JP6328535B2 - Composition for forming organic semiconductor film, organic semiconductor film, and organic semiconductor element - Google Patents

Description

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

Lightweight, low cost, and flexible, so organic semiconductors can be used for field effect transistors (FETs) and RFID (radio frequency identifiers, RF tags) used in liquid crystal displays and organic electroluminescence (EL) displays. An organic transistor having a film (organic semiconductor layer) is used.
As a method for manufacturing the organic semiconductor film, various methods have been proposed. For example, as a composition for forming an organic semiconductor film, a composition described in Patent Document 1 is known.
Patent Document 2 reports a method of obtaining an organic transistor excellent in heat resistance, atmospheric stability, and substrate wettability by mixing and applying an organic semiconductor and an insulating polymer.

Special table 2013-516054 gazette JP 2014-13920 A

However, in the conventional organic semiconductor film, sufficient characteristics have not been obtained in the mobility variation suppressing property and the temporal stability of the organic semiconductor film. This is particularly noticeable when an organic semiconductor film is produced by a printing process such as screen printing or flexographic printing.
The problem to be solved by the present invention is a composition for forming an organic semiconductor film which is excellent in mobility variation suppressing property and stability over time of the obtained organic semiconductor film, and an organic semiconductor film formed from the organic semiconductor film forming composition In addition, an organic semiconductor element having the organic semiconductor film is provided.

The above-described problems of the present invention have been solved by the means described in <1>, <10> or <11> below. It describes below with <2>-<9> and <12> which are preferable embodiments.
<1> A condensed polycyclic aromatic group having 4 or more rings in the condensed polycyclic aromatic group, wherein at least two rings in the condensed polycyclic aromatic group are a sulfur atom or a nitrogen atom. At least one selected from the group consisting of a benzene ring, a naphthalene ring and a phenanthrene ring as a partial structure in the condensed polycyclic aromatic group, which contains at least one atom selected from the group consisting of a selenium atom and an oxygen atom. An organic semiconductor containing one of these, an insulating polymer having a weight average molecular weight of 750,000 or more and a molecular weight distribution (Mw / Mn) of 1.3 or more, 4-tert-butylanisole, amylbenzene and the following formula C- An organic semiconductor film-forming composition comprising: at least one organic solvent selected from the group consisting of compounds represented by 1;

In Formula C-1, R ^b1 represents an alkyl group, an alkoxy group, a halogen atom, a cyano group, or a vinyl group, m represents an integer of 1 to 4, and when m is 2 or more, a plurality of R ^b1 are present. May be the same or different.

<2> The composition for forming an organic semiconductor film according to <1>, wherein the insulating polymer has a weight average molecular weight of 1,000,000 or more,
<3> The composition for forming an organic semiconductor film according to <1> or <2>, wherein the insulating polymer has a weight average molecular weight of 1,000,000 or more and a molecular weight distribution (Mw / Mn) of 1.7 or more. ,
<4> The composition for forming an organic semiconductor film according to <3>, wherein the insulating polymer is a mixture of two or more insulating polymers having the same composition and different weight average molecular weights,
<5> The composition for forming an organic semiconductor film according to any one of <1> to <4>, wherein the organic solvent is 1-chloronaphthalene or 1-fluoronaphthalene.
<6> The composition for forming an organic semiconductor film according to any one of <1> to <5>, wherein the number of rings in the condensed polycyclic aromatic group in the organic semiconductor is 5 or 6.
<7> The condensed polycyclic aromatic group of the organic semiconductor contains at least two heterocycles, and each of the heterocycles is a heterocycle having only one heteroatom, <1> to <6> The composition for forming an organic semiconductor film according to any one of
<8> The composition for forming an organic semiconductor film according to any one of <1> to <7>, wherein the organic semiconductor includes at least one compound represented by any one of Formulas 1 to 16.

In Formula 1, A ^1a and A ^1b each independently represent an S atom, an O atom, or a Se atom, R ^{1a to} R ^1f each independently represent a hydrogen atom or a substituent, and R ^{1a to} R ^1f At least one is a group represented by the following formula W.
-L ^W -R ^W (W)
In the formula W, L ^W is a divalent linking group represented by any of the following formulas L-1 to L-25 or two or more represented by any of the following formulas L-1 to L-25. -valent divalent linking group linking group is attached the, R ^W is an alkyl group, a cyano group, a vinyl group, an ethynyl group, an oxyethylene group, repetition number v of oxyethylene units is more than one oligo oxyethylene group, It represents a siloxane group, an oligosiloxane group having 2 or more silicon atoms, or a trialkylsilyl group.

In the formula L-. 1 to formula L-25, * represents a bonding position to ^{R W,} wavy line portion represents the other coupling position, wherein L-1, wherein L-2, the formula L-6 and wherein L each R 'is in the -13 type L-24 independently represent a hydrogen atom or a substituent, R ^N represents a hydrogen atom or a substituent, R ^si are each independently a hydrogen atom, an alkyl group, an alkenyl group, or Represents an alkynyl group.
In Formula 2, X ^2a and X ^2b each independently represent NR ²ⁱ , O atom or S atom, A ^2a represents CR ^2g or N atom, A ^2b represents CR ^2h or N atom, and R ²ⁱ represents Represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an acyl group, R ^{2a to} R ^2h each independently represents a hydrogen atom or a substituent, and at least one of R ^{2a to} R ^2h is represented by the formula W; Group.
In Formula 3, X ^3a and X ^3b each independently represent an S atom, an O atom or NR ^3g , and A ^3a and A ^3b each independently represent a CR ^3h or an N atom. R ^{3a to} R ^3h each independently represents a hydrogen atom or a substituent, and at least one of R ^{3a to} R ^3h is a group represented by the formula W.
In Formula 4, X ^4a and X ^4b each independently represent an O atom, an S atom or a Se atom, 4p and 4q each independently represent an integer of 0 to 2, R ^{4a to} R ^4j , R ^4k and R ^4m independently represents a hydrogen atom, a halogen atom or a group represented by the above formula W, and at least one of R ^{4a to} R ^4j , R ^4k and R ^4m is represented by the above formula W. a group, provided ^{that, R 4e} and ^{L W} is the formula L-2 or formula L in the formula W if at least one of a group represented by the formula W represented by ^{R 4e} and ^{R 4f} of ^{R 4f} -3 is a divalent linking group.

In Formula 5, X ^5a and X ^5b each independently represent NR ⁵ⁱ , O atom or S atom, A ^5a represents CR ^5g or N atom, A ^5b represents CR ^5h or N atom, and R ⁵ⁱ represents Represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an acyl group, an aryl group or a heteroaryl group, R ^{5a to} R ^5h each independently represent a hydrogen atom or a substituent, and at least of R ^{5a to} R ^5h One is a group represented by the above formula W.
In Formula 6, X ^{6a to} X ^6d each independently represents NR ^6g , an O atom or an S atom, and R ^6g represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an acyl group, an aryl group or a heteroaryl group. R ^{6a to} R ^6f each independently represents a hydrogen atom or a substituent, and at least one of R ^{6a to} R ^6f is a group represented by the formula W.
In Formula 7, X ^7a and X ^7c each independently represent an S atom, O atom, Se atom or NR ⁷ⁱ , X ^7b and X ^7d each independently represent an S atom, O atom or Se atom, R ^{7a to} R ⁷ⁱ each independently represents a hydrogen atom or a substituent, and at least one of R ^{7a to} R ⁷ⁱ is a group represented by the formula W.
In Formula 8, X ^8a and X ^8c each independently represent an S atom, O atom, Se atom or NR ⁸ⁱ , X ^8b and X ^8d each independently represent an S atom, O atom or Se atom, and R ^{8a to} R ⁸ⁱ each independently represents a hydrogen atom or a substituent, and at least one of R ^{8a to} R ⁸ⁱ is a group represented by the formula W.

In Formula 9, X ^9a and X ^9b each independently represent an O atom, an S atom, or a Se atom, and R ^9c , R ^9d, and R ^{9g to} R ^9j each independently represent a hydrogen atom, a halogen atom, or the formula W R ^9a , R ^9b , R ^9e and R ^9f each independently represent a hydrogen atom or a substituent.
In Formula 10, R ^{10a to} R ^10h each independently represents a hydrogen atom or a substituent, and at least one of R ^{10a to} R ^10h represents a substituent represented by Formula W above, and X ^10a and X ^10b Each independently represents an S atom, an O atom, a Se atom or NR ^10i, and each R ¹⁰ⁱ independently represents a hydrogen atom or a group represented by the above formula W.
In Formula 11, X ^11a and X ^11b each independently represent an S atom, an O atom, a Se atom, or NR ¹¹ⁿ , and R ^{11a to} R ^11k , R ^11m, and R ¹¹ⁿ each independently represent a hydrogen atom or a substituent. And at least one of R ^{11a to} R ^11k , R ^11m and R ¹¹ⁿ is a group represented by the formula W.
In Formula 12, X ^12a and X ^12b each independently represent an S atom, an O atom, a Se atom or NR ¹²ⁿ , and R ^{12a to} R ^12k , R ^12m and R ¹²ⁿ each independently represent a hydrogen atom or a substituent. And at least one of R ^{12a to} R ^12k , R ^12m and R ¹²ⁿ is a group represented by the formula W.

In Formula 13, X ^13a and X ^13b each independently represent an S atom, an O atom, a Se atom or NR ¹³ⁿ , and R ^{13a to} R ^13k , R ^13m and R ¹³ⁿ each independently represent a hydrogen atom or a substituent. And at least one of R ^{13a to} R ^13k , R ^13m and R ¹³ⁿ is a group represented by the formula W.
In Formula 14, X ^{14a to} X ^14c each independently represents an S atom, an O atom, a Se atom, or NR ¹⁴ⁱ , R ^{14a to} R ¹⁴ⁱ each independently represents a hydrogen atom or a substituent, and R ^{14a to} R ^{14 At} least one of ¹⁴ⁱ is a group represented by the above formula W.
In Equation ^15, the X 15a ^{to X 15d} are each independently, S atom, O atom, a Se atom or a ^{NR 15g, R} 15a ^{~R 15g} each independently represent a hydrogen atom or a ^{substituent, R} 15a to R ^At least one of ^{15 g} is a group represented by the above formula W.
In Equation ^16, the X 16a ^{to X 16d} are each independently, S atom, O atom, a Se atom or a ^{NR 16g, R} 16a ^{~R 16g} each independently represent a hydrogen atom or a ^{substituent, R} 16a to R ^At least one of ^{16 g} is a group represented by the above formula W.

<9> The organic semiconductor film forming composition according to <8>, wherein the organic semiconductor contains at least one compound represented by the formula 1 to formula 9 or formula 15.
<10> An organic semiconductor film formed from the composition for forming an organic semiconductor film according to any one of <1> to <9>,
<11> An organic semiconductor element having an organic semiconductor film formed from the composition for forming an organic semiconductor film according to any one of <1> to <9>,
<12> The organic semiconductor element according to <11>, which is an organic thin film transistor.

  According to the present invention, a composition for forming an organic semiconductor film excellent in mobility variation suppressing property and stability over time of the obtained organic semiconductor film, an organic semiconductor film formed from the organic semiconductor film forming composition, and the above An organic semiconductor element having an organic semiconductor film could 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. It is a top view of the metal mask used in the Example.

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.
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, the term “mobility” means carrier mobility, and means either or both of electron mobility and hole mobility.
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 two or more preferred embodiments is a more preferred embodiment.

(Composition for forming an organic semiconductor film)
The composition for forming an organic semiconductor film of the present invention (hereinafter also simply referred to as “composition”) has a condensed polycyclic aromatic group, and the number of rings in the condensed polycyclic aromatic group is 4 or more. , At least two rings in the condensed polycyclic aromatic group contain at least one atom selected from the group consisting of a sulfur atom, a nitrogen atom, a selenium atom and an oxygen atom, As a partial structure, an organic semiconductor containing at least one selected from the group consisting of a benzene ring, a naphthalene ring and a phenanthrene ring, a weight average molecular weight of 750,000 or more, and a molecular weight distribution (Mw / Mn) of 1.3 It contains the above insulating polymer, and at least one organic solvent selected from the group consisting of 4-tert-butylanisole, amylbenzene, and a compound represented by the following formula C-1. .

In Formula C-1, R ^b1 represents an alkyl group, an alkoxy group, a halogen atom, a cyano group, or a vinyl group, m represents an integer of 1 to 4, and when m is 2 or more, a plurality of R ^b1 are present. May be the same or different.

As a result of intensive studies, the inventors of the present invention contain the organic semiconductor having the specific structure, the specific polymer, and the specific organic solvent, thereby suppressing mobility variation in the obtained organic semiconductor film and It has been found that the stability over time is excellent, and the present invention has been completed.
The mechanism of the detailed effect is unknown, but by using a polymer with the above specific structure in combination with organic semiconductor elements, especially bottom contact elements, the occurrence of defects at the interface between the organic semiconductor film and the electrode or substrate It is presumed that the organic semiconductor film has excellent mobility variation suppression properties and stability over time.
The composition for forming an organic semiconductor film of the present invention is particularly suitable for producing an organic semiconductor film by a printing process such as a screen printing method or a flexographic printing method. The organic semiconductor film is formed by a screen printing method or a flexographic printing method. It is more suitably used when producing.

<Organic semiconductor>
The composition for forming an organic semiconductor film of the present invention has a condensed polycyclic aromatic group, the number of rings in the condensed polycyclic aromatic group is 4 or more, and at least 2 in the condensed polycyclic aromatic group. One ring contains at least one atom selected from the group consisting of a sulfur atom, a nitrogen atom, a selenium atom and an oxygen atom, and a benzene ring, a naphthalene ring and a phenanthrene ring as a partial structure in the condensed polycyclic aromatic group An organic semiconductor containing at least one structure selected from the group consisting of the following (hereinafter also referred to as “specific organic semiconductor” or “component A”) is contained.
However, the partial structure in the condensed polycyclic aromatic group in Component A does not include an anthracene ring. When the partial structure includes an anthracene ring, the reason is unknown, but both the mobility and thermal stability of the obtained organic semiconductor film are deteriorated.
The condensed polycyclic aromatic group is a group obtained by condensing a plurality of aromatic rings.
Examples of the aromatic ring include an aromatic hydrocarbon ring (for example, benzene ring) and an aromatic heterocyclic ring (for example, thiophene ring, furan ring, pyrrole ring, selenophene ring, imidazole ring).

Component A contains a condensed polycyclic aromatic group (condensed polycyclic aromatic structure), and this group is preferably contained as a main component. Here, the main component means that the molecular weight content of the condensed polycyclic aromatic group is 30% or more with respect to the total molecular weight of Component A, and is preferably 40% or more. The upper limit is not particularly limited, but is preferably 80% or less from the viewpoint of solubility.
The condensed polycyclic aromatic group is a ring structure formed by condensing a plurality of rings, and exhibits aromaticity.
The number of rings in the condensed polycyclic aromatic group in Component A is 4 or more, and from the viewpoint of mobility as an organic semiconductor, 4 to 9 is preferable, 4 to 7 is more preferable, and 5 or 6 is still more preferable.
In the condensed polycyclic aromatic group, at least two rings contain at least one atom selected from the group consisting of a sulfur atom, a nitrogen atom, a selenium atom, and an oxygen atom, and have a mobility as an organic semiconductor. From a viewpoint, it is preferable that 2-6 rings contain the said atom, and it is more preferable that 2-4 rings contain the said atom.
Further, from the viewpoint of mobility as an organic semiconductor, it is preferable that at least two heterocycles are contained in the condensed polycyclic aromatic group, and each heterocycle has one heteroatom. The kind of the hetero atom is not particularly limited, and examples thereof include an O atom (oxygen atom), an S atom (sulfur atom), an N atom (nitrogen atom), and an Se atom (selenium atom).
The condensed polycyclic aromatic group in Component A includes at least one structure selected from the group consisting of a benzene ring, a naphthalene ring and a phenanthrene ring as a partial structure. The partial structure does not include an anthracene ring.
Component A preferably has at least a thiophene ring structure and / or a selenophene ring structure, more preferably at least a thiophene ring structure, and a heterocyclic structure of component A from the viewpoint of mobility as an organic semiconductor. It is more preferable that all have a thiophene ring structure.

The condensed polycyclic aromatic group includes at least one structure selected from the group consisting of a benzene ring, a naphthalene ring, and a phenanthrene ring as a partial structure from the viewpoint of mobility as an organic semiconductor, A condensed polycyclic aromatic group containing the above thiophene ring and having 4 or more rings is preferable. Among these, a condensed polycyclic aromatic group containing a benzene ring, 2 or more thiophene rings, and 4 or more rings is more preferable as the partial structure.
In addition, as the condensed polycyclic aromatic group, from the viewpoint of mobility as an organic semiconductor, the number of thiophene rings in the condensed polycyclic aromatic group is preferably 3 or more, more preferably 3 to 5, Three to four are more preferable, and three are particularly preferable.
From the viewpoint of mobility as an organic semiconductor, the number of rings in the condensed polycyclic aromatic group is preferably 4-6, more preferably 5-6, and even more preferably 5. The condensed polycyclic aromatic group is particularly preferably a condensed polycyclic aromatic group containing two benzene rings and three thiophene rings and having 5 rings.

  Further, the condensed polycyclic aromatic group includes a ring (heterocycle, preferably a thiophene ring) containing at least one atom selected from the group consisting of a sulfur atom, a nitrogen atom, a selenium atom and an oxygen atom, and benzene. A group in which a ring is alternately condensed (condensed) (a group formed by condensation) is preferable.

Component A preferably contains at least one compound represented by any one of Formulas 1 to 16 from the viewpoint of mobility as an organic semiconductor, and is represented by any one of Formulas 1 to 16. More preferably, it is a compound of more than one species.
In the composition of this invention, only 1 type of component A may be contained, or 2 or more types of component A may be contained.

In Formula 1, A ^1a and A ^1b each independently represent an S atom, an O atom, or a Se atom, R ^{1a to} R ^1f each independently represent a hydrogen atom or a substituent, and R ^{1a to} R ^1f At least one is a group represented by the following formula W.
-L ^W -R ^W (W)
In the formula W, L ^W is a divalent linking group represented by any of the following formulas L-1 to L-25 or two or more represented by any of the following formulas L-1 to L-25. -valent divalent linking group linking group is attached the, R ^W is an alkyl group, a cyano group, a vinyl group, an ethynyl group, an oxyethylene group, repetition number v of oxyethylene units is more than one oligo oxyethylene group, It represents a siloxane group, an oligosiloxane group having 2 or more silicon atoms, or a trialkylsilyl group.

In Formula L-1 to Formula L-25, * represents the bonding position with R, the wavy line portion represents the other bonding position, and Formula L-1, Formula L-2, Formula L-6, and Formula L- each R 'independently in 13 formula L-24, represent a hydrogen atom or a substituent, R ^N represents a hydrogen atom or a substituent, are each R ^si independently, a hydrogen atom, an alkyl group, an alkenyl or alkynyl Represents a group.
In Formula 2, X ^2a and X ^2b each independently represent NR ²ⁱ , O atom or S atom, A ^2a represents CR ^2g or N atom, A ^2b represents CR ^2h or N atom, and R ²ⁱ represents Represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an acyl group, R ^{2a to} R ^2h each independently represents a hydrogen atom or a substituent, and at least one of R ^{2a to} R ^2h is represented by the formula W; Group.
In Formula 3, X ^3a and X ^3b each independently represent an S atom, an O atom or NR ^3g , and A ^3a and A ^3b each independently represent a CR ^3h or an N atom. R ^{3a to} R ^3h each independently represents a hydrogen atom or a substituent, and at least one of R ^{3a to} R ^3h is a group represented by the formula W.
In Formula 4, X ^4a and X ^4b each independently represent an O atom, an S atom or a Se atom, 4p and 4q each independently represent an integer of 0 to 2, R ^{4a to} R ^4j , R ^4k and R ^4m independently represents a hydrogen atom, a halogen atom or a group represented by the above formula W, and at least one of R ^{4a to} R ^4j , R ^4k and R ^4m is represented by the above formula W. a group, provided ^{that, R 4e} and ^{L W} is the formula L-2 or formula L in the formula W if at least one of a group represented by the formula W represented by ^{R 4e} and ^{R 4f} of ^{R 4f} -3 is a divalent linking group.

In Formula 5, X ^5a and X ^5b each independently represent NR ⁵ⁱ , O atom or S atom, A ^5a represents CR ^5g or N atom, A ^5b represents CR ^5h or N atom, and R ⁵ⁱ represents Represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an acyl group, an aryl group or a heteroaryl group, R ^{5a to} R ^5h each independently represent a hydrogen atom or a substituent, and at least of R ^{5a to} R ^5h One is a group represented by the above formula W.
In Formula 6, X ^{6a to} X ^6d each independently represents NR ^6g , an O atom or an S atom, and R ^6g represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an acyl group, an aryl group or a heteroaryl group. R ^{6a to} R ^6f each independently represents a hydrogen atom or a substituent, and at least one of R ^{6a to} R ^6f is a group represented by the formula W.
In Formula 7, X ^7a and X ^7c each independently represent an S atom, O atom, Se atom or NR ⁷ⁱ , X ^7b and X ^7d each independently represent an S atom, O atom or Se atom, R ^{7a to} R ⁷ⁱ each independently represents a hydrogen atom or a substituent, and at least one of R ^{7a to} R ⁷ⁱ is a group represented by the formula W.
In Formula 8, X ^8a and X ^8c each independently represent an S atom, O atom, Se atom or NR ⁸ⁱ , X ^8b and X ^8d each independently represent an S atom, O atom or Se atom, and R ^{8a to} R ⁸ⁱ each independently represents a hydrogen atom or a substituent, and at least one of R ^{8a to} R ⁸ⁱ is a group represented by the formula W.

In Formula 9, X ^9a and X ^9b each independently represent an O atom, an S atom, or a Se atom, and R ^9c , R ^9d, and R ^{9g to} R ^9j each independently represent a hydrogen atom, a halogen atom, or the formula W R ^9a , R ^9b , R ^9e and R ^9f each independently represent a hydrogen atom or a substituent.
In Formula 10, R ^{10a to} R ^10h each independently represents a hydrogen atom or a substituent, and at least one of R ^{10a to} R ^10h represents a substituent represented by Formula W above, and X ^10a and X ^10b Each independently represents an S atom, an O atom, a Se atom or NR ^10i, and each R ¹⁰ⁱ independently represents a hydrogen atom or a group represented by the above formula W.
In Formula 11, X ^11a and X ^11b each independently represent an S atom, an O atom, a Se atom, or NR ¹¹ⁿ , and R ^{11a to} R ^11k , R ^11m, and R ¹¹ⁿ each independently represent a hydrogen atom or a substituent. And at least one of R ^{11a to} R ^11k , R ^11m and R ¹¹ⁿ is a group represented by the formula W.
In Formula 12, X ^12a and X ^12b each independently represent an S atom, an O atom, a Se atom or NR ¹²ⁿ , and R ^{12a to} R ^12k , R ^12m and R ¹²ⁿ each independently represent a hydrogen atom or a substituent. And at least one of R ^{12a to} R ^12k , R ^12m and R ¹²ⁿ is a group represented by the formula W.

In Formula 13, X ^13a and X ^13b each independently represent an S atom, an O atom, a Se atom or NR ¹³ⁿ , and R ^{13a to} R ^13k , R ^13m and R ¹³ⁿ each independently represent a hydrogen atom or a substituent. And at least one of R ^{13a to} R ^13k , R ^13m and R ¹³ⁿ is a group represented by the formula W.
In Formula 14, X ^{14a to} X ^14c each independently represents an S atom, an O atom, a Se atom, or NR ¹⁴ⁱ , R ^{14a to} R ¹⁴ⁱ each independently represents a hydrogen atom or a substituent, and R ^{14a to} R ^{14 At} least one of ¹⁴ⁱ is a group represented by the above formula W.
In Equation ^15, the X 15a ^{to X 15d} are each independently, S atom, O atom, a Se atom or a ^{NR 15g, R} 15a ^{~R 15g} each independently represent a hydrogen atom or a ^{substituent, R} 15a to R ^At least one of ^{15 g} is a group represented by the above formula W.
In Equation ^16, the X 16a ^{to X 16d} are each independently, S atom, O atom, a Se atom or a ^{NR 16g, R} 16a ^{~R 16g} each independently represent a hydrogen atom or a ^{substituent, R} 16a to R ^At least one of ^{16 g} is a group represented by the above formula W.

-Compound represented by Formula 1-

In Formula 1, A ^1a and A ^1b each independently represent an S atom (sulfur atom), an O atom (oxygen atom), or an Se atom (selenium atom). A ^1a and A ^1b are preferably S atoms or O atoms. A ^1a and A ^1b may be the same or different from each other, but are preferably the same.
In Formula 1, R ^{1a to} R ^1f each independently represent a hydrogen atom or a substituent. However, at least one of R ^{1a to} R ^1f is a group represented by the formula W described later.

The compound represented by Formula 1 may have other substituents other than the group represented by Formula W described later.
Although the kind of substituent which R ^{< 1a} > -R < ^1f > of Formula 1 can take is not specifically limited, Substituent X demonstrated below is mentioned. Examples of the substituent X include a group represented by the formula W described later, a halogen atom, an alkyl group (including a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group), an alkenyl group (a cycloalkenyl group and a bicycloalkenyl group). ), Alkynyl group, aryl group, heterocyclic group (may be referred to as heterocyclic group), cyano group, hydroxy group, nitro group, carboxy group, alkoxy group, aryloxy 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, sulfamoylamino group, Kills and arylsulfonylamino groups, mercapto groups, alkylthio groups, arylthio groups, heterocyclic thio groups, sulfamoyl groups, sulfo groups, alkyl and arylsulfinyl groups, alkyl and arylsulfonyl groups, acyl groups, aryloxycarbonyl groups, alkoxycarbonyl groups 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 ), sulfato group (—OSO ₃ H), and other known substituents. In the formulas 1 to 16 of the present specification, the “substituent” preferably includes the above-described substituent X.
Among these, as a group other than the group represented by the formula W described later, a halogen atom, an alkyl group, an alkynyl group, an alkenyl group, an alkoxy group, an alkylthio group, and an aryl group are preferable, a fluorine atom, and a carbon number of 1 to 3 Substituted or unsubstituted alkyl group, substituted or unsubstituted alkynyl group having 2 to 3 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 3 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 2 carbon atoms More preferably a substituted or unsubstituted methylthio group or phenyl group, a fluorine atom, a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 3 carbon atoms, or 2 to 2 carbon atoms. Particularly preferred are 3 substituted or unsubstituted alkenyl groups, 1 to 2 carbon substituted or unsubstituted alkoxy groups, and substituted or unsubstituted methylthio groups.

In the compound represented by Formula 1, the number of substituents other than the group represented by Formula W among R ^{1a to} R ^1f is preferably 0 to 4, and preferably 0 to 2. More preferably, 0 is particularly preferable.
These substituents may further have the above substituent X.
Among these, R ^{1c to} R ^1f are each independently a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 3 carbon atoms, or 2 to 2 carbon atoms. It is preferably 3 substituted or unsubstituted alkenyl groups, 1 to 2 carbon substituted or unsubstituted alkoxy groups, or substituted or unsubstituted methylthio groups.

Next, the group represented by Formula W will be described.
-L ^W -R ^W (W)
In Formula W, L is represented by any of the following divalent linking groups represented by any of the following formulas L-1 to L-25, or two or more of the following formulas L-1 to L-25. A divalent linking group to which a divalent linking group is bonded is represented.

In the formula L-. 1 to formula L-25, * represents a bonding position to R ^W, wavy line portion represents the other coupling position. More specifically, for example, in the compound represented by Formula 1, the wavy line portion is bonded to the ring forming the skeleton represented by Formula 1. As will be described later, when Formula W is contained in another compound, the wavy line part is bonded to the ring forming the skeleton of each compound.
Incidentally, when referring to L ^W has the formula L-. 1 to formula L-25 divalent linking group linking groups bonded two or more divalent represented by any one of, * is the one linking group, the other It connects with the wavy part of the linking group.
Bonding position to the bonding position and R ^W of R 'in formula L-. 13 to Formula L-24 * may take any position on the aromatic ring or a heteroaromatic ring.
R ′ in Formula L-1, Formula L-2, Formula L-6, and Formula L-13 to Formula L-24 each independently represents a hydrogen atom or a substituent. ^RN represents a hydrogen atom or a substituent. R ^si each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group.
Formula L-1 and may form a condensed ring by combining with R ^W where each R 'is wherein L-2 adjacent to L ^W.

  Among these, the divalent linking group represented by any one of the formulas L-17 to L-21, L-23 and L-24 is represented by the following formulas L-17A to L-21A and L It is more preferably a divalent linking group represented by -23A and Formula L-24A.

Here, a substituted or unsubstituted alkyl group, an oxyethylene group, an oligooxyethylene group having a repeating number v of 2 or more, a siloxane group, an oligosiloxane group having 2 or more silicon atoms, or a substituted or unsubstituted group. If a trialkylsilyl group substitutions present at the end of the substituent, can also be interpreted as -R ^W alone in the formula W, it can be -L W ^-R and ^W interpretation in formula W.
In the present invention, when a substituted or unsubstituted alkyl group having N carbon atoms in the main chain is present at the terminal of the substituent, the linking group as much as possible is included from the terminal of the substituent, and- and it is interpreted as L ^W -R ^W, in particular backbone corresponding to R ^W in "formula L-1 1 or a group represented by corresponding to L ^W in the formula W" and "expression W is carbon It is interpreted as a substituent to which “N-1 substituted or unsubstituted alkyl group” is bonded. For example, when an n-octyl group which is an alkyl group having 8 carbon atoms is present at the terminal of the substituent, one group represented by formula L-1 in which two R ′ are hydrogen atoms, and 7 carbon atoms As a substituent bonded to the n-heptyl group.
On the other hand, in the present invention, an oxyethylene group, an oligooxyethylene group having a repeating number v of 2 or more, a siloxane group, an oligosiloxane group having 2 or more silicon atoms, or a substituted or unsubstituted trialkylsilyl group. If a group is present at the end of the substituents on including a linking group as possible from the end of the substituent, it is interpreted as R ^W alone in formula W. For example, when a — (OCH ₂ CH ₂ ) — (OCH ₂ CH ₂ ) — (OCH ₂ CH ₂ ) —OCH ₃ group is present at the end of the substituent, an oligooxyethylene having a repeating number v of oxyethylene units of 3 Interpreted as a single group substituent.

If L ^W to form a linking group attached divalent linking group represented by any one of formulas L-. 1 to formula L-25, represented by any one of formula L-. 1 to formula L-25 The number of bonds of the divalent linking group is preferably 2 to 4, and more preferably 2 or 3.

Examples of the substituent R ′ in the formula L-1, the formula L-2, the formula L-6, and the formula L-13 to the formula L-24 are the substituents that can be adopted by R ^{1a to} R ^{1f in} the formula 1 above. Can be mentioned. Among them, the substituent R ′ in formula L-6 is preferably an alkyl group, and when R ′ in formula L-6 is an alkyl group, the alkyl group has 1 to 9 carbon atoms. 4 to 9 is more preferable, and from the viewpoint of chemical stability and carrier transportability, 5 to 9 is even more preferable. When R ′ in Formula L-6 is an alkyl group, the alkyl group is preferably a linear alkyl group from the viewpoint of increasing carrier mobility.
R ^N represents a hydrogen atom or a substituent, examples of R ^N, may be mentioned those exemplified as the substituents of R ^1a to R ^1f of Formula 1 described above can take. Among them, as the R ^N, a hydrogen atom or a methyl group is preferable.
R ^si each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group, and is preferably an alkyl group. The alkyl group that R ^si can take is not particularly limited, but the preferred range of the alkyl group that R ^si can take is the preferred range of the alkyl group that the trialkylsilyl group can take when R is a trialkylsilyl group. It is the same. The alkenyl group that R ^si can take is not particularly limited, but is preferably a substituted or unsubstituted alkenyl group, more preferably a branched alkenyl group, and the alkenyl group has 2 to 3 carbon atoms. preferable. The alkynyl group that R ^si can take is not particularly limited, but is preferably a substituted or unsubstituted alkynyl group, more preferably a branched alkynyl group, and the alkynyl group has 2 to 3 carbon atoms. preferable.

^LW is a divalent linking group represented by any one of formula L-1 to formula L-5, formula L-13, formula L-17, or formula L-18, or formula L-1 to formula L -5, a divalent linking group in which two or more divalent linking groups represented by formula L-13, formula L-17, or formula L-18 are bonded together is preferably represented by formula L-1, A divalent linking group represented by any one of formula L-3, formula L-13 or formula L-18, or any of formula L-1, formula L-3, formula L-13 or formula L-18 Is more preferably a divalent linking group in which two or more divalent linking groups are bonded, and any one of Formula L-1, Formula L-3, Formula L-13, or Formula L-18 A divalent linking group represented by formula L-3, a formula L-13 or a formula L-18, and a divalent linking group represented by formula L-1. Linking group Particularly preferred is a divalent linking group in which
A divalent linking group in which a divalent linking group represented by any one of formula L-3, formula L-13 or formula L-18 and a divalent linking group represented by formula L-1 are bonded. preferably, the divalent linking group represented by the formula L-1 binds to R ^W side.
Table Moreover, L ^W, the chemical stability, particularly preferable from the viewpoint of carrier transportability is a divalent linking group containing a divalent linking group represented by the formula L-1, by the formula L-1 more particularly preferably a divalent linking group that is, L ^W is a divalent linking group represented by the formula L-1, and most preferably R ^W is a substituted or unsubstituted alkyl group .

In the formula W, R ^W is a substituted or unsubstituted alkyl group, cyano group, vinyl group, ethynyl group, oxyethylene group, oligooxyethylene group having a repeating number v of 2 or more, siloxane group, silicon atom number Represents two or more oligosiloxane groups, or a substituted or unsubstituted trialkylsilyl group.
In Formula W, when L ^W adjacent to R ^W is a divalent linking group represented by Formula L-1, R ^W is a substituted or unsubstituted alkyl group, oxyethylene group, or repeating oxyethylene unit. An oligooxyethylene group having 2 or more numbers, a siloxane group, and an oligosiloxane group having 2 or more silicon atoms are preferable, and a substituted or unsubstituted alkyl group is more preferable.
In Formula W, when L ^W adjacent to R ^W is a divalent linking group represented by any one of Formula L-2 or Formula L-4 to Formula L-25, R ^W is substituted or unsubstituted. The alkyl group is more preferably.
In Formula W, when L ^W adjacent to R ^W is a divalent linking group represented by Formula L-3, R ^W is a substituted or unsubstituted alkyl group, or a substituted or unsubstituted trialkyl. A silyl group is preferred.

For R ^W is a substituted or unsubstituted alkyl group, it preferably has a carbon number of 4 to 17, chemical stability, more preferably from the viewpoint of carrier transport property that is 6 to 14, 6 to 12 More preferably it is. R is preferably a long-chain alkyl group in the above-mentioned range, particularly a long-chain straight-chain alkyl group, from the viewpoint of increasing the linearity of the molecule and increasing the carrier mobility.
If R ^W represents an alkyl group, a straight-chain alkyl group, even branched alkyl group, it may be a cyclic alkyl group, a straight-chain alkyl groups, increases the linearity of the molecules, to increase the carrier mobility It is preferable from the viewpoint that can be achieved.
Among these, the combination of R ^W and L ^W in Formula W, in Formula 1, a divalent linking group L ^W is represented by the formula L-1, and the carbon number of R ^W is a linear or an alkyl group having from 7 to 17, or the table in ^{L W} has the formula L-3, wherein L-13 or formula L-18 linking group with the formula L-1 of any one divalent expressed in a divalent divalent linking group linking group is attached the to be, and that R ^W is a straight chain alkyl group is preferable from the viewpoint of enhancing the carrier mobility.
L ^W is a divalent linking group represented by the formula L-1, and, if ^{R W} is an alkyl group having 7 to 17 carbon atoms of straight-chain, the number of carbon atoms of ^{R W} is a linear 7-14 From the viewpoint of increasing carrier mobility, a linear alkyl group having 7 to 12 carbon atoms is particularly preferable.
L ^W has the formula L-3, wherein L-13 or bivalent divalent linking group and a divalent linking group represented by the formula L-1 of which is represented by any one of formula L-18 bound of a linking group, and, if R ^W is a straight chain alkyl group, R ^W is a linear, more preferably an alkyl group having a carbon number of 4 to 17, the straight-chain having 6 to 14 carbon atoms An alkyl group is more preferable from the viewpoints of chemical stability and carrier transportability, and a linear alkyl group having 6 to 12 carbon atoms is particularly preferable from the viewpoint of increasing carrier mobility.
On the other hand, from the viewpoint of enhancing the solubility in organic solvents, it is preferred that R ^W is a branched alkyl group.
The substituent when R ^W is an alkyl group having a substituent, can be mentioned a halogen atom, a fluorine atom is preferable. It is also possible if R ^W is an alkyl group having a fluorine atom is substituted for all the hydrogen atoms of the alkyl group fluorine atom to form a perfluoroalkyl group. However, it is preferred that R ^W is an unsubstituted alkyl group.

If R ^W is a number of repetitions is more than one oligo oxyethylene group of oxyethylene groups, herein and R represents "oligooxyethylene group", _- represented by (OCH _² CH ²⁾ v -OY It refers to a group (the repeating number v of oxyethylene units represents an integer of 2 or more, and Y at the terminal represents a hydrogen atom or a substituent). In addition, when Y at the terminal of the oligooxyethylene group is a hydrogen atom, it becomes a hydroxy group. The number of repeating oxyethylene units v is preferably 2 to 4, more preferably 2 to 3.
The terminal hydroxy group of the oligooxyethylene group is preferably sealed, that is, Y represents a substituent. In this case, the hydroxy group is preferably sealed with an alkyl group having 1 to 3 carbon atoms, that is, Y is preferably an alkyl group having 1 to 3 carbon atoms, and Y is a methyl group or an ethyl group. More preferred is a methyl group.

R ^W is a siloxane group, or, when the number of silicon atoms is two or more oligosiloxane groups, the number of repetitions of the siloxane units is preferably from 2 to 4, more preferably 2 to 3. In addition, a hydrogen atom or an alkyl group is preferably bonded to the silicon atom (Si atom). When an alkyl group is bonded to a silicon atom, the alkyl group preferably has 1 to 3 carbon atoms, and for example, a methyl group or an ethyl group is preferably bonded. The same alkyl group may be bonded to the silicon atom, or a different alkyl group or a hydrogen atom may be bonded thereto. Moreover, although all the siloxane units which comprise an oligosiloxane group may be the same or different, it is preferable that all are the same.

If L ^W adjacent to R ^W is a divalent linking group represented by the formula L-3, it is also preferred R ^W is a substituted or unsubstituted trialkylsilyl group. It Among them if R ^W is a substituted or unsubstituted trialkylsilyl group, examples of the substituent of the silyl group is not particularly limited as long as it is a substituted or unsubstituted alkyl group, a branched alkyl group Is more preferable. It is preferable that carbon number of the alkyl group couple | bonded with a silicon atom is 1-3, for example, it is preferable that a methyl group, an ethyl group, and an isopropyl group couple | bond. The same alkyl group may be bonded to the silicon atom, or different alkyl groups may be bonded to it. The substituent when R ^W is a trialkylsilyl group having a substituent on the alkyl group is not particularly limited.

In the formula W, the total number of carbon atoms contained in L ^W and R ^W is preferably 5 to 18. If the total number of carbon atoms contained in L ^W and R ^W is at least the lower limit within the above range, the carrier mobility is high, lower the driving voltage. If the total number of carbon atoms contained in L ^W and R ^W is not more than the upper limit of the above range, solubility in an organic solvent is increased.
The total number of carbon atoms contained in L ^W and R ^W is preferably 5 to 14, more preferably 6 to 14, still more preferably 6 to 12, and preferably 8 to 12. Particularly preferred.

In the compound represented by Formula 1, among R ^{1a to} R ^1f , the number of groups represented by Formula W is preferably 1 to 4, more preferably 1 to 2, and more preferably 2 It is particularly preferable that the number is individual.

In the present invention, in Formula 1, at least one of R ^1a and R ^1b is preferably a group represented by Formula W. These positions are preferable as the substitution positions in Formula 1 because they are excellent in chemical stability of the compound, and are preferable from the viewpoint of the highest occupied orbital (HOMO) level and packing of molecules in the film. It is believed that there is. In particular, in Formula 1, a high carrier concentration can be obtained by using two positions of R ^1a and R ^1b as substituents.
In Formula 1, R ^{1c to} R ^1f are each independently a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 3 carbon atoms, A substituted or unsubstituted alkenyl group having 2 to 3 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 2 carbon atoms, or a substituted or unsubstituted methylthio group is preferable.

-Compound represented by Formula 2-

In Formula 2, X ^2a and X ^2b each independently represent NR ²ⁱ (> N—R ²ⁱ ), an O atom, or an S atom. X ^2a and X ^2b are each independently preferably an O atom or an S atom from the viewpoint of ease of synthesis. On the other hand, it is preferable from the viewpoint of increasing carrier mobility that at least one of X ^2a and X ^2b is an S atom.
X ^2a and X ^2b are preferably the same linking group. It is more preferable that both X ^2a and X ^2b are S atoms.
R ²ⁱ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an acyl group, preferably a hydrogen atom or an alkyl group, more preferably an alkyl group having 1 to 14 carbon atoms, and 1 carbon atom. Particularly preferred is an alkyl group of ˜4.
When R ²ⁱ represents an alkyl group, it may be a linear alkyl group, a branched alkyl group, or a cyclic alkyl group, but the linear alkyl group increases the linearity of the molecule and increases the carrier mobility. It is preferable from the viewpoint that can be achieved.

In Formula 2, A ^2a represents CR ^2g or an N atom, A ^2b represents CR ^2h or an N atom, and R ^2g and R ^2h each independently represent a hydrogen atom or a substituent. Or A ^2a is ^{CR 2 g,} preferably ^{A 2b} is ^{CR 2h, A 2a} is ^{CR 2 g,} and more preferably ^{A 2b} is ^{CR 2h.} A ^2a and A ^2b may be the same or different from each other, but are preferably the same.
In Formula 2, R ^2e and R ^2g may be bonded to each other to form a ring, or may not be bonded to each other to form a ring, but it is preferable that they are not bonded to each other to form a ring.
In Formula 2, R ^2f and R ^2h may be bonded to each other to form a ring, or may not be bonded to each other to form a ring, but it is preferable that they are not bonded to each other to form a ring.

In Formula 2, R ^{2a to} R ^2h each independently represent a hydrogen atom or a substituent, and at least one represents a substituent represented by Formula W.
Examples of the substituent that R ^{2a to} R ^2h can independently take include the substituent X described above. The definition of the substituent represented by Formula W is as described above.
R ^{2a to} R ^2h are each independently a substituent represented by an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a heterocyclic group, an alkoxy group, an alkylthio group, or a substituent represented by the formula W. C1-C12 alkyl group, C6-C20 aryl group, C2-C12 alkenyl group, C2-C12 alkynyl group, C1-C11 alkoxy group, C5-C12 A heterocyclic group, an alkylthio group having 1 to 12 carbon atoms, and a group represented by Formula W are more preferable, a group having a linking group chain length of 3.7 Å or less and a group represented by Formula W are particularly preferable. The group represented by W is more particularly preferable.

Among the compounds represented by Formula 2, among R ^{2a to} R ^2h , 1 to 4 groups represented by Formula W are used from the viewpoint of increasing carrier mobility and increasing solubility in an organic solvent. The number is preferably 1 or 2, more preferably 2.
Although there is no restriction ^| limiting in particular in the position of the group represented by Formula W among R ^{< 2a} > -R < ^{2h >} , it is R ^{< 2e>} or R ^<2f> from a viewpoint which raises carrier mobility and raises the solubility to an organic solvent. preferable.

Of R ^{2a to} R ^2h, the number of substituents other than the group represented by Formula W is preferably 0 to 4, more preferably 0 to 2, and 0 or 1. More preferably, it is particularly preferably 0.

The substituent in the case where R ^{2a to} R ^2h are substituents other than the group represented by Formula W is preferably a group having a linking group chain length of 3.7 mm (= 0.37 nm) or less. The chain length is more preferably a group having a chain length of 1.0 to 3.7 mm, and the linking group chain length is more preferably a group having a chain length of 1.0 to 2.1 mm.
Here, the linking group chain length refers to the length from the C atom in the C (carbon atom) -R bond to the terminal of the substituent R. The structure optimization calculation can be performed using a density functional method (Gaussian 03 (Gaussian, USA) / basis function: 6-31G ^* , exchange correlation functional: B3LYP / LANL2DZ). In addition, as the molecular length of a typical substituent, the propyl group is 4.6Å, the pyrrole group is 4.6Å, the propynyl group is 4.5Å, the propenyl group is 4.6Å, the ethoxy group is 4.5Å, and the methylthio group Is 3.7Å, the ethenyl group is 3.4Å, the ethyl group is 3.5Å, the ethynyl group is 3.6Å, the methoxy group is 3.3Å, the methyl group is 2.1Å, and the hydrogen atom is 1.0Å.

When R ^{2a to} R ^2h are substituents other than the group represented by Formula W, the substituents are each independently a substituted or unsubstituted alkyl group having 2 or less carbon atoms, a substituted or unsubstituted group having 2 or less carbon atoms. It is preferably an alkynyl group, a substituted or unsubstituted alkenyl group having 2 or less carbon atoms, or a substituted or unsubstituted acyl group having 2 or less carbon atoms, and a substituted or unsubstituted alkyl group having 2 or less carbon atoms. It is more preferable.
In the case where R ^{2a to} R ^2h are substituents other than the group represented by the formula W, each of the substituents independently represents a substituted alkyl group having 2 or less carbon atoms. Group, fluorine atom, deuterium atom and the like, and a cyano group is preferable. In the case of a substituent other than the group represented by Formula W, the substituted or unsubstituted alkyl group having 2 or less carbon atoms represented by the substituent is preferably a methyl group, an ethyl group, or a cyano group-substituted methyl group. A methyl group substituted with a cyano group or a cyano group is more preferred, and a methyl group substituted with a cyano group is particularly preferred.
In the case where R ^{2a to} R ^2h are substituents other than the group represented by Formula W, each of the substituents independently represents a substituted alkynyl group having 2 or less carbon atoms, the substituents that the alkynyl group can take are heavy A hydrogen atom etc. can be mentioned. Examples of the substituted or unsubstituted alkynyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the group represented by Formula W include an ethynyl group and a deuterium atom-substituted acetylene group, An ethynyl group is preferred.
In the case where R ^{2a to} R ^2h are substituents other than the group represented by Formula W, each of the substituents independently represents a substituted alkenyl group having 2 or less carbon atoms, the substituents that the alkenyl group can take are heavy A hydrogen atom etc. can be mentioned. Examples of the substituted or unsubstituted alkenyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the group represented by Formula W include an ethenyl group and a deuterium-substituted ethenyl group, An ethenyl group is preferred.
In the case where R ^{2a to} R ^2h are substituents other than the group represented by Formula W, each of the substituents independently represents a substituted acyl group having 2 or less carbon atoms, the substituent that the acyl group can take is fluorine. An atom etc. can be mentioned. Examples of the substituted or unsubstituted acyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the group represented by Formula W include a formyl group, an acetyl group, and a fluorine-substituted acetyl group. A formyl group is preferred.

-Compound represented by Formula 3-

In Formula 3, R ^{3a to} R ^3f and R ^3g and R ^3h described later each independently represent a hydrogen atom or a substituent. However, at least one of R ^{3a to} R ^3h represents a group represented by Formula W.
Examples of the substituent represented by R ^{3a to} R ^3h include the substituent X. The definition of the group represented by Formula W is as described above.
As the substituent that R ^{3a to} R ^3f can independently take, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a heterocyclic group, an alkoxy group, an alkylthio group, or a substituent represented by the formula W is preferable, C1-C12 alkyl group, C6-C20 aryl group, C2-C12 alkenyl group, C2-C12 alkynyl group, C1-C11 alkoxy group, C5-C12 A heterocyclic group, an alkylthio group having 1 to 12 carbon atoms, or a group represented by the formula W is more preferable.

In Formula 3, X ^3a and X ^3b each independently represent an S atom, an O atom, or NR ^3g (> N—R ^3g ), and R ^3g represents a hydrogen atom or a substituent. X is preferably an S atom or an O atom. In Formula 3, X ^3a and X ^3b are preferably the same.
R ^3g is preferably a hydrogen atom, an alkyl group, or an aryl group, more preferably an alkyl group having 1 to 14 carbon atoms, and particularly preferably an alkyl group having 4 to 12 carbon atoms. It is preferable that R ^3g is a long-chain alkyl group within the above range, particularly a long-chain linear alkyl group, from the viewpoint of increasing the linearity of the molecule and increasing the carrier mobility.
When R ^3g represents an alkyl group, it may be a linear alkyl group, a branched alkyl group or a cyclic alkyl group, but the linear alkyl group increases the linearity of the molecule and increases the carrier mobility. It is preferable from the viewpoint that can be achieved.

In Formula 3, A ^3a and A ^3b each independently represent CR ^3h or an N atom, and preferably represents CR ^3h . In Formula 3, A ^3a and A ^3b may be the same or different from each other, but are preferably the same.
R ^3h is preferably a group having a linking group chain length of 3.7 mm or less, more preferably a group having a linking group chain length of 1.0 to 3.7 mm, and a linking group chain length of 1.0 to More preferably, it is a 2.1 Å group. The definition of the linking group chain length is as described above.
R ^3h is a hydrogen atom, a substituted or unsubstituted alkyl group having 2 or less carbon atoms, a substituted or unsubstituted alkynyl group having 2 or less carbon atoms, a substituted or unsubstituted alkenyl group having 2 or less carbon atoms, or a carbon number It is preferably a substituted or unsubstituted acyl group having 2 or less, more preferably a hydrogen atom or a substituted or unsubstituted alkyl group having 2 or less carbon atoms, and particularly preferably a hydrogen atom.
When R ^3h represents a substituted alkyl group having 2 or less carbon atoms, ^examples of the substituent that the alkyl group can take include a cyano group, a fluorine atom, and a deuterium atom, and a cyano group is preferable. The substituted or unsubstituted alkyl group having 2 or less carbon atoms represented by R ^3h is preferably a methyl group, an ethyl group, or a cyano group-substituted methyl group, more preferably a methyl group or a cyano group-substituted methyl group, A group-substituted methyl group is particularly preferred.
When R ^3h represents a substituted alkynyl group having 2 or less carbon atoms, ^examples of the substituent that the alkynyl group can take include a deuterium atom. Examples of the substituted or unsubstituted alkynyl group having 2 or less carbon atoms represented by R ^3h include an ethynyl group or a deuterium atom-substituted acetylene group, and an ethynyl group is preferable.
When R ^3h represents a substituted alkenyl group having 2 or less carbon atoms, ^examples of the substituent that the alkenyl group can take include a deuterium atom. ^Examples of the substituted or unsubstituted alkenyl group having 2 or less carbon atoms represented by R ^3h include an ethenyl group or a deuterium atom-substituted ethenyl group, and an ethenyl group is preferable.
When R ^3h represents a substituted acyl group having 2 or less carbon atoms, ^examples of the substituent that the acyl group can take include a fluorine atom. ^Examples of the substituted or unsubstituted acyl group having 2 or less carbon atoms represented by R ^3h include a formyl group, an acetyl group, and a fluorine-substituted acetyl group, and a formyl group is preferable.

-Compound represented by Formula 4-

In Formula 4, X ^4a and X ^4b each independently represent an O atom, an S atom, or an Se atom.
X ^4a and X ^4b are each independently preferably an O atom or an S atom, and at least one of X ^4a and X ^4b is preferably an S atom, more preferably from the viewpoint of increasing carrier mobility. X ^4a and X ^4b are preferably the same linking group. It is particularly preferred that both X ^4a and X ^4b are S atoms.

  In Formula 4, 4p and 4q each independently represent an integer of 0 to 2. 4p and 4q are each independently 0 or 1 from the viewpoint of achieving both mobility and solubility, and more preferably 4p = 4q = 0 or 4p = 4q = 1.

In Formula 4, R ^{4a to} R ^4k and R ^4m each independently represent a hydrogen atom, a halogen atom, or a group represented by Formula W, and at least one of R ^{4a to} R ^4k and R ^4m Is a group represented by formula W, provided that when at least one of R ^4e and R ^4f is a group represented by formula W, in formula W represented by R ^4e and R ^4f , L ^W is It is a bivalent coupling group represented by the said Formula L-2 or Formula L-3. In addition, the definition of group represented by Formula W is as above-mentioned.

The case where at least one of R ^4e and R ^4f is a group represented by the formula W corresponds to the case where either one of R ^4e and R ^4f is neither a hydrogen atom nor a halogen atom.
When at least one of R ^4e and R ^4f is a group represented by the formula W, in the formula W represented by the R ^4e and R ^4f , L ^W is a divalent linking group represented by the formula L-3. Preferably there is.
If at least one of R ^4e and ^{R 4f} is a group represented by the formula ^{W, R 4e} and ^{R 4f} are preferably both a group represented by the formula W.
When R ^4e and R ^4f are both hydrogen atoms or halogen atoms, R ^{4a to} R ^4d , R ^{4g to} R ^4k and R ^4m are each independently a hydrogen atom, a halogen atom or a group represented by the formula W And at least one of R ^{4a to} R ^4d , R ^{4g to} R ^4k and R ^4m is a group represented by the formula W.

In formula 4, ^examples of the halogen atom represented by R ^{4a to} R ^4k and R ^4m include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, preferably a fluorine atom, a chlorine atom, or a bromine atom. A fluorine atom or a chlorine atom is more preferable, and a fluorine atom is particularly preferable.

In the compound represented by Formula 4, among R ^{4a to} R ^4k and R ^4m , the halogen atom is preferably 0 to 4, more preferably 0 to 2, and 0 or 1 More preferably, it is particularly preferably 0.

Among the compounds represented by Formula 4, among R ^{4a to} R ^4k and R ^4m , the number of groups represented by Formula W is 1 to 4 to increase carrier mobility and solubility in organic solvents. From the viewpoint of increasing the number, it is preferably 1 or 2, more preferably 2.
Among R ^{4a to} R ^4k and R ^4m , the position of the group represented by the formula W is not particularly limited. Among them, in the present invention, in formula 4, R ^4a , R ^{4d to} R ^4g , R ^4j , R ^4k and R ^4m are each independently a hydrogen atom or a halogen atom, and R ^4b , R ^4c , R ^4h and R ⁴ⁱ is each independently a hydrogen atom, a halogen atom or a group represented by the formula W, and at least one of R ^4b , R ^4c , R ^4h and R ⁴ⁱ is a group represented by the formula W It is preferable from the viewpoint of increasing carrier mobility and increasing solubility in an organic solvent.
In the present invention, R ^4a , R ^{4c to} R ^4h and R ^4j each independently represent a hydrogen atom or a halogen atom, and R ^4b and R ⁴ⁱ each independently represent a hydrogen atom, a halogen atom or Formula W. More preferably, at least one group is a group represented by the formula W.
In the present invention, both R ^4b and R ⁴ⁱ are groups represented by the formula W, and R ^4c and R ^4h are both hydrogen atoms or halogen atoms, or both R ^4c and R ^4h are represented by the formula W. More preferably, R ^4b and R ⁴ⁱ are both hydrogen atoms or halogen atoms.
In the present invention, both R ^4b and R ⁴ⁱ are groups represented by the formula W, and R ^4c and R ^4h are both hydrogen atoms or halogen atoms, or both R ^4c and R ^4h are represented by the formula W. It is particularly preferable that R ^4b and R ⁴ⁱ are both a hydrogen atom or a halogen atom.
In Formula 4, two or more R ^{4a to} R ^4k and R ^4m may be bonded to each other to form a ring, or may not be bonded to each other to form a ring, but are not bonded to each other to form a ring. Is preferred.

-Compound represented by Formula 5-

In Formula 5, X ^5a and X ^5b each independently represent NR ⁵ⁱ , an O atom, or an S atom. X ^5a and X ^5b are each independently preferably an O atom or an S atom from the viewpoint of ease of synthesis. On the other hand, at least one of X ^5a and X ^5b is preferably an S atom from the viewpoint of increasing carrier mobility. X ^5a and X ^5b are preferably the same linking group. It is more preferable that both X ^5a and X ^5b are S atoms.
R ⁵ⁱ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an acyl group, an aryl group or a heteroaryl group, preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an acyl group, Alternatively, it is more preferably an alkyl group, still more preferably an alkyl group having 1 to 14 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms.
When R ⁵ⁱ represents an alkyl group, it may be a linear alkyl group, a branched alkyl group, or a cyclic alkyl group, but the linear alkyl group increases the linearity of the molecule and increases the carrier mobility. It is preferable from the viewpoint that can be achieved.

In Formula 5, A ^5a represents CR ^5g or an N atom, A ^5b represents CR ^5h or an N atom, and R ^5g and R ^5h each independently represent a hydrogen atom or a substituent. Or A ^5a is ^{CR 5 g,} preferably ^{A 5b} is ^{CR 5h, A 5a} it is more preferably ^{CR 5 g} and ^{A 5b} is ^{CR 5h.} A ^5a and A ^5b may be the same or different from each other, but are preferably the same.

In Formula 5, R ^5e and R ^5g may be bonded to each other to form a ring or may not be bonded to each other to form a ring, but it is preferable that they are not bonded to each other to form a ring.
In Formula 5, R ^5e and R ⁵ⁱ may be bonded to each other to form a ring, and may not be bonded to each other to form a ring, but it is preferable that they are not bonded to each other to form a ring.
In Formula 5, R ^5f and R ^5h may be bonded to each other to form a ring or may not be bonded to each other to form a ring, but it is preferable that they are not bonded to each other to form a ring.
In Formula 5, R ^5f and R ⁵ⁱ may be bonded to each other to form a ring, or may not be bonded to each other to form a ring, but it is preferable that they are not bonded to each other to form a ring.

In Formula 5, R ^{5a to} R ^5h each independently represent a hydrogen atom or a substituent, and at least one of R ^{5a to} R ^5h is a group represented by Formula W.
In addition, the substituent X mentioned above is mentioned as a substituent represented by R ^{< 5a} > -R ^<5h> . Moreover, the definition of the group represented by Formula W is as described above.

Among the compounds represented by Formula 5, among R ^{5a to} R ^5h , the number of groups represented by Formula W is 1 to 4, so that the carrier mobility is increased and the solubility in an organic solvent is increased. 1 or 2 is more preferable, and 2 is particularly preferable.
Although there is no restriction ^| limiting in particular in the position of group represented by Formula W among R ^{< 5a} > -R ^{<5h >,} it is ^R5e or ^R5f from a viewpoint which raises carrier mobility and raises the solubility to an organic solvent. preferable.
Of R ^{5a to} R ^5h, the number of substituents other than the group represented by Formula W is preferably 0 to 4, more preferably 0 to 2, and 0 or 1. More preferably, it is particularly preferably 0.

When R ^{5a to} R ^5h are substituents other than the group represented by Formula W, the substituent is preferably a group having a linking group chain length of 3.7 mm or less, and the linking group chain length is 1.0. It is more preferably a group having a length of ˜3.7 Å, and further preferably a group having a linking group chain length of 1.0 to 2.1 Å. The definition of the linking group chain length is as described above.
When R ^{5a to} R ^5h are substituents other than the group represented by Formula W, the substituents are each independently a substituted or unsubstituted alkyl group having 2 or less carbon atoms, or a substituted or unsubstituted group having 2 or less carbon atoms. It is preferably an alkynyl group, a substituted or unsubstituted alkenyl group having 2 or less carbon atoms, or a substituted or unsubstituted acyl group having 2 or less carbon atoms, and a substituted or unsubstituted alkyl group having 2 or less carbon atoms. It is more preferable.
When R ^{5a to} R ^5h are substituents other than the group represented by Formula W, each of the substituents independently represents a substituted alkyl group having 2 or less carbon atoms, the substituent that the alkyl group can take is cyano. Group, fluorine atom, deuterium atom and the like, and a cyano group is preferable. In the case of a substituent other than the group represented by Formula W, the substituted or unsubstituted alkyl group having 2 or less carbon atoms represented by the substituent is preferably a methyl group, an ethyl group, or a cyano group-substituted methyl group. Further, a methyl group or a cyano group-substituted methyl group is more preferable, and a cyano group-substituted methyl group is particularly preferable.
In the case where R ^{5a to} R ^5h are substituents other than the group represented by Formula W, each of the substituents independently represents a substituted alkynyl group having 2 or less carbon atoms, the substituents that the alkynyl group can take are heavy A hydrogen atom etc. can be mentioned. Examples of the substituted or unsubstituted alkynyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the substituent represented by Formula W include an ethynyl group or a deuterium atom-substituted acetylene group An ethynyl group is preferred.
In the case where R ^{5a to} R ^5h are substituents other than the group represented by the formula W, each of the substituents independently represents a substituted alkenyl group having 2 or less carbon atoms. A hydrogen atom etc. can be mentioned. Examples of the substituted or unsubstituted alkenyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the group represented by Formula W include an ethenyl group and a deuterium-substituted ethenyl group, An ethenyl group is preferred.
In the case where R ^{5a to} R ^5h are substituents other than the group represented by Formula W, each of the substituents independently represents a substituted acyl group having 2 or less carbon atoms, the substituent that the acyl group can take is fluorine An atom etc. can be mentioned. Examples of the substituted or unsubstituted acyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the group represented by Formula W include a formyl group, an acetyl group, or a fluorine-substituted acetyl group A formyl group is preferred.

-Compound represented by Formula 6-

In Formula 6, X ^{6a to} X ^6d each independently represents NR ^6g , an O atom or an S atom, and R ^6g represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an acyl group, an aryl group or a heteroaryl group. Represent.
X ^{6a to} X ^6d are each independently preferably an O atom or an S atom from the viewpoint of ease of synthesis. On the other hand, it is preferable from the viewpoint of increasing the carrier mobility that at least one of X ^{6a to} X ^6d is an S atom. X ^{6a to} X ^6d are preferably the same linking group. X ^6a to X ^6d is more preferably both are S atoms.
R ^6g represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an acyl group, an aryl group or a heteroaryl group, and is preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an acyl group, It is more preferably an alkyl group, further preferably an alkyl group having 1 to 14 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms.
When R ^6g represents an alkyl group, it may be a linear alkyl group, a branched alkyl group or a cyclic alkyl group, but the linear alkyl group increases the linearity of the molecule and increases the carrier mobility. It is preferable from the viewpoint that can be achieved.

In Formula 6, R ^{6a to} R ^6f each independently represent a hydrogen atom or a substituent, and at least one represents a group represented by Formula W.
In addition, the substituent X mentioned above is mentioned as a substituent represented by R ^{< 6a} > -R <^6f> . Moreover, the definition of the group represented by Formula W is as described above.
Among these, as the substituent that R ^{6a to} R ^6f can independently take, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a heterocyclic group, an alkoxy group, an alkylthio group, or a group represented by the formula W Preferably, it is an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 11 carbon atoms, or 5 carbon atoms. A -12 heterocyclic group, an alkylthio group having 1 to 12 carbon atoms, or a group represented by the formula W is more preferred, and a linking group chain length described below is a group having a length of 3.7 mm or less, or represented by the formula W. Are more preferable, and a group represented by the formula W is particularly preferable.

Among the compounds represented by Formula 6, among R ^{6a to} R ^6f , the number of groups represented by Formula W is 1 to 4 to increase carrier mobility and increase solubility in organic solvents. 1 or 2 is more preferable, and 2 is particularly preferable.
Although there is no restriction | limiting in particular in the position of the group represented by Formula W among R ^{< 6a} > -R <^6f> , it is preferable that it is R ^{< 6c} > -R <^6f> , and it is R ^<6e> or R ^<6f> raises carrier mobility. From the viewpoint of increasing the solubility in an organic solvent, it is more preferable.

Among R ^{6a to} R ^6f, the number of substituents other than the group represented by Formula W is preferably 0 to 4, more preferably 0 to 2, and 0 or 1. More preferably, it is particularly preferably 0.
In the case where R ^{6a to} R ^6f are substituents other than the group represented by Formula W, the substituent is preferably a group having a linking group chain length of 3.7 mm or less, and the linking group chain length is 1.0. It is more preferably a group having a length of ˜3.7 Å, and still more preferably a group having a linking group chain length of 1.0 to 2.1 Å. The definition of the linking group chain length is as described above.
When R ^{6a to} R ^6f are substituents other than the group represented by Formula W, the substituents are each independently a substituted or unsubstituted alkyl group having a prime number of 2 or less, a substituted or unsubstituted group having a carbon number of 2 or less. It is preferably an alkynyl group, a substituted or unsubstituted alkenyl group having 2 or less carbon atoms, or a substituted or unsubstituted acyl group having 2 or less carbon atoms, and a substituted or unsubstituted alkyl group having 2 or less carbon atoms. It is more preferable.
In the case where R ^{6a to} R ^6f are substituents other than the group represented by the formula W, each of the substituents independently represents a substituted alkyl group having 2 or less carbon atoms. Group, fluorine atom, deuterium atom and the like, and a cyano group is preferable. In the case of a substituent other than the group represented by Formula W, the substituted or unsubstituted alkyl group having 2 or less carbon atoms represented by the substituent is preferably a methyl group, an ethyl group, or a cyano group-substituted methyl group. Further, a methyl group or a cyano group-substituted methyl group is more preferable, and a cyano group-substituted methyl group is particularly preferable.
In the case where R ^{6a to} R ^6f are substituents other than the group represented by Formula W, each of the substituents independently represents a substituted alkynyl group having 2 or less carbon atoms, the substituents that the alkynyl group can take are heavy A hydrogen atom etc. can be mentioned. Examples of the substituted or unsubstituted alkynyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the group represented by Formula W include an ethynyl group and a deuterium atom-substituted acetylene group, An ethynyl group is preferred.
In the case where R ^{6a to} R ^6f are substituents other than the group represented by the formula W, each of the substituents independently represents a substituted alkenyl group having 2 or less carbon atoms, the substituents that the alkenyl group can take are heavy A hydrogen atom etc. can be mentioned. Examples of the substituted or unsubstituted alkenyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the group represented by Formula W include an ethenyl group and a deuterium-substituted ethenyl group, An ethenyl group is preferred.
In the case where R ^{6a to} R ^6f are substituents other than the group represented by Formula W, each of the substituents independently represents a substituted acyl group having 2 or less carbon atoms, the substituent that the acyl group can take is fluorine An atom etc. can be mentioned. Examples of the substituted or unsubstituted acyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the group represented by Formula W include a formyl group, an acetyl group, and a fluorine-substituted acetyl group. A formyl group is preferred.

-Compound represented by Formula 7-

In Formula 7, X ^7a and X ^7c each independently represent an S atom, an O atom, a Se atom, or NR ⁷ⁱ (> N—R ⁷ⁱ ), and X ^7b and X ^7d each independently represent an S atom or an O atom Or represents a Se atom. X ^{7a to} X ^7d are each independently preferably an O atom or an S atom from the viewpoint of ease of synthesis. On the other hand, it is preferable from the viewpoint of increasing the carrier mobility that at least one of X ^{7a to} X ^7d is an S atom. X ^{7a to} X ^7d are preferably the same linking group. X ^7a to X ^7d is more preferably both are S atoms.

In Formula 7, R ^{7a to} R ⁷ⁱ each independently represent a hydrogen atom or a substituent, and at least one of R ^{7a to} R ⁷ⁱ is a group represented by Formula W.
In addition, the substituent X mentioned above is mentioned as a substituent represented by R ^{< 7a} > -R ^<7i> . Moreover, the definition of the group represented by Formula W is as described above.
R ⁷ⁱ is preferably a hydrogen atom or an alkyl group, more preferably an alkyl group having 5 to 12 carbon atoms, and particularly preferably an alkyl group having 8 to 10 carbon atoms.
When R ⁷ⁱ represents an alkyl group, it may be a linear alkyl group, a branched alkyl group, or a cyclic alkyl group, but a linear alkyl group is preferred from the viewpoint of overlapping HOMO orbitals.

Among the compounds represented by Formula 7, among R ^{7a to} R ⁷ⁱ , the number of substituents represented by Formula W is 1 to 4 to increase carrier mobility and increase solubility in organic solvents. From the viewpoint, it is preferably 1 or 2, more preferably 2.
Although there is no restriction ^| limiting in particular in the position of group represented by Formula W among R ^{< 7a} > -R ^{<7i >} , it is R ^{< 7d>} or R ^<7h> from a viewpoint which raises carrier mobility and raises the solubility to an organic solvent. R ^7d and R ^7h are more preferable.
Of R ^{7a to} R ^{7i in} Formula 7, the number of substituents other than the group represented by Formula W is preferably 0 to 4, more preferably 0 to 2, and 0 or 1 More preferably, it is particularly preferably 0.
When R ^{7a to} R ⁷ⁱ are substituents other than the group represented by Formula W, the substituent is preferably a group having a linking group chain length of 3.7 mm or less, and the linking group chain length is 1.0. It is more preferably a group having a length of ˜3.7 Å, and further preferably a group having a linking group chain length of 1.0 to 2.1 Å. The definition of the linking group chain length is as described above.
When R ^{7a to} R ⁷ⁱ are substituents other than the group represented by Formula W, the substituents are each independently a substituted or unsubstituted alkyl group having 2 or less carbon atoms, or a substituted or unsubstituted group having 2 or less carbon atoms. Are preferably substituted or unsubstituted alkenyl groups having 2 or less carbon atoms, or substituted or unsubstituted acyl groups having 2 or less carbon atoms, and are substituted or unsubstituted alkyl groups having 2 or less carbon atoms. More preferably.
In the case where R ^{7a to} R ⁷ⁱ are substituents other than the group represented by the formula W, each of the substituents independently represents a substituted alkyl group having 2 or less carbon atoms. Group, fluorine atom, deuterium atom and the like, and a cyano group is preferable. In the case of a substituent other than the group represented by Formula W, the substituted or unsubstituted alkyl group having 2 or less carbon atoms represented by the substituent is preferably a methyl group, an ethyl group, or a cyano group-substituted methyl group. Further, a methyl group or a cyano group-substituted methyl group is more preferable, and a cyano group-substituted methyl group is particularly preferable.
In the case where R ^{7a to} R ⁷ⁱ are substituents other than the group represented by Formula W, each of the substituents independently represents a substituted alkynyl group having 2 or less carbon atoms, the substituents that the alkynyl group can take are heavy A hydrogen atom etc. can be mentioned. Examples of the substituted or unsubstituted alkynyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the substituent represented by Formula W include an ethynyl group and a deuterium atom-substituted acetylene group. An ethynyl group is preferred.
In the case where R ^{7a to} R ⁷ⁱ are substituents other than the group represented by Formula W, each of the substituents independently represents a substituted alkenyl group having 2 or less carbon atoms, the substituents that the alkenyl group can take are heavy A hydrogen atom etc. can be mentioned. Examples of the substituted or unsubstituted alkenyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the substituent represented by Formula W include an ethenyl group and a deuterium-substituted ethenyl group. An ethenyl group is preferred.
In the case where R ^{7a to} R ⁷ⁱ are substituents other than the group represented by Formula W, each of the substituents independently represents a substituted acyl group having 2 or less carbon atoms, the substituent that the acyl group can take is fluorine An atom etc. can be mentioned. Examples of the substituted or unsubstituted acyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the substituent represented by Formula W include a formyl group, an acetyl group, and a fluorine-substituted acetyl group. A formyl group is preferred.

-Compound represented by Formula 8-

In Formula 8, X ^8a and X ^8c each independently represent an S atom, an O atom, a Se atom, or NR ⁸ⁱ , and X ^8b and X ^8d each independently represent an S atom, an O atom, or a Se atom. X ^{8a to} X ^8d are each independently preferably an O atom or an S atom from the viewpoint of ease of synthesis. On the other hand, it is preferable from the viewpoint of increasing the carrier mobility that at least one of X ^{8a to} X ^8d is an S atom. X ^{8a to} X ^8d are preferably the same linking group. It is more preferable that all of X ^{8a to} X ^8d are S atoms.

In Formula 8, R ^{8a to} R ⁸ⁱ each independently represent a hydrogen atom or a substituent, and at least one of R ^{8a to} R ⁸ⁱ is a group represented by Formula W.
In addition, the substituent X mentioned above is mentioned as a substituent represented by R ^{< 8a} > -R ^<8i> . Moreover, the definition of the group represented by Formula W is as described above.
R ⁸ⁱ is preferably a hydrogen atom or an alkyl group, more preferably an alkyl group having 5 to 12 carbon atoms, and particularly preferably an alkyl group having 8 to 10 carbon atoms.
When R ⁸ⁱ represents an alkyl group, it may be a linear alkyl group, a branched alkyl group, or a cyclic alkyl group, but a linear alkyl group is preferable from the viewpoint of overlapping HOMO orbitals.

Among the compounds represented by Formula 8, among R ^{8a to} R ⁸ⁱ , the number of substituents represented by Formula W is 1 to 4 to increase carrier mobility and increase solubility in organic solvents. From the viewpoint, it is preferably 1 or 2, more preferably 2.
Although there is no restriction ^| limiting in particular in the position of group represented by Formula W among R ^{< 8a} > -R ^{<8i >} , it is R ^{< 8c>} or R ^<8g> from a viewpoint which raises carrier mobility and raises the solubility to an organic solvent. R ^8c and R ^8g are more preferable.
In addition, among R ^{8a to} R ⁸ⁱ in Formula 8, the number of substituents other than the group represented by Formula W is preferably 0 to 4, more preferably 0 to 2, and 0 or 1 More preferably, it is particularly preferably 0.

When R ^{8a to} R ⁸ⁱ are substituents other than the group represented by Formula W, the substituent is preferably a group having a linking group chain length of 3.7 mm or less, and the linking group chain length is 1.0. It is more preferably a group having a length of ˜3.7 Å, and further preferably a group having a linking group chain length of 1.0 to 2.1 Å. The definition of the linking group chain length is as described above.
When R ^{8a to} R ⁸ⁱ are substituents other than the group represented by Formula W, the substituents are each independently a substituted or unsubstituted alkyl group having 2 or less carbon atoms, or a substituted or unsubstituted group having 2 or less carbon atoms. Are preferably substituted or unsubstituted alkenyl groups having 2 or less carbon atoms, or substituted or unsubstituted acyl groups having 2 or less carbon atoms, and are substituted or unsubstituted alkyl groups having 2 or less carbon atoms. More preferably.
In the case where R ^{8a to} R ⁸ⁱ are substituents other than the group represented by Formula W, each of the substituents independently represents a substituted alkyl group having 2 or less carbon atoms, the substituent that the alkyl group can take is cyano. Group, fluorine atom, deuterium atom and the like, and a cyano group is preferable. In the case of a substituent other than the group represented by Formula W, the substituted or unsubstituted alkyl group having 2 or less carbon atoms represented by the substituent is preferably a methyl group, an ethyl group, or a cyano group-substituted methyl group. Further, a methyl group or a cyano group-substituted methyl group is more preferable, and a cyano group-substituted methyl group is particularly preferable.
In the case where R ^{8a to} R ⁸ⁱ are substituents other than the group represented by Formula W, each of the substituents independently represents a substituted alkynyl group having 2 or less carbon atoms, the substituents that the alkynyl group can take are heavy A hydrogen atom etc. can be mentioned. Examples of the substituted or unsubstituted alkynyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the group represented by Formula W include an ethynyl group and a deuterium atom-substituted acetylene group, An ethynyl group is preferred.
In the case where R ^{8a to} R ⁸ⁱ are substituents other than the group represented by Formula W, each of the substituents independently represents a substituted alkenyl group having 2 or less carbon atoms, the substituents that the alkenyl group can take are heavy A hydrogen atom etc. can be mentioned. Examples of the substituted or unsubstituted alkenyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the group represented by Formula W include an ethenyl group and a deuterium-substituted ethenyl group, An ethenyl group is preferred.
When R ^{8a to} R ⁸ⁱ are substituents other than the group represented by Formula W, each of the substituents independently represents a substituted acyl group having 2 or less carbon atoms, the substituent that the acyl group can take is fluorine. An atom etc. can be mentioned. Examples of the substituted or unsubstituted acyl group having 2 or less carbon atoms represented by the substituent in the case of a substituent other than the group represented by Formula W include a formyl group, an acetyl group, and a fluorine-substituted acetyl group. A formyl group is preferred.

-Compound represented by Formula 9-

In Formula 9, X ^9a and X ^9b each independently represent an O atom, an S atom, or an Se atom. Among these, S atom is preferable.
R ^9c , R ^9d and R ^{9g to} R ^9j each independently represent a hydrogen atom, a halogen atom or a substituent represented by the formula W. The definition of the group represented by Formula W is as described above.
R ^9a , R ^9b , R ^9e and R ^9f each independently represent a hydrogen atom or a substituent. In addition, the substituent X mentioned above is mentioned as a substituent represented by R ^{< 9a >} , R ^{< 9b>} , R ^<9e> and R ^<9f> .
R ^9c , R ^9d and R ^{9g to} R ^9j are each independently a hydrogen atom, a halogen atom or a group represented by the formula W (where L ^W is a formula L-3, a formula L-5, a formula L- 7 to Formula L-9, and a group represented by any one of Formula L-12 to Formula L-24). Among them, R ^9c , R ^9d and R ^{9g to} R ^9j are more preferably hydrogen atoms.
As the ^{L W,} wherein L-3, wherein L-5, wherein L-13, is preferably a group represented by any one of formula L-17 or Formula L-18.
At least one of R ^{9a to} R ⁹ⁱ preferably represents a group represented by Formula W.

Among the compounds represented by formula 9, among R ^{9a to} R ⁹ⁱ , the number of substituents represented by formula W is 1 to 4 to increase carrier mobility and solubility in organic solvents. From the viewpoint, 1 or 2 is more preferable, and 2 is particularly preferable.
Among R ^{9a to} R ⁹ⁱ , the position of the group represented by the formula W is not particularly limited, but R ^9b or R ^9f is from the viewpoint of increasing carrier mobility and increasing solubility in an organic solvent. R ^9b and R ^9f are more preferable.
Moreover, among R ^{9a to} R ⁹ⁱ of Formula 9, the number of substituents other than the group represented by Formula W is preferably 0 to 4, more preferably 0 to 2, and 0 or 1 It is particularly preferable that the number is 0, and it is particularly preferable that the number is 0.

-Compound represented by Formula 10-

In Formula 10, R ^{10a to} R ^10h each independently represent a hydrogen atom or a substituent, and at least one of R ^{10a to} R ^10h represents a group represented by Formula W. In addition, the substituent X mentioned above is mentioned as a substituent represented by R ^{< 10a} > -R ^<10h> . Moreover, the definition of the substituent represented by Formula W is as described above.
Among them, R ^{10a to} R ^10h each independently represents a hydrogen atom, a halogen atom or a substituent, and at least one of R ^{10a to} R ^10h is a substituted or unsubstituted arylthio group, a substituted or unsubstituted heteroary. It is preferably a ruthio group, a substituted or unsubstituted alkyloxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, or a substituted or unsubstituted alkylamino group.
In R ^{10a to} R ^{10h in} Formula 10, at least one of R ^10b and R ^10f is a substituted or unsubstituted arylthio group, a substituted or unsubstituted heteroarylthio group, a substituted or unsubstituted alkyloxycarbonyl group, a substituted Or an unsubstituted aryloxycarbonyl group or a substituted or unsubstituted alkylamino group, more preferably a substituted or unsubstituted arylthio group, or a substituted or unsubstituted heteroarylthio group, and R It is more preferable that each of ^10b and R ^10f is a substituted or unsubstituted arylthio group, or a substituted or unsubstituted heteroarylthio group, and a substituted or unsubstituted phenylthio group or a hetero group selected from the following group A: Particularly preferred is an arylthio group, Most preferably, it is a substituted or unsubstituted phenylthio group or a heteroarylthio group represented by the following formula A-17, formula A-18, or formula A-20.

The arylthio group is preferably a group having a sulfur atom linked to an aryl group having 6 to 20 carbon atoms, more preferably a naphthylthio group or a phenylthio group, and particularly preferably a phenylthio group.
The heteroarylthio group is preferably a group in which a sulfur atom is linked to a 3- to 10-membered heteroaryl group, more preferably a group in which a sulfur atom is linked to a 5- or 6-membered heteroaryl group. A group represented by any one of formulas A-14 to A-27) is particularly preferred.

In group A, R ″ and R ″ ^N each independently represent a hydrogen atom or a substituent.
In group A, each R ′ preferably independently represents a hydrogen atom or a group represented by the formula W.
In group A, R ″ ^N preferably represents a substituent, more preferably an alkyl group, an aryl group, or a heteroaryl group, and is substituted with an alkyl group, an aryl group substituted with an alkyl group, or an alkyl group. The heteroaryl group is more preferably a 5- to 5-membered alkyl group substituted with an alkyl group having 1 to 4 carbon atoms, a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. A heteroaryl group is particularly preferred.

  As the alkyloxycarbonyl group, a group in which a carbonyl group is linked to an alkyl group having 1 to 20 carbon atoms is preferable. 2-15 are more preferable and, as for carbon number of an alkyl group, 5-10 are especially preferable.

  As the aryloxycarbonyl group, a group in which a carbonyl group is linked to an aryl group having 6 to 20 carbon atoms is preferable. 6-15 are more preferable and, as for carbon number of an aryl group, 8-12 are especially preferable.

As the alkylamino group, a group in which an amino group is linked to an alkyl group having 1 to 20 carbon atoms is preferable. 2-15 are more preferable and, as for carbon number of an alkyl group, 5-10 are especially preferable.
Among R ^{10a to} R ^10h , a substituted or unsubstituted arylthio group, a substituted or unsubstituted heteroarylthio group, a substituted or unsubstituted alkyloxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, or a substituted or unsubstituted group The number of substituents other than the alkylamino group (hereinafter also referred to as other substituents) is preferably 0 to 4, more preferably 0 to 2, and 0 or 1. More preferably, it is particularly preferably 0.

X ^10a and X ^10b each independently represent an S atom, an O atom, a Se atom, or NR ^x (> N—R ^x ). It is preferable from the viewpoint of increasing carrier mobility that at least one of X ^10a and X ^10b is an S atom. X ^10a and X ^10b are preferably the same linking group. As for ^X10a and ^X10b , it is more preferable that all are S atoms.
R ^x each independently represents a hydrogen atom or a group represented by the formula W. The definition of the group represented by Formula W is as described above.

-Compound represented by Formula 11-

In Formula 11, X ^11a and X ^11b each independently represent S atom, O atom, Se atom or NR ¹¹ⁿ , and R ^{11a to} R ^11k , R ^11m and R ¹¹ⁿ each independently represent a hydrogen atom or a substituent. And at least one of R ^{11a to} R ^11k , R ^11m and R ¹¹ⁿ represents a group represented by the formula W. Examples of the substituent include the substituent X described above. The definition of the substituent represented by Formula W is as described above.

In formula 11, it is preferable from the viewpoint of increasing carrier mobility that at least one of X ^11a and X ^11b is an S atom. X ^11a and X ^11b are preferably the same linking group. It is more preferable that both X ^11a and X ^11b are S atoms.
R ^{11a to} R ^11k and R ^{11m in} Formula ¹¹ are such that at least one of R ^11c and R ¹¹ⁱ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted heteroarylthio group, It is preferably a substituted or unsubstituted alkyloxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group or a substituted or unsubstituted alkylamino group, more preferably a substituted or unsubstituted alkyl group, and R ^11c And R ¹¹ⁱ are more preferably a substituted or unsubstituted alkyl group.

-Compound represented by Formula 12-

In Formula 12, X ^12a and X ^12b each independently represent an S atom, an O atom, a Se atom or NR ¹²ⁿ , and R ^{12a to} R ^12k , R ^12m and R ¹²ⁿ each independently represent a hydrogen atom or a substituent. And at least one of R ^{12a to} R ^12k , R ^12m and R ¹²ⁿ represents a group represented by the formula W. Examples of the substituent include the substituent X described above. The definition of the substituent represented by Formula W is as described above.

In formula 12, it is preferable from the viewpoint of increasing carrier mobility that at least one of X ^12a and X ^12b is an S atom. X ^12a and X ^12b are preferably the same linking group. It is more preferable that both X ^12a and X ^12b are S atoms.
R ^{12a to} R ^12k and R ^{12m in} Formula ¹² are such that at least one of R ^12c and R ¹²ⁱ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted heteroarylthio group, It is preferably a substituted or unsubstituted alkyloxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group or a substituted or unsubstituted alkylamino group, more preferably a substituted or unsubstituted alkyl group, and R ^12c And R ¹²ⁱ are more preferably a substituted or unsubstituted alkyl group.

-Compound represented by Formula 13-

In Formula 13, X ^13a and X ^13b each independently represent an S atom, O atom, Se atom or NR ¹³ⁿ , and R ^{13a to} R ^13k , R ^13m and R ¹³ⁿ each independently represent a hydrogen atom or a substituent. And at least one of R ^{13a to} R ^13k , R ^13m and R ¹³ⁿ represents a group represented by the formula W. Examples of the substituent include the substituent X described above. The definition of the group represented by Formula W is as described above.

In formula 13, it is preferable from the viewpoint of increasing carrier mobility that at least one of X ^13a and X ^13b is an S atom. X ^13a and X ^13b are preferably the same linking group. It is more preferable that both X ^13a and X ^13b are S atoms.
R ^{13a to} R ^13k and R ^{13m in} Formula 13 are such that at least one of R ^13c and R ¹³ⁱ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted heteroarylthio group, It is preferably a substituted or unsubstituted alkyloxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group or a substituted or unsubstituted alkylamino group, more preferably a substituted or unsubstituted alkyl group, and R ^13c. And R ¹³ⁱ are more preferably a substituted or unsubstituted alkyl group.

-Compound represented by Formula 14-

In Formula 14, X ^{14a to} X ^14c each independently represents an S atom, an O atom, a Se atom, or NR ¹⁴ⁱ , R ^{14a to} R ¹⁴ⁱ each independently represents a hydrogen atom or a substituent, and R ^{14a to} R ^{14 At} least one of ¹⁴ⁱ represents a group represented by the formula W. Examples of the substituent include the substituent X described above. The definition of the group represented by Formula W is as described above.
In addition, when at least one of R ^{14a to} R ^14h is a group represented by Formula W, and R ^W is an alkyl group, L ^W is represented by any one of Formula L-2 to Formula L-25. It is preferably a group.

In Formula 14, it is preferable from the viewpoint of increasing the carrier mobility that at least one of X ^{14a to} X ^14c is an S atom. X ^{14a to} X ^14c are preferably the same linking group. X ^14a to X ^14c is more preferably both are S atoms.
As L ^W when R ^W is an alkyl group, a group represented by any one of Formula L-2 to Formula L-5, Formula L-13, Formula L-17, or Formula L-18 is preferable. , Groups represented by formula L-3, formula L-13, or formula L-18 are more preferable.
^R 14a ^{to R 14h} of formula ^14, at least one of ^{R 14b} and ^{R 14 g,} is preferably a group of the formula ^W, none of ^{R 14b} and ^{R 14 g} is represented by the formula W More preferably, it is a group.

-Compound represented by Formula 15-

In Formula 15, X ^{15a to} X ^15d each independently represents an S atom, an O atom, a Se atom, or NR ^15g , R ^{15a to} R ^15g each independently represents a hydrogen atom or a substituent, and R ^{15a to} R ^15g At least one of these represents a group represented by the formula W. Examples of the substituent include the substituent X described above. The definition of the group represented by Formula W is as described above.

In formula 15, it is preferable from the viewpoint of increasing the carrier mobility that at least one of X ^{15a to} X ^15d is an S atom. X ^{15a to} X ^15d are preferably the same linking group. X ^15a to X ^15d is more preferably both are S atoms.
^R 15a ^{to R 15f} of formula ^15, at least one of ^{R 15b} and ^{R 15e,} is preferably a group of the formula ^W, none of ^{R 15b} and ^{R 15e} is represented by the formula W More preferably, it is a group.

-Compound represented by Formula 16-

In Formula 16, X ^{16a to} X ^16d each independently represents an S atom, an O atom, a Se atom, or NR ^16g . R ^{16a to} R ^16g each independently represents a hydrogen atom or a substituent, and at least one of R ^{16a to} R ^16g represents a group represented by Formula W. Examples of the substituent include the substituent X described above. The definition of the group represented by Formula W is as described above.
R ^16c and R ^16f are a hydrogen atom, a halogen atom or a group represented by the formula W (where L ^W is a formula L-3, a formula L-5, a formula L-7 to a formula L-9, a formula A group represented by any one of L-12 to L-24). R ^16a , R ^16b , R ^16d , R ^16e and R ^16g each independently preferably represent a hydrogen atom or a substituent.
In Formula 16, L ^W is a group represented by any one of Formula L-3, Formula L-5, Formula L-7 to Formula L-9, Formula L-12 to Formula L-24, In the case where R ^16c and R ^16f are groups represented by the formula W, they are groups represented by any one of the formula L-3, the formula L-5, the formula L-13, the formula L-17, and the formula L-18. It is preferable.

In formula 16, it is preferable from the viewpoint of increasing carrier mobility that at least one of X ^{16a to} X ^16d is an S atom. X ^{16a to} X ^16d are preferably the same linking group. X ^16a to X ^16d is more preferably both are S atoms.
^R 16a ^{to R 16f} of formula ^16, at least one of ^{R 16a} and ^{R 16d,} is preferably a group of the formula ^W, none of ^{R 16a} and ^{R 16d} are represented by the formula W More preferably, it is a group.
R ^16c and R ^16f are preferably hydrogen atoms.

Component A preferably has an alkyl group on the condensed polycyclic aromatic ring in the condensed polycyclic aromatic group, more preferably an alkyl group having 6 to 20 carbon atoms, and an alkyl group having 7 to 14 carbon atoms. More preferably, it has a group. It is excellent in the mobility and thermal stability of the organic semiconductor obtained as it is the said aspect.
Component A preferably has one or more alkyl groups, more preferably 2 to 4 alkyl groups, and more preferably 2 alkyl groups on the condensed polycyclic aromatic ring in the above condensed polycyclic aromatic group. More preferably, it has a group. It is excellent in the mobility and thermal stability of the organic semiconductor obtained as it is the said aspect.

  The molecular weight of component A is not particularly limited, but the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, still more preferably 1,000 or less, and 850 or less. Is particularly preferred. By making molecular weight below the said upper limit, the solubility to a solvent can be improved. On the other hand, from the viewpoint of film quality stability of the thin film, the molecular weight is preferably 300 or more, more preferably 350 or more, and still more preferably 400 or more.

  The synthesis method of component A is not particularly limited, and can be synthesized with reference to known methods. Examples of the method for synthesizing the compounds represented by Formula 1 to Formula 16 include Journal of American Chemical Society, 116, 925 (1994), Journal of Chemical Society, 221 (1951), Org. Lett. , 2001, 3, 3471, Macromolecules, 2010, 43, 6264, Tetrahedron, 2002, 58, 10197, Japanese translations of PCT publication No. 2012-513659, Japanese Patent Application Laid-Open No. 2011-46687, Journal of Chemical Research. miniprint, 3, 601-635 (1991), Bull. Chem. Soc. Japan, 64, 3682-3686 (1991), Tetrahedron Letters, 45, 2801-2803 (2004), European Patent Publication No. 2251342, European Patent Publication No. 2301926, European Patent Publication No. 2301921, Korean Patent Publication No. 10-2012-0120886, J. Pat. Org. Chem. , 2011, 696, Org. Lett. 2001, 3, 3471, Macromolecules, 2010, 43, 6264, J. MoI. Org. Chem. , 2013, 78, 7741, Chem. Eur. J. et al. , 2013, 19, 3721, Bull. Chem. Soc. Jpn. 1987, 60, 4187; Am. Chem. Soc. , 2011, 133, 5024, Chem. Eur. J. et al. 2013, 19, 3721, Macromolecules, 2010, 43, 6264-6267, J. MoI. Am. Chem. Soc. 2012, 134, 16548-16550, and the like.

  In addition, from the viewpoint of mobility in the organic semiconductor, the component A preferably includes at least one compound represented by any one of Formulas 1 to 9, Formula 14, or Formula 15.

  Although the preferable specific example of the component A is shown below, it cannot be overemphasized that it is not limited to these.

  Although there is no restriction | limiting in particular in content of the component A in the organic-semiconductor composition of this invention, It is preferable that it is 0.005-10 mass% with respect to the total mass of an organic-semiconductor composition, 0.01-5 mass % Is more preferable, and 0.05 to 3% by mass is still more preferable.

<Insulating polymer>
The composition for forming an organic semiconductor film of the present invention is an insulating polymer having a weight average molecular weight of 750,000 or more and a molecular weight distribution (Mw / Mn) of 1.3 or more (hereinafter simply referred to as “insulating polymer” or “component B”). ").
The weight average molecular weight of the insulating polymer is preferably 750,000 to 3 million, more preferably 1 million to 2.5 million, and still more preferably 1 million to 2 million from the viewpoint of printability.
In the present invention, the number average molecular weight (Mn) and the weight average molecular weight (Mw) are obtained by dissolving TSK-GEL SuperH1000, SuperH2000, SuperH3000, and SuperH4000 in series using 8020GPC system manufactured by Tosoh Corporation. It is assumed that tetrahydrofuran is used as an eluent and measurement is performed with an ultraviolet detector (wavelength 254 nm). Polystyrene standards are used for molecular weight calibration.
The molecular weight distribution (Mw / Mn) of the insulating polymer is preferably 1.3 to 4.0, more preferably 1.7 to 3.0, from the viewpoint of suppressing mobility variation, and 1.7 to 2. 5 is more preferable.

The type of the insulating polymer is not particularly limited as long as its conductivity is 10 ⁻¹⁰ S / cm or less, and examples thereof include polystyrene resin, acrylic resin, rubber, and thermoplastic elastomer.
Typical insulating polymers include polystyrene (PS), poly (α-methylstyrene) (PαMS), poly (methyl methacrylate) (PMMA), polyvinylphenol (PVP), poly (vinyl alcohol) (PVA), poly (Vinyl acetate) (PVAc), polyvinyl chloride (PVC), polyvinylidene fluoride (PVDF), cyanoethyl pullulan (CYPEL), poly (divinyltetramethyldisiloxane-bis (benzocyclobutene)) (BCB), ethylene- Examples include propylene rubber and acrylonitrile-butadiene rubber, but are not limited thereto.
Among these, as the insulating 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 more preferably 90 mol% or more in all monomer units constituting the polymer. preferable. The upper limit is not particularly limited, but 100 mol% can be mentioned.

Component B may be contained singly or in combination of two or more.
Component B is preferably a mixture of two or more insulating polymers having the same composition and different weight average molecular weights. In addition, as a method for confirming that it is a mixture of two or more insulating polymers having the same composition and different weight average molecular weights, it is possible to confirm the composition and weight average molecular weight of each polymer used at the time of production. In addition, it can be confirmed from the composition that a polymer having the same composition is separated by a known method and a maximum value of 2 or more can be observed when the weight average molecular weight is measured.
Component B preferably has a maximum value of 2 or more when the weight average molecular weight is measured, and more preferably has two maximum values when the weight average molecular weight is measured.
Among these, the component B preferably includes polystyrene or poly (α-methylstyrene), more preferably includes two or more types of polystyrene and / or poly (α-methylstyrene), and two or more types of polystyrene. Or it is still more preferable that 2 or more types of poly ((alpha) -methylstyrene) is included.

The content of component B is preferably 0.001 to 10 mass%, more preferably 0.005 to 5.0 mass%, based on the total mass of the composition for forming an organic semiconductor film, More preferably, it is 0.01-2.0 mass%.
Further, the content of Component B is preferably 10 to 1,000% by mass, more preferably 10 to 200% by mass, and 30 to 100% by mass with respect to the content of Component A. More preferably.

In the present invention, other insulating polymers that do not fall under Component B may be used in combination with Component B.
The content of the other insulating polymer is less than 100 parts by mass, preferably 50 parts by mass or less, and 25 parts by mass or less, when the content in the composition of Component B is 100 parts by mass. More preferably, it is more preferably 10 parts by mass or less, particularly preferably 3 parts by mass or less, and most preferably no other insulating polymer is contained.

<Organic solvent>
The composition for forming an organic semiconductor film of the present invention comprises at least one organic solvent selected from the group consisting of 4-tert-butylanisole, amylbenzene and a compound represented by the following formula C-1 (hereinafter simply referred to as “ Component C ”).

In Formula C-1, R ^b1 represents an alkyl group, an alkoxy group, a halogen atom, a cyano group, or a vinyl group, m represents an integer of 1 to 4, and when m is 2 or more, a plurality of R ^b1 are present. May be the same or different.

The boiling point of Component C is preferably 200 ° C. to 280 ° C., more preferably 200 ° C. to 270 ° C., and further preferably 210 ° C. to 260 ° C. When the boiling point is 200 ° C. or higher, the printability and storage stability are excellent, and as a result, the film uniformity is excellent. Further, when the boiling point is 280 ° C. or less, the component C can be easily removed by drying at the time of film formation.
In addition, the boiling point of the component C is a boiling point measured under 1 atmosphere (760 mmHg, 1.013 × 10 ⁵ Pa), and is measured according to a conventional method. Moreover, you may employ | adopt the value as described in various literature as a boiling point of the component C.
In the present invention, Component C is a liquid at 1 atm and room temperature (25 ° C.). That is, the melting point of Component C is 25 ° C. or less, preferably 20 ° C. or less, and more preferably 10 ° C. or less.

In Formula C-1, R ^b1 represents an alkyl group, an alkoxy group, a halogen atom, a cyano group, or a vinyl group.
As an alkyl group, a C1-C6 alkyl group is preferable, a C1-C3 alkyl group is more preferable, a methyl group or an ethyl group is still more preferable, and a methyl group is especially preferable.
As an alkoxy group, a C1-C6 alkoxy group is preferable, a C1-C3 alkoxy group is more preferable, a methoxy group or an ethoxy group is still more preferable, and a methoxy group is especially preferable.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
In addition, although the said alkyl group, an alkoxy group, and a vinyl group may be unsubstituted or may have a substituent, it is preferable that it is unsubstituted.
In formula C-1, m represents an integer of 1 to 4, preferably 1 or 2, and particularly preferably 1.

  Component C includes 4-tert-butylanisole (boiling point: 222 ° C.), 1-chloronaphthalene (boiling point: 259 ° C.), 1-fluoronaphthalene (boiling point: 215 ° C.), 2,3-difluoronaphthalene (boiling point: 208 ° C) and 2-methoxynaphthalene (boiling point: 228 ° C).

Among these, 1-chloronaphthalene or 1-fluoronaphthalene is particularly preferable.
Component C may be used alone or in combination of two or more.
The content of component C in the composition of the present invention is preferably 80 to 99.9% by mass, more preferably 90 to 99.5% by mass, based on the total mass of the composition, More preferably, it is 95-99.0 mass%.

In the present invention, other solvents that do not fall under Component C may be used in combination with Component C.
The content of the other solvent is less than 100 parts by mass, preferably 50 parts by mass or less, and 25 parts by mass or less, when the content in the composition of Component C is 100 parts by mass. More preferably, it is further preferably 10 parts by mass or less, particularly preferably 3 parts by mass or less, and most preferably no other solvent is contained.

As other solvents, known solvents can be used.
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, anisole, amide / imide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone, 1-methyl-2-imidazolidinone, Examples thereof include sulfoxide solvents such as dimethyl sulfoxide, and nitrile solvents such as acetonitrile.

Other solvents may be used alone or in combination.
Among these, as other solvents, hydrocarbon solvents, halogenated hydrocarbon solvents and / or ether solvents are preferable, toluene, xylene, mesitylene, tetralin, dichlorobenzene or anisole are more preferable, and o-dichlorobenzene. Is particularly preferred.

<Other ingredients>
The composition for forming an organic semiconductor film of the present invention may contain other components in addition to Component A, Component B, Component C, other polymers and other solvents.
As other components, known additives and the like can be used.
The content of components other than Component A, Component B, Component C and other solvents in the composition for forming an organic semiconductor film of the present invention is preferably 10% by mass or less, and preferably 5% by mass or less. Is more 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.

  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 component A and, if necessary, component B to a solvent containing component C simultaneously or sequentially, and appropriately stirring.

The viscosity of the composition for forming an organic semiconductor film of the present invention is not particularly limited, but the viscosity at 25 ° C. is preferably 1 to 100 mPa · s, more preferably 2 to 50 mPa · s in terms of more excellent coating properties. More preferably, it is more preferable that it is 5-40 mPa * s, and it is especially preferable that it is 10-30 mPa * s.
As a measuring method of a viscosity, it is preferable that it is a measuring method based on JISZ8803.

(Organic semiconductor film, organic semiconductor element, and manufacturing method thereof)
The organic semiconductor film of the present invention and the organic semiconductor element of the present invention are preferably manufactured using the composition for forming an organic semiconductor film of the present invention.
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, a method of producing an organic semiconductor film by applying a drying treatment for applying the composition onto a predetermined substrate and drying the solvent containing the component C can be mentioned.
The method for applying the composition on the substrate is not particularly limited, and a known method can be adopted. For example, an inkjet method, a flexographic printing method, a gravure printing method, a screen printing method, a bar coating method, a spin coating method, a knife coating. Method, doctor blade method and the like, and flexographic printing method and screen 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. According to the above aspect, the composition can be printed on a substrate to easily form a pattern.
Especially, the manufacturing method of the organic-semiconductor film of this invention, and the manufacturing method of the organic-semiconductor element of this invention are the provision process which provides the organic-semiconductor-film formation composition of this invention on a board | substrate, and the provided organic It is preferable to include the drying process which removes a solvent from the composition for semiconductor film formation.

  For the drying treatment in the drying step, optimum conditions are appropriately selected depending on the type of the solvent containing Component A, Component B, and Component C to be used. Among them, the heating temperature is preferably 30 ° C. to 100 ° C., and more preferably 40 ° C. to 80 ° C. in terms of excellent mobility and film uniformity of the obtained organic semiconductor and excellent productivity. 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 the mobility and film uniformity of the organic semiconductor obtained.

The organic semiconductor film produced from the composition 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 element is not particularly limited, but is preferably a multi-terminal semiconductor element, more preferably a 2-5 terminal organic semiconductor element, and a 2- or 3-terminal organic semiconductor element. Further preferred.
The organic semiconductor element is preferably an element that does not use a photoelectric function. In addition, when using a photoelectric function positively, organic substance may deteriorate with light.
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 (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 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.

<Sealing layer>
The organic thin film transistor 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 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 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 composition of the present invention is a top gate-bottom contact type. The present invention can also be applied to 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.

<Number average molecular weight (Mn) and weight average molecular weight (Mw) of polymer>
The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the polymer were determined by dissolving the polymer in tetrahydrofuran and connecting TSK-GEL SuperH1000, SuperH2000, SuperH3000, and SuperH4000 in series with an 8020GPC system manufactured by Tosoh Corporation. Tetrahydrofuran was used as a measurement with an ultraviolet detector (wavelength 254 nm). Polystyrene standards were used for molecular weight calibration.

<Adjustment of molecular weight and molecular weight distribution of insulating polymer>
An insulating polymer having a desired weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) was prepared by mixing an insulating polymer made by Polyscience (Table 1 below) at different mixing ratios. In addition, all the polymers described in Table 1 had an electric conductivity of 10 ⁻¹⁰ S / cm or less.

(Examples 1-32 and Comparative Examples 1-11)
<Preparation of composition for forming organic semiconductor film>
A total amount of 50 g of organic semiconductor compound / solvent / polymer was weighed into a 50 ml glass vial at a predetermined ratio shown in Tables 2 to 4, and stirred and mixed for 10 minutes with a mix rotor (manufactured by ASONE Co., Ltd.). The composition for forming an organic semiconductor film was obtained by filtering with a 0.5 μm membrane filter.

<TFT element formation>
A bottom gate-bottom contact TFT element was formed in the following manner.

<Gate electrode formation>
On a non-alkali glass substrate (5 cm × 5 cm), a 125 nm Cr thin film was formed by sputtering, and patterning was performed using photolithography to form a gate electrode.

<Gate insulation film formation>
5 parts by mass of polyvinylphenol (Mw 25,000, manufactured by Aldrich), 5 parts by mass of melamine, and 90 parts by mass of polyethylene glycol monomethyl ether acetate were mixed by stirring and filtered through a 0.2 μm membrane filter to prepare a solution. . The obtained solution was dropped on the glass substrate on which the gate electrode was prepared, coated by spin coating (1,000 rpm, 120 seconds), and heated at 150 ° C./30 minutes to form a gate insulating film.

<Source / drain (SD) electrode formation>
A metal mask having a plurality of patterns shown in FIG. 3 was placed on the center of the substrate coated with the insulating film and irradiated with UV ozone for 30 minutes, whereby the mask opening was modified to a hydrophilic treatment surface. A source / drain electrode pattern having a channel length of 50 μm and a channel width of 320 μm was formed by inkjet printing using DMP2831 (1 picoliter head) around the modified portion. The obtained substrate was baked at 200 ° C. for 90 minutes on a hot plate in an N ₂ atmosphere (in the glove box, an environment having an oxygen concentration of 20 ppm or less), thereby forming a copper electrode having a thickness of 200 nm.

<Organic semiconductor layer formation>
The produced composition for forming an organic semiconductor film was coated on the substrate on which the source / drain electrodes were formed by a flexographic printing method. A flexo aptitude tester F1 (manufactured by IG Testing Systems Co., Ltd.) was used as the printing apparatus, and AFP DSH 1.70% (manufactured by Asahi Kasei Co., Ltd.) / Solid image was used as the flexo resin plate. The pressure between the plate and the substrate is 60 N, printing is performed at a conveyance speed of 0.4 m / second, and then dried at 50 ° C. for 2 hours to obtain an organic transistor (TFT element) having an organic semiconductor film. Produced.

<Evaluation>
-Mobility variation suppression evaluation (initial variation evaluation)-
In order to evaluate the initial variation, the mobility was measured and the coefficient of variation was calculated using a semiconductor characteristic evaluation apparatus B2900A (manufactured by Agilent). Specifically, the mobility was measured for the 30 organic transistors produced, and the coefficient of variation was calculated from the following formula using the measured mobility. It means that the smaller the variation coefficient, the smaller the difference in characteristics between elements and the smaller the variation.
Coefficient of variation = σ / μ (average)
σ: standard deviation of 30 mobilities μ (average): average of 30 mobilities Scores of 1 to 5 were made according to the value of the coefficient of variation.
5: Less than 20% 4: 20% or more, less than 40% 3: 40% or more, less than 80% 2: 80% or more, less than 160% 1: 160% or more

-Evaluation of stability over time-
The produced organic transistor element was placed in constant temperature and humidity (30 ° C., humidity 50% RH) for 28 days, and the change in characteristics over time was evaluated. Specifically, for the 30 organic transistors produced, 100 was obtained by dividing the difference between the initial mobility X and the mobility Y after aging (after 28 days at 30 ° C. and 50% RH) by the initial mobility X. Each multiplied value [{(X−Y) / X} × 100] was calculated, and the average value was calculated as the rate of change. The evaluation criteria are shown below. The smaller the rate of change, the better the stability over time.
5: Change rate is less than 20% 4: Change rate is 20% or more and less than 30% 3: Change rate is 30% or more and less than 50% 2: Change rate is 50% or more and less than 100% 1: Change rate is 100% or more

Abbreviations described in Tables 2 to 4 are as follows.
OSC-1 to 17 used in the examples are the same compounds as OSC-1 to 17 described above, respectively.

The synthesis method or manufacturer of the organic semiconductors (OSC-1 to OSC-17) is as follows.
OSC-1 was synthesized with reference to Journal of American Chemical Society, 116, 925 (1994), Journal of Chemical Society, 221 (1951), and the like.
OSC-2 was synthesized with reference to known literature (Org. Lett., 2001, 3, 3471, Macromolecules, 2010, 43, 6264, Tetrahedron, 2002, 58, 10197).
OSC-3 is disclosed in JP2012-513659A, JP2011-46687A, Journal of Chemical Research. miniprint, 3, 601-635 (1991), Bull. Chem. Soc. Japan, 64, 3682-3686 (1991), Tetrahedron Letters, 45, 2801-2803 (2004) and the like.
OSC-4 was synthesized with reference to European Patent Publication No. 2251342, European Patent Publication No. 2301926, European Patent Publication No. 2301921, and Korean Patent Publication No. 10-2012-0120886. .
OSC-5 is disclosed in known documents (J. Org. Chem., 2011, 696, Org. Lett., 2001, 3, 3471, Macromolecules, 2010, 43, 6264, J. Org. Chem., 2013, 78, 7741). Chem. Eur. J., 2013, 19, 3721).
OSC-6 is a well-known literature (Bull. Chem. Soc. Jpn., 1987, 60, 4187, J. Am. Chem. Soc. 2011, 133, 5024, Chem. Eur. J. 2013, 19, 3721). Synthesized with reference.
OSC-7 and 8 were synthesized with reference to known literature (Macromolecules, 2010, 43, 6264-6267, J. Am. Chem. Soc., 2012, 134, 16548-16550).

OSC-9 is disclosed in Document A (K. Muellen, Chem. Commun., 2008, 1548-1550.), Document B (K. Takimiya, Org. Lett., 2007, 9, 4499-4502.), Document C ( Raak; Tilak, Journal of Scientific and Industrial Research, 1958, vol. 17 B, p. 260-265., Literature D (Ghaisas; Tilak, Journal of Scientific and Ind. )) And synthesized.
OSC-10 to 13 were synthesized with reference to known literature (Journal of American Chemical Society, 129, 15732 (2007)).
OSC-14 was synthesized according to the method described in International Publication No. 2005/088770.
OSC-15 was synthesized in accordance with the method described in JP2009-190999A.
OSC-16 was synthesized according to the method described in JP 2012-206953 A.
As OSC-17, C8BTBT (manufactured by Sigma-Aldrich) was used.

The following organic solvents were used.
・ 1-Fluoronaphthalene (F0212, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ 1-Chloronaphthalene (C0212, manufactured by Tokyo Chemical Industry Co., Ltd.)
1-methylnaphthalene (132-10065, manufactured by Wako Pure Chemical Industries, Ltd.)
・ 4-tert-Butylanisole (B0961, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ 3,5-dimethylanisole (D2441, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Toluene (244511, manufactured by Sigma-Aldrich)
・ Amylbenzene (A0449, manufactured by Tokyo Chemical Industry Co., Ltd.)

  10: substrate, 20: gate electrode, 30: gate insulating film, 40: source electrode, 42: drain electrode, 50: organic semiconductor film, 51: metal mask, 52: mask portion, 53, 54: opening, 60: Sealing layer, 100, 200: Organic thin film transistor

Claims (12)

A condensed polycyclic aromatic group having 4 or more rings in the condensed polycyclic aromatic group, wherein at least two rings in the condensed polycyclic aromatic group are a sulfur atom, a nitrogen atom, and a selenium atom; And at least one selected from the group consisting of a benzene ring, a naphthalene ring, and a phenanthrene ring as the partial structure in the condensed polycyclic aromatic group. An organic semiconductor containing,
An insulating polymer having a weight average molecular weight of 750,000 or more and a molecular weight distribution (Mw / Mn) of 1.3 or more;
4-tert-butyl anisole, and at least one organic solvent selected from the group consisting of compounds represented by amyl benzene and formula C-1, viewed contains a
The composition for forming an organic semiconductor film , wherein the insulating polymer contains polystyrene or poly (α-methylstyrene) .

In Formula C-1, R ^b1 represents an alkyl group, an alkoxy group, a halogen atom, a cyano group, or a vinyl group, m represents an integer of 1 to 4, and when m is 2 or more, a plurality of R ^b1 are present. May be the same or different.   The composition for forming an organic semiconductor film according to claim 1, wherein the insulating polymer has a weight average molecular weight of 1,000,000 or more.   The composition for forming an organic semiconductor film according to claim 1 or 2, wherein the insulating polymer has a weight average molecular weight of 1,000,000 or more and a molecular weight distribution (Mw / Mn) of 1.7 or more.   The composition for forming an organic semiconductor film according to claim 3, wherein the insulating polymer is a mixture of two or more insulating polymers having the same composition and different weight average molecular weights.   The composition for forming an organic semiconductor film according to any one of claims 1 to 4, wherein the organic solvent is 1-chloronaphthalene or 1-fluoronaphthalene.   The composition for organic-semiconductor film formation of any one of Claims 1-5 whose ring number in the said condensed polycyclic aromatic group in the said organic semiconductor is 5 or 6.   The condensed polycyclic aromatic group of the organic semiconductor contains at least two heterocycles, and each of the heterocycles is a heterocycle having only one heteroatom. The composition for organic-semiconductor film formation of description. The composition for organic-semiconductor film formation of any one of Claims 1-7 in which the said organic semiconductor contains at least 1 sort (s) of the compound represented by either of the formulas 1-16.




In Formula 1, A ^1a and A ^1b each independently represent an S atom, an O atom, or a Se atom, R ^{1a to} R ^1f each independently represent a hydrogen atom or a substituent, and R ^{1a to} R ^1f At least one is a group represented by the following formula W.
-L ^W -R ^W (W)
In the formula W, L ^W is a divalent linking group represented by any of the following formulas L-1 to L-25 or two or more represented by any of the following formulas L-1 to L-25. -valent divalent linking group linking group is attached the, R ^W is an alkyl group, a cyano group, a vinyl group, an ethynyl group, an oxyethylene group, repetition number v of oxyethylene units is more than one oligo oxyethylene group, It represents a siloxane group, an oligosiloxane group having 2 or more silicon atoms, or a trialkylsilyl group.

In the formula L-. 1 to formula L-25, * represents a bonding position to ^{R W,} wavy line portion represents the other coupling position, wherein L-1, wherein L-2, the formula L-6 and wherein L each R 'is in the -13 type L-24 independently represent a hydrogen atom or a substituent, R ^N represents a hydrogen atom or a substituent, R ^si are each independently a hydrogen atom, an alkyl group, an alkenyl group, or Represents an alkynyl group.
In Formula 2, X ^2a and X ^2b each independently represent NR ²ⁱ , O atom or S atom, A ^2a represents CR ^2g or N atom, A ^2b represents CR ^2h or N atom, and R ²ⁱ represents Represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an acyl group, R ^{2a to} R ^2h each independently represents a hydrogen atom or a substituent, and at least one of R ^{2a to} R ^2h is represented by the formula W; Group.
In Formula 3, X ^3a and X ^3b each independently represent an S atom, an O atom or NR ^3g , and A ^3a and A ^3b each independently represent a CR ^3h or an N atom. R ^{3a to} R ^3h each independently represents a hydrogen atom or a substituent, and at least one of R ^{3a to} R ^3h is a group represented by the formula W.
In Formula 4, X ^4a and X ^4b each independently represent an O atom, an S atom or a Se atom, 4p and 4q each independently represent an integer of 0 to 2, R ^{4a to} R ^4j , R ^4k and R ^4m independently represents a hydrogen atom, a halogen atom or a group represented by the formula W, and at least one of R ^{4a to} R ^4j , R ^4k and R ^4m is represented by the formula W. a group, provided ^{that, R 4e} and ^{L W} is the formula L-2 or formula L in the formula W represented by ^{R 4e} and ^{R 4f} If at least one of a group represented by the formula W of ^{R 4f} -3 is a divalent linking group.
In Formula 5, X ^5a and X ^5b each independently represent NR ⁵ⁱ , O atom or S atom, A ^5a represents CR ^5g or N atom, A ^5b represents CR ^5h or N atom, and R ⁵ⁱ represents Represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an acyl group, an aryl group or a heteroaryl group, R ^{5a to} R ^5h each independently represent a hydrogen atom or a substituent, and at least of R ^{5a to} R ^5h One is a group represented by the formula W.
In Formula 6, X ^{6a to} X ^6d each independently represents NR ^6g , an O atom or an S atom, and R ^6g represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an acyl group, an aryl group or a heteroaryl group. It ^represents, R 6a ^{to R 6f} each independently represent a hydrogen atom or a ^substituent, a group at least one of R 6a ^{to R 6f} of the formula W.
In Formula 7, X ^7a and X ^7c each independently represent an S atom, O atom, Se atom or NR ⁷ⁱ , X ^7b and X ^7d each independently represent an S atom, O atom or Se atom, R ^{7a to} R ⁷ⁱ each independently represents a hydrogen atom or a substituent, and at least one of R ^{7a to} R ⁷ⁱ is a group represented by the formula W.
In Formula 8, X ^8a and X ^8c each independently represent an S atom, O atom, Se atom or NR ⁸ⁱ , X ^8b and X ^8d each independently represent an S atom, O atom or Se atom, and R ^{8a to} R ⁸ⁱ each independently represents a hydrogen atom or a substituent, and at least one of R ^{8a to} R ⁸ⁱ is a group represented by the formula W.
In Formula 9, X ^9a and X ^9b each independently represent an O atom, an S atom, or a Se atom, and R ^9c , R ^9d, and R ^{9g to} R ^9j each independently represent a hydrogen atom, a halogen atom, or the formula W R ^9a , R ^9b , R ^9e and R ^9f each independently represent a hydrogen atom or a substituent.
In Formula 10, R ^{10a to} R ^10h each independently represents a hydrogen atom or a substituent, and at least one of R ^{10a to} R ^10h represents a substituent represented by Formula W, and X ^10a and X ^10b Each independently represents an S atom, an O atom, a Se atom or NR ^10i, and each R ¹⁰ⁱ independently represents a hydrogen atom or a group represented by the formula W.
In Formula 11, X ^11a and X ^11b each independently represent an S atom, an O atom, a Se atom, or NR ¹¹ⁿ , and R ^{11a to} R ^11k , R ^11m, and R ¹¹ⁿ each independently represent a hydrogen atom or a substituent. And at least one of R ^{11a to} R ^11k , R ^11m and R ¹¹ⁿ is a group represented by the formula W.
In Formula 12, X ^12a and X ^12b each independently represent an S atom, an O atom, a Se atom or NR ¹²ⁿ , and R ^{12a to} R ^12k , R ^12m and R ¹²ⁿ each independently represent a hydrogen atom or a substituent. And at least one of R ^{12a to} R ^12k , R ^12m and R ¹²ⁿ is a group represented by the formula W.
In Formula 13, X ^13a and X ^13b each independently represent an S atom, an O atom, a Se atom or NR ¹³ⁿ , and R ^{13a to} R ^13k , R ^13m and R ¹³ⁿ each independently represent a hydrogen atom or a substituent. And at least one of R ^{13a to} R ^13k , R ^13m and R ¹³ⁿ is a group represented by the formula W.
In Formula 14, X ^{14a to} X ^14c each independently represents an S atom, an O atom, a Se atom, or NR ¹⁴ⁱ , R ^{14a to} R ¹⁴ⁱ each independently represents a hydrogen atom or a substituent, and R ^{14a to} R ^{14 At} least one of ¹⁴ⁱ is a group represented by the formula W.
In Equation ^15, the X 15a ^{to X 15d} are each independently, S atom, O atom, a Se atom or a ^{NR 15g, R} 15a ^{~R 15g} each independently represent a hydrogen atom or a ^{substituent, R} 15a to R ^At least one of ^{15 g} is a group represented by the formula W.
In Equation ^16, the X 16a ^{to X 16d} are each independently, S atom, O atom, a Se atom or a ^{NR 16g, R} 16a ^{~R 16g} each independently represent a hydrogen atom or a ^{substituent, R} 16a to R ^At least one of ^16g is a group represented by the formula W.   The composition for forming an organic semiconductor film according to claim 8, wherein the organic semiconductor contains at least one compound represented by Formula 1 to Formula 9 or Formula 15.   The organic-semiconductor film formed from the composition for organic-semiconductor film formation of any one of Claims 1-9.   The organic-semiconductor element which has an organic-semiconductor film formed from the composition for organic-semiconductor film formation of any one of Claims 1-9.   The organic-semiconductor element of Claim 11 which is an organic thin-film transistor.