JP6543320B2 - Coating solution for non-luminescent organic semiconductor device, organic transistor, compound, organic semiconductor material for non-luminescent organic semiconductor device, material for organic transistor, method for producing organic transistor, and method for producing organic semiconductor film - Google Patents

Description

  The present invention relates to a coating solution for non-luminescent organic semiconductor device, an organic transistor, a compound, an organic semiconductor material for non-luminescent organic semiconductor device, a material for an organic transistor, a method of manufacturing an organic transistor, and a method of manufacturing an organic semiconductor film. Specifically, the present invention relates to a compound having a thieno [3,2-f: 4,5-f '] bis [1] benzothiophene skeleton structure, and a thieno [3,2-f: 4,5-f' Coating solution for non-light emitting organic semiconductor device using compound having bis [1] benzothiophene skeleton structure, organic transistor, organic semiconductor material for non-light emitting organic semiconductor device, material for organic transistor, method for producing organic transistor and The present invention relates to a method of manufacturing an organic semiconductor film.

Devices using organic semiconductor materials are attracting a great deal of interest because they are expected to have various advantages over devices using inorganic semiconductor materials such as conventional silicon. As an example of a device using an organic semiconductor material, a photoelectric conversion element such as an organic thin film solar cell or a solid-state imaging element using an organic semiconductor material as a photoelectric conversion material, or a non-luminescent property (in the present specification, “The luminous efficiency of 1 lm / W or less is obtained when current is applied to the device at room temperature and a current density of 0.1 mW / cm ^{2 in} the atmosphere. Speaking of non-luminescent organic semiconductor devices, organic And organic semiconductor devices, except for light emitting organic semiconductor devices such as electroluminescent elements) (also referred to as organic thin film transistors). A device using an organic semiconductor material may be able to produce a large-area element at low temperature and at low cost, as compared to a device using an inorganic semiconductor material. Furthermore, since it is possible to easily change the material properties by changing the molecular structure, the variation of the material is abundant, and functions and elements which can not be achieved by the inorganic semiconductor material can be realized.

As the organic transistor material, it has been studied to increase the carrier mobility and enhance the transistor performance by using a compound having a condensed ring for the semiconductor active layer.
Here, as a material for an organic transistor, a compound having a thieno [3,2-f: 4,5-f ′] bis [1] benzothiophene (hereinafter, also referred to as TBBT) structure is known. For example, Non-Patent Document 1 discloses a compound C6-TBBT in which an alkyl group having 6 carbon atoms is substituted to thieno [3,2-f: 4,5-f '] bis [1] benzothiophene, an alkyl having 12 carbon atoms As a synthesis method and physical properties of a group-substituted compound C12-TBBT, absorption and emission spectra and CV (cyclic voltammetry) are disclosed. Although application to an organic transistor is described in the introduction section of Non-Patent Document 1 in Non-Patent Document 1, it is only measuring the absorption / emission spectrum of a solution and the redox potential, and formation of a film or There is no description of the physical property as a film, the organic transistor characteristic evaluation such as carrier mobility, and the like.

Tetrahedron 66 (2010) 8778-8784

  Under these circumstances, when the present inventors examined an organic transistor using a compound described in Non-Patent Document 1, the redox potential and the absorption and emission spectra of a compound having a TBBT structure inside were examined. It was found that the carrier mobility can not be increased even if the coating film is formed using the solution for measurement as it is. Therefore, it was found that improvement of carrier mobility is required.

  The problem to be solved by the present invention is to provide an organic transistor with high carrier mobility.

As a result of earnestly examining in order to solve the above-mentioned subject, to the frame which has thieno [3, 2-f: 4, 5-f '] bis [1] benzothiophene (henceforth TBBT) structure inside On the other hand, it has been found that by substituting a specific substituent, an organic transistor having high carrier mobility can be obtained, leading to the present invention.
The present invention, which is a specific means for solving the above problems, has the following configuration.

[1] A coating liquid for a non-luminescent organic semiconductor device comprising a compound represented by the following general formula (2) and a solvent having a boiling point of 100 ° C. or higher;
General formula (2)
In General Formula (2), R ¹¹ and R ¹² each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an alkoxy group, and may have a substituent,
The aromatic moiety in the general formula (2) may be substituted with a halogen atom.
[2] In the coating solution for a non-luminescent organic semiconductor device described in [1], the compound represented by the general formula (2) preferably satisfies the following condition A, condition B, condition C or condition D;
Condition A: in the general formula (2), R ¹¹ and R ¹² each independently have 3 to 30 carbon atoms in total, and
Unsubstituted linear alkyl group having 8 to 10 carbon atoms and an even number of carbon atoms,
Unsubstituted linear alkyl group having 3 to 15 carbon atoms and an odd number of carbon atoms,
A substituted linear alkyl group having 3 to 15 carbon atoms or a substituted or unsubstituted branched alkyl group having 3 to 18 carbon atoms,
The aromatic moiety in the general formula (2) may be substituted with a halogen atom;
Condition B: In the general formula (2), R ¹¹ and R ¹² each independently have 3 to 30 carbon atoms in total, and an unsubstituted linear alkyl group having 2 to 4 carbon atoms and an even carbon number. Represents
Condition C: in the general formula (2),
And R ¹¹ and R ¹² each independently have 3 to 30 carbon atoms in total, and
A substituted alkyl group having 1 or 2 carbon atoms;
Condition D: In the general formula (2), R ¹¹ and R ¹² each independently have 3 to 30 carbon atoms in total, and R ¹¹ and R ¹² have different structures.
[3] It is preferable that the compound represented by General formula (2) satisfy | fills the following conditions A for the coating liquid for non-luminous organic semiconductor devices as described in [2];
Condition A: in the general formula (2),
And R ¹¹ and R ¹² each independently have 3 to 30 carbon atoms in total, and
Unsubstituted linear alkyl group having 8 to 10 carbon atoms and an even number of carbon atoms,
Unsubstituted linear alkyl group having 3 to 15 carbon atoms and an odd number of carbon atoms,
A substituted linear alkyl group having 3 to 15 carbon atoms or a substituted or unsubstituted branched alkyl group having 3 to 18 carbon atoms,
The aromatic moiety in the general formula (2) may be substituted with a halogen atom.
[4] The coating liquid for a non-luminescent organic semiconductor device according to [3] is represented by general formula (2):
And R ¹¹ and R ¹² each independently have 3 to 30 carbon atoms in total, and
Unsubstituted linear alkyl group having 8 to 10 carbon atoms and an even number of carbon atoms,
Unsubstituted linear alkyl group having 3 to 15 carbon atoms and an odd number of carbon atoms,
It is preferable to represent
The aromatic moiety in the general formula (2) may be substituted with a halogen atom.
[5] [3] or the coating liquid for a non-luminescent organic semiconductor device according to [4] has, in the general formula (2), R ¹¹ and R ¹² each independently having 3 to 30 carbon atoms in total, and ,
It is preferable that it is a C3-C15 linear alkyl group substituted by the substituent through an ether structure or ester bond.
[6] In the coating solution for a non-luminescent organic semiconductor device according to [2], the compound represented by the general formula (2) preferably satisfies the following condition B;
Condition B: In the general formula (2), R ¹¹ and R ¹² each independently have 3 to 30 carbon atoms in total, and an unsubstituted linear alkyl group having 2 to 4 carbon atoms and an even carbon number. Represents
[7] In the coating liquid for non-luminescent organic semiconductor devices described in [2], the compound represented by General Formula (2) preferably satisfies the following condition C;
Condition C: in the general formula (2),
And R ¹¹ and R ¹² each independently have 3 to 30 carbon atoms in total, and
It is a substituted alkyl group having 1 or 2 carbon atoms.
[8] [7] The coating solution for a non-luminescent organic semiconductor device according to [7], in the general formula (2),
And R ¹¹ and R ¹² each independently have 3 to 30 carbon atoms in total, and
It is preferable that it is a C1-C2 alkyl group substituted by the substituent via an ether structure or ester bond.
[9] In the coating solution for a non-luminescent organic semiconductor device according to [2], the compound represented by the general formula (2) preferably satisfies the following condition D;
Condition D: In the general formula (2), R ¹¹ and R ¹² each independently have 3 to 30 carbon atoms in total, and R ¹¹ and R ¹² have different structures.
[10] [9] The coating solution for a non-luminescent organic semiconductor device according to [9] has, in the general formula (2), R ¹¹ and R ¹² each independently having 3 to 30 carbon atoms in total, and R ¹¹ Preferably, R ¹² is a substituted or unsubstituted linear alkyl group, and R ¹² is a substituted or unsubstituted linear or branched alkyl group different from R ¹¹ .
[11] non-emissive organic semiconductor devices for coating solution described in [10], in the general formula (2), R ¹¹ and R ¹² is the total carbon number of 3 to 30 independently, and, R ¹¹ and It is preferable that R ¹² be each independently an unsubstituted linear alkyl group, and R ¹¹ and R ¹² have different structures.
[12] An organic transistor comprising a compound represented by the following general formula (2) in a semiconductor active layer;
General formula (2)
In General Formula (2), R ¹¹ and R ¹² each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an alkoxy group, and may have a substituent,
The aromatic moiety in the general formula (2) may be substituted with a halogen atom.
[13] In the organic transistor described in [12], the compound represented by General Formula (2) preferably satisfies the following condition A;
Condition A: in the general formula (2),
And R ¹¹ and R ¹² each independently have 3 to 30 carbon atoms in total, and
Unsubstituted linear alkyl group having 8 to 10 carbon atoms and an even number of carbon atoms,
Unsubstituted linear alkyl group having 3 to 15 carbon atoms and an odd number of carbon atoms,
A substituted linear alkyl group having 3 to 15 carbon atoms or a substituted or unsubstituted branched alkyl group having 3 to 18 carbon atoms,
The aromatic moiety in the general formula (2) may be substituted with a halogen atom.
[14] A compound represented by the following general formula (2), which is
A compound satisfying the following condition A, condition B, condition C or condition D;
General formula (2)
In General Formula (2), R ¹¹ and R ¹² each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an alkoxy group, and may have a substituent,
The aromatic moiety in the general formula (2) may be substituted with a halogen atom;
Condition A: in the general formula (2), R ¹¹ and R ¹² each independently have 3 to 30 carbon atoms in total, and
Unsubstituted linear alkyl group having 8 to 10 carbon atoms and an even number of carbon atoms,
Unsubstituted linear alkyl group having 3 to 15 carbon atoms and an odd number of carbon atoms,
A substituted linear alkyl group having 3 to 15 carbon atoms or a substituted or unsubstituted branched alkyl group having 3 to 18 carbon atoms,
The aromatic moiety in the general formula (2) may be substituted with a halogen atom;
Condition B: In the general formula (2), R ¹¹ and R ¹² each independently have 3 to 30 carbon atoms in total, and an unsubstituted linear alkyl group having 2 to 4 carbon atoms and an even carbon number. Represents
Condition C: in the general formula (2),
And R ¹¹ and R ¹² each independently have 3 to 30 carbon atoms in total, and
A substituted alkyl group having 1 or 2 carbon atoms;
Condition D: In the general formula (2), R ¹¹ and R ¹² each independently have 3 to 30 carbon atoms in total, and R ¹¹ and R ¹² have different structures.
[15] In the compound described in [14], the compound represented by General Formula (2) preferably satisfies the following condition A;
Condition A: in the general formula (2),
And R ¹¹ and R ¹² each independently have 3 to 30 carbon atoms in total, and
Unsubstituted linear alkyl group having 8 to 10 carbon atoms and an even number of carbon atoms,
Unsubstituted linear alkyl group having 3 to 15 carbon atoms and an odd number of carbon atoms,
A substituted linear alkyl group having 3 to 15 carbon atoms or a substituted or unsubstituted branched alkyl group having 3 to 18 carbon atoms,
The aromatic moiety in the general formula (2) may be substituted with a halogen atom.
[16] An organic semiconductor material for a non-luminescent organic semiconductor device, comprising the compound according to [14] or [15].
The material for organic transistors containing the compound as described in [17] [14] or [15].
[18] A coating solution for a non-luminescent organic semiconductor device, comprising the compound according to [14] or [15].
[19] An organic transistor comprising the compound according to [14] or [15] in a semiconductor active layer.
[20] A process for producing a semiconductor active layer by applying the coating solution for a non-light emitting organic semiconductor device according to any one of [1] to [11] and [18] on a substrate and drying it. Method of producing an organic transistor comprising
[21] A coating solution containing a compound represented by the following general formula (2) and a solvent having a boiling point of 100 ° C. or more,
While maintaining the state in which the distance between the substrate A and the member B not fixed to the substrate A is kept constant, or the state in which the substrate A and the member B are in contact,
Drop on a part of the surface of the substrate A so as to be in contact with both the substrate A and the member B,
A method of manufacturing an organic semiconductor film, wherein a semiconductor active layer is formed by depositing crystals of the compound represented by the general formula (2) by gradually drying the dropped coating liquid.
However, when the coating solution is dropped or dried as long as the distance between the substrate A and the member B is maintained at a constant distance or the state where the substrate A and the member B are in contact is maintained. The positional relationship with the member B may be stationary or may be moved;
General formula (2)
In General Formula (2), R ¹¹ and R ¹² each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an alkoxy group, and may have a substituent,
The aromatic moiety in the general formula (2) may be substituted with a halogen atom.
[22] A coating solution obtained by dissolving the compound according to [14] or [15] in a solvent,
While maintaining the state in which the distance between the substrate A and the member B not fixed to the substrate A is kept constant, or the state in which the substrate A and the member B are in contact,
Drop on a part of the surface of the substrate A so as to be in contact with both the substrate A and the member B,
A method of manufacturing an organic semiconductor film, wherein a semiconductor active layer is formed by depositing crystals of the compound described in [14] or [15] by gradually drying the dropped coating liquid.
However, when the coating solution is dropped or dried as long as the distance between the substrate A and the member B is maintained at a constant distance or the state where the substrate A and the member B are in contact is maintained. The positional relationship with the member B may be stationary or may be moved.
[101] In the coating solution for a non-luminescent organic semiconductor device according to any one of [1] to [11], the solvent having a boiling point of 100 ° C. or more is preferably a non-halogenated solvent.
[102] In the coating solution for a non-luminescent organic semiconductor device according to any one of [1] to [11] and [18], the concentration of the compound represented by the general formula (2) is 0.4 mass % Or more is preferable.
[103] The coating solution for a non-luminescent organic semiconductor device according to any one of [1] to [11] and [18] may contain two or more compounds represented by General Formula (2) preferable.
[104] The coating liquid for non-light emitting organic semiconductor devices according to any one of [1] to [11] and [18] preferably has a viscosity of 10 mPa · s or more.
[105] It is preferable that the coating liquid for non-light emitting organic semiconductor devices according to any one of [1] to [11] and [18] contains a polymer.
[106] A coated film containing a compound represented by the following general formula (2).
General formula (2)
In General Formula (2), R ¹¹ and R ¹² each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an alkoxy group, and may have a substituent,
The aromatic moiety in the general formula (2) may be substituted with a halogen atom.
[107] A coated film comprising the compound according to [14] or [15].

  According to the present invention, an organic transistor with high carrier mobility can be provided.

FIG. 1 is a schematic view showing a cross section of a structure of an example of an organic transistor manufactured as a substrate for measuring FET characteristics in the embodiment of the present invention. FIG. 2 is a schematic view showing a cross section of the structure of the organic transistor manufactured as a substrate for measuring FET characteristics in the embodiment of the present invention. FIG. 3 is a schematic view showing an example of the method for producing an organic semiconductor film of the present invention. Specifically, while maintaining a state in which the distance between the substrate A and the member B not fixed to the substrate A is kept constant, one in the plane of the substrate A is in contact with both the substrate A and the member B. It is the schematic of the aspect which drips a coating liquid into a part, makes the positional relationship of the board | substrate A and the member B stand still, and gradually dries the coating liquid dripped. FIG. 4 is a schematic view showing another example of the method for producing an organic semiconductor film of the present invention. Specifically, while maintaining the state in which the substrate A and the member B are in contact with each other, the coating liquid is dropped on a part of the surface of the substrate A so as to be in contact with both the substrate A and the member B. It is the schematic of the aspect which makes the positional relationship of (1) stand still, and dries the dripped coating liquid gradually. FIG. 5 is a schematic view showing another example of the method for producing an organic semiconductor film of the present invention. Specifically, while maintaining the state in which the substrate A and the member B are in contact with each other, the coating liquid is dropped on a part of the surface of the substrate A so as to be in contact with both the substrate A and the member B. It is the schematic of the aspect which moves the positional relationship of and dry the dripped coating liquid gradually. FIG. 6 is a schematic view showing an example of a substrate A and a member B used in the method for producing an organic semiconductor film of the present invention.

Hereinafter, the present invention will be described in detail. The description of the configuration requirements described below may be made based on typical embodiments and specific examples, but the present invention is not limited to such embodiments. In addition, the numerical range represented using "-" in this specification means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit.
In the present invention, a hydrogen atom in the case where it is used without being particularly distinguished in the description of each general formula means that it also includes isotopes (deuterium atom etc.). Furthermore, atoms constituting a substituent are also meant to include its isotope.

[Coating solution for non-luminescent organic semiconductor device, organic transistor, compound]
A first aspect of the coating solution for a non-luminescent organic semiconductor device of the present invention comprises a compound represented by the following general formula (2) and a solvent having a boiling point of 100 ° C. or higher;
General formula (2)
In General Formula (2), R ¹¹ and R ¹² each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an alkoxy group, and may have a substituent,
The aromatic moiety in the general formula (2) may be substituted with a halogen atom.
The second aspect of the coating liquid for non-luminescent organic semiconductor devices of the present invention is a coating liquid for non-luminescent organic semiconductor devices containing the compound of the present invention described later.

The 1st aspect of the organic transistor of this invention contains the compound represented by following General formula (2) in a semiconductor active layer.
General formula (2)
In the general formula (2), R ¹¹ and R ¹² each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an alkoxy group, and may have a substituent, and in the general formula (2) The aromatic moiety may be substituted with a halogen atom.
In the first aspect of the organic transistor of the present invention, the semiconductor active layer may contain the compound represented by the general formula (2) and a solvent having a boiling point of 100 ° C. or more, and the semiconductor active layer may have the general formula (2) And the solvent having a boiling point of 100.degree. C. or more may be included in the compound represented by the above (except for the compounds satisfying the conditions A, B, C or D).
In the first aspect of the organic transistor according to the present invention, the semiconductor active layer is preferably produced from a liquid containing a compound represented by the general formula (2) and a solvent having a boiling point of 100 ° C. or more. Is more preferably produced from a liquid containing a compound represented by the general formula (2) (excluding compounds satisfying the conditions A, B, C or D) and a solvent having a boiling point of 100 ° C. or more .
The 2nd aspect of the organic transistor of this invention is an organic transistor which contains the compound of this invention mentioned later in a semiconductor active layer.

  With such a configuration, the organic transistor of the present invention has high carrier mobility. Moreover, the coating liquid for nonluminous organic semiconductor devices of this invention can provide the organic transistor of this invention with high carrier mobility. Although not bound by any theory, in the first embodiment, the reason is not known in detail using the compound represented by the general formula (2) having a specific substituent (the solubility is improved It is thought that an organic transistor with high carrier mobility can be obtained. In the first embodiment, it is preferable to further use a high boiling point solvent in order to delay the drying at the time of film formation, and in particular, the compound in which the semiconductor active layer is represented by the general formula (2) When a compound satisfying the condition C or the condition D is used, it is easier to obtain an organic transistor having a high carrier mobility. Also, in the second aspect, when the compound of the present invention described later having a specific substituent is used, the reason is not clarified in detail (it seems to have an influence such as improvement in solubility), but the carrier It is considered that an organic transistor with high mobility can be obtained.

In addition, it can not be said that what is useful as an organic EL (Electro Luminescence) element material is immediately useful as a semiconductor material for organic transistors. This is because the characteristics required of the organic compound are different between the organic EL element and the organic transistor. A mobility of about 10 ^-3 cm ² / Vs is sufficient to drive the organic EL element, and it is important to enhance the light emission efficiency rather than the charge transport property to improve the organic EL characteristics. There is a need for an element having a high light intensity and uniform light emission in the plane. Usually, organic compounds having high crystallinity (high mobility) cause luminescence defects such as in-plane electric field intensity nonuniformity, luminescence nonuniformity, luminescence quenching, etc., and thus materials for organic EL devices are crystalline. And a highly amorphous material (low mobility) is desired. On the other hand, in a semiconductor material for an organic transistor, since the required mobility is extremely high, an organic compound having high crystallinity and high molecular order is required. Also, for high mobility expression, it is preferable that the π conjugate plane is upright with respect to the substrate.

First, the coating liquid for non-light emitting organic semiconductor devices of the present invention, which can be used also as a coating liquid in the method of manufacturing an organic semiconductor film of the present invention described below, will be described.
The first and second embodiments of the coating solution for non-luminescent organic semiconductor devices of the present invention will be collectively described below.

<Compound Represented by General Formula (2)>
The compound represented by following General formula (2) is demonstrated.
General formula (2)
In the general formula (2), R ¹¹ and R ¹² each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an alkoxy group, and may have a substituent, and in the general formula (2) The aromatic moiety may be substituted with a halogen atom.
The preferable aspect of the structure of a compound represented by General formula (2) is demonstrated.
The alkyl group represented by R ¹¹ and R ¹² in the general formula (2) is not particularly limited, but is preferably an alkyl group having 1 to 30 carbon atoms, and may be cyclic, whether linear or branched. It may be. In the general formula (2), the alkyl group represented by R ¹¹ and R ¹² is an unsubstituted linear alkyl group having 3 to 30 carbon atoms in total, 8 to 10 carbon atoms, and an even carbon number, An unsubstituted linear alkyl group having 3 to 15 carbon atoms and an odd number of carbon atoms, a substituted linear alkyl group having 3 to 15 carbon atoms, or a substituted or unsubstituted branched alkyl group having 3 to 18 carbon atoms More preferable. The particularly preferable range of the alkyl group represented by R ¹¹ and R ¹² is the same as the range satisfying Condition A, Condition B, Condition C or Condition D described later.
The alkenyl group represented by R ¹¹ and R ¹² in the general formula (2) is not particularly limited, but is preferably an alkenyl group having 2 to 30 carbon atoms, more preferably an alkenyl group having 3 to 18 carbon atoms, and 5 to 5 carbon atoms Thirteen alkenyl groups are particularly preferred.
The alkynyl group represented by R ¹¹ and R ¹² in the general formula (2) is not particularly limited, but is preferably an alkynyl group having 2 to 30 carbon atoms, more preferably an alkynyl group having 3 to 18 carbon atoms, and 5 to 5 carbon atoms. Thirteen alkynyl groups are particularly preferred.
The alkoxy group represented by R ¹¹ and R ¹² in the general formula (2) is not particularly limited, but is preferably an alkoxy group having 1 to 30 carbon atoms, more preferably an alkoxy group having 3 to 18 carbon atoms, and 5 to 5 carbon atoms Thirteen alkoxy groups are particularly preferred.
In the compound represented by the above general formula (2), it is preferable that R ¹¹ and R ¹² be an alkyl group.

In the general formula (2), when the alkyl group, the alkenyl group, the alkynyl group or the alkoxy group represented by R ¹¹ and R ¹² further has a substituent, this substituent is not particularly limited, but a halogen atom or an alkenyl group ( Ethenyl group, 1-pentenyl group, 1-heptanyl group, cycloalkenyl group, bicycloalkenyl group etc., alkynyl group (1-pentynyl group, trimethylsilylethynyl group, triethylsilylethynyl group, tri-i-propylsilylethynyl group) , 2-p-propylphenylethynyl group etc., aryl group (phenyl group, naphthyl group, p-pentylphenyl group, 3,4-dipentylphenyl group, p-heptoxyphenyl group, 3,4-diheptene group) Containing an aryl group having 6 to 20 carbon atoms of a toxyphenyl group, a heterocyclic group (such as a heterocyclic group) (Including 2-hexylfuranyl group etc.), cyano group, hydroxyl group, nitro group, acyl group (including hexanoyl group, benzoyl group etc.), alkoxy group (including butoxy group etc.), aryloxy group (including Phenoxy group etc.), silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, amino group (including anilino group), acylamino group, aminocarbonylamino group (including ureido group), alkoxy and aryloxycarbonylamino Groups, alkyl and arylsulfonylamino groups, mercapto groups, alkyl and arylthio groups (including methylthio, octylthio and the like), heterocyclic thio groups, sulfamoyl groups, sulfo groups, alkyl and arylsulfinyl groups, alkyl and arylsulfonyl groups, A And aryloxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyl oxy group, phosphinyl amino group, phosphono group, silyl group (ditrimethylsiloxymethyl butoxy group Etc.), hydrazino group, ureido group, boronic acid group (-B (OH) ₂ ), phosphato group (-OPO (OH) ₂ ), sulfato group (-OSO ₃ H), and other known substituents. . Among these, a halogen atom, an alkoxy group, an acyloxy group and an alkyloxycarbonyl group are particularly preferable, and a halogen atom and an alkoxy group are most preferable.
Moreover, these substituents may further have the above-mentioned substituent.

In the compound represented by the above general formula (2), a halogen atom may be substituted to the aromatic moiety in the general formula (2), and as the halogen atom, a fluorine atom is preferable. The number of halogen atoms substituting for the aromatic moiety in the general formula (2) is preferably 0 to 6, more preferably 0 to 4, and particularly preferably 0 to 2, More preferably, it is 0.
Even when the aromatic moiety in the general formula (2) is substituted with a substituent other than a halogen atom, the aromatic moiety in the general formula (2) is unsubstituted or aromatic in the general formula (2) An organic transistor with high carrier mobility can be obtained as in the case where a halogen atom is substituted in a part, and it is possible to impart a function such as high solubility to the compound represented by General Formula (2).
The compound represented by the above-mentioned general formula (2) is also substituted when a substituent other than R ¹¹ and R ¹² is further substituted on the thiophene ring moiety substituted by R ¹¹ or R ¹² in the general formula (2) , And an organic transistor having a high carrier mobility as in the case where the thiophene ring moiety substituted by R ¹¹ or R ¹² is unsubstituted, functions such as high solubility in the compound represented by the general formula (2) It is possible to give

(Compound of the present invention)
In the present invention, the compound represented by the general formula (2) preferably satisfies the following condition A, condition B, condition C or condition D;
Condition A: in the general formula (2), R ¹¹ and R ¹² each independently have 3 to 30 carbon atoms in total, and
Unsubstituted linear alkyl group having 8 to 10 carbon atoms and an even number of carbon atoms,
Unsubstituted linear alkyl group having 3 to 15 carbon atoms and an odd number of carbon atoms,
A substituted linear alkyl group having 3 to 15 carbon atoms or a substituted or unsubstituted branched alkyl group having 3 to 18 carbon atoms,
The aromatic moiety in the general formula (2) may be substituted with a halogen atom;
Condition B: In the general formula (2), R ¹¹ and R ¹² each independently have 3 to 30 carbon atoms in total, and an unsubstituted linear alkyl group having 2 to 4 carbon atoms and an even carbon number. Represents
Condition C: in the general formula (2),
And R ¹¹ and R ¹² each independently have 3 to 30 carbon atoms in total, and
A substituted alkyl group having 1 or 2 carbon atoms;
Condition D: In the general formula (2), R ¹¹ and R ¹² each independently have 3 to 30 carbon atoms in total, and R ¹¹ and R ¹² have different structures.
Compounds satisfying the conditions A, B, C or D are novel compounds and are referred to as the compounds of the present invention. That is, the compound of the present invention is a compound represented by General Formula (2), and is a compound satisfying the following condition A, condition B, condition C or condition D. The compound of the present invention is included in the semiconductor active layer described later in the organic transistor of the present invention. That is, the compound of the present invention can be used as a material for an organic transistor.
In particular, a compound C6-TBBT in which an alkyl group having 6 carbon atoms is substituted to thieno [3,2-f: 4,5-f '] bis [1] benzothiophene described in Tetrahedron 66 (2010) 8778 to 8784. In addition to the compound C12-TBBT in which the alkyl group having 12 carbon atoms is substituted, by including the compound of the present invention in the semiconductor active layer, the carrier mobility is further enhanced in the organic transistor of the present invention.
Although not bound by any reason, the present inventors consider the following reasons. By selecting a specific alkyl chain length or shape that the compound of the present invention satisfies, the carrier mobility can be further enhanced among the organic transistors of the present invention by increasing the overlap of orbitals between molecules. .

  Hereinafter, conditions A, B, C and D which are preferable embodiments of the compound represented by the general formula (2) will be described.

(Condition A)
In the present invention, the compound represented by the general formula (2) more preferably satisfies the following condition A;
Condition A: in the general formula (2),
And R ¹¹ and R ¹² each independently have 3 to 30 carbon atoms in total, and
Unsubstituted linear alkyl group having 8 to 10 carbon atoms and an even number of carbon atoms,
Unsubstituted linear alkyl group having 3 to 15 carbon atoms and an odd number of carbon atoms,
A substituted linear alkyl group having 3 to 15 carbon atoms or a substituted or unsubstituted branched alkyl group having 3 to 18 carbon atoms,
The aromatic moiety in the general formula (2) may be substituted with a halogen atom.

The unsubstituted linear alkyl group having 8 to 10 carbon atoms and having an even number of carbon atoms represented by R ¹¹ and R ¹² is more preferably a linear alkyl group having 8 or 10 carbon atoms, and having 10 carbon atoms. Particularly preferred is a linear alkyl group. The long-chain alkyl group within the above range, in particular, a long-chain straight-chain alkyl group is preferable from the viewpoint of enhancing the linearity of the molecule and enhancing the carrier mobility.

The unsubstituted linear alkyl group having 3 to 15 carbon atoms and an odd number of carbon atoms represented by R ¹¹ and R ¹² is an unsubstituted linear alkyl group having 5 to 15 carbon atoms and an odd number of carbon atoms The unsubstituted linear alkyl group having 7 to 13 carbon atoms and having an odd number of carbon atoms is more preferable, and the unsubstituted linear alkyl group having 9 or 11 carbon atoms is particularly preferable.

It is preferable that R ¹¹ and R ^{12 be} a linear alkyl group from the viewpoint of enhancing the linearity of the molecule and enhancing carrier mobility. On the other hand, R ¹¹ and R ¹² may be branched alkyl groups from the viewpoint of enhancing the solubility in organic solvents.

The substituent in the case where R ¹¹ and R ¹² are substituted linear alkyl groups having 3 to 15 carbon atoms or branched branched alkyl groups having 3 to 18 carbon atoms is not particularly limited, but halogen atoms, alkenyl groups (Including ethenyl group, 1-pentenyl group, 1-heptanyl group, cycloalkenyl group, bicycloalkenyl group etc.), alkynyl group (1-pentynyl group, trimethylsilylethynyl group, triethylsilylethynyl group, tri-i-propylsilylethynyl) Group, 2-p-propylphenylethynyl group etc., aryl group (phenyl group, naphthyl group, p-pentylphenyl group, 3,4-dipentylphenyl group, p-heptoxyphenyl group, 3,4-diphenyl group) It may be referred to as a heterocyclic group (including a heterocyclic group (including a C6-C20 aryl group etc.) of a ptoxyphenyl group. Cyano, hydroxyl, nitro, acyl (including hexanoyl and benzoyl), alkoxy (including butoxy and the like), aryloxy (including phenoxy and the like), Silyloxy, heterocyclic oxy, acyloxy, carbamoyloxy, amino (including anilino), acylamino, aminocarbonylamino (including ureido), alkoxy and aryloxycarbonylamino, alkyl and arylsulfonylamino Group, mercapto group, alkyl and arylthio group (including methylthio group, octylthio group etc.), heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, alkyl and aryl Roxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyl oxy group, phosphinyl amino group, phosphono group, silyl group (ditrimethylsiloxymethyl butoxy group etc.) , Hydrazino group, ureido group, boronic acid group (-B (OH) ₂ ), phosphato group (-OPO (OH) ₂ ), sulfato group (-OSO ₃ H), and other known substituents.
Moreover, these substituents may further have the above-mentioned substituent.
Among these, a halogen atom, an aryl group, an alkenyl group, an alkynyl group, a heterocyclic group, an alkoxy group, an alkylthio group, an acyloxy group, an aryloxy group, an alkyloxy carbonyl group is preferable as a substituent which can be taken, a fluorine atom or carbon Aryl group having 6 to 20 atoms, alkenyl group having 2 to 12 carbon atoms (preferably 1-alkenyl group), alkynyl group having 2 to 12 carbon atoms, alkoxy group having 1 to 11 carbon atoms, acyloxy group, carbon The alkylthio group and the alkyloxycarbonyl group of the number 1 to 12 are more preferable, a halogen atom, an alkoxy group, an acyloxy group and an alkyloxycarbonyl group are particularly preferable, and a halogen atom and an alkoxy group are most preferable.
When R ¹¹ and R ¹² are an alkyl group substituted with a fluorine atom, all of the hydrogen atoms of the alkyl group are substituted with a fluorine atom even if some of the hydrogen atoms are substituted with a fluorine atom, and the perfluoroalkyl is substituted It may form a group.
However, R ¹¹ and R ¹² are preferably unsubstituted linear alkyl groups or branched alkyl groups.

When R ¹¹ and R ¹² are substituted linear alkyl groups having 3 to 15 carbon atoms, substituted linear alkyl groups having 3 to 13 carbon atoms are preferable, and substituted linear alkyl groups having 3 to 11 carbon atoms are preferred. The substituted linear alkyl group having 5 to 11 carbon atoms is particularly preferable, and the substituted linear alkyl group having 7 to 11 carbon atoms is more particularly preferable.

When R ¹¹ and R ¹² are a substituted branched alkyl group having 3 to 18 carbon atoms, a substituted branched alkyl group having 3 to 15 carbon atoms is preferable, and a substituted branched alkyl group having 3 to 13 carbon atoms is more preferable, The substituted branched alkyl group having 3 to 11 carbon atoms is particularly preferable, and the substituted branched alkyl group having 7 to 11 carbon atoms is more particularly preferable.

When R ¹¹ and R ¹² each represent a linear or branched alkyl group having a substituent, non-adjacent -CH _2- groups in the linear alkyl group or non-adjacent in a branched alkyl group- The CH ₂ -group, the trivalent tertiary carbon atom linking group or the tetravalent quaternary carbon atom linking group may be independently substituted by another atom linking group. In this case, as another atom linking group, -O-, -S-, -CO-, -COO-, -OCO-, -COS-, -SCO-, -NRCO- or -CONR- (R is hydrogen An atom or a C1-C6 alkyl group etc. can be mentioned.
However, R ¹¹ and R ^12, -CH ₂ nonadjacent in straight chain alkyl group - group or,, -CH ₂ nonadjacent in branched alkyl group - group, a trivalent tertiary carbon atom linking group, or It is preferable that the tetravalent quaternary carbon atom linking group is not substituted by another atom linking group.

In the present invention, among the compounds represented by the general formula (2) and satisfying the condition A, R ¹¹ and R ¹² each independently have 3 to 30 carbon atoms in total, and
Unsubstituted linear alkyl group having 8 to 10 carbon atoms and an even number of carbon atoms,
Unsubstituted linear alkyl group having 3 to 15 carbon atoms and an odd number of carbon atoms,
It is preferable to represent
The aromatic moiety in the general formula (2) may be substituted with a halogen atom.

In the present invention, among the compounds represented by the general formula (2) and satisfying the condition A, R ¹¹ and R ¹² each independently have 3 to 30 carbon atoms in total, and
It is preferable that it is a C3-C15 linear alkyl group substituted by the substituent through an ether structure or ester bond.
Examples of the substituent substituted through an ether structure or an ester bond, can be mentioned substituents R ¹¹ and R ¹² can be taken, an alkyl group is preferable among them, and more preferably a straight chain alkyl group. It is preferable that carbon number of the substituent substituted via ether structure or ester bond is 1-10, It is more preferable that it is 1-5, It is especially preferable that it is 2-5.

(Condition B)
In the present invention, the compound represented by the general formula (2) more preferably satisfies the following condition B;
Condition B: In the general formula (2), R ¹¹ and R ¹² each independently have 3 to 30 carbon atoms in total, and an unsubstituted linear alkyl group having 2 to 4 carbon atoms and an even carbon number. Represents

(Condition C)
In the present invention, the compound represented by the general formula (2) more preferably satisfies the following condition C;
Condition C: In the general formula (2), R ¹¹ and R ¹² each independently have 3 to 30 carbon atoms in total and is a substituted alkyl group having 1 or 2 carbon atoms.
Among the conditions C, R ¹¹ and R ¹² each independently has 3 to 30 carbon atoms in total, and is an alkyl group having 1 or 2 carbon atoms substituted with a substituent via an ether structure or an ester bond. Is preferred.
Examples of the substituent substituted through an ether structure or an ester bond, can be mentioned substituents R ¹¹ and R ¹² can be taken, an alkyl group is preferable among them, and more preferably a straight chain alkyl group. It is preferable that carbon number of the substituent substituted via ether structure or ester bond is 1-10, It is more preferable that it is 1-5, It is especially preferable that it is 2-5.

(Condition D)
In the present invention, the compound represented by the general formula (2) more preferably satisfies the following condition D;
Condition D: In the general formula (2), R ¹¹ and R ¹² each independently have 3 to 30 carbon atoms in total, and R ¹¹ and R ¹² have different structures.
Among the conditions satisfying D, R ¹¹ and R ¹² each independently have 3 to 30 carbon atoms in total, and R ¹¹ is an unsubstituted linear alkyl group, and R ¹² is a substituted or different group from R ¹¹ It is preferably an unsubstituted linear or branched alkyl group. Among them, R ¹¹ and R ¹² each independently have 3 to 30 carbon atoms in total, and R ¹¹ and R ¹² each independently represent an unsubstituted linear alkyl group, and R ¹¹ and R ¹² It is preferable that they have different structures.

The total carbon number of R ¹¹ and R ¹² is preferably independently 3 to 30, more preferably 7 to 30, particularly preferably 7 to 20, and 7 to 15 More particularly preferred is 7-11, even more particularly preferred is 9-11, and even more particularly preferred is 9-11. When the total carbon number of R ¹¹ and R ¹² is independently at least the lower limit value of the above range, the carrier mobility becomes high. When the total carbon number of R ¹¹ and R ¹² is less than or equal to the upper limit of the above range, the solubility in organic solvents is increased.

Specific examples of the compound represented by the above general formula (2) are shown below, but the compound represented by the general formula (2) which can be used in the present invention is interpreted limitedly by these specific examples. It should not be. Incidentally, R ¹¹ and R ¹² in the following Table 1 and Table 2 represent R ¹¹ and R ¹² in the general formula (2).

The compound represented by the general formula (2) preferably has a molecular weight of 3,000 or less, more preferably 2,000 or less, still more preferably 1,000 or less, and particularly preferably 850 or less. By setting the molecular weight to the upper limit value or less, the solubility in a solvent can be enhanced, which is preferable.
On the other hand, from the viewpoint of the film quality stability of the film, the molecular weight is preferably 250 or more, more preferably 300 or more, and still more preferably 350 or more.

The compound represented by General formula (2) can be synthesize | combined on the method of Tetrahedron 66 (2010) 8778-8784, or the method of the below-mentioned Example as a reference.
Any reaction conditions may be used in the synthesis of the compound represented by the general formula (2). As a reaction solvent, any solvent may be used. In addition, it is preferable to use an acid or a base to accelerate the ring formation reaction, and it is particularly preferable to use an acid. The optimum reaction conditions vary depending on the structure of the target compound, but specific reaction conditions described in the above-mentioned documents or the methods described in the following examples can be set as a reference.

  Synthetic intermediates having various substituents can be synthesized by combining known reactions. Also, each substituent may be introduced at any intermediate stage. After synthesis of the intermediate, purification by column chromatography, recrystallization or the like is preferably performed, followed by purification by sublimation purification. By sublimation purification, not only organic impurities can be separated but also inorganic salts, residual solvents and the like can be effectively removed.

<Solvent>
When forming a film on a substrate using a solution process, the material for forming the layer may be a suitable organic solvent (eg, hexane, octane, decane, toluene, xylene, mesitylene, ethylbenzene, amylbenzene, decalin, 1-methylnaphthalene, Hydrocarbon solvents such as 1-ethylnaphthalene, 1,6-dimethylnaphthalene and tetralin, for example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, propiophenone, butyrophenone, α-tetralone and β-tetralone Solvents such as dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, chlorotol ether , Halogenated hydrocarbon solvents such as 1-fluoronaphthalene, heterocyclic solvents such as pyridine, picoline, quinoline, thiophene, 3-butylthiophene, thieno [2,3-b] thiophene, 2-chlorothiophene, 3 -Chlorothiophene, 2,5-dichlorothiophene, 3,4-dichlorothiophene, 2-bromothiophene, 3-bromothiophene, 2,3-dibromothiophene, 2,4-dibromothiophene, 2,5-dibromothiophene, 3 Halogenated heterocyclic solvents such as 2,4-dibromothiophene and 3,4-dichloro-1,2,5-thiadiazole, for example, ethyl acetate, butyl acetate, amyl acetate, 2-ethylhexyl acetate, γ-butyrolactone, acetate Ester solvents such as phenyl, for example, methanol, propanol, butanol, Alcohol solvents such as ethanol, hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, ethylene glycol, for example, dibutyl ether, tetrahydrofuran, dioxane, dimethoxyethane, anisole, ethoxybenzene, propoxybenzene, isopropoxybenzene, butoxybenzene, 2- Methyl anisole, 3-methyl anisole, 4-methyl anisole, 4-ethyl anisole, dimethyl anisole (2,3-, 2,4-, 2, 5-, 2, 6-, 3,4-, 3,5- , 3, 6-), 1,4-benzodioxane, 2,3-dihydrobenzofuran, phthalane, chromane, isochroman, and other ether solvents such as N, N-dimethylformamide, N, N-dimethylacetamide , 1-me Amide / imide solvents such as lu-2-pyrrolidone, 1-methyl-2-imidazolidinone, 1,3-dimethyl-2-imidazolidinone, sulfoxide solvents such as dimethyl sulfoxide, phosphoric acid such as trimethyl phosphate A film can be formed by various coating methods by dissolving or dispersing in an ester solvent, a nitrile solvent such as acetonitrile or benzonitrile, a nitro solvent such as nitromethane or nitrobenzene, and / or water to form a coating solution. The solvents may be used alone or in combination of two or more. Among them, hydrocarbon solvents, ketone solvents, halogenated hydrocarbon solvents, heterocyclic solvents, halogenated heterocyclic solvents or ether solvents are preferable, and toluene, xylene, mesitylene, amylbenzene, tetralin, acetophenone Propiophenone, butyrophenone, α-tetralone, dichlorobenzene, anisole, ethoxybenzene, propoxybenzene, isopropoxybenzene, butoxybenzene, 2-methylanisole, 3-methylanisole, 4-methylanisole, 2,3-dihydrobenzofuran , Phthalane, chroman, isochroman, 1-fluoronaphthalene, 3-chlorothiophene, 2,5-dibromothiophene, more preferably toluene, xylene, tetralin, acetophenone, propiophenone, butyro. Enone, α-tetralone, anisole, ethoxybenzene, propoxybenzene, butoxybenzene, 2-methyl anisole, 3-methyl anisole, 4-methyl anisole, 2,3-dihydrobenzofuran, phthalan, chroman, isochroman, 1-fluoronaphthalene, Particularly preferred is 3-chlorothiophene or 2,5-dibromothiophene.
In the first embodiment of the coating solution for a non-luminescent organic semiconductor device of the present invention, among these solvents, a solvent having a boiling point of 100 ° C. or more is used. The first aspect of the coating solution for a non-luminescent organic semiconductor device of the present invention has the advantage of being able to obtain crystals with good film quality and a large area by including a solvent having a boiling point of 100 ° C. or higher, It is used suitably for the manufacturing method of the organic-semiconductor film of this invention.
Also in the second embodiment of the coating solution for non-luminescent organic semiconductor devices of the present invention, it is preferable from the same viewpoint to use a solvent having a boiling point of 100 ° C. or more.
From these viewpoints, the solvent having a boiling point of 100 ° C. or more is more preferably 150 ° C. or more, still more preferably 175 ° C. or more, and particularly preferably 200 ° C. or more.
Further, it is particularly preferable that the solvent having a boiling point of 100 ° C. or more is a non-halogenated solvent from the viewpoint of environmental load and toxicity to humans.

  The concentration of the compound represented by the general formula (2) in the coating solution is preferably 0.005 to 5% by mass, more preferably 0.01 to 3% by mass, and particularly preferably 0.1 to 2% by mass It is. With this range, it is easy to form a film of any thickness. Furthermore, it is particularly preferable that the concentration of the compound represented by General Formula (2) is 0.4% by mass or more because a coating film having a large crystal size can be easily formed, in the coating solution for non-luminescent organic semiconductor devices. In Tetrahedron 66 (2010) 8778 to 8784, a low concentration solution for measuring the oxidation-reduction potential and light emission / absorption is described, but the concentration of the non-light emitting organic semiconductor device coating solution is higher Preferred in view of the above.

The coating liquid for non-light emitting organic semiconductor devices of the present invention preferably contains a compound represented by the general formula (2) and does not contain a polymer binder.
Moreover, the coating liquid for nonluminous organic semiconductor devices of this invention may contain the compound and polymer binder which are represented by General formula (2). In this case, the material for forming the layer and the polymer binder may be dissolved or dispersed in the above-mentioned appropriate solvent to form a coating solution, and a film may be formed by various coating methods. The polymer binder can be selected from those described below.

  It is preferable from the viewpoint of film quality uniformity of the formed coating film that the coating liquid for non-light emitting organic semiconductor devices contains a polymer.

  The coating liquid for non-luminescent organic semiconductor devices may contain only one type of the compound represented by General Formula (2), or may contain two or more types. It is preferable from the viewpoint of storage stability of the coating solution (preventing crystal precipitation during storage) that the compound represented by general formula (2) is contained in two or more kinds.

  It is preferable from the viewpoint of various printability that the viscosity is 10 mPa · s or more for the non-luminescent organic semiconductor device coating solution.

  The coating solution for a non-luminescent organic semiconductor device may contain an additive other than the polymer binder, such as a surfactant, an antioxidant, a crystallization control agent, a crystal orientation control agent, and the like.

Examples of the surfactant include, but are not limited to, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene Nonionic surfactants such as sorbitan fatty acid ester, Megafac F171, F176 (Dainippon Ink & Chemicals, Inc.), Florard FC430 (Sumitomo 3M), Surfynol E1004 (Asahi Glass), OM656 PF656 and PF6320, etc. Fluorinated surfactant, polysiloxane polymer KP-341 (Shin-Etsu Chemical Co., Ltd.), KF-410 (Shin-Etsu Chemical Co., Ltd.), KF-412 (Shin-Etsu Chemical Co., Ltd.), KF -96-100 cs (Shinetsu Manabu Industry Co., Ltd.), manufactured by BYK-322 (BYK Co.) include organosiloxane polymers, such as BYK-323 (manufactured by BYK Corporation).
The content of the surfactant is preferably about 0.001 to about 1% by mass in the coating solution.

For example, as an antioxidant, a phenol type antioxidant, a phosphorus type antioxidant, and a sulfur type antioxidant etc. are mentioned.
Specific examples of phenolic antioxidants include 2,6-di-t-butyl-4-methylphenol, n-octadecyl-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl ) Propionate, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 4 4,4'-Butylidenebis- (3-methyl-6-t-butylphenol), triethylene glycol-bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate], 3,9-bis {2- [3- (3-t-Butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10- Tetraoxa spiro [5, 5] undecane etc. are mentioned.
Commercially available phenolic antioxidants include Irganox 1010, Irganox 1035, Irganox 1076, Irganox 1135, Irganox 245, Irganox 259, Irganox 295, and Irganox 3114 (all by BASF AG) Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-60, Adekastab AO-70, Adekastab AO-80, Adekastab AO-90, and Adekastab AO-330 , All made by ADEKA), Sumilyzer BHT, Sumilyzer BP-101, Sumilyzer GA-80, Sumilyzer MDP-S, Sumilyzer BBM-S, Sumilyzer GM, Sumilar The GS (F) and SMILIZER GP (all manufactured by Sumitomo Chemical Co., Ltd.), HOSTANOX O10, HOSTANOX O16, HOSTANOX O14, and HOSTANOX O3 (all manufactured by Clariant), Antage BHT, Antage W-300 , Antage W-400, and antage W500 (all manufactured by Kawaguchi Chemical Industry Co., Ltd.), and SEENOX 224M, and SEENOX 326M (all manufactured by Sipro Chemical Co., Ltd.), Yoshinox BHT, Yoshinox BB, Tominox TT, Minox 917 (all from Yoshitomi Pharmaceutical Co., Ltd.), TTHP (Toray Co., Ltd.), and the like.
Specific examples of phosphorus-based antioxidants include trisnonylphenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-t) -Butylphenyl) pentaerythritol phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octylphos Phyto, tetrakis (2,4-di-t-butylphenyl) -4,4-biphenylene-di-phosphonite and the like can be mentioned. Commercially available phosphorus antioxidants include Adekastab 1178 (Asahi Denka Co., Ltd.), Sumilyzer TNP (Sumitomo Chemical Co., Ltd.), JP-135 (Johoku Chemical Co., Ltd.), Adekastab 2112 (Asahi Denka) (Made by Co., Ltd.), JPP-2000 (made by Johoku Chemical Co., Ltd.), Weston 618 (made by GE), Adekastab PEP-24G (made by Asahi Denka Co., Ltd.), Adekastab PEP-36 (made by Asahi Denka Co., Ltd.) Adekastab HP-10 (manufactured by Asahi Denka Co., Ltd.), Sandstab P-EPQ (manufactured by Sand Co., Ltd.), Phosphite 168 (manufactured by Chiba Specialty Chemicals Co., Ltd.), and the like.
Specific examples of sulfur-based antioxidants include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, pentaerythritol Tetrakis (3-lauryl thiopropionate) etc. are mentioned. Commercially available sulfur-based antioxidants include Sumylizer TPL (Sumitomo Chemical Co., Ltd.), Yoshinox DLTP (Yoshitomi Pharmaceutical Co., Ltd.), Anthiox L (Nippon Yushi Co., Ltd.), Sumylizer TPM (Sumitomo Chemical Co., Ltd.) Ltd., Yoshinox DMTP (Yoshitomi Pharmaceutical Co., Ltd.), Anthiox M (Nippon Yushi Co., Ltd.), Sumilyzer TPS (Sumitomo Chemical Co., Ltd.), Yoshinox DSTP (Yoshitomi Pharmaceutical Co., Ltd.) , Anthiox S (manufactured by Nippon Oil and Fats Co., Ltd.), Adekastab AO-412S (manufactured by Asahi Denka Co., Ltd.), SEENOX 412S (manufactured by Shipro Kasei Co., Ltd.), Sumilyzer TDP (manufactured by Sumitomo Chemical Co., Ltd.), etc. Be
The content of the antioxidant is preferably about 0.01 to about 5% by mass in the coating solution.

<Structure of organic transistor>
The 1st aspect of the organic transistor of this invention contains the compound represented by General formula (2) in a semiconductor active layer.
The second aspect of the organic transistor of the present invention comprises the compound of the present invention in a semiconductor active layer.
That is, the organic transistor of the present invention has a semiconductor active layer containing the compound represented by the general formula (2).
The organic transistor of the present invention may further include other layers in addition to the semiconductor active layer.
The organic transistor of the present invention is preferably used as an organic field effect transistor (Field Effect Transistor, FET), and more preferably used as an insulated gate FET in which the gate and the channel are insulated.
Hereafter, although the aspect of the preferable structure of the organic transistor of this invention is demonstrated in detail using drawing, this invention is not limited to these aspects.

(Laminated structure)
There is no restriction | limiting in particular as laminated structure of an organic field effect transistor, It can be set as a thing of well-known various structures.
As an example of the structure of the organic transistor of the present invention, a structure in which an electrode, an insulator layer, a semiconductor active layer (organic semiconductor layer), and two electrodes are arranged in order on the upper surface of the lowermost substrate (bottom gate and top contact type Can be mentioned. In this structure, the electrode on the upper surface of the lowermost substrate is provided on a part of the substrate, and the insulator layer is arranged to be in contact with the substrate at a portion other than the electrode. Also, the two electrodes provided on the upper surface of the semiconductor active layer are arranged separately from each other.
The configuration of the bottom gate top contact device is shown in FIG. FIG. 1 is a schematic view showing a cross section of the structure of an example of the organic transistor of the present invention. In the organic transistor shown in FIG. 1, the substrate 11 is disposed in the lowermost layer, the electrode 12 is provided on a part of the upper surface, the electrode 12 is covered, and the insulator layer 13 is in contact with the substrate 11 in portions other than the electrode 12. Is provided. Furthermore, a semiconductor active layer 14 is provided on the upper surface of the insulator layer 13, and the two electrodes 15a and 15b are arranged separately on a part of the upper surface.
In the organic transistor shown in FIG. 1, the electrode 12 is a gate, and the electrode 15a and the electrode 15b are a drain or a source, respectively. The organic transistor shown in FIG. 1 is an insulated gate FET in which the channel, which is a current path between the drain and the source, and the gate are insulated.

As an example of the structure of the organic transistor of the present invention, a bottom gate / bottom contact type device can be mentioned.
The configuration of the bottom gate bottom contact type device is shown in FIG. FIG. 2 is a schematic view showing a cross section of the structure of the organic transistor manufactured as a substrate for measuring FET characteristics in the embodiment of the present invention. In the organic transistor of FIG. 2, the substrate 31 is disposed in the lowermost layer, the electrode 32 is provided on a part of the upper surface, and the electrode 32 is covered, and the insulator layer 33 is in contact with the substrate 31 in portions other than the electrode 32. Is provided. Further, a semiconductor active layer 35 is provided on the upper surface of the insulator layer 33, and the electrodes 34a and 34b are under the semiconductor active layer 35.
In the organic transistor shown in FIG. 2, the electrode 32 is a gate, and the electrode 34a and the electrode 34b are a drain or a source, respectively. The organic transistor shown in FIG. 2 is an insulated gate FET in which the channel, which is a current path between the drain and the source, and the gate are insulated.

  As the structure of the organic transistor of the present invention, in addition, an insulator, a top gate / top contact type device having a gate electrode on the upper part of the semiconductor active layer, or a top gate / bottom contact type device can be preferably used.

(thickness)
In the case where the organic transistor of the present invention needs to be a thinner transistor, for example, it is preferable to set the thickness of the entire transistor to 0.1 to 0.5 μm.

(Sealing)
In order to shield the organic transistor element from the air and moisture and to improve the storage stability of the organic transistor element, the entire organic transistor element may be a metal sealing can, glass, an inorganic material such as silicon nitride, a polymer material such as parylene, It may be sealed with a low molecular weight material or the like.
Hereinafter, although the preferable aspect of each layer of the organic transistor of this invention is demonstrated, this invention is not limited to these aspects.

<Board>
(material)
The organic transistor of the present invention preferably includes a substrate.
The material of the substrate is not particularly limited, and known materials can be used, for example, polyester films such as polyethylene naphthalate (PEN) and polyethylene terephthalate (PET), cycloolefin polymer films, polycarbonate films, triacetyl cellulose ( And TAC) films, polyimide films, films obtained by bonding these polymer films to ultrathin glass, ceramics, silicon, quartz, glass, etc., and silicon is preferable.

<Electrode>
(material)
The organic transistor of the present invention preferably includes an electrode.
As a constituent material of the electrode, for example, a metal material such as Cr, Al, Ta, Mo, Nb, Cu, Ag, Au, Pt, Pd, In, Ni or Nd, an alloy material of these, or a carbon material, conductive Any known conductive material such as a polymer can be used without particular limitation.

(thickness)
The thickness of the electrode is not particularly limited, but preferably 10 to 50 nm.
The gate width (or channel width) W and the gate length (or channel length) L are not particularly limited, but the ratio W / L thereof is preferably 10 or more, and more preferably 20 or more.

<Acceptor>
(material)
The organic transistor of the present invention preferably includes an acceptor for promoting carrier injection. Preferred examples of the material include known 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ) and the like.

(thickness)
The thickness of the acceptor is not particularly limited, but is preferably 5 nm or less.

<Insulating layer>
(material)
The material constituting the insulating layer is not particularly limited as long as the necessary insulating effect can be obtained. For example, fluorine-based insulating materials such as silicon dioxide, silicon nitride, PTFE (polytetrafluoroethylene), CYTOP (Cytop), polyester insulating materials And polycarbonate insulating materials, acrylic polymer insulating materials, epoxy resin insulating materials, polyimide insulating materials, polyvinyl phenol resin insulating materials, and polyparaxylylene resin insulating materials.
The upper surface of the insulating layer may be surface-treated, for example, an insulating layer in which the silicon dioxide surface is surface-treated by application of hexamethyldisilazane (HMDS), octadecyltrichlorosilane (OTS) or β-phenylitylmethoxysilane. Can be preferably used, and an insulating layer surface-treated by application of .beta.-phenylitylmethoxysilane can be more preferably used.

(thickness)
The thickness of the insulating layer is not particularly limited, but when thinning is desired, the thickness is preferably 10 to 500 nm, more preferably 20 to 200 nm, and particularly preferably 50 to 200 nm. .

<Semiconductor active layer>
(material)
The organic transistor of the present invention includes a compound in which the semiconductor active layer is represented by the general formula (2).
The semiconductor active layer may be a layer further including a polymer binder (also referred to as a polymer or a binder) described later in addition to the compound represented by General Formula (2). Moreover, the residual solvent at the time of film formation may be included.
The content of the polymer binder in the semiconductor active layer is not particularly limited, but is preferably in the range of 0 to 95% by mass, more preferably in the range of 10 to 90% by mass, and still more preferably It is used in the range of 20 to 80% by mass, particularly preferably in the range of 30 to 70% by mass.

(thickness)
The thickness of the semiconductor active layer is not particularly limited, but when thin film formation is required, the thickness is preferably 10 to 400 nm, more preferably 10 to 200 nm, and particularly preferably 10 to 100 nm. preferable.

[Method of manufacturing organic transistor]
The manufacturing method of the organic transistor of this invention includes the process of apply | coating the coating liquid for nonluminous organic semiconductor devices of this invention on a board | substrate, and making it dry, and producing a semiconductor active layer.
The method of manufacturing an organic transistor of the present invention may or may not include the method of manufacturing an organic semiconductor film of the present invention described later.
First, among the methods for manufacturing an organic transistor of the present invention, a general method will be described.

(Deposition method)
In the method of manufacturing an organic transistor of the present invention, any method may be used for forming a film of the compound of the present invention or the compound represented by the general formula (2) on a substrate.
At the time of film formation, the substrate may be heated or cooled, and by changing the temperature of the substrate, it is possible to control the film quality or the packing of molecules in the film. The temperature of the substrate is not particularly limited, but is preferably between 0 ° C. and 200 ° C., more preferably between 15 ° C. and 120 ° C., particularly preferably between 20 ° C. and 100 ° C. preferable.
When the compound of the present invention or the compound represented by the general formula (2) is formed on a substrate, it is possible to form a film by a vacuum process or a solution process, and both are preferable.

  Specific examples of film formation by vacuum process include physical vapor deposition such as vacuum evaporation, sputtering, ion plating, molecular beam epitaxy (MBE), or chemical vapor deposition (CVD) such as plasma polymerization. Method is preferred, and vacuum deposition is particularly preferred.

Here, film formation by solution process refers to a method of dissolving in a solvent in which an organic compound can be dissolved and forming a film using the solution. Specifically, a drop casting method, a casting method, a dip coating method, a die coater method, a roll coater method, a bar coater method, a coating method such as a spin coating method, an inkjet method, a screen printing method, a gravure printing method, flexographic printing Conventional methods such as printing method, offset printing method, micro contact printing method, Langmuir-Blodgett (LB) method can be used, and drop casting method, casting method, spin coating method, ink jet method, gravure printing Particular preference is given to using methods, flexographic printing, offset printing, microcontact printing.
It is preferable that the organic-semiconductor film for nonluminous organic-semiconductor devices of this invention was produced by the solution apply | coating method. Further, when the organic semiconductor film for a non-luminescent organic semiconductor device of the present invention contains a polymer binder, the material forming the layer and the polymer binder are dissolved or dispersed in an appropriate solvent to form a coating solution, Preferably, it is formed by a coating method.

  Next, a method including the method for producing an organic semiconductor film of the present invention, which is a more preferable embodiment among the methods for producing an organic transistor of the present invention, will be described.

[Method of manufacturing organic semiconductor film]
According to a first aspect of the method for producing an organic semiconductor film of the present invention, a coating liquid containing a compound represented by the following general formula (2) and a solvent having a boiling point of 100 ° C. or higher is provided:
While maintaining the state in which the distance between the substrate A and the member B not fixed to the substrate A is kept constant, or the state in which the substrate A and the member B are in contact,
Drop on a part of the surface of the substrate A so as to be in contact with both the substrate A and the member B,
Crystals of the compound represented by the general formula (2) are precipitated by gradually drying the dropped coating solution to form a semiconductor active layer;
However, when the coating solution is dropped or dried as long as the distance between the substrate A and the member B is maintained at a constant distance or the state where the substrate A and the member B are in contact is maintained. The positional relationship with the member B may be stationary or may be moved;
General formula (2)
In the general formula (2), R ¹¹ and R ¹² each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an alkoxy group, and may have a substituent, and in the general formula (2) The aromatic moiety may be substituted with a halogen atom.
In a second aspect of the method for producing an organic semiconductor film of the present invention, a coating liquid in which the compound of the present invention is dissolved in a solvent is
While maintaining the state in which the distance between the substrate A and the member B not fixed to the substrate A is kept constant, or the state in which the substrate A and the member B are in contact,
Drop on a part of the surface of the substrate A so as to be in contact with both the substrate A and the member B,
Crystals of the compound of the present invention are precipitated by gradually drying the dropped coating solution to form a semiconductor active layer;
However, when the coating solution is dropped or dried as long as the distance between the substrate A and the member B is maintained at a constant distance or the state where the substrate A and the member B are in contact is maintained. The positional relationship with the member B may be stationary or may be moved.
The first and second embodiments of the method for producing an organic semiconductor film of the present invention will be collectively described below.

The preferable aspect of the manufacturing method of the organic-semiconductor film of this invention is demonstrated based on drawing.
FIG. 3 is a schematic view showing an example of the method for producing an organic semiconductor film of the present invention.
FIG. 3A shows a state before dropping the coating solution (code 41) onto the substrate A (code 42), and a member not fixed to the substrate A (code 42) and the substrate A (code 42). A state in which the distance to B (reference numeral 43) is kept constant is maintained.
Next, in FIG. 3B, the coating liquid (code 41) is dropped on a part of the surface of the substrate A (code 42) so as to contact both the substrate A (code 42) and the member B (code 43). Show the condition.
Thereafter, FIG. 3C is a schematic view of an embodiment in which the positional relationship between the substrate A (code 42) and the member B (code 43) is stopped, and the dropped coating liquid (code 41) is gradually dried. . A coating liquid (code | symbol 41) can be obtained from the both-ends part to which film thickness became thin, and can obtain a crystal | crystallization with a big size by crystallizing.

FIG. 4 is a schematic view showing another example of the method for producing an organic semiconductor film of the present invention.
FIG. 4A shows the state before dropping the coating solution (code 41) onto the substrate A (code 42), and maintains the state in which the substrate A (code 42) and the member B (code 43) are in contact. doing.
Next, in FIG. 4 (B1), the coating solution (code 41) is dropped on a part of the surface of the substrate A (code 42) so as to contact both the substrate A (code 42) and the member B (code 43). Show the condition. The drawing viewed from the vertical direction (Y-axis direction) in FIG. 4 (B1) is FIG. 4 (B2). According to FIG. 4 (B2), it is further understood that the coating liquid (symbol 41) is dropped on a part of the surface of the substrate A (symbol 42).
Thereafter, FIG. 4C is a schematic view of an embodiment in which the positional relationship between the substrate A (code 42) and the member B (code 43) is stopped, and the dropped coating liquid (code 41) is gradually dried. . A coating liquid (code | symbol 41) can be obtained from the both-ends part to which film thickness became thin, and can obtain a crystal | crystallization with a big size by crystallizing.
When the aspect of FIG. 3 and the aspect of FIG. 4 are compared, the aspect of the film quality of the aspect of FIG. 4 which maintains the state which made the substrate A (code | symbol 42) and the member B (code 43) contact is maintained. It is preferable in that the distance between the member B (code 43) and the substrate A (code 42) can be precisely maintained.

FIG. 5 is a schematic view showing another example of the method for producing an organic semiconductor film of the present invention.
FIG. 5 (A) shows the state before dropping the coating solution (code 41) onto the substrate A (code 42), maintaining the condition that the substrate A (code 42) and the member B (code 43) are in contact. doing.
Next, in FIG. 5B, the coating liquid (code 41) is dropped on a part of the surface of the substrate A (code 42) so as to contact both the substrate A (code 42) and the member B (code 43). Show the condition.
Thereafter, FIG. 5C is a schematic view of an embodiment in which the dropped coating liquid is gradually dried by moving the positional relationship between the substrate A (code 42) and the member B (code 43). In the method for producing an organic semiconductor film of the present invention, the coating liquid is used as long as the distance between the substrate A and the member B is kept constant or the substrate A and the member B are kept in contact with each other. When dropping or drying, the positional relationship between the substrate A and the member B may be stationary or may be moved. As shown in FIG. 5C, the coating liquid (code 41) is moved from the member B (code 43) by moving the positional relationship between the substrate A (code 42) and the member B (code 43) in the −X direction of the coordinates. By drying from the far end (+ X direction of the coordinate) and crystallization, it is possible to obtain a crystal with a large size.
When the embodiment of FIG. 5 is compared with the embodiment of FIG. 4, the embodiment of FIG. 4 is preferable from the viewpoint of film quality and the viewpoint of easily obtaining crystals of a large area.

  Examples of the substrate A used in the method for producing an organic semiconductor film of the present invention include those used as a substrate of the organic transistor of the present invention, and an insulating layer is formed on the substrate of the organic transistor of the present invention Is preferred.

The member B used in the method for producing an organic semiconductor film of the present invention is not particularly limited, but the material of the member B is glass; quartz; silicon; plastics such as Teflon (registered trademark), polyethylene, polypropylene, etc. Preferably, it is more preferably glass.
The size of the member B (code 43) (for example, the length in the X-axis direction and the Y-axis direction of the member B (code 43) in FIG. 4B2) is not particularly limited, but the member B (code 43) The lower limit of the length of one side is preferably 0.1% or more of the length of one side of the substrate A (symbol 42), more preferably 1% or more, and particularly preferably 10% or more. Preferably, it is more preferably 20% or more. The upper limit of the length of one side of the member B (code 43) is preferably 80% or less of the length of one side of the substrate A (code 42), more preferably 70% or less, and 50% It is particularly preferred that
The height of the member B (code 43) (for example, the length in the Z-axis direction of the member B (code 43) in FIG. 4B1) is not particularly limited, but the height of the member B (code 43) Is preferably 1 to 50 mm, and more preferably 5 to 20 mm.
FIG. 6 shows a schematic view of the substrate A and the member B. D in FIG. 6 represents the length of the member B in the x-axis direction in FIG. 4 (B2). W in FIG. 6 represents the length of the member B in the y-axis direction in FIG. 4 (B2). H in FIG. 6 represents the length of the member B in the z-axis direction in FIG. 4 (B1). In the member B shown in FIG. 6, h / d is preferably 0.01 to 10, and more preferably 0.1 to 5 from the viewpoint of preventing falling. The w / d is preferably 1 to 1000, more preferably 5 to 100, from the viewpoint of widening the region in which crystals can be produced.

(Deposition method)
In the method for producing an organic semiconductor film of the present invention, the substrate may be heated or cooled at the time of film formation, and it is possible to control the film quality and the packing of molecules in the film by changing the temperature of the substrate. is there. The temperature of the substrate is not particularly limited, but is preferably between 0 ° C. and 200 ° C., more preferably between 15 ° C. and 100 ° C., particularly preferably between 20 ° C. and 95 ° C. preferable.
When the compound of the present invention is formed on a substrate, it is formed by a solution process.

  Here, film formation by solution process refers to a method of dissolving in a solvent in which an organic compound can be dissolved and forming a film using the solution. Specifically, ordinary methods such as various printing methods such as a drop casting method, an inkjet method, a screen printing method, a gravure printing method, a flexographic printing method, an offset printing method, a microcontact printing method can be used. It is preferable to use a casting method, an inkjet method, a gravure printing method, a flexographic printing method, an offset printing method, a microcontact printing method, and it is more preferable to use a flexographic printing method, a microcontact printing method, an inkjet method.

In the method of manufacturing an organic semiconductor film of the present invention, the coating liquid is dropped on a part of the surface of the substrate A so as to be in contact with both the substrate A and the member B.
When dropping the coating solution, drop the coating solution one drop or drop two drops or more when dropping two or more drops, a portion with a thin film thickness of the coating solution tends to occur on the substrate A, and from the end of the coating solution It is preferable because drying is easy to proceed.
When the coating solution is dropped, the volume of one droplet of the coating solution is preferably 0.01 to 0.2 ml, and more preferably 0.02 to 0.1 ml.
By dropping the coating solution on a part of the surface of the substrate A so as to be in contact with both the substrate A and the member B, the film thickness at the end of the coating solution can be reduced.
The contact angle of the coating solution to the substrate A is preferably 0 to 90 °, and more preferably 10 to 80 °.
It is preferable that the coating liquid and the member B form a meniscus, and it is more preferable from the viewpoint of film quality that a concave meniscus is formed.

  Generally, in order to form a film by a solution process, it is necessary for the material to be dissolved in the above-mentioned solvents and the like, but it is not enough to simply dissolve it. In general, even materials formed into a film by a vacuum process can be dissolved to some extent in a solvent. However, in the solution process, the material is dissolved in a solvent and applied, and then the solvent is evaporated to form a film, and many materials unsuitable for solution process film formation have high crystallinity. It has been conventionally thought that it is inappropriate to crystallize (aggregate) in the process and it is difficult to form a good film. On the other hand, according to the method for producing an organic semiconductor film of the present invention, an organic semiconductor film can be formed while depositing crystals.

(Dried)
In the method for producing an organic semiconductor film of the present invention, crystals of the compound of the present invention or the compound represented by the general formula (2) are precipitated by gradually drying the dropped coating solution to form a semiconductor active layer. Do.
It is preferable from the viewpoint of film quality to dry under reduced pressure after natural drying on the heated substrate A.
It is preferable that it is 20-100 degreeC, and, as for the temperature of the board | substrate A at the time of natural drying, it is more preferable that it is 50-80 degreeC.
The natural drying time is preferably 0.5 to 20 hours, and more preferably 1 to 10 hours.
It is preferable that it is 20-100 degreeC, and, as for the temperature at the time of vacuum-drying, it is more preferable that it is 40-80 degreeC.
The reduced pressure drying time is preferably 1 to 20 hours, and more preferably 2 to 10 hours.
The pressure at the time of reduced pressure drying is preferably 10 ⁻⁶ to 10 ⁻² Pa, and more preferably 10 ⁻⁵ to 10 ⁻³ Pa.
In the method for producing an organic semiconductor film of the present invention, crystals of the compound of the present invention or the compound represented by the general formula (2) are precipitated. Whether or not crystals are precipitated can be confirmed by observation with a polarizing microscope.

[Organic semiconductor materials for non-luminescent organic semiconductor devices]
The invention also relates to an organic semiconductor material for non-luminescent organic semiconductor devices comprising a compound of the invention.

(Non-luminescent organic semiconductor device)
In the present specification, “non-luminescent organic semiconductor device” means a device that is not intended to emit light. In particular, "non-luminescent organic semiconductor device" means a device that is not intended to emit visible light. The non-luminescent organic semiconductor device is preferably a non-luminescent organic semiconductor device using an electronic element having a layer structure of a film. Non-luminescent organic semiconductor devices include organic transistors, organic photoelectric conversion devices (solid-state imaging devices for light sensors, solar cells for energy conversion applications, etc.), gas sensors, organic rectifying devices, organic inverters, information recording devices, etc. Ru. The organic photoelectric conversion element can be used in any of light sensor application (solid-state imaging element) and energy conversion application (solar cell). Preferably, they are an organic photoelectric conversion element and an organic transistor, More preferably, they are an organic transistor. That is, as described above, the organic semiconductor material for a non-luminescent organic semiconductor device of the present invention is preferably a material for an organic transistor.

(Organic semiconductor material)
As used herein, "organic semiconductor material" refers to an organic material that exhibits the characteristics of a semiconductor. Similar to semiconductors made of inorganic materials, there are p-type (hole transporting) organic semiconductor materials conducting holes as carriers and n-type (electron transporting) organic semiconductor materials conducting electrons as carriers.
The compound of the present invention may be used as either a p-type organic semiconductor material or an n-type organic semiconductor material, but is more preferably used as a p-type. The flowability of carriers in the organic semiconductor is represented by carrier mobility μ. The carrier mobility μ is preferably high and is preferably 1 × 10 ⁻² cm ² / Vs or more, more preferably 1 × 10 ⁻¹ cm ² / Vs or more, and 3 × 10 ⁻¹ cm ² It is particularly preferable to be / Vs or more, more preferably 5 × 10 ⁻¹ cm ² / Vs or more, and even more preferably 1 cm ² / Vs or more. The carrier mobility μ can be obtained by characteristics when a field effect transistor (FET) element is manufactured or by a time-of-flight (TOF) method.

[Organic semiconductor film for non-luminescent organic semiconductor device]
It is preferable that the 1st aspect of the organic-semiconductor film for nonluminous organic-semiconductor devices of this invention contains the compound and polymer binder which are represented by following General formula (2).
General formula (2)
In the general formula (2), R ¹¹ and R ¹² each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an alkoxy group, and may have a substituent, and in the general formula (2) The aromatic moiety may be substituted with a halogen atom.
The second aspect of the organic semiconductor film for a non-luminescent organic semiconductor device of the present invention contains the compound of the present invention.
The organic semiconductor film for a non-luminescent organic semiconductor device of the present invention is preferably produced by the method for producing an organic semiconductor film of the present invention.

(material)
The present invention also relates to a first embodiment of an organic semiconductor film for a non-luminescent organic semiconductor device, which comprises a compound represented by the following general formula (2) and a polymer binder.
The present invention also relates to a second embodiment of the organic semiconductor film for non-luminescent organic semiconductor devices containing the compound of the present invention.
The second aspect of the organic semiconductor film for non-luminescent organic semiconductor devices of the present invention preferably contains the compound of the present invention and does not contain a polymer binder.
The second aspect of the organic semiconductor film for non-luminescent organic semiconductor devices of the present invention may contain the compound of the present invention and a polymer binder.

As the polymer binder, polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyimide, polyurethane, polysiloxane, polysulfone, polysulfone, polymethyl methacrylate, polymethyl acrylate, cellulose, polyethylene, polypropylene, and other insulating polymers, and their coweights Combined, 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, methyl phenyl silicone resin, methyl phenyl vinyl silicone resin, methyl vinyl silico Resin, fluorosilicone resin, acrylic rubber, ethylene acrylic rubber, chlorosulfonated polyethylene, chloropolyethylene, epichlorohydrin copolymer, polyisoprene-natural rubber copolymer, polyisoprene rubber, styrene-isoprene block copolymer Rubbers or thermoplastic elastomers such as polyester urethane copolymer, polyether urethane copolymer, polyether ester thermoplastic elastomer and polybutadiene rubber, photoconductive polymers such as polyvinyl carbazole and polysilane, polythiophene, polypyrrole, polyaniline, polypara, Conducting polymers such as phenylene vinylene, and, for example, Chemistry of Materials, 2014, 26, 647. The semiconductive polymer as described in etc. can be mentioned.
The polymer binders may be used alone or in combination of two or more.
The organic semiconductor material and the polymer binder may be uniformly mixed, or part or all of them may be phase separated, but from the viewpoint of charge mobility, the organic semiconductor in the film thickness direction in the film The structure in which the binder is phase separated is most preferable without the binder interfering with the charge transfer of the organic semiconductor.
Although a polymer binder having a high glass transition temperature is preferred in consideration of the mechanical strength of the film, a polymer binder having a low glass transition temperature is preferred for the purpose of imparting flexibility to the film. In consideration of charge mobility, polymer binders and semiconductive polymers having a structure free of polar groups are preferred.
The amount of the polymer binder used is not particularly limited, but it is preferably used in the range of 0 to 95% by mass, more preferably 10 to 90% by mass in the organic semiconductor film for non-luminescent organic semiconductor devices of the present invention. It is preferably used in the range of 20 to 80% by mass, particularly preferably in the range of 30 to 70% by mass.

Furthermore, in the present invention, when the compound of the present invention or the compound represented by the general formula (2) has the above-described structure, an organic film with good film quality can be obtained. Specifically, since the compound of the present invention or the compound represented by the general formula (2) has good crystallinity, a sufficient film thickness can be obtained, and the obtained non-luminescent organic compound of the present invention The organic semiconductor film for semiconductor devices is of good quality.
Furthermore, the organic semiconductor film for a non-luminescent organic semiconductor device of the present invention, when manufactured by the method for manufacturing an organic semiconductor film of the present invention, becomes an organic film with good film quality.

  The features of the present invention will be more specifically described below with reference to examples and comparative examples. The materials, amounts used, proportions, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as limited by the specific examples shown below.

Example 1
The compounds listed in Table 1 or Table 2 were synthesized.

<Synthesis method>
The compound 1 of the following structure used for the organic transistor of this invention was synthesize | combined according to the synthesis method shown below.

(Synthesis of Intermediate 1)
After adding 23.1 ml of tetrahydrofuran to 3.93 ml of tetramethylpiperidine (TMP) and stirring at -78 ° C, 13.8 ml of n-butyllithium (1.6 M solution in hexane) was added and then the temperature was raised to 0 ° C. Stir for time to prepare a lithium reagent.
J. Org. Chem. Tetrahydro [3,2-f: 4,5-f '] bis [1] benzothiophene, which is a known material synthesized according to the synthesis method described in 2005, 70, 4502, to tetrahydrofuran (2.969 g (10 mmol)) 100 ml was added and it stirred at -78 degreeC, and said lithium reagent was dripped at -78 degreeC using the cannula. The reaction solution was cooled to -98 ° C after 2 hours, and a solution of 9.76 g (30 mmol) of dibromodichloroethane dissolved in 30 ml of tetrahydrofuran was added dropwise using a cannula. Thereafter, the reaction solution was gradually warmed from -98 ° C to room temperature and stirred for 15 hours. The reaction solution was cooled to 0 ° C., water was added, and the precipitate was filtered off. The filtered off solid was recrystallized with 1,1,2,2-tetrachloroethane to obtain 3.95 g (8.70 mmol) of the target compound (Intermediate 1) as a pale orange solid. The obtained compound was identified by ¹ H-NMR (Nuclear Magnetic Resonance).
(Tetrachloroethane-d ₂ , 400 MHz) δ: 7.46 (2H, s), 8.12 (2H, s), 8.45 (2H, s)

(Synthesis of Compound 1)
4.8 ml (4.80 mmol) of decylmagnesium bromide (1.0 mol / L solution in diethyl ether) was added, and it was cooled to 0 ° C. and 4.8 ml (1.0 mol / L solution of tetrahydrofuran) in zinc chloride (II) 4.80 mmol) was added dropwise to prepare an organozinc reagent. The above organozinc reagent was added to a system in which 545 mg (1.20 mmol) of Intermediate 1, 49 mg (0.06 mmol) of [1,1′-bis (diphenylphosphino) ferrocene] dichloropalladium (II), and 12 ml of toluene were added. The mixture was added and stirred at room temperature for 20 minutes, then heated to 70 ° C. and stirred for 15 hours. After completion of the reaction, the reaction solution was cooled to room temperature, 50 ml of methanol was added, and the precipitated solid was separated by filtration. The solid was dissolved in heated O-dichlorobenzene and passed hot through celite and silica gel, eluting with heated O-dichlorobenzene. The solution was concentrated by an evaporator and then recrystallized from heated O-dichlorobenzene to obtain 440 mg (0.763 mmol) of the target compound 1 as a white solid.
The structure of compound 1 was identified by ¹ H-NMR. The results are shown below.
¹ H-NMR
(Tetrachloroethane-d ₂ , 400 MHz) δ: 0.82 (6 H, t, J = 7.2 Hz), 1.21 to 1.37 (28 H, m), 1.71 (4 H, quin, J = 7.4 Hz), 2.88 (4H, t, J = 7.6 Hz), 7.09 (2H, s), 8.11 (2H, s), 8.39 (2H, s)

Synthesis of Compound 4 (Synthesis Method and NMR)
Compound 4 was synthesized in the same manner as Compound 1 except that decylmagnesium bromide (1.0 M solution in diethyl ether) was changed to butylmagnesium chloride (1.0 M solution in tetrahydrofuran).
The structure of compound 4 was identified by ¹ H-NMR. The results are shown below.
¹ H-NMR
(CDCl ₃ , 400 MHz) δ: 0.98 (6 H, t, 7.2 Hz), 1.41-1.50 (4 H, m), 1.72-1.81 (4 H, m), 2.94 (4H, t, 7.0 Hz), 7.13 (2H, s), 8.15 (2H, s), 8.44 (2H, s) ppm.

Synthesis of Compound 5 Compound 5 was synthesized in the same manner as Compound 1 except that decylmagnesium bromide (1.0 M solution in diethyl ether) was changed to pentylmagnesium bromide (1.0 M solution in tetrahydrofuran).
The structure of compound 5 was identified by ¹ H-NMR. The results are shown below.
¹ H-NMR
(CDCl ₃ , 400 MHz) δ: 0.93 (6 H, t, 7.3 Hz), 1.37-1.55 (8 H, m), 1.75-1.83 (4 H, m), 2.94 (T, 7.0 Hz), 7.13 (2H, s), 8.15 (2H, s), 8.44 (2H, s) ppm.

Compound 6 was synthesized according to Tetrahedron 66 (2010) 8778-8784.
Compound 6

Synthesis of Compound 11 Compound 11 was synthesized in the same manner as Compound 1 except that decylmagnesium bromide (1.0 M solution in diethyl ether) was changed to 6-methyloctyl bromide (1.0 M solution in tetrahydrofuran).
The structure of compound 11 was identified by ¹ H-NMR. The results are shown below.
¹ H-NMR
(CDCl ₃ , 400 MHz) δ: 0.84 to 0.88 (12 H, m), 1.08 to 1.17 (4 H, m), 1.30 to 1.44 (14 H, m), 1.75 -1.83 (4H, m), 2.94 (4H, t, 7.1 Hz), 7.13 (2H, s), 8.15 (2H, s), 8.44 (2H, s) ppm .

Synthesis of Compound 18 (Synthesis Method and NMR)
Synthetic intermediate 1 (300 mg, 0.66 mmol), 2- (2-butoxyethyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (452 mg, 1.98 mmol), tris (di Benzylideneacetone) dipalladium (0) (Pd ₂ (dba) ₃ ) (30 mg, 0.033 mmol), 2-dicyclohexylphosphino-2 ′, 6′-diisopropoxybiphenyl (RuPhos) (61 mg, 0.132 mmol) , T-Butoxy sodium (381 mg, 4.00 mmol), 7 mL of toluene and 7 mL of pure water were mixed, and stirred at 80 ° C. for 2.5 hours. The reaction solution was cooled to room temperature, and separated using chloroform and pure water. The organic layer is concentrated by distillation under reduced pressure and then purified by column chromatography (silica gel, hexane: ethyl acetate = 3: 1, hexane: ethyl acetate = 2: 1, hexane: ethyl acetate = 1: 1, sequentially developed), 140 mg (0.282 mmol) of compound 18 as a white solid was obtained.
The obtained compound was identified by ¹ H-NMR.
¹ H-NMR
(CDCl ₃ , 400 MHz) δ: 0.94 (6 H, t, 7.3 Hz), 1.36 to 1.46 (4 H, m), 1.58 to 1.65 (4 H, m), 3.20 (4H, t, 7.1 Hz), 3.51 (4H, t, 7.0 Hz), 3.51 (4 H, t, 7.0 Hz), 3.77 (4 H, t, 7.2 Hz), 7 20 (2H, s), 8.15 (2H, s), 8.46 (2H, s) ppm.

Synthesis of Compound 20 Compound 20 was synthesized in the same manner as Compound 1 except that decylmagnesium bromide (1.0 M solution in diethyl ether) was changed to 4-butoxybutylmagnesium bromide (1.0 M solution in THF).
The structure of compound 20 was identified by ¹ H-NMR. The results are shown below.
¹ H-NMR
(CDCl ₃ , 400 MHz) δ: 0.93 (6 H, t, 7.4 Hz), 1.34-1.43 (4 H, m), 1.53-1.60 (4 H, m), 1.68 -1.75 (4H, m), 1.83-1.91 (4H, m), 2.97 (4H, t, 7.3 Hz), 3.42 (4 H, t, 7.0 Hz), 3 .47 (4 H, t, 7.0 Hz) ppm.

Synthesis of Compound 29
(Synthesis of Intermediate 2)
Intermediate 2 was synthesized in the same manner as in the synthesis of Intermediate 1, except that the amounts of tetramethylpiperidine (TMP), n-butyllithium and dibromodichloroethane were all reduced to half.
(Synthesis of Intermediate 3)
Intermediate in the same manner as in the synthesis of compound 4 except that intermediate 1 is changed to intermediate 2 and the equivalents of organozinc reagent and [1,1′-bis (diphenylphosphino) ferrocene] dichloropalladium (II) are halved Body 3 was synthesized.
(Synthesis of Intermediate 4)
Intermediate 4 was synthesized in the same manner as in the synthesis of Intermediate 2, except that Intermediate 3 was used instead of thieno [3,2-f: 4,5-f ′] bis [1] benzothiophene.
Compound in the same manner as in the synthesis of compound 5 except that intermediate 1 is changed to intermediate 3 and the equivalents of organozinc reagent and [1,1'-bis (diphenylphosphino) ferrocene] dichloropalladium (II) are halved 29 was synthesized.
The structure of compound 29 was identified by ¹ H-NMR. The results are shown below.
¹ H-NMR
(CDCl ₃ , 400 MHz) δ: 0.92 (3 H, t, 7.2 Hz), 0.98 (3 H, t, 7.2 Hz), 1.38 to 1.52 (6 H, m), 1.73 -1.82 (4H, m), 2.92-2.97 (4H, m), 7.13 (2H, s), 8.15 (2H, s), 8.44 (2H, s) ppm .

[Synthesis of Comparative Compound]
The comparative compound 1 of the following structure is described in J.I. Org. Chem. It synthesize | combined according to the synthesis method described in 2005, 70, 4502.

The following comparative compounds 2 to 6 were synthesized with reference to JP2013-235903A, CN102206225A, WO2011 / 126225A, JP2009-302463 PR, and JP2010-177642 PR, respectively. As a result of GPC (Gel Permeation Chromatography) measurement for Comparative Compounds 2 and 3, the weight-average molecular weight Mw (weight-average molecular weight) was 40000.

[Examples 1-1 to 1-8 and comparison elements 1-1 to 1-4]
<Device production and evaluation>
It was confirmed by high performance liquid chromatography that the material (the ratio of the absorption intensity area at 254 nm) of the material used for device preparation is 99.0% or more.

The semiconductor active layer (organic semiconductor film) was formed of the compound alone.
A 0.1 mass% solution in which any of the compounds described in the following table or the comparative compounds 1 to 4 is dissolved in anisole as a solvent is prepared and heated to 50 ° C. to obtain a coating solution for organic semiconductor devices (coating solution Say).

In the devices 1-1 to 1-8 and the comparison devices 1-1 to 1-4, the formation of the organic semiconductor film was performed by the method described in FIG. Note that 1-1 to 1-8 have the same meaning as 1-1, 1-2, 1-3, 1-4, 1-5, 1-6, 1-7, 1-8, and the branch numbers It is the same as when it represents using "-". Details are shown below.
As a substrate A, a 25 mm × 25 mm substrate was used in which a thermal oxide film 200 nm of SiO ₂ was formed on the surface of an n-type silicon substrate (0.4 mm thickness). The surface of the thermally oxidized film of the substrate A was subjected to UV-ozone cleaning and then subjected to β-phenytritrimethoxysilane treatment.

  The substrate A and the member B were placed in contact with each other at the central portion of the substrate A, as shown in FIG. 4A, on the β-phenylitylmethoxysilane-treated surface of the substrate A. The member B is made of glass and is 10 mm long × 2 mm wide × 5 mm high, and the horizontal direction (X-axis direction) in FIG. 4A is the horizontal direction of the member B, and the upper and lower sides in FIG. The direction (Z-axis direction) is the height direction of the member B, and the vertical direction (Y-axis direction) in FIG. 4 (B2) is the vertical direction of the member B.

The substrate is heated to 50 ° C., and one drop (about 0.05 ml) of the coating solution prepared by the above method is brought into contact with both the substrate A and the member B as shown in FIG. As shown in FIG. 4 (B1) and FIG. 4 (B2), the coating liquid was dropped on a part of the surface of the substrate A when dropped from the side of the member B. At the interface with the member B, a concave meniscus was formed.
As shown in FIG. 4C, while maintaining the state in which the substrate A and the member B were in contact with each other, the coating liquid was naturally dried while the positional relationship between the substrate A and the member B was kept still. Thereafter, the crystals of a compound described in the following table or any of the comparative compounds 1 to 4 were deposited by drying under reduced pressure at a pressure of 10 ^-3 MPa at 60 ° C. for 8 hours to form an organic semiconductor film. It was confirmed by observation with a polarization microscope whether or not crystals were precipitated.

  Bottom gate / top contact type organic transistor for FET characteristic measurement by depositing F4-TCNQ 1 nm and gold electrode 40 nm respectively as charge injection acceptors using the obtained organic semiconductor film as semiconductor active layer The element was obtained. The obtained organic transistor elements were referred to as elements 1-1 to 1-4 and comparative elements 1-1 to 1-4. The elements 1-1 to 1-8 and the comparison elements 1-1 to 1-4 were the organic transistor elements of the examples 1-1 to 1-8 and the comparative examples 1 to 4, respectively.

<Evaluation>
The FET characteristic of the organic transistor element of the elements 1-1 to 1-8 and the comparison elements 1-1 to 1-4 is a semiconductor parameter analyzer (Agilent, 4156C) connected with a semi-auto prober (manufactured by Vector Semicon, AX-2000) It evaluated under normal pressure and the atmosphere using.
The obtained results are shown in Table 3 below.

The source electrode of the (a) carrier mobility the organic transistor device (FET element) - between the drain electrode by applying a voltage of -80 V, by varying the gate voltage in the range of 20V-100 V, equation representing the drain current I _d I _d = (w / 2 L) μC _i (V _g −V _th ) ² (where, L is a gate length, W is a gate width, C _i is a capacity per unit area of an insulating layer, V _g is a gate voltage, Carrier mobility μ was calculated using _{Vth as} a threshold voltage.

From Table 3 above, it was found that the organic transistor devices of the devices 1-1 to 1-8 of the present invention have high carrier mobility and are preferably used as an organic semiconductor material.
On the other hand, it turned out that the carrier mobility is low in the organic transistor element of Comparative elements 1-1 to 1-4 using Comparative compounds 1 to 4 as the organic semiconductor material in the semiconductor active layer.

[Examples 2-1 to 2-14 and Comparative Examples 2-1 to 2-3]
In Example 2-1 to 2-14 and Comparative Example 2-1 to 2-3, a bottom gate / bottom contact type organic transistor element was manufactured. Details are shown below.
A 0.1% by mass anisole solution of Compound 1 heated to 100 ° C. is used as a coating solution for an organic semiconductor device and cast on a substrate for measuring FET characteristics heated to 90 ° C. in a nitrogen atmosphere, thereby producing a non-luminescent organic compound. The transistor element 2-1 was obtained. The bottom of the FET characteristic measurement substrate is provided with chromium / gold (gate width W = 100 mm, gate length L = 100 μm) disposed in a comb shape as source and drain electrodes, and SiO ₂ (film thickness 200 nm) as an insulating film A silicon substrate with a gate-bottom contact structure was used. The obtained organic transistor element is referred to as element 2-1. The element 2-1 was an organic transistor element of Example 2-1.
In the preparation of the organic transistor element of the element 2-1, an element 2-2 and an element 2-2 were prepared in the same manner as the element 2-1 except that either a compound described in Table 2 or a comparison compound was used instead of the compound 1. The comparative elements 2-1 to 2-3 were manufactured. Element 2-6 is a mixture of Compound 4 and Compound 5 so as to have a concentration of 0.05% by mass.

<Evaluation>
The FET characteristics of the organic transistor elements of the elements 2-2 to 2-14 and the comparison elements 2-1 to 2-3 were evaluated in the same manner as in Example 1-1. The results are shown in Table 4 below.

From Table 4 above, it was found that the organic transistor devices of the devices 2-2 to 2-14 of the present invention have high carrier mobility and are preferably used as an organic semiconductor material.
On the other hand, it was found that the organic transistor elements of Comparative Elements 2-1 to 2-3 using Comparative Compounds 1, 2 and 6 as the organic semiconductor material in the semiconductor active layer had low carrier mobility.

[Examples 3-1 to 3-29 and Comparative Examples 3-1 to 3-5]
On a glass substrate (Eagle XG: manufactured by Corning), Al serving as a gate electrode was vapor-deposited (thickness: 50 nm). A composition for forming a gate insulating film (polyvinylphenol / melamine = 1 part by mass / 1 part by mass of PGMEA (propylene glycol monomethyl ether acetate) solution (solid content concentration: 2% by mass)) is spin-coated thereon, and 150 ° C. Baking for 60 minutes to form a gate insulating film with a thickness of 400 nm. Furthermore, silver ink (H-1, manufactured by Mitsubishi Materials Corporation) is formed into a source electrode and a drain electrode (channel length 40 μm, channel width 200 μm) using an inkjet device DMP-2831 (manufactured by Fujifilm Daimatics Co., Ltd.) I drew it. After that, baking is performed at 180 ° C. for 30 minutes in an oven and sintering is performed to form a source electrode and a drain electrode, whereby an element substrate for TFT (Thin Film Transistor) characteristic evaluation is obtained.
The coating solutions for organic semiconductor devices listed in Table 5 below (organic semiconductor material (0.50 mass%), polymer (0.025 mass%) and toluene) were drop-cast on the element substrate for TFT characteristic evaluation. Thereafter, the resultant was dried on a hot plate at 100 ° C. for 10 minutes to form an organic semiconductor layer, to obtain a bottom gate / bottom contact type organic transistor element. The obtained organic transistor element was made into the element 3-1 to 3-29 and the comparison element 3-1 to 3-5. The elements 3-1 to 3-29 and the comparison elements 3-1 to 3-5 were used as the organic transistor elements of the examples 3-1 to 3-29 and the comparison elements 3-1 to 3-5. In the following table, F8T2 is [Poly [(9,9-dioctyl-9H-fluorene-2,7-diyl) -alt-2,2'-bithiophene] -5,5'-diyl]] (Aldrich , Mn> 20000), PMMA is Poly methyl methacrylate (Aldrich, Mw ~ 15000), Pα MS is Poly (α-methylstyrene) (Aldrich, Mw = 43700), PS is Polystyrene (Aldrich, Mw = 2000000) Represents

<Evaluation>
The FET characteristics of the organic transistor elements of the elements 3-1 to 3-29 and the comparison elements 3-1 to 3-5 were evaluated in the same manner as in Example 1. The results are shown in Table 5 below.

From Table 4 above, it was found that the organic transistor devices of the devices 3-1 to 3-29 of the present invention have high carrier mobility and are preferably used as an organic semiconductor material.
On the other hand, it turned out that the carrier mobility is low in the organic transistor element of Comparative elements 3-1 to 3-5 using Comparative compounds 1, 2 and 4 as organic semiconductor materials in the semiconductor active layer.

[Examples 4-2 to 4-4 and 4-6 to 4-8]
<Example of TFT element production by printing method>
-Inkjet method-
By coating the coating liquid for organic semiconductor device (organic semiconductor compound described in Table 6, polymer (binder), solvent, concentration) on the element substrate for TFT characteristics evaluation manufactured in Example 3-1 by the inkjet method An organic semiconductor film was formed to obtain an organic transistor element. A solid film was formed with an ejection frequency of 2 Hz and a dot pitch of 20 μm using a DPP 2831 (manufactured by Fuji Film Graphic Systems Co., Ltd.) and a 10 pL head as an inkjet apparatus. Then, the organic semiconductor layer was produced by drying at 70 degreeC for 1 hour.

-Flexo printing method-
Example 3-A coating liquid for an organic semiconductor device (the organic semiconductor compound described in Table 6, a polymer (binder), a solvent, a concentration, and BYK-323 (manufactured by BYK) 0.05% by mass as a surfactant) An organic semiconductor film was formed by coating on the TFT characteristic evaluation element substrate manufactured in 1 by flexo printing to obtain an organic transistor element. AFP DSH 1.70% (Asahi Kasei Co., Ltd.) / Solid image was used as a flexo resin plate, using a flexo aptitude testing machine F1 (manufactured by IDC Testing Systems Co., Ltd.) as a printing apparatus. The pressure between the flexo resin plate and the element substrate for TFT characteristic evaluation is 60 N, printing is performed at a conveyance speed of 0.4 m / sec, and then, the organic semiconductor layer is directly dried at 40 ° C. and room temperature for 2 hours. To obtain a bottom gate / bottom contact type organic transistor device. The obtained organic transistor element was made into the element 4-2 to 4-4 and 4-6 to 4-8. Elements 4-2 to 4-4 and 4-6 to 4-8 were the organic transistor elements of Examples 4-2 to 4-4 and 4-6 to 4-8. The viscosity of each of the elements 4-6 to 4-8 used as the ink was 10 mPa · s or more.

  As described above, according to Table 6, when the film was formed by the inkjet method or the flexographic printing method, the carrier mobility was high, and an organic transistor element having favorable characteristics which can be preferably used as an organic semiconductor material was obtained.

11 substrate 12 electrode 13 insulator layer 14 semiconductor active layer (organic layer, organic semiconductor layer)
15a, 15b Electrode 31 Substrate 32 Electrode 33 Insulator Layer 34a, 34b Electrode 35 Semiconductor Active Layer (Organic Layer, Organic Semiconductor Layer)
41 coating solution 42 substrate A
43 member B

Claims (18)

An organic transistor containing a compound represented by the following general formula (2) in a semiconductor active layer;
General formula (2)
In the above general formula (2), R ¹¹ and R ¹² each independently represent an alkenyl group, an alkynyl group or an alkoxy group having 3 to 13 carbon atoms in total which may have a substituent , or
The compound represented by the general formula (2) satisfies the following condition A, condition B, condition C or condition D:
The aromatic moiety in the general formula (2) may be substituted with a halogen atom ;
Condition A: in the general formula (2), R ¹¹ and R ¹² each independently have 3 to 30 carbon atoms in total, and
Unsubstituted linear alkyl group having 8 to 10 carbon atoms and an even number of carbon atoms,
Unsubstituted linear alkyl group having 3 to 15 carbon atoms and an odd number of carbon atoms,
Substituted linear alkyl group having 3 to 15 carbon atoms or
Substituted or unsubstituted branched alkyl group having 3 to 18 carbon atoms
Represents
Condition B: In the general formula (2), R ¹¹ and R ¹² each independently have 2 to 30 carbon atoms in total, and have 2 to 4 carbon atoms, and an even number of carbon atoms which are unsubstituted linear alkyl Represents a group;
Condition C: in the general formula (2),
And R ¹¹ and R ¹² each independently have 3 to 30 carbon atoms in total, and
A substituted alkyl group having 1 or 2 carbon atoms;
Condition D: in the general formula (2), R ¹¹ and R ¹² each independently have 3 to 30 carbon atoms in total, and R ¹¹ and R ¹² have different structures from each other;
However, when the alkyl group, the alkenyl group, the alkynyl group or the alkoxy group represented by R ¹¹ and R ¹² further has a substituent, this substituent is a halogen atom, an aryl group, an alkoxy group, an acyloxy group or an alkyloxycarbonyl group . The organic transistor according to claim 1, wherein the compound represented by the general formula (2) is represented by any one of the following structural formulas.
The organic transistor according to claim 1, wherein R ¹¹ and R ¹² are each independently an alkyl group having 3 to 30 carbon atoms in total, and R ¹¹ and R ¹² have different structures .
However, when the alkyl group represented by R ¹¹ and R ¹² further has a substituent, this substituent is a halogen atom, an aryl group, an alkoxy group, an acyloxy group or an alkyloxycarbonyl group . The organic transistor according to claim 1, wherein each of R ¹¹ and R ¹² independently represents a C3-C18 unsubstituted branched alkyl group. Each of R ¹¹ and R ¹² independently represents a substituted alkyl group having 1 or 2 carbon atoms,
Substituted linear alkyl group having 3 to 15 carbon atoms,
A substituted branched alkyl group having 3 to 18 carbon atoms, or
The organic transistor according to claim 1, which represents an alkenyl group having 3 to 13 carbon atoms in total ;
However, when the alkyl group or alkenyl group represented by R ¹¹ and R ¹² further has a substituent, this substituent is a halogen atom, an aryl group, an alkoxy group, an acyloxy group or an alkyloxycarbonyl group . A compound represented by the following general formula (2),
R ¹¹ and R ¹² below are each independently an alkenyl group, an alkynyl group or an alkoxy group having 3 to 13 carbon atoms which may have a substituent, or
A compound wherein the compound represented by the general formula (2) satisfies the following condition A, condition B, condition C or condition D;
General formula (2)
The aromatic moiety in the general formula (2) may be substituted with a halogen atom;
Condition A: in the general formula (2), R ¹¹ and R ¹² each independently have 3 to 30 carbon atoms in total, and
Unsubstituted linear alkyl group having 8 to 10 carbon atoms and an even number of carbon atoms,
Unsubstituted linear alkyl group having 3 to 15 carbon atoms and an odd number of carbon atoms,
A substituted linear alkyl group having 3 to 15 carbon atoms or a substituted or unsubstituted branched alkyl group having 3 to 18 carbon atoms;
Condition B: In the general formula (2), R ¹¹ and R ¹² each independently have 2 to 30 carbon atoms in total, and have 2 to 4 carbon atoms, and an even number of carbon atoms which are unsubstituted linear alkyl Represents a group;
Condition C: in the general formula (2),
And R ¹¹ and R ¹² each independently have 3 to 30 carbon atoms in total, and
A substituted alkyl group having 1 or 2 carbon atoms;
Condition D: in the general formula (2), R ¹¹ and R ¹² each independently have 3 to 30 carbon atoms in total, and R ¹¹ and R ¹² have different structures from each other ;
However, when the alkyl group, the alkenyl group, the alkynyl group or the alkoxy group represented by R ¹¹ and R ¹² further has a substituent, this substituent is a halogen atom, an aryl group, an alkoxy group, an acyloxy group or an alkyloxycarbonyl group . The compound of Claim 6 represented by either of following Structural formula.
The compound according to claim 6 , wherein R ¹¹ and R ¹² are each independently an alkyl group having 3 to 30 carbon atoms in total, and R ¹¹ and R ¹² have different structures from each other ;
However, when the alkyl group represented by R ¹¹ and R ¹² further has a substituent, this substituent is a halogen atom, an aryl group, an alkoxy group, an acyloxy group or an alkyloxycarbonyl group . The compound of Claim 6 in which said R < ¹¹ > and R < ¹² > respectively independently represent a C3-C18 unsubstituted branched alkyl group. Each of R ¹¹ and R ¹² independently represents a substituted alkyl group having 1 or 2 carbon atoms,
Substituted linear alkyl group having 3 to 15 carbon atoms,
A substituted branched alkyl group having 3 to 18 carbon atoms, or
The compound according to claim 6 , which represents an alkenyl group having 3 to 13 carbon atoms in total ;
However, when the alkyl group or alkenyl group represented by R ¹¹ and R ¹² further has a substituent, this substituent is a halogen atom, an aryl group, an alkoxy group, an acyloxy group or an alkyloxycarbonyl group . Non-emissive organic semiconductor device for an organic semiconductor material containing the compound according to any one of claims 6-10. Organic transistor material containing a compound according to any one of claims 6-10. Non-emissive organic semiconductor devices for coating solution containing a compound according to any one of claims 6-10;
However, it excludes the case where the solvent whose boiling point is 100 ° C or more is included. An organic transistor comprising the compound according to any one of claims 6 to 10 in a semiconductor active layer. The manufacturing method of the organic transistor including the process of producing a semiconductor active layer by apply | coating the coating liquid for nonluminous organic semiconductor devices of Claim 13 on a board | substrate, and making it dry. A coating solution in which the compound according to any one of claims 6 to 10 is dissolved in a solvent,
The distance between the substrate A and the member B not fixed to the substrate A is maintained at a constant distance, or while the substrate A and the member B are kept in contact with each other.
Dripping on a part of the surface of the substrate A so as to be in contact with both the substrate A and the member B,
A method of manufacturing an organic semiconductor film, wherein a semiconductor active layer is formed by depositing crystals of the compound according to any one of claims 6 to 10 by gradually drying the dropped coating solution.
However, the application liquid is dropped or dried as long as the distance between the substrate A and the member B is maintained at a constant distance or the substrate A and the member B are kept in contact with each other. At the time, the positional relationship between the substrate A and the member B may be stationary or may be moved;
However, the case where the said coating liquid contains the solvent of boiling-point 100 degreeC or more is remove | excluded. A compound represented by the following general formula (2A);
General formula (2A)
R ¹¹ and R ¹² each independently represent a halogen atom,
The aromatic moiety in the general formula (2A) may be substituted with a halogen atom; An intermediate compound of a compound according to any one of claims 6-10, compound according to claim 17.