JP6573983B2 - Composition for forming organic semiconductor film, compound, organic semiconductor film, organic semiconductor element - Google Patents

Description

  The present invention relates to a composition for forming an organic semiconductor film, a compound, an organic semiconductor film, and an organic semiconductor element.

Since it is possible to reduce weight, cost, and flexibility, FET (field effect transistor), RFID (radio frequency identifier: RF tag), memory, etc. used for liquid crystal displays and organic EL (electroluminescence) displays An organic thin film transistor (organic TFT (thin film transistor)) having an organic semiconductor film (organic semiconductor layer) is used in a device using the above logic circuit.
It is known that a low molecular weight organic semiconductor compound is useful as a compound for forming such an organic semiconductor film.
For example, Patent Document 1 discloses a pentacene derivative (for example, TIPS pentacene (6,13-Bis (triisopropylsilylethynyl) pentacene)) as a low molecular organic semiconductor compound having excellent carrier mobility.

Special table 2007-519227

Incidentally, in recent years, there is a situation in which further improvement in the carrier mobility of the organic thin film transistor is required from the viewpoint of improving the performance of the organic thin film transistor.
Under these circumstances, the present inventors have further studied an organic thin film transistor using TIPS pentacene as an organic semiconductor compound as disclosed in the above-mentioned Patent Document 1. As a result, heating (annealing) performed after the formation of the transistor element is performed. Through the process, it has been found that the carrier mobility greatly decreases.

  This is because the organic thin film transistor using TIPS pentacene as an organic semiconductor compound has a tendency that the TIPS pentacene contained in the organic semiconductor film is easily oxidized by air in the heating (annealing) process, and has a crystal structure in the organic semiconductor film. It was considered that the conductive path was easily lost due to the change and cracking in the crystal. That is, it has been found that there is room for further improving the heat resistance of the organic semiconductor compound.

Therefore, an object of the present invention is to provide a composition for forming an organic semiconductor film and a compound capable of forming an organic semiconductor film having excellent heat resistance.
Another object of the present invention is to provide an organic semiconductor film having excellent heat resistance and an organic semiconductor element including the same.

As a result of intensive studies on the above problems, the present inventors have found that a desired effect can be obtained by using a compound represented by the formula (1) described later, and have reached the present invention.
That is, the present inventor has found that the above problem can be solved by the following configuration.

[1] A composition for forming an organic semiconductor film comprising a compound represented by the formula (1) described later.
[2] The composition for forming an organic semiconductor film according to [1], wherein the compound represented by the above formula (1) is a compound represented by the following formula (4).
[3] In the above formula (1), L is a group consisting of a carbon atom, a silicon atom, a sulfur atom, an oxygen atom, a nitrogen atom, a carbon atom-oxygen atom-carbon atom, an m-valent aliphatic hydrocarbon ring, m The composition for forming an organic semiconductor film according to [1], which represents a valent aromatic hydrocarbon ring or an m-valent heterocyclic ring.
[4] In the above formula (4), Y ^L is a carbon atom, silicon atom, sulfur atom, oxygen atom, nitrogen atom, carbon atom-oxygen atom-carbon atom group, divalent to octavalent aliphatic hydrocarbon The composition for forming an organic semiconductor film according to [2], which represents a ring, a divalent to octavalent aromatic hydrocarbon ring, or a divalent to octavalent heterocyclic ring.
[5] The formula (4), wherein Y ^L represents a group consisting of a carbon atom, a silicon atom, a sulfur atom, an oxygen atom, a nitrogen atom, or a carbon atom-oxygen atom-carbon atom. Composition for forming an organic semiconductor film.
[6] The composition for forming an organic semiconductor film according to [1] or [3], wherein in the formula (1), m is an integer of 3 or more.
[7] The composition for forming an organic semiconductor film according to [2], [4] or [5], wherein p is 3 to 8 in the above formula (4).
[8] The composition for forming an organic semiconductor film according to any one of [1] to [7], further comprising a solvent.
[9] The composition for forming an organic semiconductor film according to any one of [1] to [8], further comprising a polymer compound.
[10] The composition for forming an organic semiconductor film according to any one of [1] to [8], further comprising a conductive polymer compound.
[11] The composition for forming an organic semiconductor film according to [10], wherein the conductive polymer compound includes a polymer in which an electron donating unit and an electron accepting unit are combined.
[12] A compound represented by the following formula (1).
[13] An organic semiconductor film comprising the compound according to [12].
[14] An organic semiconductor element comprising the organic semiconductor film according to [13].

  Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.

  In this specification, about the display of a compound, it uses in the meaning containing the salt and its ion other than the compound itself.

In this specification, when there are a plurality of substituents or linking groups or the like (hereinafter referred to as substituents or the like) indicated by a specific symbol, or when a plurality of substituents or the like are defined simultaneously, Means the same or different. The same applies to the definition of the number of substituents and the like.
In addition, unless otherwise specified, when a plurality of substituents and the like are close (particularly adjacent), it means that they may be connected to each other or condensed to form a ring.
Furthermore, in the present specification, a substituent or the like that does not clearly indicate substitution / unsubstitution means that the group may further have a substituent as long as the intended effect is not impaired. This is also synonymous for compounds that do not specify substitution / non-substitution.

  In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

ADVANTAGE OF THE INVENTION According to this invention, the composition for organic-semiconductor film formation which enables formation of the organic-semiconductor film excellent in heat resistance, and a compound can be provided.
Moreover, according to this invention, the organic-semiconductor film excellent in heat resistance and the organic-semiconductor element containing the same can also be provided.

It is a cross-sectional schematic diagram of the bottom contact type organic thin-film transistor which concerns on one Embodiment of this invention. It is a cross-sectional schematic diagram of the top contact type organic thin-film transistor which concerns on one Embodiment of this invention.

[Composition for forming an organic semiconductor film]
The composition for forming an organic semiconductor film of the present invention is characterized by containing a compound represented by the formula (1) described later.
The compound represented by the above formula (1) is a linking group L and the geometric center, high multiple π conjugated via a linking group X ^A having at least an alkylene group (A-1) ~ (A -12) It has a dendritic structure. Due to this structure, the compound represented by the formula (1) is presumed to be hardly oxidized by air even under heating, that is, excellent in heat resistance. For this reason, the organic semiconductor film formed using the composition for forming an organic semiconductor film containing the compound represented by the formula (1) has a carrier mobility even after a heating (annealing) step after the formation of the transistor element. It is difficult to decrease and has excellent heat resistance.

In addition, the present inventors have also proposed a compound represented by the above formula (1) and another conductive polymer compound (particularly, a polymer combining an electron donating unit and an electron accepting unit (so-called “D- The organic semiconductor film prepared by mixing A (donor acceptor) type polymer)) is the original carrier mobility expressed by each of the conductive polymer compound and the compound represented by the formula (1). It came to discover that higher carrier mobility was expressed than.
The effect is considered to be due to the structure of the compound represented by the formula (1).
That is, the compound represented by the above formula (1) is higher network highly flexible, which is formed by a linking group X ^A and the linking group L, by the presence of the alkylene group contained in the linking group X ^A dissolution It has a gender, also arranged in a dendritic from a geometric center via a linking group X ^a linking group L (a-1) ~ ( a-12) structure, high density by [pi-[pi stacking The crystal structure is adjusted to take molecular packing. For this reason, the compound represented by the above formula (1) is compatible with other conductive polymer compounds in the organic semiconductor film and has a conductive path that compensates for defects of the conductive polymer compounds by its crystal structure. As a result, it is presumed that excellent carrier mobility is expressed.

Hereinafter, the composition for forming an organic semiconductor film of the present invention will be described in detail.
[Compound represented by Formula (1)]
The compound represented by the following formula (1) can be used as an organic semiconductor compound in an organic semiconductor element such as an organic thin film transistor.

In the formula (1), m represents an integer of 2 or more, L represents an m-valent organic group, X ^A represents a divalent linking group represented by the following formula (2), and A represents the following formula ( It represents a monovalent organic group represented by 3).

In Formula (2), # ¹ represents a bonding position to L, # ² represents a bonding position to A, Alk ¹ , Alk ² , and Alk ³ each independently represent an alkylene group, Q ¹ , And Q ³ each independently represent —O—, —S—, —NR ¹ —, —CO—, a vinylene group, an ethynylene group, or a divalent group formed by combining these, and Q ² is —O—, —S—, —NR ¹ —, —CO—, a vinylene group, an ethynylene group, an arylene group, a heteroarylene group, or a divalent group formed by a combination thereof, each R ¹ is independently Represents a hydrogen atom or a substituent, and j, k, l, s, t, and u each independently represent 0 or 1. However, at least one of j, k, and l is 1.

In the formula (3), # ² represents the bonding position to X ^A, Z represents an arylene group, or represents heteroarylene radical, a represents 0 or an integer of 1 or more, B is represented by the following formula ( A-1) represents any monovalent organic group selected from the group consisting of groups represented by formula (A-12).

In formula (A-1) to formula (A-12), X independently represents an O atom, S atom, Se atom or NR ^A1 , Y represents an O atom or S atom, and Z _a independently represents CR ^A2 or N atom; W independently represents C (R ^A2 ) ₂ , NR ^A1 , N atom, CR ^A2 , O atom, S atom or Se atom; and R ^A1 represents Each independently represents an alkyl group, an alkenyl group, an alkynyl group, or a bonding site with another structure, which may contain at least one of -O-, -S-, and -NR ^A3- ; R ^A2 each independently represents a hydrogen atom, a substituent, or a bonding site with another structure; R each independently represents a hydrogen atom or a substituent; and R ^A3 each independently represents a hydrogen Represents an atom or a substituent. However, the formula (A1) ~ formula (A-12) has at least one ^{R A1} or ^{R A2,} and the binding site of any one of the ^{R A1} or ^{R A2} is the other structure Represents. In addition, when R ^A1 represents an alkyl group, an alkenyl group, or an alkynyl group that may contain at least one of —O—, —S—, and —NR ^A3 —, the substituent is further substituted. You may have.

In the above formula (1), m represents an integer of 2 or more, and L represents an m-valent organic group. That is, L is an organic group capable of connecting m dendritic groups represented by-(X ^A -A).
The m-valent organic group represented by L refers to a group having the minimum number of atoms when m dendritic groups represented by-(X ^A -A) are linked.
m is not particularly limited as long as it is an integer of 2 or more, but is preferably an integer of 3 or more. The upper limit is not particularly limited, but is preferably an integer of 15 or less.
Especially, it is preferable that it is 2-10 from a soluble and crystalline viewpoint, 2-8 are more preferable, 3-8 are still more preferable, and it is still more preferable that it is 3-6.

L is, for example, a carbon atom, a silicon atom, a sulfur atom, an oxygen atom, a nitrogen atom, a group consisting of a carbon atom-oxygen atom-carbon atom, an m-valent aliphatic hydrocarbon ring, an m-valent aromatic hydrocarbon ring, Or it is preferable that it is a m-valent heterocyclic ring. In addition, "group consisting of carbon atom-oxygen atom-carbon atom" means a case where W in the general formula (Y14) described later is 1.
Among these, L is a carbon atom, a silicon atom, an oxygen atom, a nitrogen atom, or a carbon atom-oxygen atom from the viewpoint of obtaining higher heat resistance and higher carrier mobility when used in combination with a conductive polymer compound. -It is preferably represented by a group consisting of carbon atoms.

The aliphatic hydrocarbon ring preferably has 3 to 15 carbon atoms, more preferably 3 to 10 carbon atoms, and still more preferably 5 to 10 carbon atoms.
The aromatic hydrocarbon ring preferably has 6 to 18 carbon atoms, more preferably 6 to 14 carbon atoms, and still more preferably 6 to 10 carbon atoms.
The heterocyclic ring is preferably a 5- to 7-membered ring having at least one N atom, O atom, S atom, or Se atom in the ring structure, and more preferably a 5- to 6-membered ring.

  Moreover, it is preferable that the compound represented by General formula (1) is a compound represented by following formula (4).

In Formula (4), Y ^L represents a divalent to octavalent organic group, R ^L1 independently represents a monovalent organic group represented by the following Formula (5), and R ^L2 represents Independently, it represents a hydrogen atom or a substituent, p represents 2 to 8, q represents 0 to 6, and when Y ^L is n-valent, p + q represents n. In addition, n represents 2-8.

In formula (5), X ^A and A have the same meanings as X ^A and A in formula (1) described above, respectively, and the preferred embodiments are also the same.

In formula (4), R ^L2 represents a hydrogen atom or a substituent. Examples of the substituent include a substituent represented by R ^A2 described later, and more specifically, an alkyl group, an alkoxy group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, or a halogen atom is preferable.
p represents 2-8, 3-8 are preferable and 3-6 are more preferable.
q represents 0-6, 0-4 are preferable and 0-3 are more preferable.

Wherein (4), ^{Y L} represents a 2-8 valent organic group.
Y ^L is, for example, a group consisting of a carbon atom, a silicon atom, a sulfur atom, an oxygen atom, a nitrogen atom, a carbon atom-oxygen atom-carbon atom, a 2-8 valent aliphatic hydrocarbon ring, a 2-8 valent fragrance. It is preferably a group hydrocarbon ring or a divalent to octavalent heterocyclic ring.
“Carbon atom” means a general formula (Y6) described later, “silicon atom” means a general formula (Y11) described later, and “sulfur atom” indicates a general formula (Y8) described later. “Oxygen atom” means a general formula (Y9) described later, and “nitrogen atom” means a general formula (Y12) described later. Further, the “group consisting of carbon atom-oxygen atom-carbon atom” means a case where W in the general formula (Y14) described later is 1. In addition, the “2 to 8 valent aliphatic hydrocarbon ring” is, for example, a general formula (Y13) described later, and the “2 to 8 valent aromatic hydrocarbon ring” is, for example, a general one described later. The formula (Y7) and the like, and “a divalent to octavalent heterocyclic ring” are, for example, general formulas (Y3) to (Y5) described later. The aliphatic hydrocarbon ring, aromatic hydrocarbon ring, and heterocyclic ring have the same meanings as the aliphatic hydrocarbon ring, aromatic hydrocarbon ring, and heterocyclic ring described in L, and the preferred ranges are also the same. .

Among them, Y ^L is a carbon atom, a silicon atom, an oxygen atom, a nitrogen atom, or carbon atom-oxygen from the viewpoint of obtaining higher heat resistance and higher carrier mobility when used in combination with a conductive polymer compound. It is preferably represented by a group consisting of an atom-carbon atom.

Shows an example of a 2-8 valent organic group represented by Y ^L below, the present invention is not limited thereto.
In each general formula, * represents a linking group with another structure, but all * in each structure may be substituted with R ^L1 represented by the above formula (5), or A part (two or more) may be substituted with R ^L1 and the rest may be substituted with R ^L2 .
In Formula (Y10), L ₁ is not particularly limited as long as it is a divalent linking group. Examples of the divalent linking group include —O—, —S—, —NR ¹ —, —CO—, vinylene group, ethynylene group, alkylene, arylene group (any of cyclic, branched, and linear) Or a heteroarylene group, or a divalent group formed by a combination thereof. R ¹ is, for example, a hydrogen atom, an alkyl group (preferably a linear or branched alkyl group having 1 to 10 carbon atoms), a halogen atom (preferably an F atom, a Cl atom, a Br atom, or an I atom. ) And an aryl group (preferably an aryl group having 6 to 20 carbon atoms). Among these, a hydrogen atom or an alkyl group is preferable.
Further, in the equation (Y14), ^{C L} represents a carbon atom or a silicon atom, W represents 0 or 1.
Further, in the equation (Y15), ^{C L} represents a carbon atom or silicon atom, ^{R a} represents a substituent (e.g., alkyl group).
In the following general formula, hydrogen atoms are not shown.

In the above formula (1), X ^A represents a divalent linking group represented by the above formula (2).
In formula (2), Alk ¹ , Alk ² , and Alk ³ each independently represent an alkylene group.
The alkylene group represented by Alk ¹ , Alk ² , and Alk ³ is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 15 carbon atoms, and still more preferably an alkylene group having 1 to 10 carbon atoms. .
The alkylene group may be linear, branched, or cyclic, but is preferably linear.

In formula (2), Q ¹ and Q ³ are each independently a divalent group formed by —O—, —S—, —NR ¹ —, —CO—, a vinylene group, an ethynylene group, or a combination thereof. Represents a group of R ¹ each independently represents a hydrogen atom or a substituent.

R ¹ represents a hydrogen atom or a substituent. Examples of the substituent include an alkyl group (preferably a linear or branched alkyl group having 1 to 10 carbon atoms) and a halogen atom (preferably an F atom). , Cl atom, Br atom, I atom) and an aryl group (preferably an aryl group having 6 to 20 carbon atoms). Among these, a hydrogen atom or an alkyl group is preferable.

In formula (2), Q ¹ and Q ³ are each independently a vinylene group, an ethynylene group, —O—, —S—, —NR ¹ —, —CO—, —O—CO—, —CO—. O—, —NR ¹ —CO—, —CO—NR ¹ —, —O—CO—O—, —NR ¹ —CO—O—, —OCO—NR ¹ —, or —NR ¹ —CO—NR ¹ - is preferably a vinylene group, ethynylene ^{group, -O -, - S -,} - NR 1 -, - CO -, - O-CO-, or, more preferably -CO-O- , Vinylene group, ethynylene group, —O—, —S—, —NR ¹ —, —CO—, or —O—CO— is more preferable.

In formula (2), Q ² is a divalent group formed by —O—, —S—, —NR ¹ —, —CO—, vinylene group, ethynylene group, arylene group, heteroarylene group, or a combination thereof. Represents a group.
In Q ^2, specific examples of ^{R 1} are the same as ^{R 1} in ^{Q 1,} and ^{Q 3} described above.
The arylene group represented by Q ² is preferably an arylene group having 6 to 20 carbon atoms, more preferably an arylene group having 6 to 14 carbon atoms, and still more preferably an arylene group having 6 to 10 carbon atoms.
The heteroarylene group represented by Q ² is preferably a 5- to 7-membered ring group having at least one N atom, O atom, S atom, or Se atom in the ring structure.

In the formula (2), Q ² represents vinylene group, ethynylene group, arylene group, heteroarylene group, —O—, —S—, —NR ¹ —, —CO—, —O—CO—, —CO—O. —, —NR ¹ —CO—, —CO—NR ¹ —, —O—CO—O—, —NR ¹ —CO—O—, —OCO—NR ¹ —, or —NR ¹ —CO—NR ¹ - is preferably a vinylene group, ethynylene group, arylene group, heteroarylene ^{group, -O -, - S -,} - NR 1 -, - CO -, - O-CO-, or, -CO-O- It is more preferable that it is a vinylene group, an ethynylene group, an arylene group, a heteroarylene group, —O—, —S—, —NR ¹ —, or —CO—.

In formula (2), j, k, l, s, t, and u each independently represent 0 or 1. However, at least one of j, k, and l is 1. That, ^{X A} of the formula (2) has at least an alkylene group.
The X ^A of the formula (2), more excellent heat resistance, and, from the viewpoint of obtaining a high carrier mobility by when used with a conductive polymer compound, the total carbon number of from 1 to 100 Is more preferable, it is more preferable that it is 1-80, and it is still more preferable that it is 1-50.
In formula (2), # ¹ represents the bonding position with L described above, and # ² represents the bonding position with A described later.

In the above formula (1), A represents a monovalent organic group represented by the above formula (3).
In formula (3), Z represents an arylene group or a heteroarylene group.

  The arylene group is not particularly limited, and examples thereof include a monocyclic divalent aromatic hydrocarbon group and a divalent aromatic hydrocarbon group such as a condensed ring structure of two or more rings.

As the monocyclic divalent aromatic hydrocarbon group, a phenylene group is preferable.
The aromatic hydrocarbon group having a condensed structure having two or more rings is preferably an aromatic hydrocarbon group having 10 to 20 carbon atoms, and a fluorene group, a naphthylene group, or an aromatic carbon group in which three or four rings are condensed. A group obtained by removing two hydrogen atoms from hydrogen is more preferred, and a group obtained by removing two hydrogen atoms from a fluorene group, naphthylene group, anthracene ring, phenanthrene ring, chrysene ring, or pyrene ring is more preferred.

The divalent aromatic hydrocarbon group may further have a substituent, and preferred substituents include at least one of —O—, —S—, and —NR ^D3 —. An alkyl group (for example, an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms is preferable, and an alkyl group having 1 to 20 carbon atoms is more preferable), and a halogen atom (F atom, Cl atom, Br atom or I atom is preferable, F atom or Cl atom is more preferable, and F atom is more preferable.
R ^D3 each independently represents a hydrogen atom or a substituent. Examples of the substituent include an alkyl group (preferably a linear or branched alkyl group having 1 to 10 carbon atoms) and a halogen atom (preferably , F atom, Cl atom, Br atom, or I atom), and an aryl group (preferably an aryl group having 6 to 20 carbon atoms). Among these, a hydrogen atom or an alkyl group is preferable.
Moreover, these substituents may further have a substituent described later.

  The heteroarylene group is not particularly limited, but is preferably a divalent aromatic heterocyclic group having at least one N atom, O atom, S atom, or Se atom in the ring structure.

The divalent aromatic heterocyclic group having at least one N atom, O atom, S atom or Se atom in the ring structure is a divalent aromatic heterocyclic group having at least one S atom in the ring structure. Is preferred.
The divalent aromatic heterocyclic group may be monocyclic or may have a condensed structure of two or more rings, but a monocyclic or bicyclic condensed heteroarylene group is more preferable. .

  Examples of the monocyclic divalent aromatic heterocyclic group include a thienylene group, a furylene group, a pyrrolylene group, and a selenophenylene group, and a thienylene group, a furylene group, or a selenophenylene group is preferable.

Examples of the aromatic heterocyclic group having a condensed structure of two or more rings include those shown below.
In the structural formulas below, the hydrogen atom is an alkyl group, alkenyl group, or alkynyl group that may contain at least one of substituents described later (for example, —O—, —S—, and —NR ^D3 — , An aromatic hydrocarbon group, an aromatic heterocyclic group, a halogen atom, etc.), R ^D3 represents a hydrogen atom or a substituent, and * represents a bonding site with another structure. The -O -, - S-, and, ^{-NR D3} - As the alkyl group which may comprise at least one of, preferably an alkyl group having 1 to 30 carbon atoms, an alkyl group having 1 to 20 carbon atoms Is more preferable. When R ^D3 represents a substituent, the substituent has the same meaning as R ^D3 described for the arylene group, and the preferred range is also the same. In addition, R ^D1 in the formula shown below has the same meaning as “substituent which the monovalent aromatic heterocyclic group may have” described in R ^A2 described later, and the preferred embodiment is also the same.

The divalent aromatic heterocyclic group may further have a substituent, and preferred substituents include at least one of —O—, —S—, and —NR ^D3 —. An alkyl group (for example, an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms is preferable, and an alkyl group having 1 to 20 carbon atoms is more preferable), an alkenyl group (preferably having 2 to 30 carbon atoms). ), An alkynyl group (preferably having 2 to 30 carbon atoms), an aromatic hydrocarbon group (preferably having 6 to 30 carbon atoms), an aromatic heterocyclic group (preferably having a 5- to 7-membered ring). , O atom, N atom, S atom, or Se atom are preferred), and halogen atom (F atom, Cl atom, Br atom, or I atom are preferred, F atom or Cl atom is more preferred, and F atom is further preferred) Preferred). It is. These may further have a substituent described later.
R ^D3 has the same meaning as R ^D3 described above for the arylene group, and the preferred range is also the same.

  In formula (3), a represents 0 or an integer of 1 or more. From the viewpoint of atmospheric stability, a is more preferably 0 to 4, and still more preferably 0 to 2.

  Although the example of the bivalent coupling group structure represented by-(Z) a- is shown below, this invention is not limited to this.

  In the formula (3), B represents any monovalent organic group selected from the group consisting of groups represented by the above formulas (A-1) to (A-12).

In formula (A-1) to formula (A-12), X each independently represents an O atom, an S atom, a Se atom, or NR ^A1, and preferably an S atom or NR ^A1 .
Y independently represents an O atom or an S atom, and an O atom is preferred.
Z _a each independently represents CR ^A2 or an N atom, preferably CR ^A2 .
Each W independently represents C (R ^A2 ) ₂ , NR ^A1 , N atom, CR ^A2 , O atom, S atom, or Se atom, and C (R ^A2 ) ₂ , CR ^A2 , or S atom is preferable.
R ^A1 is independently an alkyl group, an alkenyl group, an alkynyl group, or a bonding site with another structure, which may contain at least one of —O—, —S—, and —NR ^A3 —. Represents an alkyl group that may contain at least one of —O—, —S—, and —NR ^A3 —.
When R ^A1 represents an alkyl group that may contain at least one of —O—, —S—, and —NR ^A3 —, an alkyl group having 2 to 30 carbon atoms is preferable, and 8 to 25 carbon atoms are preferred. The alkyl group is more preferable. The alkyl group may be linear or branched.
Here, the alkyl group contains —O— means that —O— is introduced in the middle of the carbon-carbon bond of the alkyl group, or —O— is introduced to one end of the alkyl group. (Alkoxy group). The same meaning applies when the alkyl group contains —S— or —NR ^A3 —.
R ^A3 each independently represents a hydrogen atom or a substituent. Examples of the substituent represented by R ^A3 include an alkyl group (preferably a linear or branched alkyl group having 1 to 10 carbon atoms), a halogen atom (preferably an F atom, a Cl atom, a Br atom, or an I atom. ) And an aryl group (preferably an aryl group having 6 to 20 carbon atoms). Among these, a hydrogen atom or an alkyl group is more preferable.
R ^A1 may further have a substituent described later.

R ^A2 each independently represents a hydrogen atom, a substituent, or a bonding site with another structure.
The substituent represented by R ^A2 is not particularly limited, and for example, an alkyl group, a halogen atom, an aryl group, or a group that may include at least one of —O—, —S—, and —NR ^A3 — , A heteroaryl group is preferable, and an aryl group or a heteroaryl group is more preferable.

When R ^A2 represents an alkyl group that may contain at least one of —O—, —S—, and —NR ^A3 —, an alkyl group having 2 to 30 carbon atoms is preferred, and 8 to 25 carbon atoms are preferred. The alkyl group is more preferable. The alkyl group may be linear or branched.
Here, the alkyl group contains —O— means that —O— is introduced in the middle of the carbon-carbon bond of the alkyl group, or —O— is introduced to one end of the alkyl group. (Alkoxy group). The same meaning applies when the alkyl group contains —S— or —NR ^A3 —.
R ^A3 each independently represents a hydrogen atom or a substituent. Examples of the substituent represented by R ^A3 include an alkyl group (preferably a linear or branched alkyl group having 1 to 10 carbon atoms), a halogen atom (preferably an F atom, a Cl atom, a Br atom, or I atom), and an aryl group (preferably an aryl group having 6 to 20 carbon atoms). Among these, a hydrogen atom or an alkyl group is preferable.

When R ^A2 represents a halogen atom, an F atom, a Cl atom, a Br atom, or an I atom is preferable, and an F atom is more preferable.

When R ^A2 is an aryl group, the aryl group is not particularly limited. For example, a structure having only one monocyclic monovalent aromatic hydrocarbon group, a monocyclic monovalent aromatic hydrocarbon group And monovalent aromatic hydrocarbon groups such as a structure in which two or more are combined and a condensed ring structure having two or more rings.

As a structure having only one monocyclic monovalent aromatic hydrocarbon group and a combination of two or more monocyclic monovalent aromatic hydrocarbon groups, for example, a phenyl group or a biphenyl group is preferable.
The aromatic hydrocarbon group having a condensed structure having two or more rings is preferably an aromatic hydrocarbon group having 10 to 20 carbon atoms, and a fluorene group, a naphthylene group, or an aromatic carbon group in which three or four rings are condensed. A group obtained by removing one hydrogen atom from hydrogen is more preferred, and a group obtained by removing one hydrogen atom from a fluorene group, naphthylene group, anthracene ring, phenanthrene ring, chrysene ring, or pyrene ring is more preferred.

The monovalent aromatic hydrocarbon group may further have a substituent, and preferred substituents include at least one of —O—, —S—, and —NR ^A3 —. An alkyl group (for example, an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms is preferable, and an alkyl group having 1 to 20 carbon atoms is more preferable), and a halogen atom (F atom, Cl atom, Br atom or I atom is preferable, F atom or Cl atom is more preferable, and F atom is more preferable. These may further have a substituent described later.
R ^A3 has the same meaning as R ^A3 which was the explanation of the substituent represented by R ^A2 , and the preferred range is also the same.
These substituents may further have a substituent described later.

When R ^A2 is a heteroaryl group, the heteroaryl group is not particularly limited, but is a monovalent aromatic heterocyclic ring having at least one N atom, O atom, S atom, or Se atom in the ring structure. It is preferably a group.

The monovalent aromatic heterocyclic group having at least one N atom, O atom, S atom or Se atom in the ring structure is a monovalent aromatic heterocyclic group having at least one S atom in the ring structure. Is preferred.
The monovalent aromatic heterocyclic group may be monocyclic or have a condensed structure of two or more rings. Examples of the monovalent aromatic heterocyclic group include a structure having only one monocyclic monovalent aromatic heterocyclic group, a structure in which two or more monocyclic monovalent aromatic heterocyclic groups are combined, And a structure in which two or more monocyclic monovalent aromatic heterocyclic groups are combined with one or more monovalent aromatic heterocyclic groups having a condensed ring structure of two or more rings.

The monovalent aromatic heterocyclic group may further have a substituent, and preferred substituents include at least one of —O—, —S—, and —NR ^A3 —. An alkyl group (for example, an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms is preferable, and an alkyl group having 1 to 20 carbon atoms is more preferable), an alkenyl group (preferably having 2 to 30 carbon atoms). ), An alkynyl group (preferably having 2 to 30 carbon atoms), an aromatic hydrocarbon group (preferably having 6 to 30 carbon atoms), an aromatic heterocyclic group (preferably having a 5- to 7-membered ring). , O atom, N atom, S atom, or Se atom are preferred), and halogen atom (F atom, Cl atom, Br atom, or I atom are preferred, F atom or Cl atom is more preferred, and F atom is further preferred) Preferred). It is. These may further have a substituent described later.
R ^A3 has the same meaning as R ^A3 which was the explanation of the substituent represented by R ^A2 , and the preferred range is also the same.

In formula (A1) ~ formula (A-12), each equation ^has at least one ^{R A1} or ^{R A2,} and any one of the ^{R A1} or ^{R A2} is other structure Represents the binding site.
That is, for example, in the formula (A-5), X in the formula is R ^A1, and, if the R ^A1 represents a binding site with another structure, or any at least Z _a in the formula One of them is represented by CR ^A2 and R ^A2 represents a binding site with another structure to form a monovalent organic group. In addition, the coupling | bonding position with another structure is corresponded in the connection position with-(Z) a- in Formula (3).

In formulas (A-1) to (A-12), R represents a hydrogen atom or a substituent.
The substituent which R represents is synonymous with what was demonstrated as a substituent which said R ^A2 represents, and its preferable range is also the same.

  In the formula (3), B represents any monovalent organic group selected from the group consisting of the groups represented by the above formulas (A-1) to (A-12). 1) Any monovalent organic compound selected from the group consisting of groups represented by formula (A-2), formula (A-3), formula (A-5), and formula (A-8) Preferably, the group is any one selected from the group consisting of groups represented by formula (A-1), formula (A-2), formula (A-3), and formula (A-5). It is more preferably a monovalent organic group, and it may be any monovalent organic group selected from the group consisting of groups represented by formula (A-1) and formula (A-3). More preferred is a monovalent organic group represented by the formula (A-1).

Examples of groups represented by formula (A-1) to formula (A-12) are shown below, but the present invention is not limited to the following examples. In the following ^formulas, R ^{A1, R A2,} and R are each and ^{R A1, R A2,} and R in the formula (A1) ~ formula (A-12) interchangeably, preferable embodiments thereof are also the same. In the formulas shown below, any one of R ^A1 represents a binding site with another structure.

  In addition, the following are mentioned as a suitable example of group represented by Formula (A-1)-Formula (A-12). * Indicates a bonding position with another structure, and for Formula (A-5), Formula (A-6), Formula (A-11), and Formula (A-12), either Za or W Is the coupling position with other structures.

Examples of the substituent that may be further included include a halogen atom, an alkyl group (including a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group), an alkenyl group, an alkynyl group, and an aryl group. , Heterocyclic group (also referred to as “heterocyclic group”), cyano group, hydroxy group, nitro group, carboxy group, alkoxy group, aryloxy group, silyl group, alkylsilyl group, silyloxy group, heterocyclic oxy group, acyloxy Group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including anilino group), ammonio group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfo group Famoylamino group, alkyl And arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, Carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, phosphono group, silyl group, hydrazino group, ureido group, boronic acid group (-B ( _OH) 2), phosphato group (-OPO _(OH) 2), a sulfato group (-OSO ₃ H), as well as other known substituents. Further, the substituent may be further substituted with a substituent.

In the formula (3), ^{# 2} represents the bonding position to ^{X A.}
Hereinafter, specific examples of the group formed by combining and connecting group X ^A and the connecting center L, the present invention is not intended to be limited by the following examples. In the following formula, “A” intends A described above.

  Although the preferable specific example of a compound represented by Formula (1) below is shown, this invention is not limited by the following illustrations.

In the composition for forming an organic semiconductor film of the present invention, the content of the compound represented by the formula (1) is preferably 1 to 100% by mass, and preferably 1 to 90% by mass of the total solid content. More preferred.
In particular, in the composition for forming an organic semiconductor film of the present invention, when the compound represented by the formula (1) is used alone as the organic semiconductor compound, the content of the compound represented by the formula (1) is the total solid content. 1 to 100% by mass, more preferably 50 to 90% by mass, and still more preferably 50 to 85% by mass.
In addition, as described later, when the compound represented by the formula (1) and the conductive polymer compound are mixed and used as the organic semiconductor compound, the content of the compound represented by the formula (1) The total amount is preferably 5 to 60% by mass, and more preferably 5 to 50% by mass.
In addition, in the composition for organic-semiconductor film form, the compound represented by Formula (1) may be contained individually by 1 type, and 2 or more types (in combination) may be contained. When two or more compounds represented by the formula (1) are included, the total metric is preferably included in the above range.

  About the synthesis method of the compound represented by Formula (1), a representative example is described in an Example.

〔solvent〕
The composition for forming an organic semiconductor film of the present invention described later preferably contains a solvent, and preferably contains an organic solvent.
A known solvent can be used as the solvent.
Specifically, for example, hydrocarbons such as hexane, octane, decane, toluene, xylene, mesitylene, ethylbenzene, amylbenzene, decalin, 1-methylnaphthalene, 1-ethylnaphthalene, 1,6-dimethylnaphthalene, and tetralin. Solvents; for example, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, propiophenone, butyrophenone, α-tetralone, and β-tetralone; for example, dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethane, Halogenated hydrocarbon solvents such as tetrachloroethane, chlorobenzene, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, chlorotoluene, and 1-fluoronaphthalene; Heterocyclic solvents such as pyridine, picoline, quinoline, thiophene, 3-butylthiophene, and 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, 3,4-dibromothiophene, and 3,4-dichloro-1 Halogenated heterocyclic solvents such as 1,2,5-thiadiazole; ester solvents such as ethyl acetate, butyl acetate, amyl acetate, 2-ethylhexyl acetate, γ-butyrolactone, and phenyl acetate; Propanol, butanol, pentanol, hexanol, cyclohexanol, Alcohol solvents such as methyl cellosolve, ethyl cellosolve, and ethylene glycol; for example, dibutyl ether, tetrahydrofuran, dioxane, anisole, ethoxybenzene, propoxybenzene, isopropoxybenzene, butoxybenzene, 2-methylanisole, 3-methylanisole, 4 -Methylanisole, 4-ethylanisole, dimethylanisole (any one of 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5-, and 3,6- ), Ether solvents such as 1,4-benzodioxane, 2,3-dihydrobenzofuran, phthalane, chroman, and isochroman; for example, N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2- Pyrrolidone, 1-methyl-2-imidazolidinone, Amide / imide solvents such as 1,3-dimethyl-2-imidazolidinone; sulfoxide solvents such as dimethyl sulfoxide; phosphate solvents such as trimethyl phosphate; nitrile solvents such as acetonitrile and benzonitrile; And nitro-based solvents such as nitromethane and nitrobenzene.

A solvent may be used individually by 1 type and may be used in combination of multiple.
Among these, hydrocarbon solvents, ketone solvents, halogenated hydrocarbon solvents, heterocyclic solvents, halogenated heterocyclic solvents, or ether solvents are preferred, 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-dihydro Benzofuran, phthalane, chroman, isochroman, 1-fluoronaphthalene, 3-chlorothiophene, or 2,5-dibromothiophene is more preferable, and toluene, xylene, tetralin, acetophenone, propiophenone, Rophenone, α-tetralone, anisole, ethoxybenzene, propoxybenzene, butoxybenzene, 2-methylanisole, 3-methylanisole, 4-methylanisole, 2,3-dihydrobenzofuran, phthalane, chroman, isochroman, 1-fluoronaphthalene, More preferred is 3-chlorothiophene or 2,5-dibromothiophene.

From the viewpoint of film forming property, the boiling point of the solvent is preferably 100 ° C. or higher. The boiling point of the solvent is more preferably 100 to 300 ° C, further preferably 125 to 250 ° C, and particularly preferably 150 to 225 ° C.
From the viewpoint of film-forming properties, the boiling point of the solvent with the highest content is preferably 100 ° C. or higher, and the boiling points of all solvents are more preferably 100 ° C. or higher.

  When the composition for organic semiconductor formation of this invention contains a solvent, content of the compound represented by Formula (1) is 0.005-90 normally with respect to the total mass of the composition for organic semiconductor film formation. % By mass, preferably 0.005 to 50% by mass, more preferably 0.01 to 25% by mass, and still more preferably 0.05 to 15% by mass. Within the above range, the composition for forming an organic semiconductor film can be suitably used for inkjet printing and / or flexographic printing, has excellent coating properties, and can easily form an organic semiconductor film.

[Polymer compound]
The composition for forming an organic semiconductor film of the present invention may contain a polymer compound as a binder polymer. The “binder polymer” herein refers to a polymer compound that does not exhibit conductivity by itself, and does not include a later-described conductive polymer compound.

The kind in particular of a binder polymer is not restrict | limited, A well-known binder polymer can be used.
Examples of the binder polymer include polystyrene, poly (α-methylstyrene), polyvinyl cinnamate, poly (4-vinylphenyl), and poly (4-methylstyrene).

The weight average molecular weight of the binder polymer is not particularly limited, but is preferably 1,000 to 2,000,000, more preferably 3,000 to 1,000,000, and still more preferably 5,000 to 600,000.
In the present invention, the weight average molecular weight and number average molecular weight are measured by a gel permeation chromatography method (GPC (Gel Permeation Chromatography)) and are calculated by standard polystyrene. Specifically, for example, GPC uses HLC-8121GPC (manufactured by Tosoh Corporation), and TSKgel GMH _HR- H (20) HT (manufactured by Tosoh Corporation, 7.8 mm ID × 30 cm) is used as a column. In this use, 1,2,4-trichlorobenzene is used as an eluent. As conditions, the sample concentration is 0.02% by mass, the flow rate is 1.0 ml / min, the sample injection amount is 300 μl, the measurement temperature is 160 ° C., and an IR (infrared) detector is used. In addition, the calibration curve is “Standard sample TSK standard, polystyrene” manufactured by Tosoh Corporation: “F-128”, “F-80”, “F-40”, “F-20”, “F-10”, It is prepared from 12 samples of “F-4”, “F-2”, “F-1”, “A-5000”, “A-2500”, “A-1000”, and “A-500”.

  When the composition for forming an organic semiconductor film of the present invention contains a polymer compound, the content of the polymer compound in the composition for forming an organic semiconductor film of the present invention is 5 to 70 with respect to the total solid content. It is preferable that it is mass%, and it is more preferable that it is 10-50 mass%. Within the above range, the resulting organic semiconductor is more excellent in carrier mobility and stability with time under high temperature and high humidity.

[Conductive polymer compound]
The composition for forming an organic semiconductor film of the present invention may contain a conductive polymer compound.
It does not specifically limit as a conductive polymer compound, A conventionally well-known conductive polymer compound can be used.
For example, as the conductive polymer compound, a polymer compound having a conjugated molecular structure can be used. Here, the polymer having a conjugated molecular structure is a polymer having a structure in which single bonds and double bonds are alternately connected in a carbon-carbon bond on the main chain of the polymer. The conductive polymer compound used in the present invention is not necessarily a high molecular weight compound, and may be an oligomer compound. An organic thin film transistor element having a carrier mobility of 10 ⁻⁵ cm ² / Vs or more is defined as a conductive polymer.

  Examples of such conjugated polymers include thiophene compounds, pyrrole compounds, aniline compounds, acetylene compounds, p-phenylene compounds, p-phenylene vinylene compounds, p-phenylene ethynylene compounds, p-full. Olenylene vinylene compound, polyacene compound, polyphenanthrene compound, p-xylylene compound, vinylene sulfide compound, m-phenylene compound, naphthalene vinylene compound, p-phenylene oxide compound, phenylene sulfide compound, furan Examples thereof include conjugated polymers having a repeating unit derived from these monomers, using as a monomer a system compound, a selenophene compound, an azo compound, and derivatives obtained by introducing substituents into these compounds.

  The weight average molecular weight of the conductive polymer compound is not particularly limited, but is preferably 2,000 to 1,000,000, more preferably 5,000 to 300,000, still more preferably 10,000 to 150,000, and particularly preferably 20,000 to 100,000. In addition, the measuring method of a weight average molecular weight is based on the above-mentioned description.

  When the composition for forming an organic semiconductor film of the present invention contains a conductive polymer compound, the content of the conductive polymer compound in the composition for forming an organic semiconductor film of the present invention is the total solid content. It is preferable that it is 5-80 mass% with respect to it, and it is more preferable that it is 10-60 mass%. Within the above range, the resulting organic semiconductor is more excellent in carrier mobility and stability with time under high temperature and high humidity.

  In the composition for forming an organic semiconductor film of the present invention, when the compound represented by the formula (1) and the conductive polymer compound are used in combination, the mixing ratio of the compound represented by the formula (1) and the conductive polymer compound Is preferably 1: 1 to 1:30, more preferably 1: 2 to 1:20. By mixing in the above range, the compound represented by the formula (1) and the conductive polymer compound are compatible with each other, and the compound represented by the formula (1) causes defects in the conductive polymer. Since it is compensated well, the carrier mobility is remarkably excellent.

From the viewpoint that the effect of the compound represented by the formula (1) is more excellent, as a conductive polymer compound, a polymer (so-called “a combination of an electron donating (donor) unit and an electron accepting (acceptor) unit) is used. DA type polymer ") is preferably used, and more specifically, a polymer having a repeating unit represented by the following formula (X) is more preferable.
Hereinafter, the DA polymer preferably used in the present invention will be described.
<D-A type polymer>

In formula (X), A represents an electron acceptor unit including a partial structure having at least one of sp2 nitrogen atom, carbonyl group, and thiocarbonyl group in the ring structure.
D is a divalent aromatic heterocyclic group having at least one N atom, O atom, S atom, or Se atom in the ring structure, or a divalent aromatic carbon atom having a condensed structure of two or more rings. An electron donor unit containing a hydrogen group as a partial structure is represented.

(Electronic Acceptor Unit (“A” in Formula (X)))
In the above formula (X), A represents an electron acceptor unit including a partial structure having at least one of sp2 nitrogen atom, carbonyl group and thiocarbonyl group in the ring structure.
A preferably has, as a partial structure, at least one structure selected from the group consisting of structures represented by the following formulas (A-1) to (A-12), and A has the following formula (A-1): It is more preferable that the structure is represented by at least one selected from the group consisting of formula (A-12).

In formula (A-1) to formula (A-12), X each independently represents an O atom, an S atom, an Se atom, or NR ^A1 . Y each independently represents an O atom or an S atom. Z _a each independently represents CR ^A2 or an N atom. W each independently represents C (R ^A2 ) ₂ , NR ^A1 , N atom, CR ^A2 , O atom, S atom, or Se atom. R ^A1 each independently represents an alkyl group that may contain at least one of —O—, —S—, and —NR ^A3 —, and a monovalent group represented by the following formula (1-1). Or represents a binding site to another structure. R ^A2 each independently represents an alkyl group which may contain at least one of a hydrogen atom, a halogen atom, —O—, —S—, and —NR ^A3 —, and is represented by the following formula (1-1). Represents a binding site with a monovalent group or other structure. R ^A3 each independently represents a hydrogen atom or a substituent. * Each independently represents a binding site with another structure.

In formula (1-1), Ar represents an aromatic heterocyclic group or an aromatic hydrocarbon group having 5 to 18 carbon atoms. L _a is, -O -, - S-, and, ^{-NR 1S} - represents at least one of the comprise also an alkylene group having 1 to 20 carbon atoms of. L _b represents an alkyl group having 1 to 100 carbon atoms which may include at least one of —O—, —S—, and —NR ^2S —. R ^1S and R ^2S each independently represent a hydrogen atom or a substituent. l represents an integer of 1 to 5. When l is 2 or more, the plurality of L _b may be the same as or different from each other. * Represents a binding site with another structure.

In formula (A-1) to formula (A-12), X each independently represents an O atom, an S atom, a Se atom, or NR ^A1, and preferably an S atom or NR ^A1 .
Y independently represents an O atom or an S atom, and an O atom is preferred.
Z _a each independently represents CR ^A2 or an N atom, preferably CR ^A2 .
Each W independently represents C (R ^A2 ) ₂ , NR ^A1 , N atom, CR ^A2 , O atom, S atom, or Se atom, and C (R ^A1 ) ₂ , CR ^A2 , or S atom preferable.
R ^A1 each independently represents an alkyl group that may contain at least one of —O—, —S—, and —NR ^A3 —, and a monovalent group represented by the above formula (1-1). Or an alkyl group which represents a binding site to another structure and may contain at least one of -O-, -S-, and -NR ^A3- , or the above formula (1-1) The monovalent group represented by these is preferable.
When R ^A1 represents an alkyl group that may contain at least one of —O—, —S—, and —NR ^A3 —, an alkyl group having 2 to 30 carbon atoms is preferable, and 8 to 25 carbon atoms are preferred. The alkyl group is more preferable. The alkyl group may be linear or branched.
The binding site with other structure in R ^A1 is a binding site with another structure represented by * in the above formula (A-1) to formula (A-12).
R ^A2 each independently represents an alkyl group which may contain at least one of a hydrogen atom, a halogen atom, —O—, —S—, and —NR ^A3 —, and is represented by the above formula (1-1). Represents a binding site with a monovalent group or another structure, and a binding site with a hydrogen atom or another structure is preferable.
When R ^A2 represents an alkyl group that may contain at least one of —O—, —S—, and —NR ^A3 —, an alkyl group having 2 to 30 carbon atoms is preferred, and 8 to 25 carbon atoms are preferred. The alkyl group is more preferable. The alkyl group may be linear or branched.
When R ^A2 represents a halogen atom, an F atom, a Cl atom, a Br atom, or an I atom is preferable, and an F atom is more preferable.
The binding site with other structure in R ^A2 is a binding site with another structure represented by * in the above formulas (A-1) to (A-12).
R ^A3 each independently represents a hydrogen atom or a substituent. The substituent in R ^{A3 has the same meaning as} the substituent in R ^1S and R ^2S described later.

In formula (1-1), Ar represents an aromatic heterocyclic group or an aromatic hydrocarbon group having 5 to 18 carbon atoms.
Examples of the aromatic hydrocarbon group having 5 to 18 carbon atoms in Ar include, for example, a benzene ring group, a biphenyl group, a naphthalene ring group, or an aromatic hydrocarbon in which three rings are condensed (for example, a fluorene ring). Examples include a group in which a hydrogen atom has been removed. Among these, a benzene ring group, a biphenyl group, or a naphthalene ring group is preferable, and a benzene ring group is more preferable from the viewpoint that carrier mobility is further improved.
The aromatic heterocyclic group in Ar may be monocyclic or may have a condensed structure of two or more rings, but is monocyclic from the viewpoint of better carrier mobility. Is preferred. The aromatic heterocyclic group in Ar is preferably a 5- to 7-membered ring. The hetero atom contained in the aromatic heterocyclic group is preferably an N atom, an O atom, an S atom or an Se atom, and more preferably an S atom.
L _a is, -O -, - S-, and, ^{-NR 1S} - represents at least one of the comprise also an alkylene group having 1 to 20 carbon atoms of. Here, the alkylene group contains -O- means that -O- is introduced in the middle of the carbon-carbon bond of the alkylene group, or -O- is introduced at one or both ends of the alkylene group. Means if The same meaning applies when the alkylene group contains —S— or —NR ^1S —.
Alkylene group representing L _a is straight-chain, branched-chain, and may be either cyclic, but is preferably a straight-chain or branched alkylene group.
The alkylene group representing L _a is 1 to 20, from the viewpoint of carrier mobility becomes more excellent, preferably from 1 to 15, it is more a 1-10 preferable.
Note that when the alkylene group representing L _a is a branched chain, for the carbon number of the branch portion, is intended to include the number of carbon atoms of the alkylene group representing the L _a. However, _{L a} is ^{-NR 1S} - include, and if the ^{R 1S} contains a carbon ^atom, the carbon number of ^{R 1S} shall not be included in the carbon number of the alkylene group representing _{L a.}
L _b represents an alkyl group having 1 to 100 carbon atoms which may include at least one of —O—, —S—, and —NR ^2S —. Here, the alkyl group contains —O— means that —O— is introduced in the middle of the carbon-carbon bond of the alkyl group, or one end of the alkyl group (that is, connection to the above “Ar”). It means a case where -O- is introduced in (part). The same meaning applies when the alkyl group contains —S— or —NR ^2S —.
The alkyl group representing L _b may be any of linear, branched, and cyclic, but from the viewpoint that the carrier mobility and stability over time under high temperature and high humidity become better. A linear or branched alkyl group is preferable, and a branched alkyl group is more preferable. The alkyl group representing L _b is a halogen atom (preferably, F atom, Cl atom, Br atom, or an I atom, and more preferably, F atoms) as a substituent may be a halogenated alkyl group having .
The number of carbon atoms in the alkyl group representing L _b is 1 to 100, is preferably 9 to 100.
Further, from the viewpoint that the carrier mobility is more excellent, in-(L _b ) ₁ in the above formula (1-1), the carbon number of at least one L _b is 9 to 100. Preferably, it is 20 to 100, more preferably 20 to 40.
When the alkyl group representing L _b is branched, the carbon number of the branched portion is included in the carbon number of the alkyl group representing L _b . However, when L _b contains —NR ^2S — and this R ^2S contains a carbon atom, the carbon number of R ^2S is not included in the carbon number of the alkylene group representing L _b .
R ^1S and R ^2S each independently represent a hydrogen atom or a substituent. As the substituent, an alkyl group (preferably a linear or branched alkyl group having 1 to 10 carbon atoms), a halogen atom (preferably an F atom, a Cl atom, a Br atom, or an I atom), an aryl group (Preferably an aryl group having 6 to 20 carbon atoms). Among these, R ^1S and R ^2S are each independently preferably a hydrogen atom or an alkyl group, and more preferably an alkyl group.
l represents an integer of 1 to 5, but is preferably 1 or 2. When l is 2 or more, the plurality of L _b may be the same as or different from each other.
* Represents a binding site with another structure.

The D-A type polymer has at least one structure selected from the group consisting of structures represented by the following formulas (A-1) to (A-12) as A as a partial structure in formula (X). It is preferable that Formula (A-1), Formula (A-3), Formula (A-4), Formula (A-5), Formula (A-6), Formula (A-8), Formula (A- 10) and at least one structure selected from the group consisting of structures represented by formula (A-12) is more preferred as the partial structure, and the formula (A-1), formula (A-3), formula It has more as at least 1 structure chosen from the group which consists of a structure represented by (A-5), Formula (A-6), Formula (A-8), and Formula (A-12) as a partial structure. More preferably, it has at least one structure selected from the group consisting of structures represented by formula (A-3) and formula (A-6) as a partial structure. Particularly preferred Rukoto, structure represented by the formula (A-3) is most preferable.
Further, in each of the above-described embodiments, the D-A type polymer has A in the formula (X) represented by each formula, rather than an embodiment in which A in the formula (X) has a structure represented by each formula as a partial structure. The aspect which is the structure represented is more preferable.

Examples of structures represented by formula (A-1) to formula (A-12) are shown below, but the present invention is not limited to the following examples. In the following structural ^{formulas, R A1} has the same meaning as ^{R A1} in the formula (A1) ~ formula (A-12), preferable embodiments thereof are also the same.
* Represents a binding site with another structure.

(Electronic donor unit (“D” in formula (X)))
D is a divalent aromatic heterocyclic group having at least one N atom, O atom, S atom, or Se atom in the ring structure, or a divalent aromatic hydrocarbon having a condensed structure of two or more rings. An electron donor unit containing a group as a partial structure.

The divalent aromatic heterocyclic group having at least one N atom, O atom, S atom or Se atom in the ring structure is a divalent aromatic heterocyclic group having at least one S atom in the ring structure. Is preferred.
The divalent aromatic heterocyclic group may be monocyclic or may have a condensed structure of two or more rings, and a combination of two or more monocyclic divalent aromatic heterocyclic groups. Or a combination of two or more monocyclic divalent aromatic heterocyclic groups and one or more divalent aromatic heterocyclic groups having a condensed ring structure of two or more rings. preferable.
The divalent aromatic heterocyclic group may further have a substituent, and preferred substituents include at least one of —O—, —S—, and —NR ^D3 —. An alkyl group (for example, an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms is preferable, and an alkyl group having 1 to 20 carbon atoms is more preferable), an alkenyl group (preferably having 2 to 30 carbon atoms). ), An alkynyl group (preferably having 2 to 30 carbon atoms), an aromatic hydrocarbon group (preferably having 6 to 30 carbon atoms), an aromatic heterocyclic group (preferably having a 5- to 7-membered ring). , O atom, N atom, S atom and Se atom are preferred), a halogen atom (F atom, Cl atom, Br atom or I atom is preferred, F atom or Cl atom is more preferred, and F atom is further preferred. ) Or the above formula It includes a monovalent group represented by 1-1).
R ^D3 has the same meaning as R ^D3 in formula (D-1) to be described later, and the preferred embodiments are also the same.

Although the example of the said bivalent aromatic heterocyclic group is shown below, this invention is not limited by the following illustrations. In the structural formulas below, the hydrogen atom is an alkyl group, alkenyl group, alkynyl group, aromatic hydrocarbon group, aromatic which may contain at least one of —O—, —S—, and —NR ^D3 —. It may be substituted with a heterocyclic group, a halogen atom, or a group represented by the above formula (1-1), and R ^D1 has the same meaning as R ^D1 in formula (D-1) to be described later, which is preferable. The embodiment is the same, and * represents a binding site with another structure. The -O -, - S-, and, ^{-NR D3} - As the alkyl group which may comprise at least one of, preferably an alkyl group having 1 to 30 carbon atoms, an alkyl group having 1 to 20 carbon atoms Is more preferable. R ^D3 has the same meaning as R ^D3 in formula (D-1) to be described later, and the preferred embodiments are also the same.

The aromatic hydrocarbon group having a condensed structure having two or more rings is preferably an aromatic hydrocarbon group having 10 to 20 carbon atoms, and a fluorene group, a naphthylene group, or an aromatic carbon group in which three or four rings are condensed. A group obtained by removing two hydrogen atoms from hydrogen is more preferred, and a group obtained by removing two hydrogen atoms from a fluorene group, naphthylene group, anthracene ring, phenanthrene ring, chrysene ring or pyrene ring is more preferred.
The aromatic hydrocarbon Suisomoto may further have a substituent, and as preferred substituents, -O -, - S-, and, -NR D3 ^- alkyl which may contain at least one of And a monovalent group represented by the above formula (1-1). Preferred examples of the alkyl group and halogen atom that may contain at least one of —O—, —S—, and —NR ^D3 — include those described above for the divalent aromatic heterocyclic group. It is the same. R ^D3 has the same meaning as R ^D3 in formula (D-1) to be described later, and the preferred embodiments are also the same.

  Moreover, in Formula (X), it is preferable that D is a structure represented by Formula (D-1).

In the formula (D-1), each X ′ independently represents an O atom, an S atom, an Se atom, or NR ^D1 . R ^D1 independently represents a monovalent organic group which may be a monovalent group represented by the above formula (1-1). Z _d each independently represents an N atom or CR ^D2 . R ^D2 each independently represents a hydrogen atom or a monovalent organic group which may be a monovalent group represented by the above formula (1-1). M represents a single bond, a divalent aromatic heterocyclic group, a divalent aromatic hydrocarbon group, an alkenylene group, an alkynylene group, or a divalent group formed by combining these. M is substituted with an alkyl group which may contain at least one of —O—, —S— and —NR ^D3 —, or a monovalent group represented by the above formula (1-1). May be. R ^D3 each independently represents a hydrogen atom or a substituent. p and q represent the integer of 0-4 each independently. * Each independently represents a binding site with another structure.
In the above formula (D-1), each repeating unit and the above M are coupled so as to be rotatable on the coupling axis.

In formula (D-1), each X ′ independently represents an O atom, an S atom, a Se atom, or NR ^D1, and is preferably an O atom, an S atom, or an Se atom, More preferably.
Z _d each independently represents an N atom or CR ^D2, and is more preferably CR ^D2 .
R ^D1 each independently represents a monovalent organic group, and may be an alkyl group (for example, having 1 to 30 carbon atoms) that may include at least one of —O—, —S—, and —NR ^D3 —. Or an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms, an alkynyl group (preferably having 1 to 30 carbon atoms), an alkenyl group (having 2 to 30 carbon atoms). Preferred), an aromatic hydrocarbon group (preferably having 6 to 30 carbon atoms), an aromatic heterocyclic group (preferably a 5- to 7-membered ring. As the hetero atom, an O atom, an N atom, an S atom, or Se atom is preferred), halogen atom (F atom, Cl atom, Br atom, or I atom is preferred, F atom or Cl atom is more preferred, and F atom is particularly preferred), or the above formula (1-1 Is a monovalent group represented by Rukoto is preferably an alkyl group, more preferably a halogen atom, or a monovalent group represented by the above formula (1-1).
R ^D2 each independently represents a hydrogen atom or a monovalent organic group, and an alkyl group (for example, which may contain at least one of a hydrogen atom, —O—, —S—, and —NR ^D3 —) (for example, An alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms is preferable, and an alkyl group having 1 to 20 carbon atoms is more preferable), an alkynyl group (preferably having 2 to 30 carbon atoms), an alkenyl group. (Preferably having 2 to 30 carbon atoms), an aromatic hydrocarbon group (preferably having 6 to 30 carbon atoms), an aromatic heterocyclic group (preferably having a 5- to 7-membered ring. O atoms and N are preferred as heteroatoms. Atom, S atom or Se atom is preferred), halogen atom (F atom, Cl atom, Br atom or I atom is preferred, F atom or Cl atom is more preferred, and F atom is more preferred), or The above formula (1-1 Preferably in a monovalent group represented by a hydrogen atom, an alkyl group, more preferably a halogen atom, or a monovalent group represented by the above formula (1-1).
M represents a single bond, a divalent aromatic heterocyclic group, a divalent aromatic hydrocarbon group, an alkenylene group, an alkynylene group, or a divalent group formed by combining these. M is substituted with an alkyl group which may contain at least one of -O-, -S-, and -NR ^D3- , or a monovalent group represented by formula (1-1). It may be.
The divalent aromatic heterocyclic group in M may be monocyclic or have a condensed structure of two or more rings. Examples of the divalent aromatic heterocyclic group preferably used in the present invention are the same as the examples of the divalent aromatic heterocyclic group having a condensed structure of two or more rings described above.
As the divalent aromatic hydrocarbon group in M, an aromatic hydrocarbon group having 6 to 20 carbon atoms is preferable, and a phenylene group, a biphenylene group, a fluorene group, a naphthylene group, or an aromatic in which three or four rings are condensed. A group obtained by removing two hydrogen atoms from a group hydrocarbon is more preferred, and a group obtained by removing two hydrogen atoms from a fluorene group, naphthylene group, anthracene ring, phenanthrene ring, chrysene ring, or pyrene ring is more preferred.
The divalent aromatic heterocyclic group or the divalent aromatic hydrocarbon group in M may further have a substituent, and preferred substituents include —O—, —S—, and , —NR ^D3 — an alkyl group which may contain at least one (for example, an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms is preferable, and an alkyl group having 1 to 20 carbon atoms is More preferred), a halogen atom (F atom, Cl atom, Br atom or I atom is preferred, F atom or Cl atom is more preferred, and F atom is still more preferred), or in the above formula (1-1) The monovalent group represented is mentioned.
The alkenylene group in M is preferably an alkenylene group having 2 to 10 carbon atoms, more preferably an alkenylene group having 2 to 4 carbon atoms, and even more preferably an ethenylene group.
The alkynylene group in M is preferably an alkynylene group having 2 to 10 carbon atoms, more preferably an alkynylene group having 2 to 4 carbon atoms, and further preferably an ethynylene group.
R ^D3 each independently represents a hydrogen atom or a substituent. The substituent in R ^{D3 has the same meaning as} the substituent in R ^1S and R ^2S described above.
p and q are each independently an integer of 0 to 4, preferably an integer of 1 to 3, and more preferably an integer of 1 to 2. p and q are preferably the same value. Moreover, it is preferable that p + q is 2-4.
However, when p + q is 0, M is a divalent aromatic heterocyclic group having at least one N atom, O atom, S atom, or Se atom in the ring structure, or two or more condensed rings. It is preferable that a divalent aromatic hydrocarbon group having a ring structure is included as a partial structure.

Although the example of the structure of D is shown below, this invention is not limited by the following illustrations. In the structural formulas below, the hydrogen atom is an alkyl group which may contain at least one of —O—, —S—, and —NR ^D3 —, or a group represented by the above formula (1-1). may be substituted by, R ^D1 has the same meaning as R ^D1 in the formula (D1), and also the same preferred embodiment, * represents a binding site with another structure. The -O -, - S-, and, ^{-NR D3} - As the alkyl group which may comprise at least one of, preferably an alkoxy group of the alkyl group or C1-30 C1-30 An alkyl group having 8 to 30 carbon atoms is more preferable. R ^D3 has the same meaning as R ^D3 in formula (D-1), and the preferred embodiment is also the same.

(Repeating unit represented by formula (2) to formula (5))
The repeating unit represented by the above formula (X) is preferably a repeating unit represented by any one of the following formulas (2) to (5), and the following formula (2), the following formula (3) or the following The repeating unit represented by the formula (4) is more preferable, the repeating unit represented by either the following formula (2) or the following formula (3) is more preferable, and the following formula (3): The repeating unit represented is particularly preferable.

In the above formulas (2) to (5), X independently represents an O atom, an S atom, an Se atom, or NR ^A1 .
R ^A1 each independently represents an alkyl group that may contain at least one of —O—, —S—, and —NR ^A3 —, and a monovalent group represented by the above formula (1-1). Or represents a binding site to another structure.
Y each independently represents an O atom or an S atom.
Z _a each independently represents CR ^A2 or an N atom. R ^A2 each independently represents an alkyl group which may contain at least one of a hydrogen atom, a halogen atom, —O—, —S—, and —NR ^A3 —, or a bonding site with another structure. Represents. R ^A3 each independently represents a hydrogen atom or a substituent. X ′ each independently represents an O atom, an S atom, a Se atom, or NR ^D1 . R ^D1 independently represents a monovalent organic group which may be a monovalent group represented by the above formula (1-1). Z _d each independently represents an N atom or CR ^D2 . R ^D2 each independently represents a hydrogen atom or a monovalent organic group which may be a monovalent group represented by the above formula (1-1). M represents a single bond, a divalent aromatic heterocyclic group, a divalent aromatic hydrocarbon group, an alkenylene group, an alkynylene group, or a divalent group formed by combining these. M is substituted with an alkyl group which may contain at least one of —O—, —S— and —NR ^D3 —, or a monovalent group represented by the above formula (1-1). May be. R ^D3 each independently represents a hydrogen atom or a substituent. p and q represent the integer of 0-4 each independently.

In the formulas (2) to (5), X, Y, Z _a , R ^A1 , R ^A2 , and R ^A3 are X, Y, and Z in the above formulas (A-1) to (A-12), respectively. Each of _{a 1} , R ^A1 , R ^A2 and R ^A3 has the same meaning, and the preferred embodiments are also the same.
In the formulas (2) to (5), X ′, Z _d , R ^D1 , R ^D2 , R ^D3 , M, p, and q are X ′, Z _d , R ^D1 , R ^D2 , R ^D3 , M, p, and q are synonymous with each other, and preferred embodiments are also the same.

(Preferred embodiment of D-A type polymer)
In the DA type polymer, the content of the repeating unit represented by the formula (X) is preferably 60 to 100% by mass with respect to the total mass of the DA type polymer, and is 80 to 100% by mass. More preferably, it is more preferably 90 to 100% by mass, and it is particularly preferably formed substantially only from the repeating unit represented by the formula (X). In addition, being substantially formed only from the repeating unit represented by the formula (X) means that the content of the repeating unit represented by the formula (X) is 95% by mass or more, and 97 It is preferably at least mass%, more preferably at least 99 mass%.
When the content of the repeating unit represented by the formula (X) is within the above range, an organic semiconductor layer having better carrier mobility can be obtained.
Further, the DA type polymer may contain one type of repeating unit represented by the formula (X), or two or more types.

  The DA polymer is a compound having two or more repeating units represented by the formula (X), may be an oligomer having 2 to 9 repeating units, and is a high number having 10 or more repeating units n. It may be a molecule (polymer). Among these, a polymer having a repeating unit number n of 10 or more is preferable from the viewpoint of carrier mobility and physical properties of the obtained organic semiconductor layer.

  From the viewpoint of carrier mobility, the molecular weight of the DA polymer is 2,000 or more, preferably 5,000 or more, more preferably 10,000 or more, and 20,000 or more. More preferably, it is particularly preferably 30,000 or more. Further, from the viewpoint of solubility, it is preferably 1,000,000 or less, more preferably 300,000 or less, still more preferably 150,000 or less, and particularly preferably 100,000 or less. preferable.

When the D-A type polymer has a molecular weight distribution, the molecular weight of the compound means a weight average molecular weight.
In the present invention, the weight average molecular weight and the number average molecular weight of the DA type polymer are measured by a gel permeation chromatography method (GPC (Gel Permeation Chromatography)) method, and are determined by conversion with standard polystyrene. Specifically, for example, GPC uses HLC-8121GPC (manufactured by Tosoh Corporation), and TSKgel GMH _HR- H (20) HT (manufactured by Tosoh Corporation, 7.8 mm ID × 30 cm) is used as a column. In this use, 1,2,4-trichlorobenzene is used as an eluent. As conditions, the sample concentration is 0.02% by mass, the flow rate is 1.0 ml / min, the sample injection amount is 300 μl, the measurement temperature is 160 ° C., and an IR (infrared) detector is used. In addition, the calibration curve is “Standard sample TSK standard, polystyrene” manufactured by Tosoh Corporation: “F-128”, “F-80”, “F-40”, “F-20”, “F-10”, It is prepared from 12 samples of “F-4”, “F-2”, “F-1”, “A-5000”, “A-2500”, “A-1000”, and “A-500”.

In the organic semiconductor layer, only one type of D-A type polymer may be contained, or two or more types of D-A type polymers may be contained.
The structure of the terminal of the D-A type polymer is not particularly limited and depends on the presence or absence of other structural units, the type of substrate used during synthesis, or the type of quenching agent (reaction terminator) used during synthesis. Examples thereof include a hydrogen atom, a hydroxy group, a halogen atom, an ethylenically unsaturated group, an alkyl group, an aromatic heterocyclic group (preferably a thiophene ring), and an aromatic hydrocarbon group (preferably a benzene ring). It is done.

  The method for synthesizing the DA type polymer is not particularly limited, and may be synthesized with reference to a known method. For example, Special Table 2010-527327, Special Table 2007-516315, Special Table 2014-515043, Special Table 2014-507488, Special Table 2011-501451, JP 2010-18790, WO 2012/174561, Special Referring to documents such as Table 2011-514399 and Special Table 2011-514913, the electron acceptor unit precursor and the electron donor unit precursor were synthesized, and the respective precursors were combined with Suzuki coupling and Stille coupling. It can synthesize | combine by carrying out cross-coupling reaction, such as.

  Although the preferable specific example of the repeating unit represented by Formula (X) below is shown, this invention is not limited by the following illustrations.

[Other ingredients]
In the composition for forming an organic semiconductor film of the present invention, there are other components in addition to the compound represented by the formula (1), an optionally added solvent, a polymer compound as a binder, and a conductive polymer compound. It may be included.
As other components, known additives and the like can be used, and examples thereof include surfactants, antioxidants, crystallization control agents, and crystal orientation control agents.

  In the composition for forming an organic semiconductor film of the present invention, the content other than the compound represented by the formula (1), the optionally added solvent, the polymer compound as a binder, and the conductive polymer compound is solid. The amount is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 1% by mass or less, and particularly preferably 0.1% by mass or less. Within the above range, the film forming property is excellent, and the carrier mobility of the obtained organic semiconductor and the temporal stability under high temperature and high humidity are excellent.

  The manufacturing method of the composition for forming an organic semiconductor film of the present invention is not particularly limited, and a known method can be adopted. For example, by adding a predetermined amount of the compound represented by the formula (1) and a polymer compound or a conductive polymer compound that is optionally added simultaneously or sequentially, and appropriately performing a stirring treatment, A desired composition can be obtained.

[Compound represented by Formula (1)]
The compound of the present invention is represented by the above formula (1). The compound of this invention is synonymous with the compound represented by Formula (1) contained in the composition for organic-semiconductor film formation mentioned above, and its preferable aspect is also the same.
The compound of the present invention may be used alone as the organic semiconductor compound as described above, or may be used in combination with a polymer compound or a conductive polymer compound.

[Organic semiconductor film and manufacturing method thereof]
The organic semiconductor film of the present invention contains the compound of the present invention and can be formed from the above-mentioned composition for forming an organic semiconductor. The method for forming the organic semiconductor film is not particularly limited, and the composition for forming an organic semiconductor film of the present invention is applied on a predetermined substrate (for example, on the source electrode, the drain electrode, and the gate insulating film), A desired organic semiconductor film can be formed by performing a drying process as necessary.

The method for applying the composition on the substrate is not particularly limited, and a known method can be adopted, for example, an ink jet printing method, a screen printing method, a flexographic printing method, a bar coating method, a spin coating method, a knife coating method, a doctor. Examples thereof include a blade method, and an inkjet printing method, a screen printing method, or a flexographic printing method is preferable.
In addition, as a flexographic printing method, the aspect using a photosensitive resin plate as a flexographic printing plate is mentioned suitably. In some embodiments, the composition can be printed on a substrate to easily form a pattern.
The method for producing an organic semiconductor film of the present invention preferably includes a coating step in which a solvent is contained in the composition for forming an organic semiconductor film and applied as a coating solution on a substrate. More preferably, a removal step of removing the solvent from the prepared composition.

  The drying process in the removal step is a process performed as necessary, and optimal conditions are appropriately selected depending on the type of the compound represented by the formula (1) and the solvent used. Among them, the heating temperature is preferably 30 ° C. to 100 ° C., and preferably 40 ° C. to 90 ° C. in terms of excellent carrier mobility and stability over time under high temperature and high humidity of the obtained organic semiconductor element, and excellent productivity. C. is more preferable, and the heating time is preferably 10 to 300 minutes, more preferably 30 to 180 minutes.

  The thickness of the formed organic semiconductor film is not particularly limited, but is preferably 10 to 500 nm, more preferably 30 to 200 nm, from the viewpoint of carrier mobility of the obtained organic semiconductor element and stability over time under high temperature and high humidity. preferable.

  The organic semiconductor film of the present invention can be suitably used for an organic semiconductor element, and can be particularly suitably used for an organic thin film transistor.

[Organic semiconductor devices]
The organic semiconductor element of the present invention includes the above-described organic semiconductor film.
Although there is no restriction | limiting in particular as an organic semiconductor element, It is preferable that it is a 2-5 terminal organic semiconductor element, and it is more preferable that it is a 2 or 3 terminal organic semiconductor element.
Examples of the two-terminal element include a rectifying diode, a constant voltage diode, a PIN diode, a Schottky barrier diode, a surge protection diode, a diac, a varistor, and a tunnel diode.
Examples of the three-terminal element include a bipolar transistor, a Darlington transistor, a field effect transistor, an insulated gate bipolar transistor, a unijunction transistor, a static induction transistor, a gate turn thyristor, a triac, and a static induction thyristor.
Among these, a rectifying diode and transistors are preferably exemplified, and a field effect transistor is more preferably exemplified.

An organic thin film transistor (organic TFT) which is one embodiment of the organic semiconductor element of the present invention will be described with reference to the drawings.
FIG. 1 shows a schematic cross-sectional view of a bottom contact type organic thin film transistor as one embodiment of an organic thin film transistor (organic TFT).
In FIG. 1, an organic thin film transistor 100 includes a substrate 10, a gate electrode 20 disposed on the substrate 10, a gate insulating film 30 covering the gate electrode 20, and a side of the gate insulating film 30 opposite to the gate electrode 20 side. A source electrode 40 and a drain electrode 42 in contact with the surface, an organic semiconductor film 50 covering the surface of the gate insulating film 30 between the source electrode 40 and the drain electrode 42, and a sealing layer 60 covering each member are provided. That is, the organic thin film transistor 100 is a bottom gate-bottom contact type organic thin film transistor.
In FIG. 1, the organic semiconductor film 50 corresponds to a film formed from the above-described composition for forming an organic semiconductor film of the present invention.
Hereinafter, the substrate, the gate electrode, the gate insulating film, the source electrode, the drain electrode, the organic semiconductor film, the sealing layer, and the respective formation methods will be described in detail.

〔substrate〕
The substrate plays a role of supporting a gate electrode, a source electrode, a drain electrode, and the like, which will be described later.
The kind of board | substrate is not restrict | limited in particular, For example, a plastic substrate, a glass substrate, a ceramic substrate etc. are mentioned. Among these, a glass substrate or a plastic substrate is preferable from the viewpoint of applicability to each device and cost.

[Gate electrode, source electrode, drain electrode]
Examples of materials for the gate electrode, the source electrode, and the drain electrode include gold (Au), silver, aluminum (Al), copper, chromium, nickel, cobalt, titanium, platinum, tantalum, magnesium, calcium, barium, and sodium. Metals such as InO ₂ , SnO ₂ , and indium tin oxide (ITO); conductive polymers such as polyaniline, polypyrrole, polythiophene, polyacetylene, and polydiacetylene; silicon, Examples thereof include semiconductors such as germanium and gallium arsenide; carbon materials such as fullerenes, carbon nanotubes, and graphite. Among these, a metal is preferable, and silver or aluminum is more preferable.
The thicknesses of the gate electrode, the source electrode, and the drain electrode are not particularly limited, but are preferably 20 to 200 nm.

  A method for forming the gate electrode, the source electrode, and the drain electrode is not particularly limited. For example, a method of vacuum-depositing or sputtering an electrode material on a substrate, a method of applying or printing an electrode-forming composition, and the like. Can be mentioned. In the case of patterning the electrode, examples of the patterning method include a photolithography method; a printing method such as inkjet printing, screen printing, offset printing, and relief printing; a mask vapor deposition method and the like.

[Gate insulation film]
Materials for the gate insulating film include polymethyl methacrylate, polystyrene, polyvinyl phenol, polyimide, polycarbonate, polyester, polyvinyl alcohol, polyvinyl acetate, polyurethane, polysulfone, polybenzoxazole, polysilsesquioxane, epoxy resin, and phenol. Examples thereof include polymers such as resins; oxides such as silicon dioxide, aluminum oxide, and titanium oxide; and nitrides such as silicon nitride. Of these materials, a polymer is preferable in view of compatibility with the organic semiconductor film.
When a polymer is used as the material for the gate insulating film, it is preferable to use a crosslinking agent (for example, melamine) in combination. By using a crosslinking agent in combination, the polymer is crosslinked and the durability of the formed gate insulating film is improved.
The thickness of the gate insulating film is not particularly limited, but is preferably 100 to 1,000 nm.

The method for forming the gate insulating film is not particularly limited, and examples thereof include a method of applying a gate insulating film forming composition on a substrate on which a gate electrode is formed, a method of depositing or sputtering a gate insulating film material, and the like. It is done. The method for applying the gate insulating film forming composition is not particularly limited, and known methods (bar coating method, spin coating method, knife coating method, doctor blade method, etc.) can be used.
When a gate insulating film forming composition is applied to form a gate insulating film, it may be heated (baked) after application for the purpose of solvent removal, crosslinking, and the like.

(Binder polymer layer)
The organic semiconductor element of the present invention may have the binder polymer layer (not shown in FIGS. 1 and 2) between the organic semiconductor film and the gate insulating film. The binder polymer layer is preferably provided between the semiconductor film and the gate insulating film. The thickness of the binder polymer layer is not particularly limited, but is preferably 20 to 500 nm. Although the said binder polymer layer should just be a layer containing the said polymer, it is preferable that it is a layer which consists of the said binder polymer.

The method for forming the binder polymer layer is not particularly limited, and known methods (bar coating method, spin coating method, knife coating method, doctor blade method, ink jet method, etc.) can be used.
When the composition for forming a binder polymer layer is applied to form a binder polymer layer, it may be heated (baked) after coating for the purpose of solvent removal and crosslinking.

(Sealing layer)
The organic semiconductor element of the present invention preferably includes a sealing layer as the outermost layer from the viewpoint of durability. A well-known sealing agent can be used for a sealing layer.
The thickness of the sealing layer is not particularly limited, but is preferably 0.2 to 10 μm.

  The method for forming the sealing layer is not particularly limited. For example, the composition for forming the sealing layer is applied onto the substrate on which the gate electrode, the gate insulating film, the source electrode, the drain electrode, and the organic semiconductor film are formed. Methods and the like. A specific example of the method of applying the sealing layer forming composition is the same as the method of applying the gate insulating film forming composition. When the composition for forming a sealing layer is applied to form an organic semiconductor film, it may be heated (baked) after application for the purpose of solvent removal, crosslinking, and the like.

FIG. 2 shows a schematic cross-sectional view of a top contact type organic thin film transistor as another embodiment of the organic thin film transistor (organic TFT).
2, the organic thin film transistor 200 includes a substrate 10, a gate electrode 20 disposed on the substrate 10, a gate insulating film 30 covering the gate electrode 20, and an organic semiconductor film 50 disposed on the gate insulating film 30. A source electrode 40 and a drain electrode 42 disposed on the organic semiconductor film 50 and a sealing layer 60 covering each member are provided. Here, the source electrode 40 and the drain electrode 42 are formed using the composition of the present invention described above. That is, the organic thin film transistor 200 is a bottom gate-top contact type organic thin film transistor.
The substrate, gate electrode, gate insulating film, source electrode, drain electrode, organic semiconductor film, and sealing layer are as described above.

1 and 2, the embodiments of the bottom gate-bottom contact type organic thin film transistor and the bottom gate-top contact type organic thin film transistor have been described in detail. However, the organic semiconductor element of the present invention has a top gate-bottom type. It can also be suitably used for contact type organic thin film transistors and top gate-top contact type organic thin film transistors.
In addition, the organic thin-film transistor mentioned above can be used conveniently for electronic paper, a display device, etc.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “part” and “%” are based on mass.

[Compounds 1-14 and Comparative Compounds 1-7]
The structures of Compounds 1-14 and Comparative Compounds 1-7 used as organic semiconductor compounds are shown below. In Compound 6, “TIPS” represents a triisopropylsilyl group.

Hereinafter, the method for synthesizing the compound represented by the formula (1) of the present invention will be described with reference to the method for synthesizing Compound 1.
<Synthesis of Compound 1>
Compound 1 was synthesized by the method shown below.

(Synthesis of Intermediate 1)
4-Bromophenol (41.6 g, 240 mmol), 2-octyldodecyl bromide (174 g, 480 mmol), potassium carbonate (100 g, 720 mmol), and methyl ethyl ketone (480 mL) were mixed, and the resulting mixture was stirred under a nitrogen atmosphere. The mixture was stirred at 100 ° C. for 72 hours. After completion of the stirring, the resulting reaction solution was cooled to room temperature, filtered through celite, and washed with hexane. Subsequently, the filtrate was concentrated under reduced pressure, and the resulting crude product was purified by subjecting it to silica gel column chromatography (eluent: hexane) to obtain Intermediate 1 (80 g).

(Synthesis of Intermediate 2)
Intermediate 1 (30 g, 66 mmol), 4-pentyn-1-ol (18.3 mL, 198 mmol), copper iodide (630 mg, 3.3 mmol), diethylamine (90 mL), and tetrakistriphenylphosphine palladium (1.9 g) 1.7 mmol) and the resulting mixture was stirred at 70 ° C. for 4 hours under a nitrogen atmosphere. After completion of stirring, ethyl acetate (200 mL) was added to the resulting reaction solution, and the mixture was filtered through Celite to remove insolubles. Next, the filtrate was concentrated under reduced pressure, and the resulting crude product was purified by subjecting it to silica gel column chromatography (eluent: hexane / ethyl acetate = 4: 1 to 1: 1) to obtain Intermediate 2 (17.17). 5 g) was obtained.

(Synthesis of Intermediate 3)
Intermediate 2 (5.0 g, 11 mmol), 10 wt% Pd / C (3.6 g), and ethanol (25 mL) were mixed in an autoclave container to obtain a mixed solution. Next, 0.9 Mpa of hydrogen was charged into the reaction vessel, and the mixture was stirred at 30 ° C. for 4 hours. After completion of the stirring, the reaction vessel was returned to the atmosphere, the resulting reaction solution was filtered through celite, and the celite was washed with tetrahydrofuran. Next, the filtrate was concentrated under reduced pressure, and the resulting crude product was purified by subjecting it to silica gel column chromatography (eluent: hexane / ethyl acetate = 4: 1 to 2: 1) to obtain intermediate 3 (4. 2 g) was obtained.

(Synthesis of Intermediate 4)
After mixing Intermediate 3 (8.5 g, 18 mmol), imidazole (1.5 g, 22 mol), triphenylphosphine (5.8 g, 22 mol), and dichloromethane (54 mL), the mixture was 0 ° C. under nitrogen atmosphere. Cooled to. Next, iodine (5.6 g, 22 mol) was added little by little to the above mixture. After completing the addition of iodine, the reaction solution was raised to room temperature and stirred for 1 hour. To the obtained reaction solution, an aqueous sodium hydrogen sulfite solution was added to stop the reaction, followed by liquid separation to remove the aqueous layer. The organic layer was dried over magnesium sulfate and filtered. Then, the filtrate was concentrated under reduced pressure, and the resulting crude product was purified by subjecting it to silica gel column chromatography (eluent: hexane) to obtain Intermediate 4 (8.7 g).

(Synthesis of Intermediate 5)
3,6-di (2-thienyl) -2,5-dihydropyrrolo [3,4-c] pyrrole-1,4-dione (1.53 g, 5.1 mmol), potassium carbonate (2.1 g, 15. 3 mmol) and N, N-dimethylformamide (75 mL) were mixed and stirred at 100 ° C. for 1 hour under a nitrogen atmosphere. Thereafter, Intermediate 4 (8.7 g, 15 mmol) was added to the stirred mixture, and the mixture was further stirred at 100 ° C. for 6 hours. The resulting reaction solution was cooled to room temperature, filtered through celite, and washed with ethyl acetate. Next, the filtrate was concentrated under reduced pressure, and the resulting crude product was purified by subjecting it to silica gel column chromatography (eluent: hexane / ethyl acetate = 19: 1 to 9: 1) to obtain intermediate 5 (3. 2 g) was obtained.

(Synthesis of Compound 1)
(1) Under a nitrogen atmosphere, 2,2,6,6-tetramethylpiperidine (1 mL, 5.9 mmol) and dehydrated tetrahydrofuran (6.4 mL) were mixed, and the resulting mixture was cooled to -78 ° C. . Next, a 2.6M normal butyl lithium hexane solution (2.2 mL, 5.7 mmol) was added dropwise to the cooled mixture. After completion of the dropwise addition, the resulting reaction solution was heated to 0 ° C. to adjust the lithiating agent.
(2) Under a nitrogen atmosphere, Intermediate 5 (500 mg, 0.42 mmol) and dehydrated THF (5 mL) were mixed, and the resulting mixture was cooled to -78 ° C. Subsequently, the previously prepared lithiation agent (0.8 mL, corresponding to 0.46 mmol) was added dropwise to the mixture after cooling. After completion of the dropwise addition, the resulting reaction solution was stirred at −78 ° C. for 1 hour, and pentaerythrityl tetrabromide (27 mg, 0.07 mmol) was further added. Thereafter, the reaction solution was heated to 70 ° C. and stirred for 5 hours, and then the reaction solution was cooled to room temperature and water was added to stop the reaction. The reaction solution was extracted with chloroform, and then the organic layer was washed with saturated brine. The organic layer was dried over magnesium sulfate, filtered and concentrated under reduced pressure. The resulting crude product was purified by subjecting it to silica gel column chromatography (eluent: hexane / ethyl acetate = 19: 1 to 9: 1) to obtain Compound 1 (131 mg).

<Synthesis of Compounds 2-14>
Compounds 2 to 14 were also synthesized according to the synthesis method of Compound 1 above.

<Comparative compounds 1-7>
Comparative compound 1 is JP-T-2014-528908, comparative compound 2 is ACS Appl. Mater. Interfaces 2014, 6, 6765., comparative compound 3 is ACS Appl. Mater. Interfaces 2013, 5, 972, comparative compound. 4 is a compound described in JP-T-2014-528908, comparative compound 5 is a compound described in JP-A-2014-528908, and comparative compound 6 is a compound described in JP-A-2014-528908. Refer to the method described in each document. And synthesized. Comparative compound 7 is a commercially available product (manufactured by Aldrich).

[Formation and Evaluation of Organic Semiconductor Film 1]
The organic semiconductor film 1 containing the compounds 1-14 and the comparative compounds 1-7 synthesized above was prepared by the following procedure, and the carrier mobility was evaluated.

<Preparation of composition for forming organic semiconductor film>
5 mg of Compound 1 and 1 mL of chlorobenzene were weighed into a glass vial, stirred and mixed with a mix rotor (manufactured by ASONE Co., Ltd.) for 24 hours, and then filtered with a 0.45 μm membrane filter, thereby forming a composition 1A for forming an organic semiconductor film. Got.
Moreover, the composition for organic-semiconductor film formation 2A-14A and the composition for comparative-organic-semiconductor-film formation are the same methods except having used any of the compounds 2-14 and the comparative compounds 1-7 instead of the compound 1. Each of 1A-7A was prepared.

<Production of organic thin film transistor (organic TFT) element>
Al serving as a gate electrode was deposited on a glass substrate (Eagle XG: Corning) (thickness: 50 nm). On top of that, a composition for forming a gate insulating film (polyvinylphenol / melamine = 1 mass part / 1 mass part of PGMEA (propylene glycol monomethyl ether acetate) solution (solid content concentration: 2 mass%)) was spin-coated. Next, the obtained film was baked at 150 ° C. for 60 minutes to form a gate insulating film having a thickness of 400 nm. On top of that, a silver ink (silver nanocolloid H-1, manufactured by Mitsubishi Materials Corporation) is used for the source electrode and the drain electrode (channel length 40 μm, channel width) using an inkjet apparatus DMP-2831 (manufactured by Fujifilm Dimatics). (200 μm). Thereafter, the obtained laminate is baked at 180 ° C. for 30 minutes using an oven, and a portion drawn with silver ink is sintered to form a source electrode and a drain electrode, whereby an element substrate for TFT characteristic evaluation Got.
In a nitrogen glove box, the organic semiconductor film forming composition 1A prepared above is spin-coated on a TFT characteristic evaluation element substrate (500 rpm for 10 seconds, then 1,000 rpm for 30 seconds), and then the formed film is hot The organic semiconductor layer was formed by drying on a plate at 80 ° C. for 1 hour to obtain a bottom gate bottom contact type organic TFT element (hereinafter also referred to as “element”) 1A.
Moreover, the manufacturing method of the said element 1A except having used any of composition 2A-14A for organic semiconductor film formation, and composition 1A-7A for comparative organic semiconductor film formation instead of 1A for organic semiconductor film formation composition In accordance with the above, Elements 2A to 14A and Comparative Elements 1A to 7A were produced. The obtained elements 1A to 14A and comparative elements 1A to 7A were organic TFT elements of Examples 1 to 14 and Comparative Examples 1 to 7.

<Characteristic evaluation>
About each produced organic TFT element (element 1A-14A and comparison element 1A-7A), the following performance evaluation was performed in air | atmosphere using semiconductor characteristic evaluation apparatus B2900A (made by Agilent Technologies).
(A) Carrier mobility (carrier mobility before heating in the atmosphere (before heat resistance test))
A voltage of −60 V is applied between the source electrode and the drain electrode of each organic TFT element (elements 1A to 14A and comparison elements 1A to 7A), the gate voltage is changed in the range of +10 V to −60 V, and the drain current I _The carrier mobility μ was calculated using the following formula representing _d .
I _d = (w / 2L) μC _i (V _g −V _th ) ²
In the formula, L is the gate length, w is the gate width, C _i is the capacitance per unit area of the insulating layer, V _g is the gate voltage, and V _th is the threshold voltage.

(B) Carrier mobility after heating in air (after heat resistance test) and change ratio with respect to carrier mobility before heating in air (before heat resistance test) Each transistor element was heated in air at 150 ° C. for 30 minutes. Thereafter, the carrier mobility μ _{150 ° C.} after heating in the atmosphere was measured in the same manner as the measurement of carrier mobility before heating in the atmosphere. Next, the change ratio (μ _{150 °} C./μ) with respect to the carrier mobility before heating in the atmosphere was determined for each transistor element. The larger the value of μ150 _° C./μ, the better the heat resistance of the organic thin film transistor.
The evaluation criteria for μ _{150 °} C./μ were as follows. This evaluation is shown in Table 2 as “change in carrier mobility after heating in air”.

(Evaluation criteria)
“AA”: 1.0 times or more (improved mobility)
“A”: 0.8 times or more and less than 1.0 times “B”: 0.7 times or more and less than 0.8 times “C”: 0.5 times or more and less than 0.7 times “D”: 0 .2 times or more and less than 0.5 times "E": less than 0.2 times

(C) Threshold voltage change The voltage applied between the source electrode and the drain electrode was fixed to -60V, Vg was changed in the range of + 10V to -60V, and the threshold voltage Vth was measured. The closer the absolute value of this value is to 0, the better the threshold voltage.
The threshold voltage in the heat resistance test is evaluated by the difference between the threshold voltage value (absolute value) before the heat test and the threshold voltage value (absolute value) after the heat test [(absolute value of the threshold voltage after the heat test)] -(Absolute value of threshold voltage before heat resistance test)] was determined and evaluated based on this value according to the following criteria. In the following evaluation criteria, it is preferably AA. In addition, since the change in carrier mobility after heating in the atmosphere was large for the comparative compound, the threshold voltage change was not measured.

(Evaluation criteria)
“AA”: less than 5V “A”: 5V or more and less than 10V “B”: 10V or more

From the results shown in Table 1, the following can be understood.
It was confirmed that all of the organic TFT elements of Examples 1 to 14 were excellent in heat resistance without lowering the carrier mobility even after passing through the heating step in the air after forming the transistor element. In particular, it is selected from the group consisting of the groups represented by the formula (A-1), formula (A-2), formula (A-3), formula (A-5), and formula (A-8) described above. In the case of having any of the monovalent organic groups (particularly preferably, the monovalent organic group of the group represented by the formula (A-1)), the change in the threshold voltage before and after the heating step is small and more stable. It was confirmed that the obtained device performance was obtained.

Further, when Examples 1, 2, 7, and 10 are compared, the linking group L (the linking group L or Y ^L is preferably a carbon atom, a silicon atom, a sulfur atom, an oxygen atom, a nitrogen atom, or a carbon atom— It was shown that better heat resistance can be obtained by appropriately selecting a group consisting of an oxygen atom and a carbon atom.
Further, as shown in Example 13, when the linking group L was an aromatic hydrocarbon ring, the evaluation value was decreased as a whole.

On the other hand, as is clear from Comparative Examples 1 to 3 and 6, the desired effect when introducing an organic group of non-alkylene structure as the linking group X ^A is not expressed.
Further, as apparent from Comparative Examples 4 and 5, be introduced organic group alkylene structure as the linking group X ^A, no desired effect is expressed if the number of carbon atoms does not satisfy the formula (1) It was.
Further, as is clear from Comparative Example 7, the desired effect was not exhibited with TIPS pentacene.

[Formation and Evaluation of Organic Semiconductor Film 2]
The organic semiconductor film 2 prepared by mixing any of the compounds 1, 2, 3, 5, 6, 9 and the comparative compounds 1, 2, 4, 5, 6 synthesized above and a conductive polymer is prepared by the following procedure. The carrier mobility was evaluated.

<Preparation of composition for forming organic semiconductor film>
2 mg of compound 1, 3 mg of conductive polymer P1: PDPP2T-TT-OD (Mw: 40000-60000, manufactured by Aldrich) or P2 (Mw: 20000-40000, synthesized according to a known synthesis method), and 1 mL of chlorobenzene Weighing into a glass vial, stirring and mixing for 24 hours with a mix rotor (manufactured by AS ONE Co., Ltd.), and then filtering the resulting mixed solution with a 0.45 μm membrane filter to obtain composition 1B for forming an organic semiconductor film It was.
In addition, a composition 2B for forming an organic semiconductor film was formed in the same manner except that any one of compounds 2, 3, 5, 6, 9 and comparative compounds 1, 2, 4, 5, 6 was used instead of compound 1. 3B, 5B, 6B, and 9B and comparative organic semiconductor film forming compositions 1B, 2B, 4B, 5B, and 6B were prepared, respectively.
In addition, a reference organic semiconductor film-forming composition P1 was obtained with the same composition as in the above-described organic semiconductor film-forming composition 1B, except that 2 mg of the compound 12 was replaced with the conductive polymer (P1).
Moreover, in the composition 1B for forming an organic semiconductor film described above, a reference organic semiconductor film forming composition P2 was obtained with the same composition except that 12 mg of the compound 12 was replaced with the conductive polymer (P2).

(P1: PDPP2T-TT-OD)

(P2)

Next, using the organic semiconductor film-forming composition 1B obtained above, a bottom-gate / bottom-contact type organic TFT element 1B was produced according to the method described in the organic semiconductor film 1. In forming the organic semiconductor film 2, annealing was performed at 150 ° C. for 1 hour in a glove box instead of the drying step.
Subsequently, the obtained device was measured for carrier mobility according to the above-described property evaluation method (a), and judged according to the following evaluation criteria.
Further, instead of the organic semiconductor film forming composition 1B, the organic semiconductor film forming compositions 2B, 3B, 5B, 6B, 9B, the comparative organic semiconductor film forming compositions 1B, 2B, 4B, 5B, 6B, and the reference Except for using any one of the organic semiconductor film forming compositions P1 and P2 for manufacturing, the elements 2B, 3B, 5B, 6B, and 9B, the comparative elements 1B, 2B, 4B, 5B, 6B and reference elements P1 and P2 were respectively produced.
The obtained elements 2B, 3B, 5B, 6B, 9B and comparative elements 1B, 2B, 4B, 5B, 6B were used as organic TFT elements of Examples 15 to 20 and Comparative examples 8 to 12. Reference elements P1 and P2 were organic TFT elements of Reference Examples 1 and 2. For these elements, the carrier mobility was measured under the same conditions as those of the organic TFT element 1B, and the determination was made according to the following evaluation criteria.
In Table 2, only the results based on the organic TFT elements of Examples 15 to 20 are shown.

  Further, “carrier mobility” shown in Table 2 indicates carrier mobility of a compound alone. As a procedure, first, in the method for producing the organic semiconductor film 1, the compound 1 described in Table 1 is replaced with the compound described in Table 2 (compounds 1, 2, 3, 5, 6, or 9). A bottom gate bottom contact type organic TFT element was produced in the same manner except that annealing was performed at 150 ° C. for 1 hour in a glove box instead of the drying step. Subsequently, according to the above-mentioned characteristic evaluation method (a), the carrier mobility was measured and judged according to the following evaluation criteria.

(Evaluation criteria)
"S": 0.3cm ² / Vs greater than or equal to "AA": 0.2cm ² / Vs or more ~0.3cm less than ² / Vs "A": 0.1cm ² / Vs or more ~0.2cm less than ² / Vs " B ": 0.05 cm ² / Vs or more ~0.1cm less than ² / Vs" C ": 0.02 cm ² / Vs or more ~0.05cm less than ² / Vs" D ": 10 ^-4 cm ² / Vs or more and Less than 0.02 cm ² / Vs “E”: less than 10 ⁻⁴ cm ² / Vs

  Hereinafter, various evaluation results of Examples 15 to 20 are shown in Table 2.

In each of the organic TFT elements of Examples 15 to 20, the organic semiconductor film was formed by mixing the compound represented by the formula (1) and the conductive polymer compound as an organic semiconductor compound, and thus the carrier mobility was increased. It was confirmed that it was greatly improved.
The results are shown in Table 2, an organic semiconductor element composed of the reference conductive polymer P1 (reference element P1), an organic semiconductor element composed of the reference conductive polymer P2 (reference element P2), and Table 2. Compared to the carrier mobility of the organic semiconductor element composed of each compound 1, 3, 4, 5, 6, 9 alone ("carrier mobility" in Table 2), it was extremely high. . In addition, from the result of Examples 1-14, it was confirmed that the film | membrane obtained by the compound 1, 3, 4, 5, 6, or 9 contained in Examples 15-20 is excellent in heat resistance.
In Comparative Examples 8 to 12 (Comparative Elements 1B, 2B, 4B, 5B, and 6B), even when an organic semiconductor film is formed by mixing a comparative compound and a conductive polymer compound as an organic semiconductor compound, carrier mobility is increased. There was almost no change, and the desired effect was not exhibited.

  10: substrate, 20: gate electrode, 30: gate insulating film, 40: source electrode, 42: drain electrode, 50: organic semiconductor film, 60: sealing layer, 100, 200: organic thin film transistor

Claims (14)

The composition for organic-semiconductor film formation containing the compound represented by following formula (1).
In the formula (1), m represents an integer of 2 or more, L represents an m-valent organic group, X ^A represents a divalent linking group represented by the following formula (2), and A represents the following formula ( It represents a monovalent organic group represented by 3).
In Formula (2), # ¹ represents a bonding position to L, # ² represents a bonding position to A, Alk ¹ , Alk ² , and Alk ³ each independently represent an alkylene group, Q ¹ , And Q ³ each independently represent —O—, —S—, —NR ¹ —, —CO—, a vinylene group, an ethynylene group, or a divalent group formed by combining these, and Q ² is —O—, —S—, —NR ¹ —, —CO—, a vinylene group, an ethynylene group, an arylene group, a heteroarylene group, or a divalent group formed by a combination thereof, each R ¹ is independently Represents a hydrogen atom or a substituent, and j, k, l, s, t, and u each independently represent 0 or 1. However, at least one of j, k, and l is 1.
In the formula (3), # ² represents the bonding position to X ^A, Z represents an arylene group, or represents heteroarylene radical, a represents 0 or an integer of 1 or more, B is represented by the following formula ( A-1) represents any monovalent organic group selected from the group consisting of groups represented by formula (A- 10 ).
In the formula (A-1) to the formula (A- 10 ), each X independently represents an O atom, an S atom, a Se atom or NR ^A1, and each Y independently represents an O atom or an S atom; _a independently represents CR ^A2 or N atom; W independently represents C (R ^A2 ) ₂ , NR ^A1 , N atom, CR ^A2 , O atom, S atom or Se atom; and R ^A1 represents Each independently represents an alkyl group, an alkenyl group, an alkynyl group, or a bonding site with another structure, which may contain at least one of -O-, -S-, and -NR ^A3- ; R ^A2 each independently represents a hydrogen atom, a substituent, or a bonding site with another structure, each R independently represents a hydrogen atom or a substituent, and each R ^A3 independently represents a hydrogen atom or a substituent. Represents a group. However, the formula (A1) ~ formula (A- 10) has at least one ^{R A1} or ^{R A2,} and the binding site of any one of the ^{R A1} or ^{R A2} is the other structure Represents. In addition, when R ^A1 represents an alkyl group, an alkenyl group, or an alkynyl group that may contain at least one of —O—, —S—, and —NR ^A3 —, the substituent is further substituted. You may have. The composition for organic-semiconductor film formation of Claim 1 whose compound represented by said Formula (1) is a compound represented by following formula (4).
In formula (4), Y ^L represents a divalent to octavalent organic group,
R ^L1 each independently represents a monovalent organic group represented by the following formula (5),
R ^L2 each independently represents a hydrogen atom or a substituent,
p represents 2 to 8, q represents 0 to 6, and when Y ^L is n-valent, p + q represents n. In addition, n represents 2-8.
Wherein (5), ^{X A,} and A, ^{X A} in the formula (1), and A and are each synonymous.   In the formula (1), L represents a carbon atom, a silicon atom, a sulfur atom, an oxygen atom, a nitrogen atom, a group consisting of a carbon atom-oxygen atom-carbon atom, an m-valent aliphatic hydrocarbon ring, an m-valent aroma. The composition for forming an organic semiconductor film according to claim 1, which represents an aromatic hydrocarbon ring or an m-valent heterocyclic ring. In the formula (4), Y ^L is a carbon atom, a silicon atom, a sulfur atom, an oxygen atom, a nitrogen atom, a carbon atom - oxygen atom - a group consisting of carbon atoms, 2-8 monovalent aliphatic hydrocarbon ring, 2 The composition for forming an organic semiconductor film according to claim 2, which represents a ˜8-valent aromatic hydrocarbon ring or a 2-8 valent heterocycle. The organic semiconductor according to claim 4, wherein Y ^L in the formula (4) represents a group consisting of a carbon atom, a silicon atom, a sulfur atom, an oxygen atom, a nitrogen atom, or a carbon atom-oxygen atom-carbon atom. Film forming composition.   The composition for organic-semiconductor film formation of Claim 1 or Claim 3 whose m is an integer greater than or equal to 3 in said Formula (1).   The composition for organic-semiconductor film formation of Claim 2, 4 or 5 whose p is 3-8 in said Formula (4).   Furthermore, the composition for organic-semiconductor film formation of any one of Claims 1-7 containing a solvent.   Furthermore, the composition for organic-semiconductor film formation of any one of Claims 1-8 containing a high molecular compound.   Furthermore, the composition for organic-semiconductor film formation of any one of Claims 1-8 containing a conductive polymer compound.   The composition for forming an organic semiconductor film according to claim 10, wherein the conductive polymer compound includes a polymer in which an electron donating unit and an electron accepting unit are combined. A compound represented by the following formula (1).
In the formula (1), m represents an integer of 2 or more, L represents an m-valent organic group, X ^A represents a divalent linking group represented by the following formula (2), and A represents the following formula ( It represents a monovalent organic group represented by 3).
In Formula (2), # ¹ represents a bonding position to L, # ² represents a bonding position to A, Alk ¹ , Alk ² , and Alk ³ each independently represent an alkylene group, Q ¹ , And Q ³ each independently represent —O—, —S—, —NR ¹ —, —CO—, a vinylene group, an ethynylene group, or a divalent group formed by combining these, and Q ² is —O—, —S—, —NR ¹ —, —CO—, a vinylene group, an ethynylene group, an arylene group, a heteroarylene group, or a divalent group formed by a combination thereof, each R ¹ is independently Represents a hydrogen atom or a substituent, and j, k, l, s, t, and u each independently represent 0 or 1. However, at least one of j, k, and l is 1.
In the formula (3), # ² represents the bonding position to X ^A, Z represents an arylene group, or represents heteroarylene radical, a represents 0 or an integer of 1 or more, B is represented by the following formula ( A-1) represents any monovalent organic group selected from the group consisting of groups represented by formula (A- 10 ).
In the formula (A-1) to the formula (A- 10 ), each X independently represents an O atom, an S atom, a Se atom or NR ^A1, and each Y independently represents an O atom or an S atom; _a independently represents CR ^A2 or N atom; W independently represents C (R ^A2 ) ₂ , NR ^A1 , N atom, CR ^A2 , O atom, S atom or Se atom; and R ^A1 represents Each independently represents an alkyl group, an alkenyl group, an alkynyl group, or a bonding site with another structure, which may contain at least one of -O-, -S-, and -NR ^A3- ; R ^A2 each independently represents a hydrogen atom, a substituent, or a bonding site with another structure, each R independently represents a hydrogen atom or a substituent, and each R ^A3 independently represents a hydrogen atom. Or represents a substituent. However, the formula (A1) ~ formula (A- 10) has at least one ^{R A1} or ^{R A2,} and the binding site of any one of the ^{R A1} or ^{R A2} is the other structure Represents. In addition, when R ^A1 represents an alkyl group, an alkenyl group, or an alkynyl group that may contain at least one of —O—, —S—, and —NR ^A3 —, the substituent is further substituted. You may have.   An organic semiconductor film comprising the compound according to claim 12.   An organic semiconductor element comprising the organic semiconductor film according to claim 13.