New compounds and their uses

Abstract

The present invention provides a compound that has excellent chemical stability, high solubility in a solvent, and exhibits excellent carrier mobility. A compound represented by the following formula (1): [Formula 1] TIFF2023519108000024.tif50128[X in formula (1) 1 , X 2 , X 3 , R 1 ~R 10 are as defined in the specification.]

Description

[Technical field]

[0001] The present invention relates to a novel compound and its use. More specifically, the present invention relates to a novel compound and its production method, an organic semiconductor solution composition containing the compound, an organic semiconductor film formed from the organic semiconductor solution composition, and an organic thin film transistor having the organic semiconductor film. [Background technology]

[0002] In recent years, organic semiconductor materials have attracted attention because they can be processed at lower temperatures than inorganic semiconductor materials, thereby reducing manufacturing costs, and they have the advantage of being able to be used in solution processes to produce larger screens, such as flexible substrate devices. Research and development of various organic semiconductor materials is therefore being actively conducted.

[0003] Acene compounds such as pentacene and tetracene have long been known as organic semiconductor materials with high carrier mobility, but they have problems such as low chemical stability and low solubility in solvents. Patent Document 1 presents organic compounds whose chemical stability is improved by substituting part of the acene skeleton with sulfur, selenium, or the like, and Patent Document 2 presents organic compounds whose solubility is improved by introducing a substituent into the acene skeleton.

[0004] Patent Document 3 discloses that an organic compound that contains a thiophene structure or a furan structure in its basic skeleton, has a substituent such as an alkyl group introduced therein, and further has a nonlinear molecular structure with low symmetry, exhibits high carrier mobility and has improved chemical stability and solubility.

[0005] However, conventional organic semiconductor materials are prone to deterioration in their semiconductor properties (such as carrier mobility) due to intermolecular misalignment that occurs due to molecular fluctuations in the crystal structure caused by temperature changes, crystal grain boundaries present in the organic semiconductor film, and deformed areas caused by external forces applied to the organic semiconductor film, and so there is still room for improvement. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] International Publication No. WO2006 / 077888 [Patent Document 2] International Publication No. WO2005 / 080304 [Patent Document 3] International Publication No. WO2013 / 125599 Summary of the Invention [Problem to be solved by the invention]

[0007] That is, an object of the present invention is to provide a compound which has excellent chemical stability, high solubility in a solvent, and exhibits excellent carrier mobility. Another object of the present invention is to provide a method for producing the above compound. Another object of the present invention is to provide an organic semiconductor solution composition containing the above compound. Another object of the present invention is to provide an organic semiconductor film formed from the above organic semiconductor solution composition. Another object of the present invention is to provide an organic thin-film transistor having the above organic semiconductor film. [Means for solving the problem]

[0008] In order to solve the above problems, the present inventors conducted research based on the idea that degenerating the highest occupied molecular orbital (HOMO) and the orbital one level below the HOMO (NHOMO, next highest occupied molecular orbital) to allow two π electron orbitals with different orbital shapes to contribute to orbital overlap would improve carrier mobility and reduce the influence of intermolecular misalignment. As a result, they found that a specific dinaphthochalcogenophene-type fused ring compound exhibits high carrier mobility. The present invention was completed based on this finding.

[0009] That is, the present invention provides a compound (sometimes referred to as an organic semiconductor material) represented by the following formula (1). [ka] [In formula (1), X 1 is an oxygen atom, a sulfur atom, a selenium atom, or a tellurium atom, and X 2 and X 3 are the same or different and are carbon atoms, oxygen atoms, sulfur atoms, selenium atoms, or tellurium atoms. 2 and X 3 Except when R is also a carbon atom. 1 and R 2 are the same or different and are a hydrogen atom or an organic group; R 3 ~R 10 R is the same or different and is a hydrogen atom, a halogen atom, or an organic group. 3 and R 4 , R 5 and R 6 , R 7 and R 8 , R 8 and R 9 , and R 9 and R 10 may be bonded to each other to form a ring together with the adjacent carbon atoms. A double line including a dashed line represents a single bond or a double bond.

[0010] The present invention also provides a compound represented by the following formula (1'): [ka] [In formula (1'), X 1 , X 2 and X 3 are the same as those in formula (1), and R 1' and R 2' are the same or different organic groups. A double line including a dashed line represents a single bond or a double bond.]

[0011] In the above formula (1'), X 1 is sulfur atom, X 2 and X 3One of the atoms is a carbon atom and the other is a sulfur atom, R 1' and R 2' are preferably the same or different organic groups.

[0012] The present invention also provides a process for producing the compound represented by formula (1-5), which comprises the step of obtaining the compound represented by formula (1-5) from the compound represented by formula (1-4). [ka] [In formulas (1-4) and (1-5), X 1 , X 2 , X 3 and double lines including dashed lines each have the same meaning as in formula (1).

[0013] The present invention also provides an organic semiconductor solution composition containing the above compound and at least one solvent.

[0014] The present invention also provides an organic semiconductor film formed from the above organic semiconductor solution composition.

[0015] The present invention also provides an organic thin film transistor having the above organic semiconductor film. Effect of the Invention

[0016] Since the compound of the present invention has excellent chemical stability and high solubility in a solvent, a large-area, highly uniform organic semiconductor film can be formed by coating or printing the organic semiconductor solution composition. The organic semiconductor film of the present invention exhibits excellent carrier mobility, and therefore can realize a high-performance organic thin-film transistor. [Brief description of the drawings]

[0017] [Figure 1] FIG. 1 is a schematic cross-sectional view of a top-contact / bottom-gate type organic thin-film transistor. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] The compound of the present invention, a method for producing the compound, an organic semiconductor solution composition containing the compound (organic semiconductor material), an organic semiconductor film formed from the organic semiconductor solution composition, and an organic thin film transistor having the organic semiconductor film will be described below.

[0019] [Compound] The compound of the present invention is represented by formula (1). [ka] In formula (1), X 1 is an oxygen atom, a sulfur atom, a selenium atom, or a tellurium atom, and X 2 and X 3 are the same or different and are carbon atoms, oxygen atoms, sulfur atoms, selenium atoms, or tellurium atoms. 2 and X 3 Except when R is also a carbon atom. 1 and R 2 are the same or different and are a hydrogen atom or an organic group; R 3 ~R 10 R is the same or different and is a hydrogen atom, a halogen atom, or an organic group. 3 and R 4 , R 5 and R 6 , R 7 and R 8 , R 8 and R 9 , and R 9 and R 10 may be bonded to each other to form a ring together with the adjacent carbon atoms.

[0020] X in formula (1) 1 is preferably a sulfur atom or a selenium atom in terms of exhibiting higher carrier mobility, and is more preferably a sulfur atom in terms of further improving chemical stability.

[0021] X in formula (1) 2 and X 3Preferably, one of X is a sulfur atom or a selenium atom and the other is a carbon atom, in that these atoms exhibit higher carrier mobility; 2 is a sulfur atom and X 3 More preferably, is a carbon atom.

[0022] R in the above formula (1) 1 and R 2 The organic group in the above is preferably an alkyl group having 1 to 40 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, an alkynyl group having 2 to 22 carbon atoms, an aryl group having 6 to 20 carbon atoms, a cycloalkyl group having 3 to 40 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a monovalent heterocyclic group, and more preferably an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a monovalent heterocyclic group. These may have a substituent.

[0023] Above R 1 and R 2 The alkyl group in the above is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, more preferably 3 to 20 carbon atoms, and even more preferably 5 to 15 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a 2-methylpropyl group, a butyl group, a pentyl group, a 2,2-dimethylpropyl group, a hexyl group, a 1-methylpentyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a Examples of such groups include ethyl group, tetradecyl group, pentadecyl group, 2,6-dimethyloctyl group, icosyl group, 2-decyltetradecyl group, 2-hexyldodecyl group, 2-ethyloctyl group, 2-decyltetradecyl group, 2-butyldecyl group, 1-octylnonyl group, 2-ethyloctyl group, 2-octyldecyl group, 2-octyldodecyl group, 7-hexylpentadecyl group, 2-octyltetradecyl group, and 2-ethylhexyl group.

[0024] Above R 1 and R 2The alkenyl group according to the above is preferably a straight-chain or branched-chain alkenyl group having 2 to 18 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 2 to 8 carbon atoms. Examples of the alkenyl group include a vinyl group, a 1-propenyl group, a 2-propenyl group, a 2-methyl-1-propenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 3-methyl-2-butenyl group, a 1-pentenyl group, a 2-pentenyl group, a 3-pentenyl group, a 4-pentenyl group, a 4-methyl-3-pentenyl group, a 1-hexenyl group, a 3-hexenyl group, a 5-hexenyl group, a 1-heptenyl group, a 1-octenyl group, a 1-nonenyl group, and a 1-decenyl group.

[0025] Above R 1 and R 2 The alkynyl group according to the above is preferably a straight-chain or branched-chain alkynyl group having 2 to 18 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 2 to 8 carbon atoms. Examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 1-butynyl group, a 2-butynyl group, a 3-butynyl group, a 1-pentynyl group, a 2-pentynyl group, a 3-pentynyl group, a 4-pentynyl group, a 1-hexynyl group, a 2-hexynyl group, a 3-hexynyl group, a 4-hexynyl group, a 5-hexynyl group, a 1-heptynyl group, a 1-octynyl group, a 1-nonynyl group, a 1-decynyl group, a trimethylsilylethynyl group, a triethylsilylethynyl group, a tri-i-propylsilylethynyl group, and a 2-p-propylphenylethynyl group.

[0026] Above R 1 and R 2 The aryl group according to the above is preferably an aryl group having 6 to 18 carbon atoms, more preferably 6 to 14 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an acenaphthylenyl group, a biphenylyl group, a 2,4,6-trimethylphenyl group, a p-(t-butyl)phenyl group, a 4-methyl-2,6-dipropylphenyl group, a 4-fluorophenyl group, a 4-trifluoromethylphenyl group, a p-pentylphenyl group, a 3,4-dipentylphenyl group, a p-heptoxyphenyl group, and a 3,4-diheptoxyphenyl group.

[0027] Above R 1 and R 2 The cycloalkyl group in the above is preferably a cyclic alkyl group having 3 to 20 carbon atoms, more preferably 4 to 20 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, and an adamantyl group.

[0028] Above R 1 and R 2 The alkoxy group according to the above is a linear or branched alkoxy group preferably having 1 to 18 carbon atoms, more preferably having 1 to 12 carbon atoms, and even more preferably having 1 to 8 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, an n-pentyloxy group, an isopentyloxy group, a neopentyloxy group, a tert-pentyloxy group, an n-hexyloxy group, an isohexyloxy group, a heptyloxy group, an octyloxy group, a nonyloxy group, and a decyloxy group.

[0029] Above R 1 and R 2 Examples of the monovalent heterocyclic group include 5- to 22-membered (preferably 5- or 6-membered) aromatic heterocyclic groups and aliphatic heterocyclic groups having carbon atoms and 1 to 4 heteroatoms selected from oxygen atoms, sulfur atoms, and nitrogen atoms in the ring.

[0030] Examples of the aromatic heterocyclic group include monocyclic aromatic heterocyclic groups (such as a furanyl group, a 2-hexylfuranyl group, a thienyl group, a pyridyl group, a pyrimidinyl group, a pyrrolyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, a benzthiazolyl group, a benzoxazolyl group, a benzimidazolyl group, and a selenophenyl group), and condensed aromatic heterocyclic groups (such as a quinolyl group and an isoquinolyl group).

[0031] Examples of the aliphatic heterocyclic group include monocyclic aliphatic heterocyclic groups (such as a piperidyl group, a morpholinyl group, a piperazinyl group, and a tetrahydrofuryl group), and condensed aliphatic heterocyclic groups (such as a chromenyl group, a tetrahydroquinolinyl group, and a tetrahydroisoquinolinyl group).

[0032] Above R 1 and R 2 Examples of the substituents that may be possessed by the alkyl group include halogen atoms (fluorine atoms, etc.), cyano groups, hydroxyl groups, nitro groups, acyl groups (hexanoyl groups, benzoyl groups, etc.), alkoxy groups (butoxy groups, etc.), aryloxy groups (phenoxy groups, etc.), silyloxy groups, heterocyclic oxy groups, acyloxy groups, carbamoyloxy groups, amino groups, anilino groups, acylamino groups, aminocarbonylamino groups (ureido groups), alkoxy and aryloxycarbonylamino groups, alkyl and arylsulfonylamino groups, mercapto groups, alkyl and arylthio groups (methylthio groups, octyl Examples of the substituent include an alkyl group (such as an alkylthio group), a heterocyclic thio group, a sulfamoyl group, a sulfo group, an alkyl and arylsulfinyl group, an alkyl and arylsulfonyl group, an alkyl and aryloxycarbonyl group, a carbamoyl group, an aryl and heterocyclic azo group, an imido group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, a phosphono group, a silyl group (such as a ditrimethylsiloxymethylbutoxy group), a hydrazino group, a ureido group, a boronic acid group (-B(OH)2), a phosphato group (-OPO(OH)2), a sulfato group (-OSOH), and other known substituents.

[0033] Examples of the halogen atom in the above formula (1) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom is preferred in that it exhibits higher carrier mobility.

[0034] R in the above formula (1) 3 ~R 10 The organic group represented by the above R 1 and R 2Among them, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms is preferable. The substituents which these may have are also as defined above in R 1 and R 2 The same applies to the above.

[0035] Above R 3 ~R 10 In R, which is an adjacent combination 3 and R 4 , R 5 and R 6 , R 7 and R 8 , R 8 and R 9 , and R 9 and R 10 may be bonded to form a ring. The ring may be an aromatic ring or a non-aromatic ring.

[0036] In formula (1), X 2 , X 3 and a 5-membered ring containing a double line including a dashed line is a non-aromatic ring if both double lines including the dashed line are single bonds, and is an aromatic ring if one of them is a double bond, but is preferably an aromatic ring.

[0037] The compound of the present invention has high solubility in solvents due to the flexible dinaphthochalcogenophene-type structure and the introduction of substituents. Therefore, the following organic semiconductor solution composition can be prepared at a desired concentration, and the compound can be suitably used for producing an organic semiconductor film by a simple solution process such as a coating method or a printing method. Since the compound of the present invention has excellent chemical stability, it can also be used for producing an organic semiconductor film by a vapor phase process such as a vacuum deposition method, an MBE (Molecular Beam Epitaxy) method, a sputtering method, a laser deposition method, or a vapor transport growth method.

[0038] The compound of the present invention also exhibits stable and excellent carrier mobility, and although the reason for this is not yet completely clear, it is speculated that this is because the energy levels of the HOMO and NHOMO are very close to each other due to the structure having five-membered heterocyclic rings at both ends, and thus the NHOMO as well as the HOMO contribute to the overlap of the π-electron orbitals.

[0039] Among the compounds of the present invention, the compound represented by formula (1') is preferred since it can adequately achieve both solubility in a solvent and orbital overlap. [ka] In formula (1'), X 1 , X 2 and X 3 are the same as those in formula (1), and R 1' and R 2' are the same or different organic groups, and the double line including the dashed line represents a single bond or a double bond.

[0040] R in the above formula (1') 1' and R 2' The organic group in the above is preferably an alkyl group having 1 to 40 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, an alkynyl group having 2 to 22 carbon atoms, an aryl group having 6 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a monovalent heterocyclic group.

[0041] R in the above formula (1') 1' and R 2' The alkyl group, alkenyl group, alkynyl group, aryl group, monovalent heterocyclic group, cycloalkyl group, alkoxy group, and the substituents that these groups may have are R 1 and R 2 The same applies to the above.

[0042] In the above formula (1'), X 1 , X 2 , X 3 The contents relating to the double line including the dashed line are the same as those in the above formula (1).

[0043] Among the compounds represented by the above formula (1'), X 1 is sulfur atom, X 2 and X 3 One of the groups is a carbon atom and the other is a sulfur atom, and R 1' and R 2' More preferred are compounds in which are the same or different organic groups.

[0044] Among the compounds represented by the above formula (1'), X 1 is sulfur atom, X 2 is sulfur atom, X 3 is a carbon atom, and R 1' and R 2' Further preferred are compounds of formula (1"), wherein are the same or different organic groups. [ka] R in the above formula (1") 1' and R 2' The organic group represented by the formula (1') is an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a monovalent heterocyclic alkyl group, an aryl group, or a monovalent heterocyclic group, and is the same as that in the formula (1') above.

[0045] [Method of manufacturing the compound] The compound represented by the above formula (1) of the present invention can be produced, for example, by a process in which a compound represented by the following formula (1-1) and a compound represented by the following formula (1-2) are cross-coupled to obtain a compound represented by the following formula (1-3), and then the formyl group of the compound represented by formula (1-3) is epoxidized to obtain a compound represented by the following formula (1-4), a process in which the compound represented by formula (1-4) is subjected to condensed ring formation to obtain a compound represented by formula (1-5), and a further process in which a substituent is introduced into the compound represented by formula (1-5).

[0046] (Cross-coupling, epoxidation of formyl groups) The compound represented by formula (1-4) can be produced, for example, by cross-coupling a compound represented by formula (1-1) with a compound represented by formula (1-2) to obtain a compound represented by formula (1-3), and then converting the formyl group of the compound represented by formula (1-3) into an epoxy group. [ka] In formulas (1-1) to (1-4), X 1 , X 2 , X 3 and the double line including the dashed line each represent the same as in formula (1), where A represents an organic sulfonyloxy group, and B represents a boronic acid group (-B(OH)2).

[0047] Examples of the organic sulfonyloxy group include a methanesulfonyloxy group, a p-toluenesulfonyloxy group, a trifluoromethylsulfonyloxy group, and a camphorsulfonyloxy group. Of these, the trifluoromethylsulfonyloxy group is preferable.

[0048] The above B may be a boronic acid ester group (such as a pinacol boronic acid ester group, a diisopropyl boronic acid ester group, or a propylene glycol boronic acid ester group).

[0049] In the step of obtaining the compound represented by formula (1-3), the compound represented by formula (1-1) and the compound represented by formula (1-2) are cross-coupled under general Suzuki-Miyaura coupling conditions.

[0050] The compound represented by formula (1-1) can be synthesized, for example, from a 5-halogenated benzofuran, a 5-halogenated benzothiophene or the like as a starting material by using known means such as methoxy substitution of the halogen atom, formylation at the 4-position, deprotection of the methoxy group, and organic sulfonyloxylation.

[0051] The compound represented by formula (1-2) can be synthesized by a known method, for example, by reacting furan, thiophene, or the like with diborane to introduce a boronic acid group (-B(OH)2), and then esterifying the boronic acid group as necessary. Also, it can be obtained as a commercial product.

[0052] The compound represented by formula (1-4) can be obtained by epoxidizing the formyl group of the compound represented by formula (1-3) in the presence of a sulfur ylide obtained by reacting a metal hydroxide with a sulfonium compound or a sulfoxonium compound in situ.

[0053] Examples of the sulfonium compound include trimethylbromosulfur (Me3SBr), trimethylchlorosulfur (Me3SCl), and trimethyliodosulfur (Me3SI), and examples of the sulfoxonium compound include trimethyloxobromosulfur (Me3OSBr), trimethyloxochlorosulfur (Me3OSCl), and trimethyloxoiodosulfur (Me3OSI), etc. These may be used alone or in combination of two or more.

[0054] The reaction temperature (solution temperature) for the reaction of converting a formyl group to an epoxy group is preferably 0 to 100° C., more preferably 50 to 80° C. The reaction time is usually 1 to 50 hours, preferably 1 to 25 hours.

[0055] Examples of the base catalyst include KOH, NaOH, etc. These may be used alone or in combination of two or more kinds. The amount of the base catalyst used is preferably 1 to 10 mol per 1 mol of the compound represented by formula (1-3).

[0056] The amount of Me3SI used is preferably 2 to 4 mol per mol of the compound represented by formula (1-3).

[0057] (Formation of condensed ring) In the process for obtaining the compound represented by formula (1-5), a fused ring having a six-membered aromatic ring containing the carbon that constitutes the epoxy group in the compound represented by formula (1-4) is formed in the presence of a Lewis acid catalyst. [ka] In formulas (1-4) and (1-5), X 1 , X 2 , X 3 , and double lines including dashed lines each indicate the same meaning as in formula (1).

[0058] The reaction temperature (solution temperature) is preferably 0 to 120° C., more preferably 20 to 100° C. The reaction time is usually 1 to 100 hours, preferably 1 to 50 hours.

[0059] Examples of Lewis acid catalysts include indium(III) chloride, aluminum(III) chloride, thallium(III) chloride, etc. These may be used alone or in combination of two or more. The amount of the Lewis catalyst used is preferably 0.1 to 2 mol per mol of the compound represented by formula (1-1).

[0060] (Introduction of Substituents) The compound represented by the above formula (1) is R 1 ~R 10 The above halogen atoms or organic groups can be introduced into the compound represented by formula (1-5) using a known aromatic substitution reaction or a known cross-coupling reaction.

[0061] The compound represented by the above formula (1') of the present invention can be prepared by similarly adding the above R 1' and R 2' The above-mentioned organic group can be introduced into the compound represented by the formula:

[0062] The compound represented by the above formula (1″) of the present invention can also be obtained by, for example, adding the above R 1' and R 2' The above-mentioned organic group can be introduced into the compound represented by the formula:

[0063] The reactions for obtaining the compounds represented by the above formulae (1), (1'), (1"), and (1-1) to (1-5) are preferably carried out in the presence of a solvent. Examples of the solvent include water, alcohol solvents (methanol, ethanol, isopropanol, butyl cellosolve, etc.), nitrogen-containing solvents (acetonitrile, N-methyl-2-pyrrolidone, N,N-dimethylformamide, etc.), halogenated hydrocarbon solvents (dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, etc.), ether solvents (diethyl ether, t-butyl methyl ether, tetrahydrofuran, 1,4-dioxane, dimethoxyethane, dichloromethyl methyl ether, etc.), glycol solvents (ethylene glycol, propylene glycol monomethyl ether-2-acetate, etc.), aromatic hydrocarbon solvents (benzene, toluene, xylene, anisole, etc.), ketone solvents (methyl isobutyl ketone, acetone, etc.), and ester solvents (ethyl acetate, ethyl lactate, γ-butyrolactone, etc.). These may be used alone or in combination of two or more.

[0064] In addition, the compounds represented by formulas (1-1) to (1-5) obtained in each reaction may be used in the next reaction after being purified by a known purification method such as column chromatography or recrystallization, or may be used in the next reaction as a crude product.

[0065] [Organic semiconductor solution composition] The organic semiconductor solution composition of the present invention contains the above-mentioned compound (organic semiconductor material) and a solvent. The organic semiconductor material may be used alone or in combination of two or more kinds.

[0066] (solvent) Examples of the solvent include aliphatic hydrocarbon solvents (pentane, hexane, heptane, etc.), halogenated hydrocarbon solvents (dichloromethane, chloroform, 1,2-dichloroethane, etc.), ether solvents (diethyl ether, t-butyl methyl ether, tetrahydrofuran, dioxane, etc.), alcohol solvents (methanol, ethanol, isopropanol, butyl cellosolve, etc.), ester solvents (ethyl acetate, ethyl lactate, γ-butyrolactone, etc.), ketone solvents (methyl isobutyl ketone, acetone, etc.), nitrogen-containing solvents (a Examples of organic solvents include acetonitrile, N-methyl-2-pyrrolidone, N,N-dimethylformamide, etc., sulfur-containing solvents (dimethyl sulfoxide, etc.), halogenated aromatic hydrocarbon solvents (chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1-chloronaphthalene, 2-chloronaphthalene, 4-chlorobiphenyl, etc.), aromatic hydrocarbon solvents (benzene, toluene, xylene, etc.), and alicyclic hydrocarbon solvents (cyclohexane, cyclopentanone, cyclohexanone, etc.).

[0067] The boiling point of the solvent is preferably from 20 to 120°C, more preferably from 20 to 100°C.

[0068] The water content of the solvent used in the composition of the present invention is preferably 0.25% by weight or less. If the water content in the composition of the present invention is high, the carrier mobility tends to decrease due to inhibition of crystallization or carrier trapping of moisture. The water content is preferably 0.15% by weight or less, more preferably 0.05% by weight or less. The water content can be measured by the Karl Fischer method.

[0069] The organic semiconductor solution composition of the present invention may contain a polymer compound as a binder, if necessary, in addition to the organic semiconductor material and the solvent. When a polymer compound is contained, the film-forming properties of the organic semiconductor solution composition are improved, such as enabling high-speed film formation by the edge casting method or continuous edge casting method described below, even when an organic semiconductor material with low solubility is used.

[0070] (polymer compound) The polymer compound that may be contained in the organic semiconductor of the present invention preferably does not affect the electrical properties of the organic semiconductor material, and examples thereof include epoxy resins, melamine resins, phenolic resins, polyurethane resins, acrylic resins (polymethyl methacrylate, poly(2,2,2-trifluoroethyl methacrylate), etc.), polystyrene resins (polystyrene, poly-α-methylstyrene, polyvinylphenol, polypentafluorostyrene, etc.), cellulose resins, butyral resins (polyvinyl butyral, etc.), polyvinyl resins (polyvinyl alcohol, polyvinyl acetate, poly(2-vinylpyridine), polyvinyl chloride, polyvinylidene chloride, polytetrafluoroethylene, etc.), benzocyclobutene resins, silicone resins (cage-shaped oligosilsesquioxanes, etc.), polyolefin resins (polyethylene, polypropylene, polycycloolefins, etc.), polyamide resins, polyester resins, polycarbonate resins, etc.

[0071] When the organic semiconductor solution composition of the present invention contains the polymer compound, the content thereof is, for example, preferably 0.01 to 20% by weight, more preferably 0.1 to 10% by weight, based on 100% by weight of the organic semiconductor solution composition. When the content of the polymer compound is within this range, the film-forming property of the organic semiconductor solution composition tends to be improved.

[0072] The content of the solvent in the total amount of the organic semiconductor solution composition of the present invention (the total amount when two or more kinds are contained) is, for example, preferably 99.999% by weight or less, more preferably 99.990% by weight or less, and even more preferably 99.900% by weight or less. The lower limit is, for example, preferably 90% by weight or more, more preferably 93% by weight or more, and even more preferably 95% by weight or more.

[0073] The content of the solute (particularly, the organic semiconductor material) in the organic semiconductor solution composition of the present invention (the total amount when two or more kinds are contained) is, for example, preferably 0.02 parts by weight or more, more preferably 0.03 parts by weight or more, and even more preferably 0.04 parts by weight or more, relative to 100 parts by weight of the solvent. The upper limit is preferably 1 part by weight or less, more preferably 0.5 parts by weight or less, and even more preferably 0.1 parts by weight or less.

[0074] The organic semiconductor solution composition of the present invention can be prepared, for example, by mixing the above-mentioned solvent, the above-mentioned solute, and a polymer compound that is blended as necessary, and heating the mixture at 30 to 200° C. for 0.1 to 5 hours in an air, nitrogen, or argon atmosphere.

[0075] The organic semiconductor solution composition of the present invention can be prepared in various concentrations for the organic semiconductor material having excellent solubility in a solvent, and the crystallization state of the organic semiconductor film formed therefrom can be changed freely over a wide range from crystalline to amorphous. When the crystallization state of the organic semiconductor film changes, the carrier mobility also changes. Therefore, by using the organic semiconductor solution composition of the present invention, the crystallization state of the organic semiconductor film can be adjusted freely, and the carrier mobility of the organic semiconductor film can be stably reproduced.

[0076] [Organic semiconductor film] The organic semiconductor film of the present invention can be formed by applying or printing the above-mentioned organic semiconductor solution composition of the present invention onto a substrate, and drying it.

[0077] Examples of methods for applying or printing the organic semiconductor solution composition onto a substrate include application methods (drop casting, spin coating, dip coating, blade, edge casting, continuous edge casting, etc.), printing methods (screen printing, inkjet printing, mask printing, offset printing, flexography printing, microcontact printing, lithographic printing, intaglio printing, letterpress printing, etc.), etc. Among these, the edge casting method, continuous edge casting method, etc. are preferred in that a large-area organic single crystal semiconductor film can be easily obtained at low cost.

[0078] Examples of substrate materials onto which the organic semiconductor solution composition can be applied or printed include glass, metals (gold, copper, silver, etc.), inorganic substances (crystalline silicon substrates, amorphous silicon substrates, etc.), and resins (triacetyl cellulose resins, norbornene resins, polyester resins, polyvinyl resins, polyolefin resins, etc.). Among these, a resin substrate is preferred since it allows a large-area organic semiconductor film to be obtained at low cost.

[0079] The drying can be carried out, for example, by heating under normal pressure or reduced pressure at 20 to 200° C. for 0.5 to 24 hours. Heating may be performed on the organic semiconductor solution composition or on the substrate.

[0080] The organic semiconductor film of the present invention may also be heat-treated after formation in order to control the crystal structure or volatilize the solvent.

[0081] The thickness of the organic semiconductor film is preferably from 1 to 1000 nm, more preferably from 1 to 100 nm, and further preferably from 1 to 50 nm.

[0082] The organic semiconductor film of the present invention may be used after being peeled off from the base material after being formed, or may be used in the state in which it is formed on the substrate or the like.

[0083] The organic semiconductor film of the present invention may be uniformly coated by the coating method described above and then patterned into a predetermined shape by a photolithography method or the like, or may be printed into a pattern of a predetermined shape by the printing method described above.

[0084] [Organic thin-film transistor] The organic thin-film transistor of the present invention has the organic semiconductor film of the present invention as a semiconductor layer. The organic thin film transistor of the present invention has a gate electrode, an organic semiconductor film (semiconductor layer), a gate insulating film provided between the gate electrode and the organic semiconductor film (semiconductor layer), and a source electrode and a drain electrode provided in contact with the organic semiconductor film (semiconductor layer) and connected via the organic semiconductor film (semiconductor layer) on a substrate. In this organic thin film transistor, the organic semiconductor film and the gate insulating film are provided adjacent to each other. The organic thin-film transistor of the present invention is not particularly limited in structure as long as it comprises the above-mentioned layers. For example, it may be of any structure such as a bottom contact type (bottom contact / bottom gate type, bottom contact / top gate type) or a top contact type (top contact / bottom gate type, top contact / top gate type), and among these, the top contact / bottom gate type is preferred.

[0085] A schematic cross-sectional view of a top-contact / bottom-gate type, which is a preferred example, is shown in FIG. The top-contact / bottom-gate organic thin-film transistor 10 includes a substrate 100 , a conductive film (gate electrode) 101 , a gate insulating film 102 , an organic semiconductor film 103 , a source electrode 104 A, a drain electrode 104 B, and a protective layer 105 .

[0086] Applications of the organic thin film transistor of the present invention include, for example, electronic paper, display devices, sensors, electronic tags, sensors, and the like. EXAMPLES

[0087] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0088] Compounds according to the examples and comparative examples were synthesized and the carrier mobility was evaluated.

[0089] <Method for evaluating carrier mobility> Organic thin film transistors were produced by the method described below, and the carrier mobility was evaluated under normal atmospheric pressure of 1 atm (temperature: room temperature) using a semiconductor parameter analyzer (Agilent, 4156C) connected to a semi-automatic prober (Vector Semicon, AX-2000). Carrier mobility μ(cm 2 / Vs) is measured by applying a voltage of -150 V between the source and drain electrodes of an organic thin-film transistor and varying the gate voltage in the range of -5 V to -150 V. d and the drain current I d The calculation was performed using the following formula:

[0090] I d =(W / 2L)μC i (V g -V th ) 2 In the formula, L is the gate length, W is the gate width, μ is the carrier mobility, and C i is the capacitance per unit area of ​​the gate insulating film, V g is the gate voltage, V th and represent the threshold voltage, respectively.

[0091] <Identification of Compounds> The compounds in the examples and each intermediate compound were identified using tetramethylsilane as an internal standard. 1 The analysis was performed by H-NMR (400 MHz). Deuterated chloroform (CDCl3) or 1,1,2,2-tetrachloroethane-d2 (CDCl2CDCl2) was used as the solvent.

[0092] [Example 1] The following compound C10-TBNT was synthesized and its carrier mobility was evaluated.

[0093] <Synthesis method> Compound C10-TBNT was synthesized via the following steps.

[0094] (Synthesis of intermediate compound 1b) [ka] In the above scheme, MeONa represents sodium methoxide, and DMF represents N,N-dimethylformamide.

[0095] Under an argon atmosphere, at room temperature (28°C), sodium methoxide (19.0g, 352mmol) was added to a solution of 5-bromobenzothiophene 1a (50.0g, 235mmol) in a mixed solvent of N,N-dimethylformamide and methanol (300mL, DMF / MeOH=250mL / 50mL), and the mixture was heated to 110°C while stirring. At 110°C, copper bromide (3.37g, 23.5mmol) was further added, and the suspension was stirred at 110°C for 5 hours. After cooling the suspension to room temperature, 100mL of ammonium chloride aqueous solution was poured in to stop the reaction. This was extracted with ethyl acetate, dried over sodium sulfate, and concentrated under reduced pressure to obtain a red oil. This was purified by column chromatography (developing solvent = petroleum ether: ethyl acetate = 10:1 (volume ratio)) to obtain compound 1b (34.0g, 207mmol, yield 38%) as a white solid.

[0096] 1 H-NMR (CDCl3, room temperature) δ:7.74(d, 1H, J=8.4Hz), 7.44(d, 1H, J=5.6Hz), 7.28(d, 1H, J=2.4Hz), 7.26(d, 1H, J=5.6Hz), 7.02(dd, 1H, J1=2.4Hz, J2=8.4Hz), 3.88(s,3H)

[0097] (Synthesis of intermediate compound 1c) [ka] In the above scheme, DCM refers to dichloromethane.

[0098] Under an argon atmosphere, at -40°C, tin tetrachloride (1 mol / L dichloromethane solution, 124 mL, 124 mmol) was added to a solution of compound 1b (10.0 g, 60.9 mmol) in dichloromethane (600 mL), and dichloromethyl methyl ether (8.3 mL, 91.3 mmol) was further added, and the mixture was stirred at -70 to -50°C for 3 hours. Then, the mixture was left while stirring until it reached room temperature. After cooling the mixture to 0°C, 500 mL of calcium bicarbonate aqueous solution was poured and stirred for 2 hours until gas generation ceased. This was extracted with dichloromethane and concentrated under reduced pressure to obtain a red solid. This was purified by column chromatography (developing solvent = petroleum ether: ethyl acetate = 50: 1 (volume ratio)) to obtain compound 1c (9.8 g, 51.2 mmol, yield 84%) as a red solid.

[0099] 1 H-NMR (CDCl3, room temperature) δ:10.74(s, 1H), 8.42(d, 1H, J=4.8Hz), 8.03(d, 1H, J=9.2Hz), 7.68(d, 1H, J=5.2Hz), 7.09(d, 1H, J=8.8Hz), 4.00(s,3H)

[0100] (Synthesis of intermediate compound 1d) [ka] In the above scheme, BBr3 represents boron tribromide.

[0101] Under an argon atmosphere, at room temperature (28°C), boron tribromide (12mL, 122mmol) was added to a solution of compound 1c (19.5g, 101mmol) in dichloromethane (1000mL), and the mixture was stirred at room temperature (28°C) for 12 hours. After cooling the mixture to 0°C, 500mL of water was poured in and the mixture was stirred for 2 hours. This was extracted with dichloromethane and ethyl acetate, and concentrated under reduced pressure to obtain a red solid. This was purified by column chromatography (developing solvent = dichloromethane) to obtain compound 1d (16.9g, 94.9mmol, yield 84%) as a red solid.

[0102] 1H-NMR (CDCl3, room temperature) δ:10.55(s, 1H), 7.07(d, 1H, J=9.2Hz), 7.71-7.78(m, 2H), 7.02(d, 1H, J=8.8Hz)

[0103] (Synthesis of intermediate compound 1e) [ka] In the above scheme, Tf2O represents trifluoromethanesulfonic anhydride, Tf represents trifluoromethylsulfonyl, and DMAP represents dimethylpropionamide.

[0104] Trifluoromethanesulfonic anhydride (52 mL, 30.9 mmol) was added to a dichloromethane (600 mL) solution of compound 1d (10.6 g, 59.5 mmol) and dimethylpropionamide (18.2 g, 149 mmol) under an argon atmosphere at -10°C, and the mixture was stirred at room temperature (28°C) for 30 minutes. The reaction was stopped by pouring 200 mL of water at 0°C into the mixture. The mixture was washed twice with 350 mL of 1 mol / L hydrochloric acid and twice with 300 mL of saturated saline, dried over sodium sulfate, and concentrated under reduced pressure to obtain compound 1e as a fluorescent solid.

[0105] 1 H-NMR (CDCl3, room temperature) δ:10.61(s, 1H), 8.45(d, 1H, J=5.4Hz), 8.19(d, 1H, J=8.4Hz), 7.87(d, 1H, J=5.4Hz), 7.40(d, 1H, J=8.4Hz)

[0106] (Synthesis of intermediate compound 1g) [ka]

[0107] Compound 1e (49.3 mmol), compound 1f (3.68 g, 21.4 mmol), tripotassium phosphate (17.1 g, 64.3 mmol), and a mixed solvent of 600 mL of 1,4-dioxane and 60 mL of water were added to a 1L three-neck flask, and argon replacement was performed three times. Tetrakis(triphenylphosphine)palladium (11.4 g, 9.86 mmol) was added, and the mixture was stirred at 110 ° C for 12 hours. The mixture was cooled to room temperature (28 ° C), and then 200 mL of an aqueous ammonium chloride solution was poured into it, extracted with ethyl acetate, and concentrated under reduced pressure to obtain a yellow solid. This was washed with a mixed solvent (petroleum ether: ethyl acetate = 10: 1 (volume ratio)), filtered, and compound 1g (15.3 g) was obtained as a yellow solid.

[0108] 1 H-NMR (CDCl3, room temperature) δ:10.43(s, 1H), 8.50(d, 2H, J=5.4Hz), 8.16(d, 2H, J=8.2Hz), 7.78(d, 2H, J=5.4Hz), 7.61(d, 2H, J=8.2Hz), 7.17(s,2H)

[0109] (Synthesis of intermediate compound 1h) [ka] In the above scheme, MeCN represents acetonitrile.

[0110] Compound 1g (31.1 mmol), potassium hydroxide (powder, 9.6 g, 171 mmol), and trimethyliodosulfur (19.1 g, 93.4 mmol) were added to a 2L three-neck flask, and argon replacement was performed for 30 minutes, after which 1600 mL of acrylonitrile was added. The suspension was stirred at 65-70 ° C for 12 hours. After cooling to room temperature (28 ° C), unreacted potassium hydroxide was removed from the suspension by filtration, 1000 mL of water was poured, and the suspension was extracted four times with 500 mL of dimethylmethane, dried with sodium sulfate, and then concentrated under reduced pressure to obtain a brown solid. This was purified by column chromatography (developing solvent = petroleum ether: ethyl acetate = 10: 1 (volume ratio)) to obtain compound 1h (8.1 g, 18.7 mmol, yield 60%) as a brown solid.

[0111] 1 H-NMR (CDCl3, room temperature) δ:7.87-7.90(m, 4H), 7.55(d, 1H, J=5.6Hz), 7.49(d, 1H, J=8.4Hz), 7.15(s, 2H), 4.45-4.46(m, 1H), 3.15-3.17(m, 1H), 2.83-2.86(m, 1H)

[0112] (Synthesis of compound 1i) [ka]

[0113] Indium trichloride (870 mg, 3.93 mmol) was added to a 2 L three-neck flask and heated under reduced pressure for 30 minutes using a hot gun. Compound 1h (3.40 g, 7.86 mmol) was added to the flask, and argon was replaced three times, after which 1300 mL of dichloromethane was added. The suspension was stirred for 48 hours under reflux. After cooling to room temperature (28 ° C), 500 mL of water was poured in, and the mixture was extracted four times with 500 mL of dichloromethane and concentrated under reduced pressure to obtain a brown solid. This was washed three times with 300 mL of methanol, two times with 300 mL of water, and three times with 300 mL of methanol, and dried under reduced pressure to obtain a gray solid 1i (3.05 g, 7.70 mmol, yield 98%).

[0114] 1 H-NMR (CDCl2CDCl2, 120℃) δ:8.39-8.50(m, 4H), 8.08-8.22(m, 6H), 7.68-7.73(m, 2H)

[0115] (Synthesis of intermediate compound 1j) [ka]

[0116] 1) Compound 1i (4.56 g, 11.5 mmol) was placed in a 1 L three-neck flask and dried under an argon atmosphere for 30 minutes, after which 600 mL of tetrahydrofuran (water absorption rate less than 50 ppm) was added, and the mixture was cooled to -60°C, followed by addition of normal butyllithium (1.6 mol / L hexane solution, 25.1 mL, 40 mmol), and the mixture was stirred for 30 minutes at -60°C. After the mixture changed from brown to green, the temperature was raised to -10°C and the mixture was stirred for 30 minutes, and further cooled to -60°C again and stirred for 2 hours. 2) 1 After confirming that the mixture was lithiated with H-NMH, 1,2-dibromo-1,1,2,2-tetrachloroethane (13.0 g, 40 mmol) was added to the mixture and stirred at -60°C for 12 hours. After warming to room temperature (28°C), 200 mL of water was poured in, extracted with ethyl acetate, and concentrated under reduced pressure to obtain a brown solid. This was washed three times with 300 mL of methanol, two times with 300 mL of water, two times with 300 mL of methanol, and one time with 100 mL of dichloromethane, and dried under reduced pressure to obtain compound 1j (6.04 g, 10.9 mmol, yield 95%) as a gray solid.

[0117] 1 H-NMR (CDCl2CDCl2, 120℃) δ:7.9-8.5(m, 10H)

[0118] (Synthesis of compound C10-TBNT) [ka] In the above scheme, PdCl2(dppf)·CH2Cl2 represents [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium·dichloromethane acetate.

[0119] 1) Under an argon atmosphere, at 0°C, zinc chloride (1.0 mol / L tetrahydrofuran solution, 1.44 mL, 1.44 mmol) was added to a solution of n-decylmagnesium bromide (0.73 mol / L tetrahydrofuran solution, 1.85 mL, 1.35 mmol) in toluene (23 mL), and lithium chloride (0.5 mol / L tetrahydrofuran solution, 2.88 mL, 1.44 mml) was added thereto, and the mixture was stirred at 0°C for 20 minutes to obtain a colorless and transparent zinc reagent solution. 2) At room temperature (28°C), compound 1j (250 mg, 0.451 mmol) and [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium·dichloromethane complex (29.5 mg, 0.0361 mmol) were added to the zinc reagent solution, and the mixture was heated to 100°C with stirring and further stirred for 2 hours. After gradually cooling to room temperature (28°C), methanol was poured to precipitate the solid, which was filtered and dried under reduced pressure to obtain a crude product. 140 mL of ortho-dichlorobenzene was added to the crude product and heated to 120°C to obtain a solution, which was purified by passing through silica gel, and further purified by recrystallization (recrystallization solvent = ortho-dichlorobenzene, heated to dissolve at 80°C and gradually cooled to 28°C) to obtain compound C10-TBNT (218 g, 0.321 mmol, yield 71%) as a cream-colored solid.

[0120] 1 H-NMR (CDCl2CDCl2, 100℃) δ:8.35(d, 2H, J=8.7Hz, ArH), 8.32(d, 2H, J=8.7, Hz, ArH), 8.06(d, 2H, J=8.7, Hz, ArH), 7.95(d, 2H, J=8.7, Hz, ArH), 7 .73(s,2H, ArH), 3.04(t, 4H, J=7.3, Hz, Ar-CH2), 1.82-1.89(m, 4H, Ar-CH2-CH2), 1.29-1.57(m, 28H, Ar-CH2-CH2-C7H 14 ), 0.88(t, 6H, J=7.1Hz, CH3)

[0121] <Fabrication of organic thin-film transistors> The above compound C10-TBNT was mixed in orthodichlorobenzene so as to have a concentration of 0.1% by weight, and heated at 120° C. for 3 hours to prepare an organic semiconductor solution composition. The surface of a thermal oxide film of an n-type silicon substrate (20 mm×20 mm, 0.4 mm thick) having a 500 nm thick thermal oxide film (silicon oxide film) on its surface was cleaned with ultraviolet light and ozone, and then treated with β-phenethyltrimethoxysilane. A glass member (10 mm × 2 mm, thickness 5 mm) was placed in close contact with the center of the β-phenethyltrimethoxysilane-treated surface of the above substrate, and the substrate was heated to 50°C. One drop (approximately 0.05 mL) of the above organic semiconductor solution composition was then dripped onto the side of the glass member using a pipette to form a liquid film that surrounded the glass member and had a concave meniscus. The liquid film was heated at normal pressure for 2 hours at a substrate temperature of 110°C, and then cooled under reduced pressure (10 -3 The substrate was dried at 200 Pa and 80° C. for 12 hours to precipitate crystals of the compound C10-TBNT. The glass member was then removed to form a ring-shaped organic semiconductor film (film thickness 50 nm) of uniform thickness on the substrate. The organic semiconductor film was masked, and tetracyanoquinodimethane was evaporated (thickness: 2 nm), and then gold was evaporated (thickness: 40 nm) to obtain an organic thin-film transistor (gate width (W) of 110 μm, gate length (L) of 100 μm, ratio (W / L) of 1.1 for source and drain electrodes) for measuring field-effect transistor characteristics.

[0122] <Evaluation of carrier mobility> The carrier mobility of the compound C10-TBNT in the obtained organic thin-film transistor was evaluated by the above-mentioned method, and it was found to be 2.2 cm 2 / Vs.

[0123] [Example 2] The following compound C9-TBNT was synthesized from compound 1j obtained in the same manner as in Example 1, and the carrier mobility was evaluated in the same manner as in Example 1.

[0124] (Synthesis of compound C9-TBNT) [ka]

[0125] 1) Under an argon atmosphere at 0°C, zinc chloride (1.0 mol / L tetrahydrofuran solution, 1.73 mL, 1.73 mmol) was added to a solution of normal nonylmagnesium bromide (0.7 mol / L tetrahydrofuran solution, 2.29 mL, 1.62 mmol) in toluene (27 mL), and lithium chloride (0.5 mol / L tetrahydrofuran solution, 3.46 mL, 1.73 mmol) was added thereto, followed by stirring at 0°C for 20 minutes to obtain a colorless and transparent zinc reagent solution. 2) At room temperature (28°C), compound 1j (300mg, 0.541mmol) and [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium·dichloromethane complex (35.4mg, 0.0433mmol) were added to the zinc reagent solution, and the mixture was heated to 100°C with stirring and further stirred for 3 hours. After gradually cooling to room temperature (28°C), methanol was poured to precipitate the solid, which was filtered and dried under reduced pressure to obtain a crude product. 360mL of ortho-dichlorobenzene was added to the crude product and heated to 120°C to obtain a solution, which was purified by passing through silica gel, and further purified by recrystallization (recrystallization solvent = ortho-dichlorobenzene, heated to dissolve at 80°C and gradually cooled to 28°C) to obtain compound C9-TBNT (256g, 0.378mmol, yield 70%) as a cream-colored solid.

[0126] 1 H-NMR (CDCl2CDCl2, 100℃) δ:8.35(d, 2H, J=8.7Hz, ArH), 8.32(d, 2H, J=8.7, Hz, ArH), 8.06(d, 2H, J=8.7, Hz, ArH), 7.95(d, 2H, J=8.7, Hz, ArH), 7 .73(s,2H, ArH), 3.04(t, 4H, J=7.6, Hz, Ar-CH2), 1.82-1.89(m, 4H, Ar-CH2-CH2), 1.30-1.56(m, 24H, Ar-CH2-CH2-C6H 12 ), 0.89(t, 6H, J=6.4Hz, CH3)

[0127] For the compound C9-TBNT, the carrier mobility is 6.6 cm 2 / Vs.

[0128] [Comparative Example 1] The following comparative compound 1 was synthesized according to the synthesis method described in Patent Document 3 (International Publication WO2013 / 125599), and the carrier mobility was evaluated in the same manner as in Example 1. 2 / Vs. [ka]

[0129] From the above, it was found that the organic semiconductor materials of Examples 1 and 2 exhibited superior carrier mobility to the organic semiconductor material of Comparative Example 1. [Industrial Applicability]

[0130] By applying the organic semiconductor solution composition containing the compound according to the present invention to an inkjet printing method or an edge casting method, a high-performance organic semiconductor film and an organic thin film transistor can be obtained at low cost. [Explanation of symbols]

[0131] 10 Organic Thin-Film Transistors 100 Substrates 101 Conductive film (gate electrode) 102 Gate insulating film 103 Organic semiconductor film 104A Conductive film (source electrode) 104B Conductive film (drain electrode) 105 Protective film

Claims

1. A compound represented by formula (1). [Formula 1] [In formula (1), X １ is an oxygen atom, a sulfur atom, a selenium atom, or a tellurium atom; X ２ and X ３ are the same or different and are carbon atoms, oxygen atoms, sulfur atoms, selenium atoms, or tellurium atoms. ２ and X ３ Except when R is also a carbon atom. １ and R ２ are the same or different and each is a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, an alkynyl group having 2 to 22 carbon atoms, an aryl group having 6 to 20 carbon atoms, a cycloalkyl group having 3 to 40 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a monovalent heterocyclic group; R ３ ~R １０ are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 40 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, an alkynyl group having 2 to 22 carbon atoms, an aryl group having 6 to 20 carbon atoms, a cycloalkyl group having 3 to 40 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a monovalent heterocyclic group. A double line including a dashed line represents a single bond or a double bond. X 2 and X 3 as well as the 5-membered ring including the double line including the dashed line are aromatic rings.]

2. The compound according to claim 1, represented by formula (1'): [Case 2] [In formula (1'), １ , X ２ and X ３ are the same as those in formula (1), and R １’ and R ２’are the same or different and each represents an alkyl group having 1 to 40 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, an alkynyl group having 2 to 22 carbon atoms, an aryl group having 6 to 20 carbon atoms, a cycloalkyl group having 3 to 40 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a monovalent heterocyclic group. A double line including a dashed line represents a single bond or a double bond. X 2 and X 3 as well as the 5-membered ring including the double line including the dashed line are aromatic rings.]

3. In formula (1'), X １ is a sulfur atom, X ２ and X ３ The compound according to claim 2, wherein one of the above is a carbon atom and the other is a sulfur atom.

4. A method for producing the compound according to any one of claims 1 to 3, comprising a step of obtaining a compound represented by formula (1-5) from a compound represented by formula (1-4). [C3] [In formulas (1-4) and (1-5), X １ , X ２ , X ３ and the double line including the dashed line each have the same meaning as in formula (1). The five-membered ring including X 2 and X 3 and the double line including the dashed line is an aromatic ring.

5. 4. An organic semiconductor solution composition comprising the compound according to claim 1 and at least one solvent.

6. An organic semiconductor film formed from the organic semiconductor solution composition according to claim 5 .

7. An organic thin film transistor comprising the organic semiconductor film according to claim 6 .

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