Composition

Abstract

An object of the present invention is to provide a composition capable of producing an organic thin film transistor having excellent carrier mobility even under low temperature conditions. The composition of the present invention contains a compound represented by the following formula (1) and an alcohol represented by the following formula (S1).

Description

Technical Field

[0001] The present invention relates to a composition. Background Art

[0002] Due to their ability to be lightweight, low-cost, and flexible, research is underway into the use of organic thin film transistors (organic TFTs) having an organic semiconductor film (organic semiconductor layer) in devices such as FETs (field effect transistors) used in liquid crystal displays and organic EL (Electric Luminescence) displays, RFIDs (radiofrequency identifiers: RF tags), and logic circuits including memories.

[0003] As a compound for forming such an organic semiconductor film, Patent Document 1 discloses an organic semiconductor compound having an azaperylene skeleton.

[0004] Previous technical literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Publication No. 2018-6745 Summary of the invention

[0007] Technical issues to be solved by the invention

[0008] The present inventors have found that there is room for improvement in the production conditions for producing an organic thin film transistor using the compound having an azaperylene skeleton described in Patent Document 1. For example, it is required to be able to produce an organic thin film transistor with excellent carrier mobility at a relatively low temperature (eg, room temperature).

[0009] Therefore, an object of the present invention is to provide a composition capable of producing an organic thin-film transistor having excellent carrier mobility even under low-temperature conditions.

[0010] Means for solving technical problems

[0011] As a result of intensive studies on the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by the following structure, and have completed the present invention.

[0012] [1]

[0013] A composition comprising a compound represented by the formula (1) described below and an alcohol represented by the formula (S1) described below.

[0014] [2]

[0015] The composition according to [1], wherein in the formula (1) described below, B 11 ~B 18 At least one of them is -N=.

[0016] 〔3〕

[0017] The composition according to any one of [1] to [3], further comprising an organic solvent other than the alcohol represented by the formula (S1) described below.

[0018] [4]

[0019] The composition according to [3], wherein the organic solvent consists of only one or more atoms selected from the group consisting of carbon atoms, hydrogen atoms and halogen atoms.

[0020] 〔5〕

[0021] The composition according to [3] or [4], wherein in the composition, the content of the alcohol represented by the formula (S1) described below relative to the total content of the alcohol represented by the formula (S1) described below and the organic solvent described above is 10% by volume or more.

[0022] [6]

[0023] The composition according to any one of [1] to [5], wherein in the composition, the alcohol represented by the formula (S1) described below is an alcohol represented by the formula (S2) described below.

[0024] 〔7〕

[0025] The composition according to any one of [1] to [6], wherein in the composition, the alcohol represented by the formula (S1) described below is an alcohol represented by the formula (S3) described below.

[0026] [8]

[0027] The composition according to any one of [1] to [7], which is a composition for forming an organic semiconductor layer.

[0028] 〔9〕

[0029] The composition according to any one of [1] to [8], which is a composition for forming an organic semiconductor layer for an organic thin film transistor.

[0030] Effects of the Invention

[0031] As will be described below, according to the present invention, it is possible to provide a composition capable of producing an organic thin film transistor having excellent carrier mobility even under low temperature conditions. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1This is a schematic cross-sectional view showing the structure of a bottom gate-bottom contact type organic thin film transistor as an example of an organic thin film transistor.

[0033] Figure 2 It is a schematic cross-sectional view showing the structure of a bottom gate-top contact type organic thin film transistor as another example of the organic thin film transistor.

[0034] Figure 3 This is a schematic diagram showing an example of a method for forming an organic semiconductor film of an organic thin film transistor.

[0035] Figure 4 This is a schematic diagram showing another example of a method for forming an organic semiconductor film of an organic thin film transistor.

[0036] Figure 5 This is a schematic diagram showing another example of a method for forming an organic semiconductor film of an organic thin film transistor.

[0037] Figure 6 This is a schematic diagram showing an example of a substrate and members used in a method of forming an organic semiconductor film of an organic thin-film transistor. DETAILED DESCRIPTION

[0038] Hereinafter, the present invention will be described in detail.

[0039] In the present specification, a numerical range expressed using "to" indicates a range including the numerical values ​​described before and after "to" as the lower limit and the upper limit.

[0040] In this specification, unless otherwise specified, room temperature refers to 20°C.

[0041] In this specification, unless otherwise specified, the volume refers to the volume at room temperature.

[0042] In this specification, the expression of a compound includes not only the compound itself but also its salt and ion, and also includes a form in which a part of the structure is changed within the range that the intended effect is not impaired.

[0043] Furthermore, compounds not explicitly indicating substitution or unsubstitution may have a substituent within a range that does not impair the intended effect. This also applies to substituents, linking groups, and the like (hereinafter referred to as substituents, etc.).

[0044] In the present specification, when the expression "may" or the like is used, the condition of "may" or the like may or may not be satisfied. For example, "may have a substituent" also includes "may not have a substituent".

[0045] In this specification, when there are multiple substituents etc. represented by specific symbols, or when multiple substituents etc. are specified at the same time, unless otherwise specified, the substituents etc. may be the same or different from each other. The same applies to the number of substituents etc. Furthermore, when multiple substituents etc. are close to each other (especially adjacent to each other), unless otherwise specified, they may be connected to each other to form a ring.

[0046] In the present invention, when the number of carbon atoms of a group is limited, unless otherwise specified, the number of carbon atoms of the group refers to the total number of carbon atoms including substituents.

[0047] In the present specification, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0048] In the present invention, when a group can form an acyclic skeleton and a cyclic skeleton, unless otherwise specified, the group includes a group having an acyclic skeleton and a group having a cyclic skeleton.

[0049] For example, unless otherwise specified, an aliphatic hydrocarbon group, an alkyl group, an alkenyl group, and an alkenyl group also include groups having any of linear, branched, and cyclic structures.

[0050] As more specific examples, the alkyl group includes a linear alkyl group, a branched alkyl group, and a cyclic (cyclo) alkyl group.

[0051] When the group can form a cyclic skeleton, the lower limit of the number of atoms of the group forming the cyclic skeleton is 3 or more, and preferably 5 or more, regardless of the lower limit of the number of atoms specifically described for the group. The cycloalkyl group includes a bicycloalkyl group, a tricycloalkyl group, and the like.

[0052] The composition of the present invention contains a compound represented by the formula (1) described below (hereinafter also referred to as a specific compound) and an alcohol represented by the formula (S1) described below.

[0053] The mechanism by which the problems of the present invention are solved by such a structure is not necessarily clear, but the present inventors believe it to be as follows.

[0054] That is, the alcohol represented by formula (S1) is a fluorinated alcohol with high acidity. The hydrogen atom in the hydroxyl group of the alcohol represented by formula (S1) can react with the heteroatom (especially, X 11 ~X 14 can be oxygen atoms and / or B 11 ~B 18The specific compound in the composition is solvated by the alcohol represented by formula (S1). Therefore, even at low temperatures (e.g., room temperature), the solubility of the specific compound in the composition of the present invention is good. Due to this characteristic of the composition of the present invention, it is believed that even if the temperature when the composition is applied to precipitate the specific compound in order to prepare an organic semiconductor film is a low temperature condition, the crystallinity of the precipitated specific compound is good, and the carrier mobility of the obtained organic thin film transistor is improved.

[0055] Furthermore, in the composition of the present invention, the specific compound is well dissolved in the composition, so analysis using liquid chromatography or the like is relatively easy, and the purity of the specific compound in the composition is easy to confirm and / or adjust, and the high performance and stable quality of the organic thin film transistor can be easily achieved.

[0056] [Compound represented by formula (1) (specific compound)]

[0057] First, the compound (specific compound) represented by formula (1) will be described.

[0058] [Chemical formula 1]

[0059]

[0060] In formula (1), A 11 and A 12 Respectively represent -O-, -N(R N )-or-P(R N )-. 11 and A 12 Preferably, -N(R N )-. 11 and A 12 They can be the same or different.

[0061] R N represents a hydrogen atom or a substituent.

[0062] As can be used as R N The substituents of are not particularly limited. For example, groups selected from the following substituent group Z can be mentioned.

[0063] <Substituent group Z>

[0064] The substituent group Z includes a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a silyl group, an alkoxy group, an amino group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkylthio group, an arylthio group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a silyloxy group, a heterocyclic group, an amino group, a The following are examples of the compounds of the present invention: arylazo, arylazo, arylazo, acylazo, acylazo, acylazo, acylazo, acylazo, acylazo, acylazo, acylazo, acylazo, acylazo, acylazo, acylazo, acylazo, acylazo, acylazo, acylazo, acylazo, acylazo, acylazo, acylazo, acylazo, acylazo, acylazo, acylazo, acylazo, acylazo, acylazo, acylazo, acylazo, acylazo, acylazo, acylazo, acylazo, acylazo, acylazo, acylazo, acylazo, acylazo, acylazo,

[0065] The above-mentioned group selected from the substituent group Z may further have a substituent.

[0066] Examples of the halogen atom included in the substituent group Z include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom or a chlorine atom is preferred.

[0067] The alkyl group included in the substituent group Z is not particularly limited, but is preferably an alkyl group having 1 (3) to 30 carbon atoms, more preferably an alkyl group having 1 (3) to 20 carbon atoms, and still more preferably an alkyl group having 4 to 20 carbon atoms. In addition, the numbers in parentheses indicate the number of carbon atoms in the case of a cycloalkyl group.

[0068] Examples of the alkyl group which may have a substituent included in the substituent group Z include a methyl group, an ethyl group, a propyl group, a 2-methylpropyl group, a butyl group, an amyl group, a pentyl group, group), 1-methylpentyl, 2,2-dimethylpropyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, 3,7-dimethyloctyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, 2,6-dimethyloctyl, eicosyl, 2-decyltetradecyl, 2-hexyldodecyl, 2-ethyloctyl, 2-decyltetradecyl, 2-butyldecyl, 1-octylnonyl, 2-ethyloctyl, 2-octyldecyl, 2-octyldodecyl, 7-hexylpentadecyl, 2-octyltetradecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, benzyl, 2-cyclohexylethyl, p-chlorobenzyl, 2-phenylethyl, trifluoromethyl, perfluoroethyl, 2,2,3,3,4,4,4-heptafluorobutyl, C5F 11 C2H4-、C6F 13C2H4-, 3-aminopropyl, 4-aminobutyl, 5-ethoxypentyl, (meth)acryloxypropyl, (meth)acryloxypentyl, 4-hydroxybutyl, 4-sulfobutyl, 10-phosphonodecyl, 2-hydroxyethoxymethyl, 2-imidazolylethoxymethyl, 4-(N,N-dimethylamino)butyl and 5-norbornenemethyl.

[0069] The alkenyl group included in the substituent group Z is not particularly limited, but is preferably an alkenyl group having 2 to 20 carbon atoms, more preferably an alkenyl group having 2 to 12 carbon atoms, and further preferably an alkenyl group having 2 to 8 carbon atoms.

[0070] Examples of the alkenyl group which may have a substituent and is included in the substituent group Z include a vinyl group, an allyl group, a 2-butenyl group, a 1-pentenyl group, and a 4-pentenyl group.

[0071] The alkynyl group included in the substituent group Z is not particularly limited, but is preferably an alkynyl group having 2 to 20 carbon atoms, more preferably an alkynyl group having 2 to 12 carbon atoms, and further preferably an alkynyl group having 2 to 8 carbon atoms.

[0072] Examples of the alkynyl group which may have a substituent and is included in the substituent group Z include an ethynyl group, a propargyl group, a 1-pentynyl group, a trimethylsilylethynyl group, a triethylsilylethynyl group, a triisopropylsilylethynyl group, and a 2-p-propylphenylethynyl group.

[0073] The aryl group included in the substituent group Z is not particularly limited, but is preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 12 carbon atoms.

[0074] Examples of the aryl group which may have a substituent and is included in the substituent group Z include phenyl, naphthyl, 2,4,6-trimethylphenyl, p-(tert-butyl)phenyl, 4-methyl-2,6-dipropylphenyl, 4-fluorophenyl, 4-trifluoromethylphenyl, p-pentylphenyl, 3,4-dipentylphenyl, p-heptyloxyphenyl and 3,4-diheptyloxyphenyl.

[0075] Examples of the heterocyclic group included in the substituent group Z include heterocyclic groups having 3 or more ring atoms and containing at least 1 heteroatom and 1 to 30 carbon atoms as ring atoms. The heterocyclic group includes an aromatic heterocyclic group (heteroaryl group) and an aliphatic heterocyclic group.

[0076] Examples of heteroatoms constituting the ring include nitrogen atoms, oxygen atoms, and sulfur atoms, and the number of heteroatoms is not particularly limited, and is, for example, 1 to 2. The number of carbon atoms constituting the ring is preferably 3 to 20, and more preferably 5 to 12.

[0077] The heterocyclic group is preferably a 5-membered ring, a 6-membered ring or a condensed ring thereof.

[0078] Examples of the heterocyclic group included in the substituent group Z include thienyl, thiazolyl, imidazolyl, pyridyl, pyrimidyl, quinolyl, furanyl, selenophenyl, piperidyl, morpholinyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, 2-hexylfuranyl and pyranyl.

[0079] The optionally substituted silyl group included in the substituent group Z is not particularly limited, but is preferably a silyl group having a group selected from an alkyl group and an aryl group as a substituent and having 3 to 40 (more preferably 3 to 30, and even more preferably 3 to 24) carbon atoms.

[0080] Examples of the silyl group which may have a substituent and is included in the substituent group Z include a trimethylsilyl group, a triphenylsilyl group, and a dimethylphenylsilyl group.

[0081] The alkoxy group included in the substituent group Z is not particularly limited, but an alkoxy group having 1 to 20 carbon atoms is preferred, an alkoxy group having 1 to 12 carbon atoms is more preferred, and an alkoxy group having 1 to 8 carbon atoms is further preferred.

[0082] Examples of the alkoxy group included in the substituent group Z include a methoxy group, an ethoxy group, and a butoxy group.

[0083] The amino group which may have a substituent included in the substituent group Z is not particularly limited, but is preferably an amino group or an amino group having a group selected from an alkyl group and an aryl group as a substituent and having 1 to 20 carbon atoms (more preferably 1 to 10, and even more preferably 1 to 6).

[0084] Examples of the amino group which may have a substituent and which is included in the substituent group Z include an amino group, a methylamino group, a dimethylamino group, a diethylamino group, a dibenzylamino group, and an anilino group.

[0085] The aryloxy group included in the substituent group Z is not particularly limited, but is preferably an aryloxy group having 6 to 20 carbon atoms, more preferably an aryloxy group having 6 to 16 carbon atoms, and further preferably an aryloxy group having 6 to 12 carbon atoms.

[0086] Examples of the aryloxy group included in the substituent group Z include a phenoxy group and a 2-naphthyloxy group.

[0087] The acyl group included in the substituent group Z is not particularly limited, but is preferably an acyl group having 1 to 20 carbon atoms, more preferably an acyl group having 1 to 16 carbon atoms, and still more preferably an acyl group having 1 to 12 carbon atoms.

[0088] Examples of the acyl group which may have a substituent and is included in the substituent group Z include an acetyl group, a hexanoyl group, a benzoyl group, a formyl group, and a pivaloyl group.

[0089] The alkoxycarbonyl group included in the substituent group Z is not particularly limited, but is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, more preferably an alkoxycarbonyl group having 2 to 16 carbon atoms, further preferably an alkoxycarbonyl group having 2 to 12 carbon atoms, and particularly preferably a methoxycarbonyl group or an ethoxycarbonyl group.

[0090] The aryloxycarbonyl group included in the substituent group Z is not particularly limited, but is preferably an aryloxycarbonyl group having 7 to 20 carbon atoms, more preferably an aryloxycarbonyl group having 7 to 16 carbon atoms, further preferably an aryloxycarbonyl group having 7 to 10 carbon atoms, and particularly preferably a phenoxycarbonyl group.

[0091] The acyloxy group included in the substituent group Z is not particularly limited, but is preferably an acyloxy group having 2 to 20 carbon atoms, more preferably an acyloxy group having 2 to 16 carbon atoms, and still more preferably an acyloxy group having 2 to 10 carbon atoms.

[0092] Examples of the acyloxy group which may have a substituent and is included in the substituent group Z include an acetoxy group, a benzoyloxy group, and a (meth)acryloyloxy group.

[0093] The acylamino group included in the substituent group Z is not particularly limited, but is preferably an acylamino group having 2 to 20 carbon atoms, more preferably an acylamino group having 2 to 16 carbon atoms, and still more preferably an acylamino group having 2 to 10 carbon atoms.

[0094] Examples of the acylamino group included in the substituent group Z include acetylamino and benzoylamino.

[0095] The aminocarbonylamino group included in the substituent group Z is not particularly limited, but is preferably an aminocarbonylamino group having 2 to 20 carbon atoms, more preferably an aminocarbonylamino group having 2 to 16 carbon atoms, further preferably an aminocarbonylamino group having 2 to 12 carbon atoms, and particularly preferably a urea group.

[0096] The alkoxycarbonylamino group included in the substituent group Z is not particularly limited, but is preferably an alkoxycarbonylamino group having 2 to 20 carbon atoms, more preferably an alkoxycarbonylamino group having 2 to 16 carbon atoms, further preferably an alkoxycarbonylamino group having 2 to 12 carbon atoms, and particularly preferably a methoxycarbonylamino group.

[0097] The aryloxycarbonylamino group included in the substituent group Z is not particularly limited, but is preferably an aryloxycarbonylamino group having 7 to 20 carbon atoms, more preferably an aryloxycarbonylamino group having 7 to 16 carbon atoms, further preferably an aryloxycarbonylamino group having 7 to 12 carbon atoms, and particularly preferably a phenoxycarbonylamino group.

[0098] The alkylthio group included in the substituent group Z is not particularly limited, but is preferably an alkylthio group having 1 to 20 carbon atoms, more preferably an alkylthio group having 1 to 16 carbon atoms, and further preferably an alkylthio group having 1 to 12 carbon atoms. Examples of the alkylthio group included in the substituent group Z include a methylthio group, an ethylthio group, and an octylthio group.

[0099] The arylthio group included in the substituent group Z is not particularly limited, but is preferably an arylthio group having 6 to 20 carbon atoms, more preferably an arylthio group having 6 to 16 carbon atoms, further preferably an arylthio group having 6 to 12 carbon atoms, and particularly preferably a phenylthio group.

[0100] The above-mentioned group selected from the substituent group Z may further have a substituent. Examples of such a substituent include groups selected from the substituent group Z.

[0101] In the group further having a substituent (also referred to as a combined group), the number of substituents that may be further possessed is not particularly limited, but is, for example, preferably 1 to 6, and more preferably 1 to 3.

[0102] The group formed by the combination is not particularly limited, and examples thereof include groups in which each of the above groups, which are preferably selected from the above substituent group Z, is substituted with another group selected from the substituent group Z. Specifically, examples thereof include alkyl groups, aryl groups, heterocyclic groups (heteroaryl groups), alkoxy groups (including hydroxyalkoxy groups, halogenated alkoxy groups, and heteroarylalkoxy groups), amino groups, acyloxy groups, hydroxyl groups, sulfate groups, silyl groups, (meth)acryloyloxy groups, and phosphono groups, halogenated aryl groups, or (fluoro)alkylaryl groups, or alkynyl groups having silyl groups as substituents. Furthermore, examples thereof include groups obtained by removing one hydrogen atom from the compound represented by formula (1).

[0103] More specifically, there can be mentioned the groups exemplified in the above-mentioned substituent group Z or the groups in the compounds exemplified below or used in the examples.

[0104] As the group formed by the combination, among the above, an alkyl group having a halogen atom as a substituent (haloalkyl group), an alkyl group having a heterocyclic group as a substituent or an alkyl group having an aryl group as a substituent is preferred, an alkyl group having a fluorine atom as a substituent (fluoroalkyl group), an alkyl group having a heterocyclic group as a substituent or an alkyl group having an aryl group as a substituent is more preferred, and an alkyl group having an aryl group as a substituent is further preferred.

[0105] As can be used as R NThe above-mentioned group selected from the substituent group Z is preferably an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a heterocyclic group or a silyl group, more preferably an alkyl group (preferably having 1 to 20 carbon atoms), an aryl group (preferably having 6 to 20 carbon atoms) or a heteroaryl group (containing at least one of the above-mentioned heteroatoms as a ring-constituting atom. Preferably, it is a group of a 5-membered ring, a 6-membered ring or a condensed ring thereof. Preferably, the ring-constituting carbon atoms are 3 to 20.), and further preferably an alkyl group (preferably having 4 to 20 carbon atoms).

[0106] Among them, as can be used as R N The substituent is preferably an unsubstituted alkyl group, a halogenated alkyl group, an alkyl group having an aryl group as a substituent, or an alkyl group having a heterocycle as a substituent.

[0107] In A 11 and A 12 R N In the case of two R N They can be the same or different.

[0108] In formula (1), B 11 ~B 18 Respectively represent -N= or -C(R M )=. Among them, R M represents a hydrogen atom or a substituent.

[0109] As can be used as R M The substituents of are not particularly limited, and examples thereof include groups selected from the above-mentioned substituent group Z. The group selected from the substituent group Z may further have a substituent. Examples of such substituents include groups selected from the substituent group Z. Examples of groups further having a substituent include groups that can be used as R N The group consisting of the above combination includes, specifically, the groups listed above, and further includes a group having a methine group bonded to a carbon atom of the compound represented by formula (1).

[0110] Among them, as can be used as R MThe substituent of the group is preferably an alkyl group, an alkenyl group, an alkynyl group, an alkoxycarbonyl group, an aryl group, an alkoxy group, a heterocyclic group (especially, a heteroaryl group), an amino group, a halogen atom, a cyano group, a carboxyl group, a nitro group or a mercapto group, and more preferably an alkyl group (an unsubstituted alkyl group, an alkyl group having an aryl group as a substituent, or an alkyl group having a heterocyclic ring as a substituent, etc.), an alkenyl group (an unsubstituted alkenyl group, an alkenyl group having a silyl group as a substituent, an alkenyl group having an aryl group as a substituent, or an alkenyl group having a heterocyclic ring as a substituent, etc.), an alkynyl group (an unsubstituted alkynyl group, an alkynyl group having a silyl group as a substituent, an alkynyl group having an aryl group as a substituent, etc.) The present invention further preferably comprises an alkyl group, an alkynyl group having a silyl group as a substituent, an alkynyl group having a heterocycle as a substituent, etc.), an aryl group, an alkoxy group, a heterocyclic group (especially a heteroaryl group), a halogen atom or a cyano group, and more preferably an unsubstituted alkyl group, an alkenyl group (an unsubstituted alkenyl group, an alkenyl group having a silyl group as a substituent, an alkenyl group having an aryl group as a substituent, or an alkenyl group having a heterocycle as a substituent, etc.), an alkynyl group (an unsubstituted alkynyl group, an alkynyl group having a silyl group as a substituent, an alkynyl group having an aryl group as a substituent, or an alkynyl group having a heterocycle as a substituent, etc.), an aryl group, a heterocyclic group (especially a heteroaryl group), a halogen atom or a cyano group.

[0111] Can be used as R M The substituents may form a ring. The substituents may form a ring. Examples of the ring-forming method include a method in which substituents are mutually bonded to form a ring and a method in which a plurality of substituents share one atom to form a ring.

[0112] As a form in which substituents are bonded to each other to form a ring, for example, two vinyl groups are bonded to each other to form a ring. M In one embodiment, the carbon atoms to which the substituents are bonded collectively form a benzene ring. In another embodiment, a plurality of substituents share one atom to form a ring, for example, two substituents are integrated to form a sulfur atom (-S- group).

[0113] Preferred B 11 ~B 18 At least one of them is -N=, more preferably 1 to 6 of them are -N=, further preferably 1 or 2 of them are -N=, and particularly preferably 2 of them are -N=.

[0114] B that can be used for -N= is not particularly limited. 11 ~B 18 All can be -N=. For example, preferably B 12 , B 13 , B 16 and B 17 At least one of them is -N=, and more preferably B 12 and B 16 One or both of them are -N=.

[0115] Can be used as B 11 ~B 18In the -N= group, the nitrogen atom may have a substituent. For example, an N-oxide group (N→O group) and a salt having a counter anion may be mentioned.

[0116] In formula (1), X 11 ~X 14 Each represents an oxygen atom or a sulfur atom, preferably an oxygen atom. 11 ~X 14 More preferably, they are all oxygen atoms.

[0117] Here, A 11 and A 12 With X 11 ~X 14 The combination of is not particularly limited, but preferably A 11 and A 12 -N(R N )-and X 11 ~X 14 A combination of oxygen atoms.

[0118] The specific compound is preferably a compound represented by the following formula (2).

[0119] [Chemical formula 2]

[0120]

[0121] In formula (2), A 11 , A 12 and X 11 ~X 14 The meanings of are respectively the same as those of A in formula (1) 11 , A 12 and X 11 ~X 14 The meanings of are the same, and the preferred embodiments are also the same. 11 , A 12 and X 11 ~X 14 Preferred combinations are also as described above.

[0122] R 21 ~R 26 represents a hydrogen atom or a substituent. 21 ~R 26 The substituents have the same meanings as those used as R M The substituents of have the same meanings and the preferred forms are also the same. 21 ~R 26 They may be bonded to each other or to the carbon atom forming the isoquinolinequinoline skeleton to form a ring.

[0123] Although specific examples of the above-mentioned specific compounds are shown below and in Examples, the present invention is not limited thereto.

[0124] In the following specific example, A is shown 11 and A 12 All are -N(R N )-compounds, but in the following specific examples, it is also possible to cite A 11 and A 12 (NR in the following specific example N1 and NR N2 ) is substituted with -O- or -P(R N Here, as -P(R N )-R N , which can be exemplified by R in the following specific example N1 or R N2 Same group.

[0125] In the following specific examples, TIPS represents a triisopropylsilyl group, and * represents a bonding portion. N1 -C7H 13 (C6H 13 )C8H 17 The R of compound No.3 N1 and R N2 、R of compound No.20 27 、R of compound No.28 N2 、R of compound No.38 N1 and R N2 、R of compound No.55 22 、R of compound No.63 N1 and R N2 、R of compound No.80 22 、R of compound No.88 N2 、R of compound No.98 N2 、R of compound No.108 N1 and R N2 And R of compound No.133 N1 and R N2 -nC6H 13 .

[0126] [Chemical formula 3]

[0127]

[0128]

[0129] [Chemical formula 4]

[0130]

[0131] [Chemical formula 5]

[0132]

[0133]

[0134] [Chemical formula 6]

[0135]

[0136]

[0137] [Chemical formula 7]

[0138]

[0139] [Chemical formula 8]

[0140]

[0141]

[0142] [Chemical formula 9]

[0143]

[0144] [Chemical formula 10]

[0145]

[0146]

[0147] [Chemical formula 11]

[0148]

[0149]

[0150] [Chemical formula 12]

[0151]

[0152]

[0153] [Chemical formula 13]

[0154]

[0155] [Chemical formula 14]

[0156]

[0157]

[0158] In addition, in the compounds Nos. 131 to 140, R N1 and / or R N2 It is a 2-phenylethyl (-CH2-CH2-Ph) compound.

[0159] The compounds represented by Nos. 141 to 232 are compounds having the central structure shown below.

[0160] [Chemical formula 15]

[0161]

[0162] [Chemical formula 16]

[0163]

[0164] [Chemical formula 17]

[0165]

[0166] [Chemical formula 18]

[0167]

[0168] [Chemical formula 19]

[0169]

[0170] [Chemical formula 20]

[0171]

[0172] [Chemical formula 21]

[0173]

[0174] The compounds represented by Nos. 233 to 262 are compounds having the central structure shown below.

[0175] [Chemical formula 22]

[0176]

[0177] [Chemical formula 23]

[0178]

[0179] [Chemical formula 24]

[0180]

[0181] [Chemical formula 25]

[0182]

[0183] From the viewpoint of improvement of carrier mobility and durability, and further material stability, the molecular weight of the specific compound is preferably 350 or more, more preferably 400 or more, and further preferably 500 or more. Furthermore, from the viewpoint of solubility, the molecular weight is preferably 3000 or less, more preferably 2000 or less, and further preferably 1000 or less.

[0184] The synthesis method of the specific compound is not particularly limited, and the specific compound can be synthesized by referring to a common method. For example, the synthesis method of Patent Document 1 can be referred to.

[0185] The specific compound may be used alone or in combination of two or more.

[0186] In the composition of the present invention, relative to the total solid content, the content of the specific compound is preferably 10% by mass or more, more preferably 30% by mass or more, and further preferably 50% by mass or more. Its upper limit can be set to 100% by mass. In the case where the composition contains a binder polymer described later, the upper limit is, for example, preferably 90% by mass or less, and further preferably 80% by mass or less.

[0187] The solid content of the composition refers to the components that form the organic semiconductor film described later, excluding the solvent (for example, the alcohol represented by formula (S1) and the organic solvent described later). Furthermore, as long as it is a component that forms the organic semiconductor film described later, it is considered to be a solid component even if it is in a liquid state.

[0188] [Alcohol represented by formula (S1)]

[0189] The alcohol represented by formula (S1) is described.

[0190] [Chemical formula 26]

[0191]

[0192] In formula (S1), R S1 ~R S6 Each independently represents a hydrogen atom, a fluorine atom or a substituent.

[0193] Can be used as R S1 ~R S6 The above-mentioned substituent is a substituent other than a fluorine atom, and examples thereof include groups other than a fluorine atom in the groups selected from the above-mentioned substituent group Z. The group selected from the substituent group Z may further have a substituent. As such a substituent, a group selected from the substituent group Z can be mentioned.

[0194] Can be used as R S1 ~R S6The substituent is preferably a halogen atom (preferably a chlorine atom), an alkyl group or an alkoxy group other than a fluorine atom. As a substituent that the alkyl group and the alkoxy group may further have, for example, a halogen atom (preferably a fluorine atom or a chlorine atom) can be mentioned.

[0195] R S1 ~R S6 At least 4 of them are fluorine atoms, preferably 4 to 6 of them are fluorine atoms, more preferably 5 to 6 of them are fluorine atoms, and further preferably all of them are fluorine atoms.

[0196] In formula (S1), R S7 represents a hydrogen atom or a substituent.

[0197] Can be used as R S7 The substituents include, for example, groups selected from the substituent group Z (preferably, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, a hydroxyl group, a cyano group or a carboxyl group).

[0198] The group selected from the substituent group Z may further have a substituent. Examples of such a substituent include a group selected from the substituent group Z (preferably an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, a hydroxyl group, a cyano group or a carboxyl group).

[0199] Can be used as R S7 The above substituent is preferably a methyl group, a trifluoromethyl group or a phenyl group.

[0200] The alcohol represented by formula (S1) is preferably a compound represented by formula (S2).

[0201] [Chemical formula 27]

[0202]

[0203] In formula (S2), R S1 ~R S3 Each independently represents a hydrogen atom, a fluorine atom or a substituent.

[0204] R S7 represents a hydrogen atom or a substituent.

[0205] R in formula (S2) S1 ~R S3 and R S7 With R in formula (S1) S1 ~R S3 and R S7 same.

[0206] Among them, R S1 ~R S3 At least one of them is a fluorine atom, preferably 1 to 3 of them are fluorine atoms, more preferably 2 to 3 of them are fluorine atoms, and further preferably all of them are fluorine atoms.

[0207] The alcohol represented by formula (S1) is more preferably a compound represented by formula (S3).

[0208] [Chemical formula 28]

[0209]

[0210] In formula (S3), R S7 represents a hydrogen atom or a substituent.

[0211] R in formula (S3) S7 With R in formula (S1) S7 same.

[0212] The alcohol represented by formula (S1) is preferably liquid at room temperature.

[0213] The standard boiling point of the alcohol represented by the formula (S1) is preferably 25 to 250°C, more preferably 40 to 200°C.

[0214] Although specific examples of the alcohol represented by the formula (S1) are shown below and in the Examples, the present invention is not limited thereto.

[0215] [Chemical formula 29]

[0216]

[0217] [Chemical formula 30]

[0218]

[0219] [Chemical formula 31]

[0220]

[0221] [Chemical formula 32]

[0222]

[0223] The alcohol represented by formula (S1) may be used alone or in combination of two or more.

[0224] In the composition of the present invention, the content of the alcohol represented by formula (S1) is preferably 3 to 99.999% by mass, more preferably 5 to 99.999% by mass, and particularly preferably 10 to 99.999% by mass, based on the total mass of the composition.

[0225] [Organic solvents]

[0226] The composition of the present invention preferably further contains an organic solvent.

[0227] The organic solvent referred to here is a compound other than the alcohol represented by formula (S1).

[0228] When the composition of the present invention contains an organic solvent, it is considered that the organic solvent interacts with the specific compound at a site different from the site where the alcohol represented by formula (S1) and the specific compound are hydrogen-bonded, thereby improving the solubility of the specific compound in the composition.

[0229] The organic solvent is not particularly limited, and examples thereof include hydrocarbon solvents such as hexane, cyclohexane, octane, decane, toluene, xylene, mesitylene, ethylbenzene, pentylbenzene, decalin, 1-methylnaphthalene, 1-ethylnaphthalene, 1,6-dimethylnaphthalene and tetralin.

[0230] Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, propiophenone, isophorone or butyrophenone,

[0231] Halogenated hydrocarbon solvents such as dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, chlorotoluene, 1-chloronaphthalene, 1-fluoronaphthalene, etc.

[0232] Heterocyclic solvents such as pyridine, methylpyridine, quinoline, thiophene, 3-butylthiophene and thieno[2,3-b]thiophene,

[0233] Halogenated heterocyclic solvents such as 2-chlorothiophene, 3-chlorothiophene, 2,5-dichlorothiophene, 3,4-dichlorothiophene, 2-bromothiophene, 3-bromothiophene, 2,3-dibromothiophene, 2,4-dibromothiophene, 2,5-dibromothiophene, 3,4-dibromothiophene and 3,4-dichloro-1,2,5-thiadiazole,

[0234] Ester solvents such as ethyl acetate, butyl acetate, amyl acetate, 2-ethylhexyl acetate, γ-butyrolactone and phenyl acetate,

[0235] Alcohol solvents such as methanol, propanol, butanol, pentanol, hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve and ethylene glycol,

[0236] Ether solvents such as dibutyl ether, tetrahydrofuran, dioxane, dimethoxyethane, anisole, ethoxybenzene, propoxybenzene, isopropoxybenzene, butoxybenzene, 2-methyl anisole, 3-methyl anisole, 4-methyl anisole, 4-ethyl anisole, dimethyl anisole (any of 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5-, 3,6-) and 1,4-benzodioxane,

[0237] N,N-dimethylformamide, N,N-dimethylacetamide, 1-methyl-2-pyrrolidone, 1-methyl-2-imidazolidinone, 1,3-dimethyl-2-imidazolidinone and other amide or imide solvents,

[0238] Sulfoxide solvents such as dimethyl sulfoxide,

[0239] Phosphate ester solvents such as trimethyl phosphate, nitrile solvents such as acetonitrile and benzonitrile, and

[0240] Nitro solvents such as nitromethane and nitrobenzene, etc.

[0241] Among them, the organic solvent is preferably a compound composed of only one or more atoms selected from the group consisting of carbon atoms, hydrogen atoms, and halogen atoms.

[0242] When the organic solvent is a compound composed only of these atoms, it is considered that the improvement in the solubility of the specific compound can be promoted while the hydrogen bond between the alcohol represented by the formula (S1) and the specific compound is well maintained.

[0243] Among them, hydrocarbon solvents or halogenated hydrocarbon solvents are preferred, and toluene, ethylbenzene, xylene, mesitylene, chloroform, dichloromethane, tetrachloroethane, 1,2-dichlorobenzene, chlorobenzene, 1-methylnaphthalene, 1-chloronaphthalene, 1-fluoronaphthalene, 1,2,4-trichlorobenzene, 1-ethylnaphthalene, 1,6-dimethylnaphthalene or tetralin is more preferred.

[0244] In the composition of the present invention, the content of the organic solvent is preferably 3 to 99.9% by mass, more preferably 5 to 99.5% by mass, based on the total mass of the composition.

[0245] The organic solvent may be used alone or in combination of two or more.

[0246] In the composition of the present invention, the total content of the alcohol represented by formula (S1) and the organic solvent is preferably 90 to 99.999 mass %, more preferably 95 to 99.999 mass %, and further preferably 96 to 99.999 mass % relative to the total mass of the composition.

[0247] Furthermore, in the composition of the present invention, the content of the alcohol represented by formula (S1) relative to the total content of the alcohol represented by formula (S1) and the organic solvent is preferably 5% by volume or more, preferably 10% by volume or more. The upper limit is 100% by volume or less, preferably 99% by volume or less, and more preferably 95% by volume or less.

[0248] [Binder polymer]

[0249] The composition of the present invention may contain a binder polymer. From the viewpoint of obtaining an organic semiconductor film with high film quality, the composition preferably contains a binder polymer.

[0250] The type of binder polymer is not particularly limited, and known binder polymers can be used. Examples of the binder polymer include insulating polymers including polystyrene, poly(α-methylstyrene), polycarbonate, polyarylate, polyester, polyamide, polyimide, polyurethane, polysiloxane, polysulfone, polymethyl methacrylate, polymethyl acrylate, cellulose, polyethylene, and polypropylene, and copolymers thereof.

[0251] In addition, for example, rubbers and thermoplastic elastomer polymers including ethylene-propylene rubber, acrylonitrile-butadiene rubber, hydrogenated nitrile rubber, fluororubber, perfluoroelastomer, tetrafluoroethylene propylene copolymer, ethylene-propylene-diene copolymer, styrene-butadiene rubber, polychloroprene, polyneoprene, butyl rubber, methylphenyl silicone resin, methylphenyl vinyl silicone resin, methylvinyl silicone resin, fluorosilicone resin, acrylic rubber, ethylene acrylic rubber, chlorosulfonated polyethylene, chloropolyethylene, epichlorohydrin copolymer, polyisoprene-natural rubber copolymer, polyisoprene rubber, styrene-isoprene block copolymer, polyester urethane copolymer, polyether urethane copolymer, polyether ester thermoplastic elastomer and polybutadiene rubber can also be mentioned.

[0252] Further, for example, photoconductive polymers including polyvinylcarbazole and polysilane, conductive polymers including polythiophene, polypyrrole, polyaniline and polyphenylene vinylene, and semiconductor polymers described in Chemistry of Materials, 2014, 26, 647 can be cited.

[0253] If charge mobility is considered, the binder polymer preferably has a structure without polar groups. Here, polar groups refer to functional groups with heteroatoms other than carbon atoms and hydrogen atoms. Since there is a structure without polar groups, polystyrene or poly (alpha-methylstyrene) is preferred as the binder polymer. And, semiconductor polymers are also preferred.

[0254] The glass transition temperature of the binder polymer is not particularly limited and can be appropriately set according to the application. For example, in the case of imparting strong mechanical strength to the organic semiconductor film, it is preferred that the glass transition temperature is higher. On the other hand, in the case of imparting flexibility to the organic semiconductor film, it is preferred that the glass transition temperature is lower.

[0255] The binder polymer may be used alone or in combination of two or more.

[0256] When the composition contains a binder polymer, from the viewpoint of further improving the carrier mobility and durability of the organic semiconductor film of the organic thin film transistor, the content of the binder polymer in the composition is preferably 90% by mass or less, more preferably 70% by mass or less, relative to the total solid content of the composition. The lower limit is not particularly limited, but is preferably 10% by mass or more, more preferably 20% by mass or more, relative to the total solid content of the composition.

[0257] The weight average molecular weight of the binder polymer is not particularly limited, but is preferably 10 to 10 million, more preferably 30 to 5 million, and even more preferably 50 to 3 million. The weight average molecular weight of the binder polymer can be determined by gel permeation chromatography (GPC).

[0258] In the composition, the specific compound and the binder polymer may be uniformly mixed, or part or all of the specific compound may be phase-separated from the binder polymer. From the viewpoint of ease of coating or coating uniformity, it is preferred that the specific compound and the binder polymer be uniformly mixed at least during coating.

[0259] [Other ingredients]

[0260] The composition may contain components other than those described above. Examples of such components include various additives.

[0261] As additives, additives commonly used in the composition can be used, and more specifically, surfactants, antioxidants, crystallization controllers, and crystal orientation controllers can be cited. As surfactants and antioxidants, paragraphs 0136 and 0137 of Japanese Patent Publication No. 2015-195362 can be cited, and these contents are incorporated into this specification.

[0262] The additives may be used alone or in combination of two or more.

[0263] The content of the additive in the composition is not particularly limited. From the viewpoint of excellent film formability and further improvement of carrier mobility and heat resistance, it is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 1% by mass or less, relative to the total solid content of the composition.

[0264] From the viewpoint of printability, the viscosity of the composition is preferably 10 mPa·s or more.

[0265] [Preparation method]

[0266] The method for preparing the composition is not particularly limited, and a common preparation method can be used. For example, the composition can be prepared by adding a predetermined amount of each component to the alcohol represented by formula (S1) and / or an organic solvent and stirring appropriately.

[0267] If necessary, heating may be performed while or after stirring the components. The heating temperature is not particularly limited, and is, for example, determined within the range of 40 to 150° C. When a solvent is used, the temperature is determined to be within the above range and lower than the boiling point of the solvent.

[0268] Among them, the alcohol represented by formula (S1) in the composition of the present invention and a mixed solution of the alcohol and an organic solvent added as needed can usually be used to produce a composition without heating (below 40° C.) because the specific compound is well dissolved.

[0269] Furthermore, as described above, the specific compound represented by formula (1) is well soluble even at room temperature, so when the composition does not substantially contain a binder polymer, the composition of the present invention can be easily analyzed by liquid chromatography or the like to determine the purity of the specific compound represented by formula (1).

[0270] For example, when the composition is analyzed by liquid chromatography and the detection wavelength is set to 254 nm, the area ratio of the peak derived from the specific compound to the total peak surface area is preferably 95% or more, more preferably 99% or more.

[0271] [Organic Thin Film Transistor]

[0272] The composition of the present invention is preferably used as a composition for forming an organic semiconductor layer, and more preferably used as a composition for forming an organic semiconductor layer for an organic thin film transistor.

[0273] Hereinafter, an organic thin film transistor (hereinafter also referred to as “organic TFT”) which can be produced using the composition of the present invention will be described.

[0274] The organic TFT has an organic semiconductor film described below. As a result, the organic TFT exhibits a high carrier mobility, and can effectively suppress the decrease over time in the atmosphere, thereby performing stable driving. The ambient temperature and humidity in the atmosphere are not particularly limited as long as they are the temperature and humidity in the use environment of the organic TFT. For example, as the temperature, room temperature (20°C) can be cited, and as the humidity, 10 to 90 RH% can be cited.

[0275] The organic TFT is preferably used as an organic field effect transistor (FET), and more preferably used as an insulated gate type FET in which a gate and a channel are insulated.

[0276] The thickness of the organic TFT is not particularly limited, but if the transistor is to be made thinner, the thickness of the entire organic TFT is preferably set to 0.1 to 0.5 μm, for example.

[0277] An organic TFT may include an organic semiconductor film (also referred to as an organic semiconductor layer or a semiconductor active layer) containing a specific compound, and may further include a source electrode, a drain electrode, a gate electrode, and a gate insulating film.

[0278] The organic TFT preferably has a gate electrode, an organic semiconductor film, a gate insulating film provided between the gate electrode and the organic semiconductor film, and a source electrode and a drain electrode provided in contact with the organic semiconductor film and connected via the organic semiconductor film on a substrate. In the organic TFT, the organic semiconductor film and the gate insulating film are provided adjacent to each other.

[0279] As long as the organic TFT has the above-mentioned layers, its structure is not particularly limited. For example, it can have any structure of bottom gate-bottom contact type, top gate-bottom contact type, bottom gate-top contact type and top gate-top contact type. As an organic TFT, a bottom gate type (bottom gate-bottom contact type or bottom gate-top contact type) in which the gate electrode is provided between the substrate and the organic semiconductor film is preferred.

[0280] Hereinafter, an example of an organic TFT will be described with reference to the drawings.

[0281] <Bottom gate-bottom contact type organic TFT>

[0282] Figure 1 1 is a schematic cross-sectional view showing the structure of a bottom gate-bottom contact type organic TFT 10 as an example of an organic TFT.

[0283] like Figure 1 As shown, the organic TFT 10 includes a substrate (base material) 1 , a gate electrode 2 , a gate insulating film 3 , a source electrode 4A and a drain electrode 4B, an organic semiconductor film 5 , and a sealing layer 6 in this order.

[0284] Hereinafter, a substrate (base material), a gate electrode, a gate insulating film, a source electrode, a drain electrode, an organic semiconductor film, and a sealing layer, and methods for producing these will be described.

[0285] (Substrate)

[0286] The substrate plays a role of supporting the gate electrode, the source electrode, the drain electrode and other layers.

[0287] The type of substrate is not particularly limited, and examples thereof include plastic substrates, silicon substrates, glass substrates, and ceramic substrates. Among them, a glass substrate or a plastic substrate is preferred from the viewpoint of applicability to each device and cost.

[0288] The thickness of the substrate is not particularly limited. The upper limit of the thickness of the substrate is preferably 10 mm or less, more preferably 2 mm or less, and further preferably 1.5 mm or less. The lower limit of the thickness of the substrate is preferably 0.01 mm or more, and more preferably 0.05 mm or more.

[0289] (Gate Electrode)

[0290] The gate electrode can be any electrode commonly used as a gate electrode of an organic TFT without particular limitation.

[0291] The material (electrode material) for forming the gate electrode is not particularly limited, and examples thereof include metals including gold, silver, aluminum, copper, chromium, nickel, cobalt, titanium, platinum, magnesium, calcium, barium and sodium, conductive oxides including InO2, SnO2 and / or indium tin oxide (ITO), conductive polymers including polyaniline, polypyrrole, polythiophene, polyacetylene and polydiacetylene, semiconductors including silicon, germanium and gallium arsenide, and carbon materials including fullerene, carbon nanotubes and graphite. Among them, the above metals are preferred, and silver or aluminum is more preferred.

[0292] The thickness of the gate electrode is not particularly limited, but is preferably 20 to 200 nm.

[0293] The gate electrode may be a gate electrode that functions as the substrate, and in this case, the substrate may not be provided.

[0294] The method for forming the gate electrode is not particularly limited, and examples thereof include a method of vacuum evaporating (hereinafter, also referred to as "evaporation") or sputtering the above-mentioned electrode material on a substrate, and a method of coating or printing an electrode-forming composition containing the above-mentioned electrode material. In addition, in the case of patterning the gate electrode, examples of patterning methods include printing methods including inkjet printing, screen printing, offset printing, and relief printing (flexographic printing), photolithography, and mask evaporation.

[0295] (Gate insulation film)

[0296] The gate insulating film is not particularly limited as long as it is a layer having insulating properties, and may be a single layer or a multilayer.

[0297] The material for forming the gate insulating film is not particularly limited, and examples thereof include polymers including polymethyl methacrylate, polystyrene, polyvinylphenol, melamine resin, polyimide, polycarbonate, polyester, polyvinyl alcohol, polyvinyl acetate, polyurethane, polysulfone, polybenzoxazole, polysilsesquioxane, epoxy resin and phenolic resin, inorganic oxides including silicon dioxide, aluminum oxide and titanium oxide, and nitrides including silicon nitride. Among them, the above polymers are preferred from the viewpoint of compatibility with the organic semiconductor film, and the above inorganic oxides are preferred from the viewpoint of uniformity of the film, and silicon dioxide is more preferred.

[0298] These materials may be used alone or in combination of two or more.

[0299] The film thickness of the gate insulating film is not particularly limited, but is preferably 100 to 1000 nm.

[0300] The method for forming the gate insulating film is not particularly limited, and examples thereof include a method of applying a gate insulating film-forming composition containing the above-mentioned material on a substrate having a gate electrode formed thereon, and a method of vapor depositing or sputtering the above-mentioned material.

[0301] (Source electrode and drain electrode)

[0302] In an organic TFT, a source electrode is an electrode that allows current to flow in from the outside through wiring, and a drain electrode is an electrode that sends current out to the outside through wiring.

[0303] The source electrode and the drain electrode may be formed of the same material as the electrode material for forming the gate electrode, but preferably metals, more preferably gold or silver.

[0304] The thickness of the source electrode and the drain electrode is not particularly limited, but each is preferably 1 nm or more, more preferably 10 nm or more. The upper limit of the thickness of the source electrode and the drain electrode is preferably 500 nm or less, more preferably 300 nm or less.

[0305] The interval between the source electrode and the drain electrode (gate length L) can be appropriately determined, but is preferably 200 μm or less, and more preferably 100 μm or less. In addition, the gate width W can be appropriately determined, but is preferably 5000 μm or less, and more preferably 1000 μm or less. The ratio of the gate width W to the gate length L is not particularly limited, but for example, the ratio W / L is preferably 10 or more, and more preferably 20 or more.

[0306] The method for forming the source electrode and the drain electrode is not particularly limited, and examples thereof include a method of vacuum evaporating or sputtering an electrode material on a substrate having a gate electrode and a gate insulating film formed thereon, and a method of coating or printing an electrode forming composition. The patterning method for patterning the source electrode and the drain electrode is the same as the patterning method for the gate electrode described above.

[0307] (Organic semiconductor film)

[0308] Among them, the organic semiconductor film is preferably used as an organic semiconductor film of an organic thin film transistor. Hereinafter, the case where the organic semiconductor film of the present invention is used as an organic semiconductor film of an organic thin film transistor will be described.

[0309] As the organic semiconductor film in the organic TFT, an organic semiconductor film containing a specific compound is used. The specific compound contained in the organic semiconductor film may be one kind or two or more kinds.

[0310] If an organic semiconductor film contains a specific compound, the carrier mobility of the organic semiconductor film can be improved, and even if it is used or stored (placed) in the atmosphere, its high carrier mobility can be maintained. The reason is not clear, but it is believed that the orbital energy of the lowest unoccupied molecular orbital of the specific compound is low.

[0311] The content of the specific compound in the organic semiconductor film is not particularly limited and can be appropriately set. For example, the content of the specific compound relative to the total mass of the organic semiconductor film is preferably 10% by mass or more, more preferably 30% by mass or more, and further preferably 50% by mass or more. The upper limit is not particularly limited, and the content of the specific compound relative to the total mass of the organic semiconductor film can be 100% by mass. In the case where the organic semiconductor film contains a binder polymer or other components, the upper limit of the content of the specific compound relative to the total mass of the organic semiconductor film is preferably 90% by mass or less, more preferably 80% by mass or less.

[0312] The organic semiconductor film may contain the above-mentioned binder polymer in addition to the specific compound. The binder polymer may be used alone or in combination of two or more.

[0313] The state of inclusion of the specific compound and the binder polymer in the organic semiconductor film is not particularly limited, but from the viewpoint of carrier mobility, it is preferred that the specific compound and the binder polymer are phase-separated from each other in the film thickness direction.

[0314] The content of the binder polymer in the organic semiconductor film is not particularly limited and can be appropriately set. In the case where the organic semiconductor film contains a binder polymer, the content of the binder polymer relative to the total mass of the organic semiconductor film is preferably 90% by mass or less, more preferably 70% by mass or less. There is no particular lower limit, and the content of the binder polymer relative to the total mass of the organic semiconductor film can be set to 0% by mass or more, preferably 10% by mass or more, and more preferably 20% by mass or more.

[0315] The organic semiconductor film may contain the above-mentioned additives in addition to the specific compound. The additives may be used alone or in combination of two or more.

[0316] When the organic semiconductor film contains an additive, the content of the additive relative to the total mass of the organic semiconductor film is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less.

[0317] The film thickness of the organic semiconductor film can be appropriately determined depending on the organic TFT to which it is applied, but is preferably 10 to 500 nm, more preferably 20 to 200 nm.

[0318] The organic semiconductor film can be formed by applying the above composition. The details of the method for forming the organic semiconductor film will be described later.

[0319] In addition, the use of the organic semiconductor film containing the specific compound is not limited to the organic semiconductor film for organic TFT, and it can also be used as an organic semiconductor film provided in each of the above-mentioned organic semiconductor devices.

[0320] (Sealing layer)

[0321] The organic TFT having the above-mentioned organic semiconductor film can also be driven stably in the atmosphere, so there is no need to seal the entire organic TFT to block any substance in the atmosphere (oxygen) and moisture. However, for the purpose of stable driving for a longer period of time, the entire organic TFT can be sealed with a metal sealing can, or a sealant can be used to form a sealing layer.

[0322] The sealing layer can use a sealing agent (sealing layer forming composition) generally used in organic TFTs. Examples of the sealing agent include inorganic materials including glass and silicon nitride, and polymer materials and low molecular weight materials including polyparaxylene.

[0323] The sealing layer can be formed by a common method such as coating and drying using the above-mentioned sealing agent.

[0324] The thickness of the sealing layer is not particularly limited, but is preferably 0.2 to 10 μm.

[0325] <Bottom gate-top contact organic TFT>

[0326] Figure 2 1 is a schematic cross-sectional view showing the structure of a bottom gate-top contact type organic TFT 20 as an example of an organic TFT.

[0327] like Figure 2 As shown, the organic TFT 20 includes a substrate 1 , a gate electrode 2 , a gate insulating film 3 , an organic semiconductor film 5 , a source electrode 4A, a drain electrode 4B, and a sealing layer 6 in this order.

[0328] The organic TFT 20 has a different layer structure (stacking method), but is otherwise the same as the organic TFT 10. Therefore, the substrate, gate electrode, gate insulating film, source electrode, drain electrode, organic semiconductor film and sealing layer are the same as those of the bottom gate-bottom contact type organic TFT, and thus their description is omitted.

[0329] <Method for producing organic TFT>

[0330] The method for producing an organic TFT is not particularly limited as long as it includes a step of applying a composition on a substrate to form an organic semiconductor film.

[0331] The gate electrode, the gate insulating film, the source electrode, the drain electrode and the sealing layer can all be manufactured or formed by the above method.

[0332] Next, the process of forming the organic semiconductor film will be described.

[0333] In this process, the above-mentioned composition is used.

[0334] In the present invention, "coating the composition on the substrate" includes not only a method of directly coating the composition on the substrate, but also a method of coating the composition on the substrate via another layer provided on the substrate. The other layer of the coating composition (a layer in contact with the organic semiconductor film and serving as the base of the organic semiconductor film) is inevitably determined by the structure of the organic TFT. For example, in the case where the organic TFT is a bottom gate type, the composition is coated at least on the surface of the gate insulating film.

[0335] When forming an organic semiconductor film, the substrate may be heated or cooled. By changing the temperature of the substrate, the deposition of specific compounds in the film can be controlled.

[0336] The temperature of the substrate is not particularly limited, but is preferably set within a range of 0 to 200°C, more preferably within a range of 10 to 150°C, and still more preferably within a range of 15 to 40°C.

[0337] When the composition of the present invention is used, even when the temperature of the substrate is set within a temperature range near room temperature, the specific compound in the film can be deposited well.

[0338] The method of forming an organic semiconductor film using the composition of the present invention is generally a so-called solution method.

[0339] The specific compound is also stable in the atmosphere. Therefore, the solution method can be performed in the atmosphere, and the composition can be applied over a large area.

[0340] As the coating method of the composition in the solution method, a common method can be used. For example, a coating method including drop coating, casting, dip coating, die coating, roller coating, rod coating and spin coating, various printing methods including inkjet, screen printing, gravure, flexographic printing, offset printing and micro-touch printing, and Langmuir-Blodgett (LB) method can be cited. Among them, drop coating, casting, spin coating, inkjet, gravure, flexographic printing, offset printing or micro-touch printing are preferred.

[0341] The method for applying the composition in the preferred embodiment of the solution method described below is preferably inkjet printing, gravure printing, flexographic printing, offset printing or micro-contact printing, and more preferably flexographic printing, micro-contact printing or inkjet printing.

[0342] In the solution method, the composition applied on the substrate is preferably dried, more preferably gradually dried. By drying the composition applied on the substrate, crystals of a specific compound can be precipitated to form an organic semiconductor film.

[0343] As a drying method for the composition, from the viewpoint of film quality, it is preferred to dry under reduced pressure after natural drying or after heat drying on a heated substrate. The temperature of the substrate during natural drying or heat drying can be appropriately changed according to the boiling point of the solvent in the composition, and therefore cannot be limited, but is preferably 10 to 200° C., more preferably 15 to 150° C. The time for natural drying or heat drying is preferably 0.5 to 20 hours, more preferably 1 to 10 hours.

[0344] The temperature of the substrate during the reduced pressure drying is preferably 10 to 150° C., more preferably 15 to 100° C. The time for the reduced pressure drying is preferably 1 to 20 hours, more preferably 2 to 10 hours. The pressure during the reduced pressure drying is preferably 10 -6 ~9.9x10 4 Pa, more preferably 10 -5 ~10 4 Pa.

[0345] The composition thus dried can be shaped into a predetermined shape or pattern shape as required.

[0346] (Solution method)

[0347] Hereinafter, preferred embodiments of the solution method will be described with reference to the drawings, but the solution method is not limited to the following embodiments.

[0348] As one method of the solution method, the following method can be cited: a composition (hereinafter, also referred to as a "coating liquid") is dripped (coated) on a part of the surface of the substrate in a manner that the composition contacts the substrate and a component disposed on the substrate (hereinafter, also referred to as a "component"), and then the dripped coating liquid is dried. The substrate and component used in this method will be described later.

[0349] In this embodiment, the component maintains a state of being in contact with the substrate, or maintains a state of not being fixed to the substrate and maintaining a constant distance from the substrate.

[0350] As long as the substrate and the component maintain the above state, the relative positional relationship between the substrate and the component can be fixed or changed when the coating liquid is dripped or dried. From the viewpoint of production efficiency, it is preferred to change the relative positional relationship between the substrate and the component by moving the component relative to the substrate. In addition, from the viewpoint of the film quality and crystal size of the obtained organic semiconductor film, it is preferred to fix the relative positional relationship between the substrate and the component by making the component stationary relative to the substrate.

[0351] The method of dripping the coating liquid in this mode is not particularly limited. From the viewpoint that the thickness of the coating liquid film on the substrate is easy to become thinner and it is easy to start drying from the end of the coating liquid film, when dripping the coating liquid, it is preferred to drip one drop of the coating liquid, or (when dripping two or more drops of the coating liquid) drip one drop at a time. When dripping the coating liquid, the volume of one drop of the coating liquid is preferably 0.01 to 0.2 mL, and more preferably 0.02 to 0.1 mL.

[0352] By dropping the coating liquid onto a part of the surface of the substrate so as to contact both the substrate and the member, the thickness of the edge of the coating liquid film can be reduced.

[0353] The contact angle (25°C) of the coating liquid relative to the substrate is not particularly limited, but is preferably 0 to 90°, more preferably 10 to 20°. The contact angle of the coating liquid relative to the substrate is obtained by measuring the angle between the droplet and the substrate after 1 second of dripping the coating liquid. Specifically, the liquid volume is set to 1.0 μL or more, and the static contact angle is measured by a drop method using a Teflon (registered trademark) needle. The different substrates treated in the same manner are measured multiple times (usually 5 times), and the average value is calculated, and the value is used as the contact angle.

[0354] The coating liquid preferably forms a meniscus with respect to the member, and more preferably forms a concave meniscus with respect to the member from the viewpoint of film quality.

[0355] Below, reference Figure 3 A method of applying the coating liquid while maintaining the distance between the substrate and the member in this embodiment constant will be described. Figure 3 This is a schematic diagram showing an example of a method for forming an organic semiconductor film of an organic TFT.

[0356] In this method, first, the substrate 42 and the component 43 are arranged at predetermined positions. Specifically, before the coating liquid 41 is dropped onto the substrate, the substrate 42 and the component 43 are arranged at predetermined positions. Figure 3 At this time, the distance between the substrate 42 and the component 43 that is not in contact with the substrate 42 is kept constant. The distance between the substrate 42 and the component 43 varies depending on the coating amount and viscosity of the coating liquid, and therefore cannot be determined in general, but can be set appropriately.

[0357] Then, if Figure 3 As shown in (B), the coating liquid 41 is dropped onto a part of the surface of the substrate 42 (near the facing portion of the substrate 42 and the member 43 ) so as to contact both the substrate 42 and the member 43 .

[0358] Then, the coating liquid 41 is dried while the relative positional relationship between the substrate 42 and the component 43 is fixed ( Figure 3 (C)). The drying method is not particularly limited, but the drying method of the above composition is preferred. Thus, on the substrate 42, the coating liquid 41 is dried from the two ends (end edges) where the film thickness is thinner toward the inside, so that the specific compound is crystallized. Thus, the specific compound can be arranged at a predetermined position as a crystal with a larger size.

[0359] After the coating liquid 41 is dried, the member 43 is peeled off from the substrate 42 by, for example, pulling up the member 43 perpendicularly to the main surface of the substrate 42. Thus, an organic semiconductor film with good film quality can be formed without leaving traces of the member 43 on the formed crystal.

[0360] In this manner, an organic semiconductor film composed of crystals of a specific compound can be formed.

[0361] Below, reference Figure 4 A method of applying the coating liquid while the substrate and the member are in contact with each other in this embodiment will be described. Figure 4 This is a schematic diagram for explaining another example of a method for forming an organic semiconductor film of an organic TFT.

[0362] In this method, first, the substrate 42 and the component 43 are arranged in a contact state. Specifically, before the coating liquid 41 is dropped onto the substrate 42, the substrate 42 and the component 43 are arranged respectively. Figure 4 (A) The position shown.

[0363] Then, if Figure 4 (B1) and Figure 4 As shown in (B2), the coating liquid 41 is dropped onto a portion of the surface of the substrate 42 (near the contact portion between the substrate 42 and the component 43) in such a manner that the coating liquid 41 contacts both the substrate 42 and the component 43. Figure 4 As shown in (B2), the coating liquid 41 preferably surrounds the contact portion between the substrate 42 and the component 43. Figure 4 (B1) is a front view of a substrate coated with a coating liquid, Figure 4 (B2) is a top view of a substrate coated with a coating liquid. Figure 4 (B1) and Figure 4 (B2) contains the three-dimensional coordinates (X, Y, Z).

[0364] Then, in a state where the relative positional relationship between the substrate 42 and the component 43 is fixed, the coating liquid 41 is preferably dried as described above ( Figure 4 (C)). The drying method is not particularly limited, but the drying method of the above composition is preferred. Thus, on the substrate 42, the coating liquid 41 is dried from the edge where the film thickness is thinner toward the inside, so that the specific compound is crystallized. Thus, the specific compound can be arranged at a predetermined position as a crystal with a larger size.

[0365] After the coating liquid 41 is dried, the member 43 is peeled off from the substrate 42 by, for example, pulling up the member 43 perpendicularly to the main surface of the substrate 42. Figure 4 As shown in (D), an organic semiconductor film 5 composed of crystals of a specific compound having good film quality can be formed without leaving traces of the member 43 on the crystals of the specific compound.

[0366] From the perspective of film quality and the perspective of not requiring a mechanism to hold component 43 and being able to maintain the distance (contact state) of component 43 relative to substrate 42, a method of applying the coating liquid while the substrate 42 and component 43 are in contact with each other is more preferred than a method of applying the coating liquid while the distance between the substrate 42 and component 43 is kept constant.

[0367] Below, reference Figure 5 Another method of applying the coating liquid while the substrate and the member are in contact with each other in this embodiment will be described. Figure 5 This is a schematic diagram for explaining another example of a method for forming an organic semiconductor film of an organic TFT.

[0368] This method and Figure 4 The method shown is different in that the crystallization of a specific compound is promoted by moving the member 43 relative to the substrate 42 while the distance between the substrate 42 and the member 43 is kept constant.

[0369] In this method, first, the substrate 42 and the component 43 are arranged in a contact state. Specifically, before the coating liquid 41 is dropped onto the substrate 42, the substrate 42 and the component 43 are arranged respectively. Figure 5 (A) The position shown.

[0370] Then, if Figure 5 As shown in (B), the coating liquid 41 is dropped onto a portion of the surface of the substrate 42 (near the contact portion between the substrate 42 and the component 43) in such a manner that the coating liquid 41 contacts both the substrate 42 and the component 43. Figure 4 As shown in (B2), the coating liquid 41 preferably surrounds the contact portion between the substrate 42 and the member 43.

[0371] Then, the component 43 is moved relative to the substrate 42 while the distance between the substrate 42 and the component 43 is kept constant, and the coating liquid 41 is dried. Figure 5 (C) moves relative to the substrate 42 in the direction of the arrow (X-axis negative direction). The coating liquid 41 is dried from the end of the member 43 on the side opposite to the moving direction (X-axis positive direction) toward the moving direction (X-axis negative direction), thereby crystallizing the specific compound. Thus, the specific compound can be arranged at a predetermined position as a crystal with a large size.

[0372] After the coating liquid 41 is dried, the member 43 is peeled off from the substrate 42 by, for example, pulling up the member 43 perpendicularly to the main surface of the substrate 42. Thus, an organic semiconductor film composed of a specific compound with good film quality can be formed without leaving traces of the member 43 on the crystals of the specific compound.

[0373] The substrate 42 used in this embodiment corresponds to a substrate of an organic TFT, and is preferably a substrate having a gate insulating film formed thereon.

[0374] The component 43 used in this embodiment is not particularly limited, but the material of the component 43 is preferably an inorganic material (more preferably glass, quartz or silicon) or a plastic (more preferably Teflon (registered trademark), polyethylene or polypropylene), and more preferably glass.

[0375] The shape of the member 43 used in this embodiment is not particularly limited as long as it has a smooth surface facing the substrate 42 , but is preferably a rectangular parallelepiped.

[0376] Figure 6 This is a schematic diagram showing an example of a substrate 42 and a member 43 used in this embodiment. Figure 6 In FIG. 1 , the shape of the component 43 is a rectangular parallelepiped, d and w respectively represent the length of one side and the other side of the surface of the component 43 facing the substrate 42 , and h represents the height of the component 43 .

[0377] The size of the component 43 used in this embodiment is not particularly limited. Figure 6 In the case of the rectangular parallelepiped shown in FIG. 1 , the length of one side of the main surface (the surface coated with the coating liquid) of the substrate 42 is equal to the length of one side and the length of the other side of the surface of the component 43 facing the substrate 42 ( Figure 6 The lower limit of d and W in ( ) is preferably 0.1% or more, more preferably 1% or more, further preferably 10% or more, and particularly preferably 20% or more. Furthermore, the upper limit of the length of one side and the other side relative to the length of one side of the main surface of the substrate 42 is preferably 80% or less, more preferably 70% or less, and further preferably 50% or less. The height of the component 43 ( Figure 6 The ratio h) of the height h of the component 43 to the length d is preferably 1 to 50 mm, more preferably 5 to 20 mm. Furthermore, the ratio h / d of the height h of the component 43 to the length d is preferably 0.01 to 10, and from the viewpoint of the configuration stability of the component 43, it is more preferably 0.1 to 5. Furthermore, the ratio w / d of the length w of the component 43 to the length d is preferably 1 to 1000, and from the viewpoint of enabling a wide range of crystallization of a specific compound, it is more preferably 5 to 100.

[0378] In this way, crystals of the specific compound can be precipitated to form an organic semiconductor film. Whether the crystals of the specific compound have been precipitated can be confirmed by observing the organic semiconductor film using a polarizing microscope (trade name: Eclipse LV100N POL (transmission / reflection illumination type), manufactured by Nikon Corporation, eyepiece: 10x magnification, objective lens: 5-20x magnification).

[0379] <Applications of organic TFT>

[0380] The use of the organic TFT is not particularly limited, and it can be used, for example, in electronic paper, display devices, sensors, and electronic tags.

[0381] Example

[0382] Below, use embodiment to describe the present invention in more detail.As long as the material, usage amount, ratio, processing content and processing flow shown in the following examples do not depart from the gist of the present invention, then can be appropriately changed.Therefore, the scope of the present invention should not be interpreted restrictively by the specific example shown below.

[0383] [Composition]

[0384] <Production of Composition of Example 1>

[0385] The following compound (1) (1.0 mg) as an organic semiconductor film-forming compound and a chloroform / 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) solvent (mixing ratio (volume ratio): chloroform / HFIP=4 / 1) were mixed to prepare a mixed solution so that the total amount became 10 g.

[0386] The mixed solution was irradiated with ultrasonic waves at room temperature (15 minutes) to obtain the composition of Example 1.

[0387] [Chemical formula 33]

[0388]

[0389] <Manufacturing of other compositions>

[0390] The compositions of various Examples or Comparative Examples were prepared by the same production process as that of the composition of Example 1 except that the types of the organic semiconductor film-forming compound and / or the solvent used were changed.

[0391] In addition, the organic semiconductor film-forming compound used in the compositions of Examples 12 and 13 has the same structure as the organic semiconductor film-forming compound used in the compositions of Examples 1 to 11, but the purification process and degree implemented when synthesizing the organic semiconductor film-forming compound are different, and the purity is lower.

[0392] <Evaluation of solubility>

[0393] The obtained composition was observed with the naked eye, and the solubility of the composition was evaluated based on the following criteria.

[0394] A: The compound for forming an organic semiconductor film is completely dissolved in the composition.

[0395] B: Undissolved residue of the compound for forming an organic semiconductor film is observed in the composition

[0396] C: The compound for forming an organic semiconductor film is not dissolved in the composition

[0397] <Purity evaluation by liquid chromatography>

[0398] Each composition was analyzed under the following conditions, and the area ratio of the peak derived from the object (organic semiconductor film-forming compound) to the total peak surface area at a detection wavelength of 254 nm was calculated and evaluated based on the following criteria.

[0399] A: The area ratio of the object is 99% or more

[0400] B: The area ratio of the object is 95% or more and less than 99%

[0401] C: The area ratio of the object is less than 95%

[0402] D: The object could not be detected because it was insoluble.

[0403] Chromatographic column: Connect two TOSOH CORPORATION TSKgel Silica-150, particle size 5μm, column size 4.6mmI.D.×25cm

[0404] Eluent: Chloroform / hexafluoroisopropanol = 9 / 1

[0405] Flow rate: 0.8mL / min,

[0406] Injection volume: 10 μL

[0407] Column temperature: 25°C

[0408] Detection wavelength: 254nm

[0409] [Organic Thin Film Transistor]

[0410] <Manufacturing of organic thin film transistors>

[0411] As a substrate for measuring FET characteristics, a substrate (size: 25 mm×25 mm) having a thermal oxide film (thickness: 200 nm) of SiO2 on the surface of an n-type silicon substrate (thickness: 0.4 mm, equivalent to a substrate 1 having a gate electrode 2) 1 was prepared. The surface of the thermal oxide film (gate insulating film 3) of the substrate was cleaned with ultraviolet (UV)-ozone and then treated with β-phenylethyltrimethoxysilane.

[0412] A glass member having a size of 10 mm in length×2 mm in width×5 mm in height was prepared. Figure 4 The component 43 shown, such as Figure 4 As shown in (A), the member is arranged at the center of the surface of the substrate 1 treated with β-phenethyltrimethoxysilane in a state of contact with the treated surface.

[0413] Next, use a pipette to place the substrate 1 ( Figure 4 In the figure, it is shown by symbol 42. Figure 4 As shown in (A), one drop of the composition prepared by the above method (about 0.05 mL) was dripped from the side of component B in the vicinity of the contact portion between substrate 42 and component 43 so as to contact substrate 42 and component 43. Figure 4 (B1) and Figure 4 As shown in (B2), the coating liquid surrounds the above-mentioned contact portion and forms a concave meniscus at the interface between the contact portion and the member 43.

[0414] like Figure 4 As shown in (C), the coating liquid 41 is dried at room temperature while the substrate 42 and the component 43 are kept in contact with each other and the positional relationship between the substrate 42 and the component 43 is kept static. -3 The organic semiconductor film was dried under reduced pressure for 8 hours at a pressure of Pa to produce a crystalline film. Next, the component 43 was pulled up perpendicularly to the substrate 42 to be peeled off from the substrate 42. Thus, a Figure 4 (D) shows a ring-shaped organic semiconductor film 5 having the uniform film thickness (film thickness: 10 to 50 nm).

[0415] The obtained organic semiconductor film 5 was observed using a polarizing microscope Eclipse LV100N POL (transmitted / reflected illumination type, manufactured by Nikon Corporation, eyepiece: 10x magnification, objective lens: 5-20x magnification) to confirm that crystals of the compound (organic semiconductor film-forming compound) were precipitated.

[0416] A mask having a predetermined opening was placed on the organic semiconductor film 5 thus obtained, and gold was evaporated to form a source electrode 4A and a drain electrode 4B (all with a thickness of 40 nm, a gate width W = 2 mm, a gate length L = 50 μm, and a ratio W / L = 40). In this way, an organic thin film transistor (referred to as OTFT in each table) T for measuring FET characteristics was manufactured.

[0417] <Evaluation of organic thin film transistors>

[0418] The carrier mobility of each of the produced organic thin film transistors was evaluated under a normal pressure atmosphere of 1 atmosphere (temperature: room temperature) using a semiconductor parameter analyzer (Agilent 4156C) connected to a semi-automatic prober (Vector Semiconductor CO., LTD. AX-2000).

[0419] (Evaluation of Carrier Mobility (Relative Mobility))

[0420] 1. Determination of carrier mobility μ after fabrication

[0421] A voltage of -80 V was applied between the source electrode and the drain electrode of each organic thin film transistor, and the gate voltage was changed in the range of +20 V to -100 V. The drain current I d The following formula calculates the carrier mobility μ(cm 2 / Vs).

[0422] I d =(w / 2L)μC i (Vg -V th ) 2

[0423] Where L is the gate length, w is the gate width, μ is the carrier mobility, and C i Indicates the capacitance per unit area of ​​the gate insulating film, V g Represents the gate voltage, V th Represents the threshold voltage.

[0424] The relative mobility was calculated according to the following formula with the mobility of Example 1 (the mobility calculated using the organic thin film transistor produced using the composition of Example 1) as a reference, and was evaluated according to the following criteria.

[0425] The higher the carrier mobility μ, the more preferable it is. In this test, it is preferably Class C or higher, more preferably Class B or higher, and even more preferably Class A.

[0426] Relative mobility = (mobility of the example or comparative example) / (mobility of Example 1)

[0427] A: Relative mobility is 1.0 or more

[0428] B: Relative mobility is 0.5 or more and less than 1.0

[0429] C: Relative mobility is 0.1 or more and less than 0.5

[0430] D: Relative mobility is less than 0.1

[0431] [result]

[0432] The results are shown in Table 1.

[0433] In Table 1, the column "Structure" indicates whether the structure of the compound for forming an organic semiconductor film contained in the composition is any one of (X), (Y), and (Z) shown below.

[0434] The "Group" column shows the groups possessed by the organic semiconductor film-forming compound when the structure of the compound is (X) or (Y), X 1 , X 2 , Y 1 , Y 2 In addition, the "Ph" is a phenyl group. 11 "C8H 17 "CH2CH2C6F 13 All the groups represented by " are straight-chain groups.

[0435] The "Solvent" column shows the type (upper row) and volume ratio (lower row) of the solvent contained in the composition. When the composition contains only one solvent, the volume ratio is not described.

[0436] In the "Solvent" column, the solvent described in the "A" column is the alcohol represented by the formula (S1), and the solvent described in the "B" column is an organic solvent other than this.

[0437] [Chemical formula 34]

[0438]

[0439] [Table 1]

[0440]

[0441] [Table 2]

[0442]

[0443] HFIP = Hexafluoroisopropanol

[0444] HFMP = 1,1,1,3,3,3-hexafluoro-2-methyl-2-propanol

[0445] NFTB = nonafluorotert-butyl alcohol

[0446] HFPP = 1,1,1,3,3,3-hexafluoro-2-phenyl-2-propanol

[0447] TFE=2,2,2-trifluoroethanol

[0448] TCE=1,1,2,2-Tetrachloroethane

[0449] THF = Tetrahydrofuran

[0450] PhCl = Chlorobenzene

[0451] PhCN = Benzonitrile

[0452] From the results shown in Table 1, it was confirmed that an organic thin film transistor having excellent carrier mobility can be produced even under low temperature conditions by using the composition of the present invention.

[0453] Furthermore, it was confirmed that the composition of the present invention dissolves the organic semiconductor film-forming composition well and can be analyzed by liquid chromatography, making it easy to confirm and / or adjust the purity of the composition, and making it easy to achieve high performance and stable quality of organic thin-film transistors.

[0454] From the results of Examples 19 and 18, it was confirmed that when the composition contained an organic solvent other than the alcohol represented by formula (S1), the solubility of the composition and the carrier mobility of the obtained organic thin film transistor were more excellent.

[0455] Comparison of Examples 16 and 17 confirmed that when the content of the alcohol represented by formula (S1) relative to the total content of the solvent (the total content of the alcohol represented by formula (S1) and the organic solvent other than the alcohol represented by formula (S1)) is 10 volume % or more, the solubility of the composition and the carrier mobility of the obtained organic thin film transistor are better.

[0456] By comparing Examples 1 to 8 with Examples 9 to 11 and 24, it was confirmed that when the organic solvent other than the alcohol represented by formula (S1) is a compound composed of only one or more atoms selected from the group consisting of carbon atoms, hydrogen atoms and halogen atoms, the solubility of the composition and the carrier mobility of the obtained organic thin film transistor are better.

[0457] From the comparison among Examples 1, 12, and 13, it was confirmed that when the purity of the specific compound was higher, the carrier mobility of the obtained organic thin film transistor was more excellent.

[0458] From the comparison between Example 1 and Example 23, it was confirmed that B in the specific compound 11 ~B 18 There exists a B with -N= 11 ~B 18 In this case, the carrier mobility of the obtained organic thin film transistor is more excellent.

[0459] Explanation of symbols

[0460] 1-substrate, 2-gate electrode, 3-gate insulating film, 4A-source electrode, 4B-drain electrode, 5-organic semiconductor film (organic semiconductor layer), 6-sealing layer, 10, 20-organic thin film transistor (organic TFT), 41-coating liquid, 42-substrate, 43-components.

Claims

1. A composition for forming an organic semiconductor layer, comprising a compound represented by the following formula (1), an alcohol represented by the following formula (S3), and a halogenated hydrocarbon solvent, In the composition, the content of the alcohol represented by the formula (S3) is 10% by volume or more and 95% by volume or less relative to the total content of the alcohol represented by the formula (S3) and the halogenated hydrocarbon solvent, The alcohol represented by the formula (S3) is liquid at room temperature. The halogenated hydrocarbon solvent is selected from the group consisting of dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, chlorotoluene, 1-chloronaphthalene and 1-fluoronaphthalene, In formula (1), A 11 and A 12 Each independently represents -O- or -N(R N )-, B 11 ~B 18 Each independently represents -N= or -C(R M )=, where B 12 and B 16 One or two of them are -N=, R N represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms having a halogen atom or an aryl group having 6 to 20 carbon atoms as a substituent, R M represents a hydrogen atom, an unsubstituted alkyl group having 1 to 20 carbon atoms, or a cyano group, X 11 ~X 14 each independently represents an oxygen atom, In formula (S3), R S7 It represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms. 2 . The composition according to claim 1 , which is a composition for forming an organic semiconductor layer for an organic thin film transistor.

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