synthesis of bis [(6-hydroxy) n-hexyl] dithienobenzodithiophene (step (B)))
Under a nitrogen atmosphere, 937 mg (7.0 mmol) of aluminum chloride and 70 ml of tetrahydrofuran (dehydrated grade) were added to a 200 ml three-necked flask. Thereafter, 950 mg (1.6 mmol) of bis [(5-methoxycarbonyl) pentanoyl] dithienobenzodithiophene synthesized in the previous step was added and stirred at 0 ° C. for 10 minutes. To the obtained mixture, 1010 mg (26.7 mmol) of sodium borohydride was added and stirred under reflux for 32 hours. The reaction was quenched by adding water to the resulting mixture and extracted with dichloromethane. The organic phase was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain 371 mg of bis [(6-hydroxy) n-hexyl] dithienobenzodithiophene (yield 46%).
MS m / z: 503 (M ^<+> , 100%).
(Synthesis of bis [6- (triisopropylsiloxy) n-hexyl] dithienobenzodithiophene (step (C)))
Under a nitrogen atmosphere, 350 mg (0.70 mmol) of bis [(6-hydroxy) n-hexyl] dithienobenzodithiophene synthesized in the previous step and 50 ml of dichloromethane (dehydrated grade) were added to a 200 ml three-necked flask. Thereafter, 572 mg (8.4 mmol) of imidazole and 1080 mg (5.6 mmol) of triisopropylsilyl chloride were added to the mixture, and the mixture was stirred at room temperature for 60 hours. The obtained mixture was concentrated, and the residue was purified by silica gel column chromatography (hexane / dichloromethane). The resulting concentrate was purified by recrystallization once from toluene / hexane and then twice from toluene to obtain 90 mg of bis [6- (triisopropylsiloxy) n-hexyl] dithienobenzodithiophene (yield) 16%).
LC purity: 99.2%.
¹ H-NMR (CDCl ₃ , 25 ° C.): δ = 8.16 (s, 2H), 7.02 (s, 2H), 3.68 (t, J = 6.6 Hz, 4H), 2.94 (T, J = 7.6 Hz, 4H), 1.84-1.72 (m, 4H), 1.62-1.52 (m, 4H), 1.48-1.38 (m, 8H) 1.14-1.00 (m, 42H).
MS m / z: 815 (M ^<+> , 100%).
Elemental analysis: C; 64.95, H; 8.41. (Theoretical value C; 64.81, H; 8.65)
Example 2 Synthesis of bis [2- (triisopropylsiloxy) ethyl] dithienobenzodithiophene

(Synthesis of bis (2-methyloxalyl) dithienobenzodithiophene (step (A)))
In the step (A) of Example 1, the same procedure as in the step (A) of Example 1 except that 2-methyloxalyl chloride was used instead of 5- (methoxycarbonyl) pentanoyl chloride and the reaction time was 120 hours. The operation was repeated to obtain 892 mg of bis (2-methyloxalyl) dithienobenzodithiophene (yield 94%).
MS m / z: 475 (M ^<+> , 100%).
(Synthesis of bis [(2-hydroxy) ethyl] dithienobenzodithiophene (step (B)))
In the step (B) of Example 1, 850 mg of bis (2-methyloxalyl) dithienobenzodithiophene was used instead of 950 mg (1.6 mmol) of bis [(5-methoxycarbonyl) pentanoyl] dithienobenzodithiophene. 8 mmol), and the reaction time was 18 hours, and the same operation as in step (B) of Example 1 was repeated to obtain 373 mg of bis [(2-hydroxy) ethyl] dithienobenzodithiophene (yield). Rate 53%).
MS m / z: 391 (M ^<+> , 100%).
(Synthesis of bis [2- (triisopropylsiloxy) ethyl] dithienobenzodithiophene (step (C)))
Instead of 350 mg (0.70 mmol) of bis [(6-hydroxy) n-hexyl] dithienobenzodithiophene in the step (C) of Example 1, 350 mg of bis [(2-hydroxy) ethyl] dithienobenzodithiophene ( 0.90 mmol) and the reaction time was 50 hours, and the same operation as in step (C) of Example 1 was repeated to obtain 110 mg of bis [2- (triisopropylsiloxy) ethyl] dithienobenzodithiophene. Obtained (yield 17%).
LC purity: 99.3%.
MS m / z: 703 (M ^<+> , 100%).
Elemental analysis: C; 61.50, H; 7.64. (Theoretical value C; 61.48, H; 7.74)
Example 3 Synthesis of bis [6- (triethylsiloxy) n-hexyl] dithienobenzodithiophene

(Synthesis of bis [(5-methoxycarbonyl) pentanoyl] dithienobenzodithiophene (step (A)))
The same operation as in step (A) of Example 1 was repeated to obtain 1050 mg of bis [(5-methoxycarbonyl) pentanoyl] dithienobenzodithiophene (yield 90%).
MS m / z: 587 (M ^<+> , 100%).
(Synthesis of bis [(6-hydroxy) n-hexyl] dithienobenzodithiophene (step (B)))
In the step (B) of Example 1, the same operation as in the step (B) of Example 1 was repeated except that the reaction time was 20 hours, and bis [(6-hydroxy) n-hexyl] dithienobenzodi 408 mg of thiophene was obtained (yield 50%).
MS m / z: 503 (M ^<+> , 100%).
(Synthesis of bis [6- (triethylsiloxy) n-hexyl] dithienobenzodithiophene (step (C)))
In the step (C) of Example 1, the same operation as in the step (C) of Example 1 was repeated except that triethylsilyl chloride was used instead of triisopropylsilyl chloride and the reaction time was 55 hours. 82 mg of 6- (triethylsiloxy) n-hexyl] dithienobenzodithiophene was obtained (yield 16%).
LC purity: 99.2%.
MS m / z: 731 (M ^<+> , 100%).
Elemental analysis: C; 62.45, H; 8.10. (Theoretical value C; 62.41, H; 7.9)
Example 4 (Synthesis of bis [6- (tertiarybutyldimethylsiloxy) n-hexyl] dithienobenzodithiophene)

(Synthesis of bis [(5-methoxycarbonyl) pentanoyl] dithienobenzodithiophene (step (A)))
In the step (A) of Example 1, except that the reaction time was 100 hours, the same operation as in the step (A) of Example 1 was repeated to repeat bis [(5-methoxycarbonyl) pentanoyl] dithienobenzodithiophene. 1080 mg was obtained (yield 92%).
MS m / z: 587 (M ^<+> , 100%).
(Synthesis of bis [(6-hydroxy) n-hexyl] dithienobenzodithiophene (step (B)))
In the step (B) of Example 1, except that the charged amount of bis [(5-methoxycarbonyl) pentanoyl] dithienobenzodithiophene was 1000 mg (1.7 mmol) and the reaction time was 20 hours, Example 1 By repeating the same operation as in the step (B), 397 mg of bis [(6-hydroxy) n-hexyl] dithienobenzodithiophene was obtained (yield 46%).
MS m / z: 503 (M ^<+> , 100%).
(Synthesis of bis [6- (tertiarybutyldimethylsiloxy) n-hexyl] dithienobenzodithiophene (step (C)))
In the step (C) of Example 1, the same operation as in the step (C) of Example 1 was repeated except that tertiary butyldimethylsilyl chloride was used instead of triisopropylsilyl chloride and the reaction time was 76 hours. Thus, 121 mg of bis [6- (tertiarybutyldimethylsiloxy) n-hexyl] dithienobenzodithiophene was obtained (yield 24%).
LC purity: 99.4%.
MS m / z: 731 (M ^<+> , 100%).
Elemental analysis: C; 62.39, H; 7.89. (Theoretical value C; 62.41, H; 7.9)
Example 5 (Synthesis of bis [6- (triisopropylsiloxy) n-hexyl] dithienobenzodifuran)

(Synthesis of bis [(5-methoxycarbonyl) pentanoyl] dithienobenzodifuran (step (A)))
In the step (A) of Example 1, 541 mg (2.0 mmol) of dithienobenzodifuran was used instead of 605 mg (2.0 mmol) of dithienobenzodithiophene, and the reaction time was 100 hours. The same operation as in step (A) of Example 1 was repeated to obtain 887 mg of bis [(5-methoxycarbonyl) pentanoyl] dithienobenzodifuran (yield 80%).
MS m / z: 555 (M ^<+> , 100%).
(Synthesis of bis [(6-hydroxy) n-hexyl] dithienobenzodifuran (step (B)))
In the step (B) of Example 1, bis [(5-methoxycarbonyl) pentanoyl] dithienobenzodifuran was used instead of 950 mg (1.6 mmol) of bis [(5-methoxycarbonyl) pentanoyl] dithienobenzodithiophene. Except that 850 mg (1.5 mmol) was used and the reaction time was 28 hours, the same operation as in step (B) of Example 1 was repeated to repeat bis [(6-hydroxy) n-hexyl] dithienobenzodifuran. 308 mg was obtained (43% yield).
MS m / z: 471 (M ^<+> , 100%).
(Synthesis of bis [6- (triisopropylsiloxy) n-hexyl] dithienobenzodifuran (step (C)))
In Step (C) of Example 1, instead of 350 mg (0.70 mmol) of bis [(6-hydroxy) n-hexyl] dithienobenzodithiophene, bis [(6-hydroxy) n-hexyl] dithienobenzo Except for 300 mg (0.64 mmol) of difuran and a reaction time of 47 hours, the same operation as in step (C) of Example 1 was repeated to repeat bis [6- (triisopropylsiloxy) n-hexyl] dithienobenzo 101 mg of difuran was obtained (yield 20%).
LC purity: 99.1%.
MS m / z: 783 (M ^<+> , 100%).
Elemental analysis: C; 67.59, H; 9.10. (Theoretical value C; 67.47, H; 9.01)
Example 6 Synthesis of bis [6- (triisopropylsiloxy) n-hexyl] difurobenzodifuran

(Synthesis of bis [(5-methoxycarbonyl) pentanoyl] difurobenzodifuran (step (A)))
In the step (A) of Example 1, instead of dithienobenzodithiophene 605 mg (2.0 mmol), difluorobenzodifuran 476 mg (2.0 mmol) was used, and the reaction time was changed to 98 hours. The same operation as in step (A) of Example 1 was repeated to obtain 920 mg of bis [(5-methoxycarbonyl) pentanoyl] difurobenzodifuran (yield 88%).
MS m / z: 523 (M ^<+> , 100%).
(Synthesis of bis [(6-hydroxy) n-hexyl] difurobenzodifuran (step (B)))
In the step (B) of Example 1, bis [(5-methoxycarbonyl) pentanoyl] difurobenzodifuran was used instead of 950 mg (1.6 mmol) of bis [(5-methoxycarbonyl) pentanoyl] dithienobenzodithiophene. Except that 900 mg (1.7 mmol) was used and the reaction time was 25 hours, the same operation as in step (B) of Example 1 was repeated to repeat bis [(6-hydroxy) n-hexyl] difurobenzodifuran. 430 mg was obtained (57% yield).
MS m / z: 439 (M ^<+> , 100%).
(Synthesis of bis [6- (triisopropylsiloxy) n-hexyl] difurobenzodifuran (step (C)))
In step (C) of Example 1, instead of 350 mg (0.70 mmol) of bis [(6-hydroxy) n-hexyl] dithienobenzodithiophene, bis [(6-hydroxy) n-hexyl] difurobenzo Except for difuran 400 mg (0.91 mmol) and reaction time 68 hours, the same operation as in step (C) of Example 1 was repeated to repeat bis [6- (triisopropylsiloxy) n-hexyl] difurobenzo. 98 mg of difuran was obtained (14% yield).
LC purity: 99.3%.
MS m / z: 751 (M ^<+> , 100%).
Elemental analysis: C; 70.40, H; 9.47. (Theoretical value C; 70.35, H; 9.39)
Example 7
9.4 mg of bis [6- (triisopropylsiloxy) n-hexyl] dithienobenzodithiophene and 617 mg of toluene synthesized in Example 1 were added, dissolved by heating at 50 ° C., and then allowed to stand at room temperature (25 ° C.). . It was confirmed that the solution state was maintained after 10 hours at 25 ° C. (the concentration of bis [6- (triisopropylsiloxy) n-hexyl] dithienobenzodithiophene was 1.5% by weight).

  2.8 mg of bis [6- (triisopropylsiloxy) n-hexyl] dithienobenzodithiophene synthesized in Example 1 and 1400 mg of toluene were added, dissolved by heating at 50 ° C., and then allowed to cool at room temperature (25 ° C.). Then, a solution for forming a drop cast organic semiconductor layer was prepared (0.20% by weight colorless solution).

  Then, a drop cast organic semiconductor layer forming solution (on a silicon substrate (resistance value: 0.004Ω, with a 200 nm silicon oxide film on the surface)) that is n-type highly doped with arsenic having a diameter of 2 inches in air is obtained ( A 0.20% by weight colorless solution) 0.5 ml was filled into a microsyringe and drop-cast. The organic semiconductor layer of bis [6- (triisopropylsiloxy) n-hexyl] dithienobenzodithiophene having a film thickness of 100 nm was produced by natural drying at room temperature (25 ° C.).

  A shadow mask having a channel length of 20 μm and a channel width of 500 μm was placed on the organic semiconductor layer, and gold was vacuum-deposited to form a source / drain electrode pair, thereby producing a bottom gate-top contact type p-type organic thin film transistor.

Using the semiconductor parameter analyzer (4200SCS, manufactured by Keithley), the electrical properties of the fabricated organic thin-film transistor are scanned with a drain voltage (Vd = -50V) and a gate voltage (Vg) from +10 to -70V in increments of 1V. Was evaluated. The carrier mobility of holes was 1.2 cm ² / V · s. Furthermore, the electrical properties of the organic thin film transistor after annealing at 130 ° C. for 15 minutes were measured. As a result, the hole carrier mobility was 1.1 cm ² / V · s, and no deterioration in performance due to the heat treatment was observed. .

Example 8
Instead of bis [6- (triisopropylsiloxy) n-hexyl] dithienobenzodithiophene in Example 7, bis [2- (triisopropylsiloxy) ethyl] dithienobenzodithiophene synthesized in Example 2 was used. Except for the above, the same operations as in Example 7 were repeated for evaluation. It was confirmed that the organic semiconductor solution maintained the solution state after 10 hours at 25 ° C. (the concentration of bis [2- (triisopropylsiloxy) ethyl] dithienobenzodithiophene was 1.5% by weight).

The carrier mobility of holes in the organic thin film transistor produced in the same manner as in Example 7 was 1.0 cm ² / V · s. Furthermore, the electrical properties of the organic thin film transistor after annealing at 130 ° C. for 15 minutes were measured. As a result, the hole carrier mobility was 0.98 cm ² / V · s, and no deterioration in performance due to the heat treatment was observed. .

Example 9
Instead of bis [6- (triisopropylsiloxy) n-hexyl] dithienobenzodithiophene in Example 7, bis [6- (triethylsiloxy) n-hexyl] dithienobenzodithiophene synthesized in Example 3 was used. Except that, the same operations as in Example 7 were repeated for evaluation. The organic semiconductor solution was confirmed to remain in solution after 10 hours at 25 ° C. (the concentration of bis [6- (triethylsiloxy) n-hexyl] dithienobenzodithiophene was 1.5% by weight) .

The carrier mobility of holes in the organic thin film transistor produced in the same manner as in Example 7 was 1.1 cm ² / V · s. Further, the electrical properties of the organic thin film transistor after annealing at 130 ° C. for 15 minutes were measured. As a result, the hole carrier mobility was 1.0 cm ² / V · s, and no deterioration in performance due to the heat treatment was observed. .

Example 10
Bis [6- (tertiarybutyldimethylsiloxy) n-hexyl] dithienobenzodi synthesized in Example 4 instead of bis [6- (triisopropylsiloxy) n-hexyl] dithienobenzodithiophene in Example 7 Evaluation was repeated by repeating the same operation as in Example 7 except that thiophene was used. It was confirmed that the organic semiconductor solution maintained the solution state even after 10 hours at 25 ° C. (the concentration of bis [6- (tertiarybutyldimethylsiloxy) n-hexyl] dithienobenzodithiophene was 1.5). weight%).

The carrier mobility of holes in the organic thin film transistor produced in the same manner as in Example 7 was 1.3 cm ² / V · s. Further, the electrical properties of the organic thin film transistor after annealing at 130 ° C. for 15 minutes were measured. As a result, the hole carrier mobility was 1.3 cm ² / V · s, and no deterioration in performance due to the heat treatment was observed. .

Example 11
In place of bis [6- (triisopropylsiloxy) n-hexyl] dithienobenzodithiophene in Example 7, bis [6- (triisopropylsiloxy) n-hexyl] dithienobenzodifuran synthesized in Example 5 was used. Evaluations were repeated by repeating the same operations as in Example 7 except that they were used. It was confirmed that the organic semiconductor solution maintained the solution state even after 10 hours at 25 ° C. (The concentration of bis [6- (triisopropylsiloxy) n-hexyl] dithienobenzodifuran was 1.5% by weight. ).

The carrier mobility of holes in the organic thin film transistor produced in the same manner as in Example 7 was 1.2 cm ² / V · s. Further, the electrical properties of the organic thin film transistor after annealing at 130 ° C. for 15 minutes were measured. As a result, the hole carrier mobility was 1.2 cm ² / V · s, and no deterioration in performance due to the heat treatment was observed. .

Example 12
In place of bis [6- (triisopropylsiloxy) n-hexyl] dithienobenzodithiophene in Example 7, bis [6- (triisopropylsiloxy) n-hexyl] difurobenzodifuran synthesized in Example 6 was used. Evaluations were repeated by repeating the same operations as in Example 7 except that they were used. It was confirmed that the organic semiconductor solution maintained the solution state even after 10 hours at 25 ° C. (The concentration of bis [6- (triisopropylsiloxy) n-hexyl] difurobenzodifuran was 1.5% by weight. ).

The carrier mobility of holes in the organic thin film transistor produced in the same manner as in Example 7 was 1.0 cm ² / V · s. Furthermore, the electrical properties of the organic thin film transistor after annealing at 130 ° C. for 15 minutes were measured. As a result, the hole carrier mobility was 0.92 cm ² / V · s, and no deterioration in performance due to the heat treatment was observed. .

Comparative Example 1 (Di-n-octylbenzothienobenzothiophene)
Di-n-octylbenzothienobenzothiophene 12.2 mg and toluene 801 mg were added, heated and dissolved at 50 ° C., and allowed to stand at room temperature (25 ° C.). It was confirmed that the solution state was maintained after 10 hours at 25 ° C. (the concentration of di-n-octylbenzothienobenzothiophene was 1.5% by weight).

Then, an organic semiconductor layer of di-n-octylbenzothienobenzothiophene having a film thickness of 51 nm was produced in the same manner as in Example 7, and a bottom gate-top contact p-type organic thin film transistor was further produced. The hole carrier mobility was 0.17 cm ² / V · s. Furthermore, the electrical properties of the organic thin film transistor after annealing at 130 ° C. for 15 minutes were measured. However, the transistor operation cannot be obtained, and the material is inferior in heat resistance.

Comparative Example 2 (6,13-bis [(triisopropylsilyl) ethynyl] pentacene)
After adding 11.8 mg of 6,13-bis [(triisopropylsilyl) ethynyl] pentacene and 775 mg of toluene, the mixture was heated and dissolved at 50 ° C. and allowed to stand at room temperature (25 ° C.). It was confirmed that the solution state was maintained after 10 hours at 25 ° C. (the concentration of 6,13-bis [(triisopropylsilyl) ethynyl] pentacene was 1.5% by weight).

Then, an organic semiconductor layer of 6,13-bis [(triisopropylsilyl) ethynyl] pentacene having a film thickness of 60 nm is fabricated in the same manner as in Example 7, and a bottom gate-top contact type p-type organic thin film transistor is fabricated. Produced. The carrier mobility of holes was 0.052 cm ² / V · s, which was inferior to the carrier mobility.

  Since the novel heteroacene derivative of the present invention provides high carrier mobility and is excellent in solubility in a solvent and heat resistance of a transistor element, application as a semiconductor device material typified by an organic thin film transistor can be expected.

: It is a figure which shows the structure by the cross-sectional shape of an organic thin-film transistor.

(A): Bottom gate-top contact type organic thin film transistor (B): Bottom gate-bottom contact type organic thin film transistor (C): Top gate-top contact type organic thin film transistor (D): Top gate-bottom contact type organic thin film transistor 1: Organic semiconductor layer 2: Substrate 3: Gate electrode 4: Gate insulating layer 5: Source electrode 6: Drain electrode

Claims (7)

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

(In the formula, R ¹ and R ² each independently represent a hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms. R ³ and R ⁴ are each independently hydrogen. An atom and a hydrocarbon group having 1 to 20 carbon atoms, each of R ⁵ and R ⁶ independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a carbon atom having 1 to 20 carbon atoms containing silicon; T ^{1 to} T ⁴ each independently represents a sulfur atom or an oxygen atom, n represents an integer of 2 to 20, and m represents an integer of 1 to 10. The heteroacene derivative according to claim 1, wherein the heteroacene derivative represented by the general formula (1) is represented by the following general formula (2).

(In the formula, R ¹ and R ² each independently represent a hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms. T ^{1 to} T ⁴ are each independently a sulfur atom. Or represents an oxygen atom, n represents an integer of 2 to 20, and m represents an integer of 1 to 10.) The heteroacene derivative according to claim 1 or 2, wherein the heteroacene derivative represented by the general formula (1) or the general formula (2) is represented by the following general formula (3).

(Wherein, ^{R 1} and ^{R 2} are each independently a hydrocarbon group having 1 to 20 carbon atoms, or an integer of .n 2 to 20 showing an alkoxy group having a carbon number of 1-20, m is 1-10 Indicates an integer.) An organic semiconductor layer forming solution obtained by dissolving or dispersing the heteroacene derivative according to any one of claims 1 to 3 in a liquid medium. The organic-semiconductor layer characterized by including 1 or more types of the heteroacene derivative in any one of Claims 1-3. 6. An organic thin film transistor comprising an organic semiconductor layer according to claim 5 and a gate electrode, which are provided on a base material with a source electrode and a drain electrode, with an insulating layer interposed therebetween. A semiconductor device comprising the organic thin film transistor according to claim 6.

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