JPWO2016076197A1 - Organic semiconductor device and compound - Google Patents

Abstract

An object of the present invention is to provide an organic semiconductor element having a low mobility variation and having a high mobility without annealing at a high temperature, and a method for manufacturing the same. Another object of the present invention is to provide a novel compound suitable as an organic semiconductor. Furthermore, the present invention provides an organic semiconductor film having a low mobility variation and a high mobility without performing an annealing process at a high temperature, and an organic semiconductor film forming composition capable of suitably forming the organic semiconductor film. Aimed to do. The organic semiconductor element of the present invention has an organic semiconductor layer containing an organic semiconductor having a repeating unit represented by Formula 1.

Description

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

Since it can be reduced in weight, cost, and flexibility, it has an organic semiconductor film (organic semiconductor layer) on FETs (field effect transistors), RFIDs (RF tags), etc. used in liquid crystal displays and organic EL displays. Organic transistors are used.
As a conventional organic semiconductor, the one described in Patent Document 1 is known.

Special table 2010-527327

The problem to be solved by the present invention is to provide an organic semiconductor element having a low mobility variation and a high mobility without performing an annealing process at a high temperature, and a method for manufacturing the same.
Another problem to be solved by the present invention is to provide a novel compound suitable as an organic semiconductor.
Furthermore, another problem to be solved by the present invention is to suitably form an organic semiconductor film having a small mobility variation and a high mobility without performing an annealing process at a high temperature, and the organic semiconductor film. It is to provide a composition for forming an organic semiconductor film.

The above-described problems of the present invention have been solved by means described in the following <1>, <5>, <10>, <15>, or <16>. It is described below together with <2> to <4>, <6> to <9>, <11> to <14>, and <17> to <20>, which are preferred embodiments.
<1> An organic semiconductor element comprising an organic semiconductor layer containing an organic semiconductor having a repeating unit represented by Formula 1,

In Formula 1, X represents any of CR ¹² ₂ , O, S, Se, NR ¹² , SiR ¹² ₂ , R ¹² independently represents a hydrogen atom or a monovalent organic group, Y ¹¹ and Y ¹² each independently represents O, S, N-CN, or CQ ₂ , and Q represents CN, CF ₃ , C (═O) R ¹³ , C (═O) OR ¹³ , or SO ₂ R ^13. R ¹³ represents a monovalent organic group, a plurality of R ¹³ may be bonded to each other to form a ring, and Y ¹¹ and Y ¹² do not simultaneously become O, and R ¹¹ is a monovalent group. Ar ¹¹ , Ar ¹² and Ar ¹³ each independently represents an aromatic hydrocarbon group, an aromatic heterocyclic group, a vinylene group or an ethynylene group, and m11 represents an integer of 0 to 2. , M12 represents an integer of 0-4, m13 represents an integer of 0-2,
<2> The organic semiconductor element according to <1>, wherein X is any one of O, S, and NR ¹² .
<3> The organic semiconductor element according to <1> or <2>, wherein Y ¹¹ and Y ¹² are both S, or both are C (CN) ₂ .
<4> The organic semiconductor element according to any one of <1> to <3>, wherein the repeating unit represented by Formula 1 is a repeating unit represented by Formula 2.

In Formula 2, X represents any of CR ¹² ₂ , O, S, Se, NR ¹² , and SiR ¹² ₂ , R ¹² independently represents a hydrogen atom or a monovalent organic group, Y ¹¹ and Y ¹² each independently represents O, S, N-CN, or CQ ₂ , and Q represents CN, CF ₃ , C (═O) R ¹³ , C (═O) OR ¹³ , or SO ₂ R ^13. R ¹³ represents a monovalent organic group, a plurality of R ¹³ may be bonded to each other to form a ring, and Y ¹¹ and Y ¹² do not simultaneously become O, and R ¹¹ is a monovalent group. Ar ¹² represents an aromatic hydrocarbon group, an aromatic heterocyclic group, a vinylene group or an ethynylene group, m12 represents an integer of 0 to 4, and X ²¹ and X ²² each independently , O, S, Se, NR 12 ', SiR 12' represents one of the _2, R ^{12 'each} independently represent a hydrogen atom or a monovalent organic group, R ²¹ to R ²⁴ is To respectively independently represent a hydrogen atom or a monovalent organic group, m11 'represents an integer of 0 to 2, m13' is an integer of 0 to 2,
<5> a compound having a repeating unit represented by formula 1,

In Formula 1, X represents any of CR ¹² ₂ , O, S, Se, NR ¹² , SiR ¹² ₂ , R ¹² independently represents a hydrogen atom or a monovalent organic group, Y ¹¹ and Y ¹² each independently represents O, S, N-CN, or CQ ₂ , and Q represents CN, CF ₃ , C (═O) R ¹³ , C (═O) OR ¹³ , or SO ₂ R ^13. R ¹³ represents a monovalent organic group, a plurality of R ¹³ may be bonded to each other to form a ring, and Y ¹¹ and Y ¹² do not simultaneously become O, and R ¹¹ is a monovalent group. Ar ¹¹ , Ar ¹² and Ar ¹³ each independently represents an aromatic hydrocarbon group, an aromatic heterocyclic group, a vinylene group or an ethynylene group, and m11 represents an integer of 0 to 2. , M12 represents an integer of 0-4, m13 represents an integer of 0-2,
<6> The compound according to <5>, wherein X is any one of O, S and NR ¹²
<7> The compound according to <5> or <6>, wherein Y ¹¹ and Y ¹² are both S, or both are C (CN) ₂ .
<8> The compound according to any one of <5> to <7>, wherein the repeating unit represented by Formula 1 is a repeating unit represented by Formula 2.

In Formula 2, X represents any of CR ¹² ₂ , O, S, Se, NR ¹² , and SiR ¹² ₂ , R ¹² independently represents a hydrogen atom or a monovalent organic group, Y ¹¹ and Y ¹² each independently represents O, S, N-CN, or CQ ₂ , and Q represents CN, CF ₃ , C (═O) R ¹³ , C (═O) OR ¹³ , or SO ₂ R ^13. R ¹³ represents a monovalent organic group, a plurality of R ¹³ may be bonded to each other to form a ring, and Y ¹¹ and Y ¹² do not simultaneously become O, and R ¹¹ is a monovalent group. Ar ¹² represents an aromatic hydrocarbon group, an aromatic heterocyclic group, a vinylene group or an ethynylene group, m12 represents an integer of 0 to 4, and X ²¹ and X ²² each independently , O, S, Se, NR 12 ', SiR 12' represents one of the _2, R ^{12 'each} independently represent a hydrogen atom or a monovalent organic group, R ²¹ to R ²⁴ is To respectively independently represent a hydrogen atom or a monovalent organic group, m11 'represents an integer of 0 to 2, m13' is an integer of 0 to 2,
<9> The compound according to any one of <5> to <8>, which is an organic semiconductor,
<10> A composition for forming an organic semiconductor film, comprising a compound having a repeating unit represented by Formula 1 and a solvent,

In Formula 1, X represents any of CR ¹² ₂ , O, S, Se, NR ¹² , SiR ¹² ₂ , R ¹² independently represents a hydrogen atom or a monovalent organic group, Y ¹¹ and Y ¹² each independently represents O, S, N-CN, or CQ ₂ , and Q represents CN, CF ₃ , C (═O) R ¹³ , C (═O) OR ¹³ , or SO ₂ R ^13. R ¹³ represents a monovalent organic group, a plurality of R ¹³ may be bonded to each other to form a ring, and Y ¹¹ and Y ¹² do not simultaneously become O, and R ¹¹ is a monovalent group. Ar ¹¹ , Ar ¹² and Ar ¹³ each independently represents an aromatic hydrocarbon group, an aromatic heterocyclic group, a vinylene group or an ethynylene group, and m11 represents an integer of 0 to 2. , M12 represents an integer of 0-4, m13 represents an integer of 0-2,
<11> X is is O, S, one of NR ^12, the organic semiconductor film forming composition as described in <10>,
<12> The composition for forming an organic semiconductor film according to <10> or <11>, wherein Y ¹¹ and Y ¹² are both S, or both are C (CN) ₂ .
<13> The composition for forming an organic semiconductor film according to any one of <10> to <12>, wherein the repeating unit represented by Formula 1 is a repeating unit represented by Formula 2.

In Formula 2, X represents any of CR ¹² ₂ , O, S, Se, NR ¹² , and SiR ¹² ₂ , R ¹² independently represents a hydrogen atom or a monovalent organic group, Y ¹¹ and Y ¹² each independently represents O, S, N-CN, or CQ ₂ , and Q represents CN, CF ₃ , C (═O) R ¹³ , C (═O) OR ¹³ , or SO ₂ R ^13. R ¹³ represents a monovalent organic group, a plurality of R ¹³ may be bonded to each other to form a ring, and Y ¹¹ and Y ¹² do not simultaneously become O, and R ¹¹ is a monovalent group. Ar ¹² represents an aromatic hydrocarbon group, an aromatic heterocyclic group, a vinylene group or an ethynylene group, m12 represents an integer of 0 to 4, and X ²¹ and X ²² each independently , O, S, Se, NR 12 ', SiR 12' represents one of the _2, R ^{12 'each} independently represent a hydrogen atom or a monovalent organic group, R ²¹ to R ²⁴ is To respectively independently represent a hydrogen atom or a monovalent organic group, m11 'represents an integer of 0 to 2, m13' is an integer of 0 to 2,
<14> The composition for forming an organic semiconductor film according to any one of <10> to <13>, further containing a binder polymer,
<15> The manufacturing method of an organic semiconductor element including the application | coating process which apply | coats the composition for organic-semiconductor film formation as described in any one of <10>-<14> on a board | substrate,
<16> an organic semiconductor film containing a compound having a repeating unit represented by formula 1,

In Formula 1, X represents any of CR ¹² ₂ , O, S, Se, NR ¹² , SiR ¹² ₂ , R ¹² independently represents a hydrogen atom or a monovalent organic group, Y ¹¹ and Y ¹² each independently represents O, S, N-CN, or CQ ₂ , and Q represents CN, CF ₃ , C (═O) R ¹³ , C (═O) OR ¹³ , or SO ₂ R ^13. R ¹³ represents a monovalent organic group, a plurality of R ¹³ may be bonded to each other to form a ring, and Y ¹¹ and Y ¹² do not simultaneously become O, and R ¹¹ is a monovalent group. Ar ¹¹ , Ar ¹² and Ar ¹³ each independently represents an aromatic hydrocarbon group, an aromatic heterocyclic group, a vinylene group or an ethynylene group, and m11 represents an integer of 0 to 2. , M12 represents an integer of 0-4, m13 represents an integer of 0-2,
<17> X is O, S, is either NR ^12, the organic semiconductor film according to <16>,
<18> The organic semiconductor film according to <16> or <17>, wherein Y ¹¹ and Y ¹² are both S, or both are C (CN) ₂ .
<19> The organic semiconductor film according to any one of <16> to <18>, wherein the repeating unit represented by Formula 1 is a repeating unit represented by Formula 2.

In Formula 2, X represents any of CR ¹² ₂ , O, S, Se, NR ¹² , and SiR ¹² ₂ , R ¹² independently represents a hydrogen atom or a monovalent organic group, Y ¹¹ and Y ¹² each independently represents O, S, N-CN, or CQ ₂ , and Q represents CN, CF ₃ , C (═O) R ¹³ , C (═O) OR ¹³ , or SO ₂ R ^13. R ¹³ represents a monovalent organic group, a plurality of R ¹³ may be bonded to each other to form a ring, and Y ¹¹ and Y ¹² do not simultaneously become O, and R ¹¹ is a monovalent group. Ar ¹² represents an aromatic hydrocarbon group, an aromatic heterocyclic group, a vinylene group or an ethynylene group, m12 represents an integer of 0 to 4, and X ²¹ and X ²² each independently , O, S, Se, NR 12 ', SiR 12' represents one of the _2, R ^{12 'each} independently represent a hydrogen atom or a monovalent organic group, R ²¹ to R ²⁴ is To respectively independently represent a hydrogen atom or a monovalent organic group, m11 'represents an integer of 0 to 2, m13' is an integer of 0 to 2,
<20> The organic semiconductor film according to any one of <16> to <19>, which is formed by a solution coating method.

According to the present invention, it is possible to provide an organic semiconductor element having a low mobility variation and a high mobility without performing an annealing process at a high temperature, and a method for manufacturing the same.
Moreover, according to this invention, the novel compound suitable as an organic semiconductor can be provided.
Furthermore, according to the present invention, there is little variation in mobility, and the organic semiconductor film has a high mobility without performing an annealing process at a high temperature, and the organic semiconductor film that can suitably form the organic semiconductor film. A forming composition can be provided.

It is a cross-sectional schematic diagram of one aspect | mode of the organic-semiconductor element of this invention. It is a cross-sectional schematic diagram of another one aspect | mode of the organic-semiconductor element of this invention.

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 the specification of the present application, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. The organic EL element in the present invention refers to an organic electroluminescence element.
In the notation of a group (atomic group) in this specification, the notation which does not describe substitution and unsubstituted includes what has a substituent with what does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In addition, the chemical structural formula in this specification may be expressed as a simplified structural formula in which a hydrogen atom is omitted.
In the present invention, “mass%” and “wt%” are synonymous, and “part by mass” and “part by weight” are synonymous.
In the present invention, a combination of preferred embodiments is more preferred.

(Organic semiconductor device)
The organic semiconductor element of the present invention includes an organic semiconductor layer containing an organic semiconductor having a repeating unit represented by Formula 1 (hereinafter also referred to as “specific organic semiconductor compound”).

As a result of intensive studies, the present inventors have found that there is little variation in mobility of the obtained organic semiconductor element and organic semiconductor film by containing the specific organic semiconductor compound, and high mobility without performing annealing treatment at a high temperature. As a result, the present invention has been completed.
Although the mechanism of expression of the detailed effect is unknown, it is considered that the specific organic semiconductor compound has a uniform film quality, and thus variation in mobility can be suppressed.

<Specific organic semiconductor compound>
In the present invention, the specific organic semiconductor compound has a repeating unit represented by the following formula 1.

In Formula 1, X represents any of CR ¹² ₂ , O, S, Se, NR ¹² , SiR ¹² ₂ , R ¹² independently represents a hydrogen atom or a monovalent organic group, Y ¹¹ and Y ¹² each independently represents O, S, N-CN, or CQ ₂ , and Q represents CN, CF ₃ , C (═O) R ¹³ , C (═O) OR ¹³ , or SO ₂ R ^13. R ¹³ represents a monovalent organic group, a plurality of R ¹³ may be bonded to each other to form a ring, and Y ¹¹ and Y ¹² do not simultaneously become O, and R ¹¹ is a monovalent group. Ar ¹¹ , Ar ¹² and Ar ¹³ each independently represents an aromatic hydrocarbon group, an aromatic heterocyclic group, a vinylene group or an ethynylene group, and m11 represents an integer of 0 to 2. , M12 represents an integer of 0 to 4, and m13 represents an integer of 0 to 2.

The specific organic semiconductor compound of the present invention is a novel compound.
Moreover, the specific organic semiconductor compound of this invention can be used suitably for an organic semiconductor element, an organic semiconductor film, and the composition for organic-semiconductor film formation.

In Formula 1, X represents any one of CR ¹² ₂ , O, S, Se, NR ¹² , and SiR ¹² ₂ , more preferably any of O, S, and NR ¹² , and more preferably S. preferable.
R ¹² each independently represents a hydrogen atom or a monovalent organic group, preferably an alkyl group, more preferably an alkyl group having 1 to 30 carbon atoms, and still more preferably an alkyl group having 1 to 15 carbon atoms. The alkyl group may be linear, branched or cyclic.

Y ¹¹ and Y ¹² each independently represent O, S, N—CN, or CQ ₂ , where Q is CN, CF ₃ , C (═O) R ¹³ , C (═O) OR ¹³ , or SO ₂ R ¹³ is represented, and both Y ¹¹ and Y ¹² are preferably S, or both are preferably C (CN) ₂ , more preferably S.
Y ¹¹ and Y ¹² may be different, but are preferably the same from the viewpoint of production suitability.
R ¹³ represents a monovalent organic group, preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and an alkyl group having 1 to 10 carbon atoms. Is more preferable.
A plurality of R ¹³ may be bonded to each other to form a ring. The ring formed by a plurality of R ¹³ may be further condensed with an aromatic ring such as a benzene ring.
Further, Y ¹¹ and Y ¹² do not become O at the same time.

R ¹¹ represents a monovalent organic group, preferably an alkyl group, an aryl group or a heteroaryl group, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a heteroaryl group having 4 to 20 carbon atoms. Is more preferable, a C1-C40 alkyl group is still more preferable, and a C1-C30 alkyl group is especially preferable.
R ¹¹ may have a vinylene group or an ethynylene group at the bonding position with the N atom.
The alkyl group may be linear, branched or cyclic.
As the aryl group, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable.
As the heteroaryl group, one hydrogen atom is removed from a ring selected from the group consisting of a thiophene ring, a pyrrole ring, a thiazole ring, an imidazole ring, a furan ring, a benzothiophene ring, a benzothiazole ring, and a benzimidazole ring. A thiophene ring is preferred.
The alkyl group, aryl group and heteroaryl group may have a substituent. Preferred substituents include alkyl groups, aryl groups, and groups obtained by removing one hydrogen atom from polysiloxane, and alkyl groups having 1 to 8 carbon atoms are preferred. The aryl group is preferably a phenyl group. As the polysiloxane, dimethylpolysiloxane is preferable, and dimethylpolysiloxane having 3 to 8 Si atoms is preferable.

Ar ¹¹ , Ar ¹² and Ar ¹³ each independently represent an aromatic hydrocarbon group, an aromatic heterocyclic group, a vinylene group or an ethynylene group.
Ar ¹¹ and Ar ¹³ are preferably an aromatic hydrocarbon group or an aromatic heterocyclic group, and may have a polycyclic structure, but preferably a monocyclic structure.
As an aromatic hydrocarbon group, a C6-C20 arylene group is preferable, a phenylene group or a naphthylene group is preferable, and a phenylene group is more preferable.
Although it does not specifically limit as a hetero atom of an aromatic heterocyclic ring, S, O, N, and Se are illustrated, As an aromatic heterocyclic group, a thiophen ring, a furan ring, a pyran ring, a pyrrole ring, a pyridine ring, a pyrazine ring , A pyrimidine ring, a pyridazine ring, a selenophene ring, an imidazole ring, and a group obtained by removing two hydrogen atoms from a ring selected from the group consisting of thienothiophene rings, thiophene ring, furan ring, pyrrole ring, pyridine ring And a group obtained by removing two hydrogen atoms from a ring selected from the group consisting of a selenophene ring and a thienothiophene ring, and a group obtained by removing two hydrogen atoms from a thiophene ring is more preferred.
Moreover, the aromatic hydrocarbon group or the aromatic heterocyclic group may have a substituent. Preferable substituents include an alkyl group, an alkyl group having 1 to 20 carbon atoms is preferable, and an alkyl group having 8 to 20 carbon atoms is more preferable.
From the viewpoint of production suitability, Ar ¹¹ and Ar ¹³ are preferably the same.

Ar ¹² represents an aromatic hydrocarbon group, an aromatic heterocyclic group, a vinylene group, or an ethynylene group, and preferably represents a condensed polycyclic aromatic group, a vinylene group, or a thienylene group.
As the aromatic hydrocarbon group, an arylene group having 6 to 20 carbon atoms is preferable, and a phenylene group, a naphthylene group, or a group in which two hydrogen atoms are removed from an anthracene ring is preferable.
Although it does not specifically limit as a hetero atom of an aromatic heterocyclic ring, S, O, N, and Se are illustrated, As an aromatic heterocyclic group, a thiophen ring, a furan ring, a pyran ring, a pyrrole ring, a pyridine ring, a pyrazine ring , A pyrimidine ring, a pyridazine ring, a selenophene ring, an imidazole ring, and a group obtained by removing two hydrogen atoms from a ring selected from the group consisting of thienothiophene rings, thiophene ring, furan ring, pyrrole ring, pyridine ring A group obtained by removing two hydrogen atoms from a ring selected from the group consisting of a selenophene ring and a thienothiophene ring, and two hydrogen atoms from a ring selected from the group consisting of a thiophene ring and a thienothiophene ring Is more preferable, and a group in which two hydrogen atoms are removed from the thiophene ring is more preferable.
The aromatic hydrocarbon group or aromatic heterocyclic group may have a substituent. Preferable substituents include an alkyl group, an alkyl group having 1 to 20 carbon atoms is preferable, and an alkyl group having 8 to 20 carbon atoms is more preferable.
Ar ¹² preferably represents a condensed polycyclic aromatic group in which a plurality of aromatic hydrocarbon groups or aromatic heterocyclic groups are condensed. When Ar ¹² represents a condensed polycyclic aromatic group, it is preferably a 3-7 ring condensed ring, and more preferably a 3-5 ring condensed ring. The condensed ring may contain a non-aromatic heterocyclic group such as cyclotetramethylene silane.
Also, if the Ar ¹² represents a fused polycyclic aromatic group, preferably a structure represented by any one of the following formulas AR-1~AR-10.

In Formula AR-1 to Formula AR-10, X ^A1 , X ^A2 , X ^A4 , and X ^A5 each independently represent any of S, O, CR ^AR ₂ , NR ^AR , SiR ^AR ₂ , and R Each ^AR independently represents a monovalent organic group. R ^AR is preferably an alkyl group having 8 to 20 carbon atoms.
Among these, AR-1 to AR-6, AR-9, or AR-10 is preferable, and any of AR-1 to AR-5 is more preferable, and AR-1 or AR- More preferably, it is 5.
The polycyclic aromatic hydrocarbon group or the polycyclic aromatic heterocyclic group may have a substituent. Preferable substituents include an alkyl group, an alkyl group having 1 to 30 carbon atoms is preferable, and an alkyl group having 8 to 20 carbon atoms is more preferable.

m11 represents an integer of 0 to 2, m12 represents an integer of 0 to 4, m13 represents an integer of 0 to 2, and the total of m11, m12, and m13 is preferably 1 or more.
When Ar ¹² is a vinylene group or an ethynylene group, m12 is preferably 1, and m11 and m13 are each independently preferably 1 or 2.
When Ar ¹² is an aromatic hydrocarbon group or an aromatic heterocyclic group, m12 is preferably 1 or 2, and m11 and m13 are each independently preferably 0 or 1.
When Ar ¹² is a condensed polycyclic aromatic group, m12 is preferably 1, and m11 and m13 are each independently preferably 0 or 1.

  Moreover, it is preferable that the repeating unit represented by Formula 1 is a repeating unit represented by Formula 2.

In the formula ^{2, X, Y 11, Y} 12, R 11, Ar 12 and, m12 is, X in each formula ^{1, Y 11, Y 12,} R 11, Ar 12, and is synonymous with m12, The preferred ranges are also the same. X ²¹ and X ²² each independently represents any of O, S, Se, NR ¹² , and SiR ¹² ₂ , and R ¹² each independently represents a hydrogen atom or a monovalent organic group. R ^{21 to} R ²⁴ each independently represents a hydrogen atom or a monovalent organic group, m 11 ′ represents an integer of 0 to 2, and m 13 ′ represents an integer of 0 to 2.

X ²¹ and X ²² each independently represent any of O, S, Se, NR ^{12 ′} , and SiR ^{12 ′} ₂ , more preferably any of O, S, and NR ^{12 ′} , and S. More preferably.
R ^{12 ′} each independently represents a hydrogen atom or a monovalent organic group, preferably an alkyl group, more preferably an alkyl group having 1 to 30 carbon atoms, and still more preferably an alkyl group having 1 to 15 carbon atoms. The alkyl group may be linear, branched or cyclic.
R ^{21 to} R ²⁴ each independently represents a hydrogen atom or a monovalent organic group, preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 8 to 20 carbon atoms.
m11 ′ represents an integer of 0 to 2, m13 ′ represents an integer of 0 to 2, and the total of m11 ′, m12, and m13 ′ is preferably 1 or more.
When Ar ¹² is a vinylene group or an ethynylene group, m12 represents 1, and m11 ′ and m13 ′ are preferably each independently 1 or 2.
When Ar ¹² is an aromatic hydrocarbon group or an aromatic heterocyclic group, m12 is preferably 1 or 2, and m11 ′ and m13 ′ are each independently preferably 0 or 1.
When Ar ¹² is a condensed polycyclic aromatic group, m12 is preferably 1, and m11 ′ and m13 ′ are each independently preferably 0 or 1.

  In the specific organic semiconductor compound, the content of the repeating unit represented by Formula 1 is preferably 60 to 100% by mass and more preferably 80 to 100% by mass with respect to the total mass of the specific organic semiconductor compound. Preferably, it is 90-100 mass%.

The weight average molecular weight of the specific organic semiconductor compound is not particularly limited, but is preferably 1,000 to 2,000,000, more preferably 10,000 to 1,000,000, and still more preferably 50,000 to 500,000.
By setting the molecular weight within the above range, both solubility in a solvent and film quality stability of the thin film can be achieved.
In the present invention, the weight average molecular weight and the number average molecular weight are measured by a gel permeation chromatography method (GPC) method and are calculated by standard polystyrene. Specifically, for example, GPC uses HLC-8220GPC (manufactured by Tosoh Corporation), and TSKgeL SuperHZM-H, TSKgeL SuperHZ4000, TSKgeL SuperHZ2000 (4.6 mm ID × 15 cm, manufactured by Tosoh Corporation) are used as columns. Three are used and THF (tetrahydrofuran) is used as an eluent. As conditions, the sample concentration is 0.35% by mass, the flow rate is 0.35 ml / min, the sample injection amount is 10 μl, the measurement temperature is 40 ° C., and an IR detector is used. The calibration curve is “Standard sample TSK” manufactured by Tosoh Corporation.
“standard, polystyrene”: “F-40”, “F-20”, “F-4”, “F-1”, “A-5000”, “A-2500”, “A-1000”, “n-” Prepared from 8 samples of “propylbenzene”.
The organic semiconductor layer described later, the organic semiconductor film described later, or the composition for forming an organic semiconductor film includes two or more specific organic semiconductor compounds even if only one specific organic semiconductor compound is included. However, from the viewpoint of orientation, only one type is preferable.

  As specific examples of the specific organic semiconductor compound represented by Formula 1 used in the present invention, compounds (E-1 to E-26) containing the repeating units shown below are preferably exemplified. It is not limited to the example.

  Among these, E-1, E-3, E-4, E-5, and E-8 are preferable, and E-1, E-4, and E-5 are more preferable.

  The method for synthesizing the specific organic semiconductor compound is not particularly limited, and can be synthesized with reference to known methods. For example, JP 2011-168747 A, Macromol. , 2013, 46, 3887. And J.A. Org. Chem. 1985, 50, 1681. Etc. can be synthesized with reference to the above.

  The content of the specific organic semiconductor compound in the organic semiconductor layer of the organic semiconductor element of the present invention or the organic semiconductor film of the present invention described later is 30 to 100% by mass with respect to the total mass of the organic semiconductor layer or the organic semiconductor film. It is preferable that it is 50-100 mass%, It is more preferable that it is 70-100 mass%. Moreover, when not containing the binder polymer mentioned later, it is preferable that the said content is 90-100 mass% with respect to the total mass of an organic-semiconductor layer or an organic-semiconductor film, and it is 95-100 mass%. More preferred.

(Compound)
The compound of the present invention has a repeating unit represented by Formula 1.

In Formula 1, X, Y ¹¹ , Y ¹² , R ¹¹ , Ar ¹¹ , Ar ¹² , Ar ¹³ , m11, m12, and m13 are X, Y ¹¹ , Y ¹² , R ¹¹ , and R ¹³ in the specific organic semiconductor compound, respectively. ^{Ar 11, Ar 12, Ar 13} , m11, m12, and have the same meanings as m13, preferable embodiments thereof are also the same.

The compound of the present invention is preferably an organic semiconductor compound.
In addition, the content, weight average molecular weight, specific examples and synthesis method of the repeating unit represented by Formula 1 in the compound of the present invention are the same as those in the specific organic semiconductor compound, and the preferred embodiments are also the same.

<Binder polymer>
The organic semiconductor layer of the organic semiconductor element of the present invention preferably contains a binder polymer.
The organic semiconductor element of the present invention may be an organic semiconductor element having the organic semiconductor layer and a layer containing a binder polymer.
The kind in particular of a binder polymer is not restrict | limited, A well-known binder polymer can be used.
Binder polymers include insulating polymers such as polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyimide, polyurethane, polysiloxane, polysulfone, polymethyl methacrylate, polymethyl acrylate, cellulose, polyethylene, polypropylene, and their co-polymers. Mention of semiconducting polymers such as coalescence, polysilane, polycarbazole, polyarylamine, polyfluorene, polythiophene, polypyrrole, polyaniline, polyparaphenylene vinylene, polyacene, polyheteroacene, and their copolymers, rubber, thermoplastic elastomers Can do.
Among these, as the binder polymer, a polymer compound having a benzene ring (a polymer having a monomer unit having a benzene ring group) is preferable. The content of the monomer unit having a benzene ring group is not particularly limited, but is preferably 50 mol% or more, more preferably 70 mol% or more, and still more preferably 90 mol% or more in all monomer units. The upper limit is not particularly limited, but 100 mol% can be mentioned.
Examples of the binder polymer include polystyrene, poly (α-methylstyrene), polyvinyl cinnamate, poly (4-vinylphenyl), poly (4-methylstyrene), and poly [bis (4-phenyl) (2,4 , 6-trimethylphenyl) amine], poly [2,6- (4,4-bis (2-ethylhexyl) -4Hcyclopenta [2,1-b; 3,4-b ′] dithiophene) -alt-4, 7- (2,1,3-benzothiadiazole)] and the like, and poly (α-methylstyrene) is particularly preferable.

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.
Moreover, when using the solvent mentioned later, it is preferable that the binder polymer has higher solubility in the solvent used than the specific organic semiconductor compound. It is excellent in the mobility and thermal stability of the organic semiconductor obtained as it is the said aspect.
It is preferable that content of the binder polymer in the organic-semiconductor layer of the organic-semiconductor element of this invention is 1-200 mass parts with respect to 100 mass parts of content of a specific organic semiconductor compound, It is 10-150 mass parts. Is more preferable, and it is still more preferable that it is 20-120 mass parts. It is excellent in the mobility and thermal stability of the organic semiconductor obtained as it is the said range.

<Other ingredients>
The organic semiconductor layer in the organic semiconductor element of the present invention may contain other components in addition to the specific organic semiconductor compound and the binder polymer.
As other components, known additives and the like can be used.
The content of the components other than the specific organic semiconductor compound and the binder polymer in the organic semiconductor layer is preferably 10% by mass or less, and preferably 5% by mass or less, based on the total mass of the organic semiconductor layer. It is more preferable that the amount is not more than mass%, and it is particularly preferable that it is not more than 0.1% by mass. When it is in the above range, the film forming property is excellent, and the mobility and thermal stability of the obtained organic semiconductor are excellent.

  The method for forming the organic semiconductor layer in the organic semiconductor element of the present invention is not particularly limited, and a composition for forming an organic semiconductor film of the present invention described later is applied on the source electrode, the drain electrode, and the gate insulating film, A desired organic semiconductor layer can be formed by performing a drying treatment as necessary.

The organic semiconductor element of the present invention is preferably manufactured using the composition for forming an organic semiconductor film of the present invention described later.
A method for producing an organic semiconductor film or an organic semiconductor element using 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, there is a method (also referred to as “solution coating method”) in which an organic semiconductor film is manufactured by applying the composition onto a predetermined substrate and performing a drying treatment 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 inkjet printing method, a flexographic printing method, a bar coating method, a spin coating method, a knife coating method, a doctor blade method, or the like. The inkjet printing method and the flexographic printing method are 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.
Especially, it is preferable that the manufacturing method of the organic-semiconductor element of this invention includes the application | coating process which apply | coats the composition for organic-semiconductor film formation of this invention on a board | substrate, The composition for organic-semiconductor film formation of this invention is a solvent. It is more preferable to include a coating step for coating the composition for forming an organic semiconductor film of the present invention on a substrate and a removing step for removing the solvent from the coated composition.

The composition for forming an organic semiconductor film of the present invention to be described later preferably contains a solvent, and more preferably contains an organic solvent.
A known solvent can be used as the solvent.
Specifically, for example, hydrocarbon solvents such as hexane, octane, decane, toluene, xylene, mesitylene, ethylbenzene, decalin, 1-methylnaphthalene, for example, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Halogenated hydrocarbon solvents such as dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene, chlorotoluene, ester solvents such as ethyl acetate, butyl acetate, amyl acetate, methanol, propanol, Alcohol solvents such as butanol, pentanol, hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, ethylene glycol, dibutyl ether Ether solvents such as tetrahydrofuran, dioxane and anisole, amide solvents such as N, N-dimethylformamide and N, N-dimethylacetamide, imides such as 1-methyl-2-pyrrolidone and 1-methyl-2-imidazolidinone And nitrile solvents such as acetonitrile, sulfoxide solvents such as dimethyl sulfoxide, and acetonitrile.

A solvent may be used individually by 1 type and may be used in combination of multiple.
Among these, hydrocarbon solvents, halogenated hydrocarbon solvents, aromatic solvents, aromatic heterocyclic solvents, and / or ether solvents are preferred, and toluene, xylene, mesitylene, tetralin, dichlorobenzene, or anisole are preferred. More preferred.

It is preferable from a viewpoint of film forming property that the boiling point of a solvent is 100 degreeC or more. 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.
In addition, it is preferable that the boiling point of the solvent with most content is 100 degreeC or more, and it is more preferable that the boiling points of all the solvents are 100 degreeC or more.

  When the solvent is contained, the content of the specific organic semiconductor compound in the composition for forming an organic semiconductor film of the present invention is 0.05 to 50% by mass with respect to the total mass of the composition for forming an organic semiconductor film. Preferably, it is 0.1 to 25% by mass, more preferably 0.25 to 15% by mass, particularly preferably 0.4 to 10% by mass, and inclusion of a binder polymer The amount is preferably 0.01 to 50% by mass, more preferably 0.05 to 25% by mass, and 0.1 to 10% by mass with respect to the total mass of the composition for forming an organic semiconductor film. More preferably. Within the above range, the coating property is excellent and the organic semiconductor film can be easily formed.

  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 specific organic semiconductor compound and the solvent used. Among them, the heating temperature is preferably 30 ° C. to 100 ° C., more preferably 40 ° C. to 80 ° C., and the heating time is excellent in terms of mobility and thermal stability of the obtained organic semiconductor and excellent productivity. 10 to 300 minutes are preferable, and 30 to 180 minutes are more preferable.

  The thickness of the formed organic semiconductor layer is not particularly limited, but is preferably 10 to 500 nm, and more preferably 30 to 200 nm, from the viewpoint of the mobility and thermal stability of the obtained organic semiconductor.

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.
The organic semiconductor element is preferably not a photoelectric conversion element.
Furthermore, the organic semiconductor element of the present invention is preferably a non-light emitting 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.

One embodiment of the organic thin film transistor of the present invention will be described with reference to the drawings.
FIG. 1 is a schematic cross-sectional view of one embodiment of the organic semiconductor element (organic thin film transistor (organic TFT)) of the present invention.
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. 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.
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.

<Board>
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.
The material of the plastic substrate may be a thermosetting resin (for example, epoxy resin, phenol resin, polyimide resin, polyester resin (for example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN)) or thermoplastic resin (for example, phenoxy). Resin, polyether sulfone, polysulfone, polyphenylene sulfone, etc.).
Examples of the material for the ceramic substrate include alumina, aluminum nitride, zirconia, silicon, silicon nitride, silicon carbide, and the like.
Examples of the glass substrate material include soda glass, potash glass, borosilicate glass, quartz glass, aluminum silicate glass, and lead glass.

<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. Metal: conductive oxide such as InO ₂ , SnO ₂ , indium tin oxide (ITO); conductive polymer such as polyaniline, polypyrrole, polythiophene, polyacetylene, polydiacetylene; semiconductor such as silicon, germanium, gallium arsenide; fullerene And carbon materials such as carbon nanotubes and graphite. Among these, a metal is preferable, and silver or aluminum is more preferable.
The thickness of the gate electrode, source electrode, and drain electrode is not particularly limited, but is preferably 20 to 200 nm.

  The method for forming the gate electrode, the source electrode, and the drain electrode is not particularly limited, and examples thereof include a method of vacuum-depositing or sputtering an electrode material on a substrate, and a method of applying or printing an electrode-forming composition. In the case of patterning the electrode, examples of the patterning method include a photolithography method; a printing method such as ink jet printing, screen printing, offset printing, letterpress printing; and a mask vapor deposition method.

<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, phenol resin And the like; 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 composition for forming a gate insulating film on a substrate on which a gate electrode is formed, and a method of depositing or sputtering a gate insulating film material. 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) 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.

<Organic semiconductor film>
The organic semiconductor film of the present invention is a film formed from the composition for forming an organic semiconductor film of the present invention.
The method for forming the organic semiconductor film is not particularly limited, and the above-described composition is applied on the source electrode, the drain electrode, and the gate insulating film, and is subjected to a drying treatment as necessary, thereby obtaining a desired organic semiconductor. A film can be formed.

<Binder polymer layer>
The organic semiconductor element of the present invention preferably has a binder polymer layer between the organic semiconductor layer and the insulating film, and more preferably has a binder polymer layer between the organic semiconductor layer 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 a known method (bar coating method, spin coating method, knife coating method, doctor blade method, ink jet method) can be used.
When a binder polymer layer forming composition is applied to form a binder polymer layer, it may be heated (baked) after application for the purpose of solvent removal, crosslinking and the like.

<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 on the substrate on which the gate electrode, the gate insulating film, the source electrode, the drain electrode, and the organic semiconductor film are formed. The method etc. are mentioned. 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 an organic semiconductor film is formed by applying the sealing layer forming composition, it may be heated (baked) after application for the purpose of solvent removal, crosslinking and the like.

FIG. 2 is a schematic cross-sectional view of another embodiment of the organic semiconductor element (organic thin film transistor) of the present invention.
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. 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.

(Composition for forming an organic semiconductor film)
The composition for forming an organic semiconductor film of the present invention is characterized by containing a specific organic semiconductor compound and a solvent.
Moreover, it is preferable that the composition for organic-semiconductor film formation of this invention contains a binder polymer.
The specific organic semiconductor compound, the binder polymer, and the solvent in the composition for forming an organic semiconductor film of the present invention have the same meanings as the specific organic semiconductor compound, the binder polymer, and the solvent described above, and preferred embodiments are also the same.

The composition for forming an organic semiconductor film of the present invention may contain other components in addition to the specific organic semiconductor compound and the binder polymer.
As other components, known additives and the like can be used.
The content of the components other than the specific organic semiconductor compound and the binder polymer in the composition for forming an organic semiconductor film of the present invention is preferably 10% by mass or less based on the total solid content of the composition for forming an organic semiconductor film, It is more preferably 5% by mass or less, further preferably 1% by mass or less, and particularly preferably 0.1% by mass or less. When it is in the above range, the film forming property is excellent, and the mobility and thermal stability of the obtained organic semiconductor are excellent. In addition, solid content is the quantity of the component except volatile components, such as a solvent.

The viscosity of the composition for forming an organic semiconductor film of the present invention is not particularly limited, but is preferably 3 to 100 mPa · s, more preferably 5 to 50 mPa · s, and more preferably 9 to 40 mPa · s in terms of more excellent coating properties. Further preferred. In addition, the viscosity in this invention is a viscosity in 25 degreeC.
As a measuring method of a viscosity, it is preferable that it is a measuring method based on JISZ8803.

  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, a desired composition can be obtained by adding a predetermined amount of a specific organic semiconductor compound in a solvent and appropriately performing a stirring treatment. Moreover, when using a binder polymer, a specific organic-semiconductor compound and a binder polymer can be added simultaneously or sequentially, and a composition can be produced suitably.

(Organic semiconductor film)
The organic semiconductor film of the present invention contains a specific organic semiconductor.
The organic semiconductor film of the present invention preferably contains a binder polymer.
The specific organic semiconductor compound and the binder polymer in the organic semiconductor film of the present invention include the specific organic semiconductor compound described above in the organic semiconductor element of the present invention, a polymer and an oligomer obtained by polymerizing the specific organic semiconductor compound, and It is synonymous with a binder polymer, and its preferable aspect is also the same.

The composition for forming an organic semiconductor film of the present invention may contain other components in addition to the specific organic semiconductor compound, the polymer and oligomer obtained by polymerizing the specific organic semiconductor compound, and the binder polymer.
As other components, known additives and the like can be used.
The specific organic semiconductor compound in the organic semiconductor film of the present invention, the polymer and oligomer obtained by polymerizing the specific organic semiconductor compound, and the content of components other than the binder polymer are 10 with respect to the total mass of the organic semiconductor film. It is preferably at most mass%, preferably at most 5 mass%, more preferably at most 1 mass%, particularly preferably at most 0.1 mass%. When it is in the above range, the film forming property is excellent, and the mobility and thermal stability of the obtained organic semiconductor are excellent. In addition, solid content is the quantity of the component except volatile components, such as a solvent.

Although the film thickness of the organic-semiconductor film of this invention is not restrict | limited in particular, 10-500 nm is preferable and 30-200 nm is more preferable from a viewpoint of the mobility and thermal stability of the organic semiconductor obtained.
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 transistor (organic thin film transistor).
The organic semiconductor film of the present invention can be suitably produced using the composition for forming an organic semiconductor film of the present invention.

  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.

(Organic semiconductor compound)
E-1 to E-6, which are organic semiconductor compounds used in the organic semiconductor layer, are the same as E-1 to E-6 described as specific examples of the organic semiconductor compound.
Moreover, the structure of comparative compound C-1 to C-4 is shown below.

<Synthesis of compounds>
Compound E-1 was synthesized by the following synthesis scheme. Specifically, J. et al. Mater. Chem. 2012, 22, 14639. JP, 2011-168747, Macromol. , 2013, 46, 3887. And J.A. Org. Chem. 1985, 50, 1681. The synthesis intermediate IM was synthesized according to the following scheme.
Synthetic intermediate IM (235 mg, 0.298 mmol), 2,5-bis (trimethylstannyl) thieno [3,2-b] thiophene (manufactured by Tokyo Chemical Industry Co., Ltd., 139 mg, 0.298 mol), tri (o -Tolyl) phosphine (manufactured by Wako Pure Chemical Industries, 18 mg, 0.06 mmol), tris (dibenzylideneacetone) dipalladium (manufactured by Tokyo Chemical Industry Co., Ltd., 14 mg, 0.015 mmol), dehydrated toluene (Wako Pure) Yaku Kogyo Co., Ltd., 15 mL) was mixed and stirred at 100 ° C. for 60 hours under a nitrogen atmosphere. After the reaction solution was cooled to room temperature, 300 mL of methanol was added and stirred for 2 hours. The precipitate was filtered and washed with methanol, and then Soxhlet extracted with methanol, acetone, hexane, dichloromethane and chloroform in order to remove soluble impurities. Subsequently, after Soxhlet extraction with dichlorobenzene and concentration of the solution under reduced pressure, methanol was added, and the precipitated solid was filtered and washed with methanol to obtain 176 mg of Compound 1 (yield 77%).
Compounds E-2 to E-6 were also synthesized by a method according to Compound E-1.

Comparative compound C-1 is a compound described in JP-T-2010-527327.
Comparative compound C-2 was obtained from Macromol. , 2013, 46, 3887. It is compound P3 as described in above.
Comparative compounds C-3 and C-4 are described in J. Org. Phys. Chem. C, 2014, 118, 3953. Compound TPD-Th-S and Compound TPD-Fu-S described in 1.
Compounds E-1 to E-6 and comparative compounds C-1 to C-4 are both high in purity (254 nm absorption intensity area ratio) by high performance liquid chromatography (manufactured by Tosoh Corporation, TSKgel ODS-100Z). It was confirmed that it was 99.8% or more.

<Starting materials used>
3,4-thiophenedicarboxylic anhydride used for the synthesis of compound E-1 was purchased from Tokyo Chemical Industry Co., Ltd.

<Other reagents used>
2-n-octyl-1-dodecylamine (manufactured by Tokyo Chemical Industry Co., Ltd.)
Trimethyl (2-thienyl) tin (manufactured by Wako Pure Chemical Industries, Ltd.)
NBS: N-bromosuccinimide (manufactured by Wako Pure Chemical Industries, Ltd.)
Lawson Reagent (Wako Pure Chemical Industries, Ltd.)

<Binder polymer>
The polymer used as the binder is shown below.
PαMS: poly-α-methylstyrene, weight average molecular weight 437,000, manufactured by Sigma-Aldrich Corporation PTAA: poly [bis (4-phenyl) (2,4,6-trimethylphenyl) amine], number average molecular weight 7,000 to 10,000, Sigma-Aldrich PCPDTBT: Poly [2,6- (4,4-bis (2-ethylhexyl) -4Hcyclopenta [2,1-b; 3,4-b ′] dithiophene) -alto-4 , 7- (2,1,3-benzothiadiazole)], weight average molecular weight 7,000 to 20,000, manufactured by Sigma-Aldrich

<Preparation of coating solution for organic semiconductor film formation>
The organic semiconductor compound (0.5% by mass) / binder polymer (concentration described in Table 1) / anisole (boiling point 154 ° C.) listed in Table 1 was weighed into a glass vial and mixed rotor (manufactured by ASONE Co., Ltd.). After stirring and mixing for 10 minutes, the coating solution for forming an organic semiconductor film (composition for forming an organic semiconductor film) was obtained by filtering with a 0.5 μm membrane filter. In Table 1, the case where the binder polymer is described as “-” indicates that the binder polymer is not added.
In Table 1, the concentration of the binder polymer described in parentheses is mass% in the coating solution.

<TFT device fabrication>
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 part by weight / 1 part by weight (w / w) PGMEA (propylene glycol monomethyl ether acetate) solution (solid content concentration: 2% by weight)) is spun A gate insulating film having a thickness of 400 nm was formed by coating and baking at 150 ° C. for 60 minutes. On top of that, silver ink (H-1, manufactured by Mitsubishi Materials Corporation) is formed into a source electrode and a drain electrode (channel length: 40 μm, channel width: 200 μm) using an inkjet device DMP-2831 (manufactured by Fujifilm Dimatics). Drawn. Thereafter, baking was performed at 180 ° C. for 30 minutes in an oven, sintering was performed, and a source electrode and a drain electrode were formed to obtain an element substrate for TFT characteristic evaluation.
Each organic semiconductor film-forming coating solution is spin-coated on the element substrate for TFT characteristic evaluation (500 rpm, 10 seconds, then 1,000 rpm, 30 seconds), and then on a hot plate at 50 ° C. for 10 minutes, or 180 ° C. 10 By drying (annealing) for a minute, an organic semiconductor layer was formed, and a bottom gate bottom contact type organic TFT element was obtained.

<Characteristic evaluation>
The following performance evaluation was performed under the atmosphere using a semiconductor characteristic evaluation apparatus B2900A (manufactured by Agilent Technologies).
(A) Carrier mobility, and (b) mobility variation A voltage of −60 V is applied between the source electrode and the drain electrode of each organic TFT element, and the gate voltage is changed in the range of +10 V to −60 V, and the drain The carrier mobility μ was calculated using the following formula representing the current I _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.
The value of carrier mobility shown in Table 1 is an average value of 10 elements. The carrier mobility μ is preferably as high as possible. Practically, it is preferably 1.0 × 10 ⁻² cm ² / Vs or more, and more preferably 1.0 × 10 ⁻¹ cm ² / Vs or more. In addition, since the characteristics are too low for those whose mobility is less than 1.0 × 10 ⁻⁵ cm ² / Vs, “<1.0 × 10 ⁻⁵ ” is described in the table, and the following evaluation is performed. There wasn't.
In addition, the variation coefficient calculated by the following formula for the carrier mobility of 10 elements was evaluated in the following 5 stages and used as an index of mobility variation. It shows that the mobility variation between elements is so small that this value is small. Practically, it is preferably A or B, more preferably A.
Variation coefficient = standard deviation ÷ average value x 100
A: Less than 15% B: 15% or more and less than 30% C: 30% or more and less than 50% D: 50% or more

  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 (20)

  It has an organic semiconductor layer containing an organic semiconductor having a repeating unit represented by Formula 1,
  Organic semiconductor element.

  In Formula 1, X is CR¹² ₂, O, S, Se, NR¹², SiR¹² ₂Represents one of the following: R¹²Each independently represents a hydrogen atom or a monovalent organic group;¹¹And Y¹²Are each independently O, S, N-CN, or CQ₂Where Q is CN, CF_Three, C (= O) R¹³, C (= O) OR ¹³Or SO₂R¹³Represents R¹³Represents a monovalent organic group and a plurality of R¹³May combine with each other to form a ring, and Y¹¹And Y¹²Are not simultaneously O and R¹¹Represents a monovalent organic group, Ar¹¹, Ar¹², Ar¹³Each independently represents an aromatic hydrocarbon group, an aromatic heterocyclic group, a vinylene group or an ethynylene group, m11 represents an integer of 0 to 2, m12 represents an integer of 0 to 4, and m13 represents 0. Represents an integer of ~ 2. The organic semiconductor element according to claim 1, wherein X is any one of O, S, and NR ¹² . The organic semiconductor element according to claim 1, wherein Y ¹¹ and Y ¹² are both S, or both are C (CN) ₂ .   The organic-semiconductor element of any one of Claims 1-3 whose repeating unit represented by Formula 1 is a repeating unit represented by Formula 2.

  In Formula 2, X is CR¹² ₂, O, S, Se, NR¹², SiR¹² ₂Represents one of the following: R¹²Each independently represents a hydrogen atom or a monovalent organic group;¹¹And Y¹²Are each independently O, S, N-CN, or CQ₂Where Q is CN, CF_Three, C (= O) R¹³, C (= O) OR ¹³Or SO₂R¹³Represents R¹³Represents a monovalent organic group and a plurality of R¹³May combine with each other to form a ring, and Y¹¹And Y¹²Are not simultaneously O and R¹¹Represents a monovalent organic group, Ar¹²Represents an aromatic hydrocarbon group, aromatic heterocyclic group, vinylene group or ethynylene group, m12 represents an integer of 0 to 4, and X^{twenty one}And X^{twenty two}Are independently O, S, Se, NR^{12 '}, SiR^{12 '} ₂Represents one of the following: R^{12 '}Each independently represents a hydrogen atom or a monovalent organic group, R^{twenty one}~ R^{twenty four}Each independently represents a hydrogen atom or a monovalent organic group, m11 'represents an integer of 0-2, and m13' represents an integer of 0-2.   A compound having a repeating unit represented by Formula 1.

  In Formula 1, X is CR¹² ₂, O, S, Se, NR¹², SiR¹² ₂Represents one of the following: R¹²Each independently represents a hydrogen atom or a monovalent organic group;¹¹And Y¹²Are each independently O, S, N-CN, or CQ₂Where Q is CN, CF_Three, C (= O) R¹³, C (= O) OR ¹³Or SO₂R¹³Represents R¹³Represents a monovalent organic group and a plurality of R¹³May combine with each other to form a ring, and Y¹¹And Y¹²Are not simultaneously O and R¹¹Represents a monovalent organic group, Ar¹¹, Ar¹², Ar¹³Each independently represents an aromatic hydrocarbon group, an aromatic heterocyclic group, a vinylene group or an ethynylene group, m11 represents an integer of 0 to 2, m12 represents an integer of 0 to 4, and m13 represents 0. Represents an integer of ~ 2. The compound according to claim 5, wherein X is any of O, S, and NR ¹² . The compound according to claim 5 or 6, wherein Y ¹¹ and Y ¹² are both S, or both are C (CN) ₂ .   The compound according to any one of claims 5 to 7, wherein the repeating unit represented by Formula 1 is a repeating unit represented by Formula 2.

  In Formula 2, X is CR¹² ₂, O, S, Se, NR¹², SiR¹² ₂Represents one of the following: R¹²Each independently represents a hydrogen atom or a monovalent organic group;¹¹And Y¹²Are each independently O, S, N-CN, or CQ₂Where Q is CN, CF_Three, C (= O) R¹³, C (= O) OR ¹³Or SO₂R¹³Represents R¹³Represents a monovalent organic group and a plurality of R¹³May combine with each other to form a ring, and Y¹¹And Y¹²Are not simultaneously O and R¹¹Represents a monovalent organic group, Ar¹²Represents an aromatic hydrocarbon group, aromatic heterocyclic group, vinylene group or ethynylene group, m12 represents an integer of 0 to 4, and X^{twenty one}And X^{twenty two}Are independently O, S, Se, NR^{12 '}, SiR^{12 '} ₂Represents one of the following: R^{12 '}Each independently represents a hydrogen atom or a monovalent organic group, R^{twenty one}~ R^{twenty four}Each independently represents a hydrogen atom or a monovalent organic group, m11 'represents an integer of 0-2, and m13' represents an integer of 0-2.   The compound according to any one of claims 5 to 8, which is an organic semiconductor.   The composition for organic-semiconductor film formation containing the compound which has a repeating unit represented by Formula 1, and a solvent.

  In Formula 1, X is CR¹² ₂, O, S, Se, NR¹², SiR¹² ₂Represents one of the following: R¹²Each independently represents a hydrogen atom or a monovalent organic group;¹¹And Y¹²Are each independently O, S, N-CN, or CQ₂Where Q is CN, CF_Three, C (= O) R¹³, C (= O) OR ¹³Or SO₂R¹³Represents R¹³Represents a monovalent organic group and a plurality of R¹³May combine with each other to form a ring, and Y¹¹And Y¹²Are not simultaneously O and R¹¹Represents a monovalent organic group, Ar¹¹, Ar¹², Ar¹³Each independently represents an aromatic hydrocarbon group, an aromatic heterocyclic group, a vinylene group or an ethynylene group, m11 represents an integer of 0 to 2, m12 represents an integer of 0 to 4, and m13 represents 0. Represents an integer of ~ 2. The composition for forming an organic semiconductor film according to claim 10, wherein X is any one of O, S, and NR ¹² . The composition for forming an organic semiconductor film according to claim 10 or 11, wherein Y ¹¹ and Y ¹² are both S, or both are C (CN) ₂ .   The composition for organic-semiconductor film formation of any one of Claims 10-12 whose repeating unit represented by Formula 1 is a repeating unit represented by Formula 2.

  In Formula 2, X is CR¹² ₂, O, S, Se, NR¹², SiR¹² ₂Represents one of the following: R¹²Each independently represents a hydrogen atom or a monovalent organic group;¹¹And Y¹²Are each independently O, S, N-CN, or CQ₂Where Q is CN, CF_Three, C (= O) R¹³, C (= O) OR ¹³Or SO₂R¹³Represents R¹³Represents a monovalent organic group and a plurality of R¹³May combine with each other to form a ring, and Y¹¹And Y¹²Are not simultaneously O and R¹¹Represents a monovalent organic group, Ar¹²Represents an aromatic hydrocarbon group, aromatic heterocyclic group, vinylene group or ethynylene group, m12 represents an integer of 0 to 4, and X^{twenty one}And X^{twenty two}Are independently O, S, Se, NR^{12 '}, SiR^{12 '} ₂Represents one of the following: R^{12 '}Each independently represents a hydrogen atom or a monovalent organic group, R^{twenty one}~ R^{twenty four}Each independently represents a hydrogen atom or a monovalent organic group, m11 'represents an integer of 0-2, and m13' represents an integer of 0-2.   The composition for organic-semiconductor film formation of any one of Claims 10-13 which further contains a binder polymer.   The manufacturing method of an organic-semiconductor element including the application | coating process which apply | coats the composition for organic-semiconductor film formation of any one of Claims 10-14 on a board | substrate.   An organic semiconductor film containing a compound having a repeating unit represented by Formula 1.

  In Formula 1, X is CR¹² ₂, O, S, Se, NR¹², SiR¹² ₂Represents one of the following: R¹²Each independently represents a hydrogen atom or a monovalent organic group;¹¹And Y¹²Are each independently O, S, N-CN, or CQ₂Where Q is CN, CF_Three, C (= O) R¹³, C (= O) OR ¹³Or SO₂R¹³Represents R¹³Represents a monovalent organic group and a plurality of R¹³May combine with each other to form a ring, and Y¹¹And Y¹²Are not simultaneously O and R¹¹Represents a monovalent organic group, Ar¹¹, Ar¹², Ar¹³Each independently represents an aromatic hydrocarbon group, an aromatic heterocyclic group, a vinylene group or an ethynylene group, m11 represents an integer of 0 to 2, m12 represents an integer of 0 to 4, and m13 represents 0. Represents an integer of ~ 2. The organic semiconductor film according to claim 16, wherein X is any one of O, S, and NR ¹² . 18. The organic semiconductor film according to claim 16, wherein Y ¹¹ and Y ¹² are both S, or both are C (CN) ₂ .   The organic semiconductor film according to any one of claims 16 to 18, wherein the repeating unit represented by Formula 1 is a repeating unit represented by Formula 2.

  In Formula 2, X is CR¹² ₂, O, S, Se, NR¹², SiR¹² ₂Represents one of the following: R¹²Each independently represents a hydrogen atom or a monovalent organic group;¹¹And Y¹²Are each independently O, S, N-CN, or CQ₂Where Q is CN, CF_Three, C (= O) R¹³, C (= O) OR ¹³Or SO₂R¹³Represents R¹³Represents a monovalent organic group and a plurality of R¹³May combine with each other to form a ring, and Y¹¹And Y¹²Are not simultaneously O and R¹¹Represents a monovalent organic group, Ar¹²Represents an aromatic hydrocarbon group, aromatic heterocyclic group, vinylene group or ethynylene group, m12 represents an integer of 0 to 4, and X^{twenty one}And X^{twenty two}Are independently O, S, Se, NR^{12 '}, SiR^{12 '} ₂Represents one of the following: R^{12 '}Each independently represents a hydrogen atom or a monovalent organic group, R^{twenty one}~ R^{twenty four}Each independently represents a hydrogen atom or a monovalent organic group, m11 'represents an integer of 0-2, and m13' represents an integer of 0-2.   The organic-semiconductor film of any one of Claims 16-19 formed into a film by the solution coating method.

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