WO2015029910A1

WO2015029910A1 - Organic semiconductor device, as well as compound, composition, and coating film for same

Info

Publication number: WO2015029910A1
Application number: PCT/JP2014/072052
Authority: WO
Inventors: 寛記杉浦; 野村　公篤
Original assignee: 富士フイルム株式会社
Priority date: 2013-08-30
Filing date: 2014-08-22
Publication date: 2015-03-05
Also published as: JP6085236B2; JP2015050231A

Abstract

The present invention has the purpose of providing an organic semiconductor compound which increases crystallinity (packing properties) of an organic semiconductor polymer, achieves both carrier mobility and solubility at a higher level, shows superior carrier mobility if used in a semiconductor layer, and for which application properties are also good. The present invention also has the purpose of providing a composition using the compound, a coating film, and an organic semiconductor device for which the compound is included in a semiconductor layer. The present invention is an organic semiconductor device for which a semiconductor layer contains a compound represented in formula (1). In formula (1), D indicates a donor structural unit represented in formula (2) or formula (3). Symbols in formula (2) and formula (3) indicate specific groups or atoms. A indicates an acceptor structural unit comprising an aromatic ring of a side-chain direction fused-ring structure. S¹ and S² indicate specific groups or bonds. l, n, m1, m2, and p indicate specific integers. Moreover, D and A comprise at least one of an alkyl group, an alkenyl group, and an alkynyl group.

Description

Organic semiconductor device, compound used for the same, composition and coating film

The present invention relates to an organic semiconductor device suitable for use as an organic thin film transistor, an organic photoelectric conversion device, an organic thermoelectric conversion device, or the like. Moreover, this invention relates to the compound suitable for using for the semiconductor layer of an organic-semiconductor device, the composition containing this compound, and a coating film.

Organic semiconductor polymers are being researched as new semiconductor materials to replace inorganic semiconductor materials in the electronics field. Since organic semiconductor polymers have a wide variety of molecular structures, they can be used to manufacture semiconductor devices with various characteristics, and have the advantage that the area of the semiconductor layer can be easily increased compared to inorganic semiconductor materials. Yes. Today, organic electroluminescence elements that emit light when voltage is applied, organic thin film transistors that control the amount of current and voltage, organic photoelectric conversion devices that convert light energy into power, organic thermoelectric conversion devices that convert heat energy into power, etc. The range of applications of organic semiconductor polymers is diverse.

The organic semiconductor polymer is a donor-acceptor type π-electron conjugated polymer having a repeating unit in which a donor-type structural unit and an acceptor-type structural unit are connected via a spacer structure capable of π-electron conjugation if necessary. . The polymer needs to be soluble in an organic solvent (hereinafter simply referred to as “solubility”) for film formation, and thus has a soluble group such as an alkyl group. Current mainstream donor-acceptor type organic semiconductor polymers are donor-like structural units (for example, dithienosilol, cyclopentadithiophene, benzodi) having a structure condensed in the main chain direction of the polymer (condensed in the main chain direction) as described below. Thiophene) and an acceptor structural unit (for example, benzothiadiazole, thienopyrroledione, thieno [3,4-b] thiophene) having a structure condensed in the side chain direction of the polymer (side chain direction condensed ring) It has a repeating unit (see Non-Patent Document 1, for example).

In addition, as a polymer composed of a structural unit having only a side chain direction condensed ring, Patent Document 1 describes a polymer having a repeating unit in which a thienothiazole structural unit and a thienopyrrole dione structural unit are linked, and a synthesis method thereof. ing. Non-Patent Document 2 describes a polymer having a repeating unit in which structural units of isothianaphthene, thiophene, benzothiadiazole and thiophene are connected in this order.

International Publication No. 2013 / 056355A1

Organic semiconductor polymers generally require high carrier mobility when used in a semiconductor layer of an organic semiconductor device. The higher the carrier mobility when used in the semiconductor layer, the higher the power generation efficiency when the polymer is used in the semiconductor layer of a photoelectric conversion device or a thermoelectric conversion device, for example. However, a conventional donor-acceptor type organic semiconductor polymer is composed of a main chain direction condensed ring donor structural unit and a side chain direction condensed ring acceptor structural unit as described above. Therefore, as described below, the polymer main chain part can overlap (pack) closely between molecules, but the soluble group part cannot overlap closely. Therefore, the conventional donor-acceptor type polymer cannot be said to have sufficient crystallinity (packing property), and there is a restriction on the carrier mobility, and if the carrier mobility is increased by increasing the crystallinity (packing property). Solubility had to be sacrificed. That is, the conventional donor-acceptor type polymer has a trade-off between carrier mobility and solubility.

In order to get rid of the above trade-off, the present inventors have not only the main chain part of the donor-acceptor type polymer but also the soluble group part to make the structure regularity more densely between the molecules. We considered increasing (improving packing properties) and further improving carrier mobility without sacrificing solubility.

The present invention improves the crystallinity (packing property) of an organic semiconductor polymer, achieves both carrier mobility and solubility at a higher level, exhibits excellent carrier mobility when used in a semiconductor layer, and has good coating characteristics. It is an object to provide a semiconductor compound and an organic semiconductor device containing the compound in a semiconductor layer.
Furthermore, this invention makes it a subject to provide the composition and coating film containing the said organic-semiconductor compound.

The present inventors have made extensive studies in view of the above problems. As a result, it has been found that a specific side chain direction condensed ring structure that has been conventionally incorporated into a polymer as an acceptor structural unit can function as a donor structural unit. In other words, a specific side chain direction condensed ring structure has a deepest maximum occupied orbital (HOMO) level in the monomer state and a weak donor property. The knowledge which showed the donor property equivalent to or more than a ring structure was acquired.
Furthermore, it has been found that a donor-acceptor type polymer having a very high structure regularity including a soluble group can be obtained by making both the donor and acceptor structural units into a side-chain direction condensed ring structure. It has been found that due to its high structural regularity, this polymer forms a highly crystalline coating film by arranging the main chain and the soluble group as shown below, and exhibits excellent carrier mobility.

The present invention has been completed through further studies based on these findings.

That is, according to the present invention, the following means are provided.
[1] An organic semiconductor device containing a compound represented by the following formula (1) in a semiconductor layer.

In formula (1), D represents a donor structural unit represented by formula (2) or formula (3). A represents an acceptor structural unit composed of an aromatic ring having a side-chain direction condensed ring structure. S ¹ and S ² represent ethenylene, ethynylene, arylene group, heteroarylene group, azo group, or —C═N—. l and n are integers of 1 to 4, and m1 and m2 are integers of 0 to 2. p represents an integer of 2 to 2000.
In the formula (2), X ²¹ and X ²² represent a sulfur atom, an oxygen atom, a selenium atom or —NR ²² —, and Y ²¹ represents a nitrogen atom or —C (—L ²² —R ²³ ) ═. However, when both X ²¹ and X ²² are sulfur atoms, Y ²¹ is —C (—L ²² —R ²³ ) =. L ²¹ and L ²² are a single bond, —O—, —S—, —NR ⁵ —, —Si (R ⁵ ) ₂ —, —C (═O) O—, —C (═S) O—, -C (= O) S-, -SC (= O)-, -OC (= O)-, -OC (= S)-, -C (= O)-, -C (= S)-,- C (═O) NR ⁵ —, —NR ⁵ C (═O) —, —S (═O) —, —S (═O) ₂ —, —S (═O) ₂ O—, —OS (= O) ₂ —, —S (═O) ₂ NR ⁵ —, —NR ⁵ S (═O) ₂ —, an arylene group, a heteroarylene group, an alkenylene group or an alkynylene group, or an arylene group, a heteroarylene group A group formed by combining two or more groups selected from a group, an alkenylene group, an alkynylene group, a carbonyl group, and an acyloxy group. R ²¹ to R ²³ represent a hydrogen atom or a monovalent substituent. R ⁵ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group.
In the formula (3), X ³¹ represents a sulfur atom, an oxygen atom, a selenium atom or —NR ³¹ —. Y ³¹ to Y ³⁴ represent a nitrogen atom or —C (—L ³¹ —R ³² ) ═. L ³¹ of Y ³¹ and Y ^{34 has} the same meaning as L ^22, and R ³² of Y ³¹ and Y ^{34 has} the same ^meaning as R ²³ . L ³¹ of Y ³² and Y ^{33 has} the same meaning as L ^21, and R ³² of Y ³² and Y ^{33 has} the same ^meaning as R ²¹ . R ³¹ has the same meaning as R ²² described above.
In formulas (2) and (3), * indicates a linking site.
However, D and A have at least one group selected from an alkyl group, an alkenyl group, and an alkynyl group.

[2] The organic semiconductor device according to [1], wherein the compound represented by the formula (1) is represented by the following formula (4).

In the formula (4), D, A, l, n and p have the same meanings as D, A, l, n and p in the above formula (1), respectively.

[3] The organic semiconductor device according to [1] or [2], which satisfies the following (a1) to (b1):
(A1) In the above formula (2), R ²¹ is an alkyl group having 6 to 24 carbon atoms, an alkenyl group, or an alkynyl group, and has no other aliphatic group having 6 or more carbon atoms.
(B1) In the above formula (3), one or both of Y ³² and Y ³³ is —C (—L ³¹ —R ³² ) =, and R ³² is an alkyl group having 6 to 24 carbon atoms, alkenyl Group or alkynyl group, and has no other aliphatic group having 6 or more carbon atoms.
[4] The organic semiconductor device according to any one of [1] to [3], wherein the acceptor structural unit A is represented by any of the following formulas (5) to (12).

In the formula (5), X ⁵¹ and X ⁵² represent a sulfur atom, oxygen atom, selenium atom or —NR ⁵² —, and Y ⁵¹ represents a nitrogen atom or —C (—L ⁵² —R ⁵³ ) ═. L ⁵¹ and L ⁵² are a single bond, —O—, —S—, —NR ⁵ —, —Si (R ⁵ ) ₂ —, —C (═O) O—, —C (═S) O—, — C (= O) S-, -SC (= O)-, -OC (= O)-, -OC (= S)-, -C (= O)-, -C (= S)-, -C (═O) NR ⁵ —, —NR ⁵ C (═O) —, —S (═O) —, —S (═O) ₂ —, —S (═O) ₂ O—, —OS (═O ) ₂ —, —S (═O) ₂ NR ⁵ —, —NR ⁵ S (═O) ₂ —, an arylene group, a heteroarylene group, an alkenylene group or an alkynylene group, or an arylene group, a heteroarylene group , A group formed by combining two or more groups selected from an alkenylene group, an alkynylene group, a carbonyl group, and an acyloxy group. R ⁵ has the same meaning as ^{R 5} in ^{L 21} in the formula (2). R ⁵¹ to R ⁵³ represent a hydrogen atom or a monovalent substituent.
In formula (6), X ⁶¹ has the same meaning as X ⁵¹ in formula (5). Z ⁶¹ and Z ⁶² represent an oxygen atom or a sulfur atom. W ⁶¹ represents —NR ⁶² —, —CR ⁶³ R ⁶⁴ —, or> C = CR ⁶⁵ R ⁶⁶ . R ⁶² to R ⁶⁶ represent a hydrogen atom or a monovalent substituent.
Wherein ^{(7), X 71} has the same meaning as ^{X 51} in the formula (5). Y ⁷¹ to Y ^{74 each} represents a nitrogen atom or —C (—L ⁷¹ —R ⁷² ) ═. L ^{71 in} Y ⁷¹ and Y ^{74 has} the same meaning as L ⁵² in the above formula (5), and L ^{71 in} Y ⁷² and Y ⁷³ has the same meaning as L ⁵¹ in the above formula (5). R ⁷² represents a hydrogen atom or a monovalent substituent.
Wherein ^{(8), X 81} has the same meaning as ^{X 52} in the formula (5). Y ⁸¹ to Y ^{84 each} represents a nitrogen atom or —C (—L ⁸¹ —R ⁸² ) ═. ^{L 81} of Y ⁸³ has the same meaning as ^{L 51} in the formula ^(5), ^{L 81} of Y ^{81, Y 82} and ^{Y 84} has the same meaning as ^{L 52} in the formula (5). R ⁸² represents a hydrogen atom or a monovalent substituent.
In Formula (9), W ⁹¹ represents —NR ⁹¹ — or —CR ⁹² R ⁹³ —, and R ⁹¹ to R ⁹³ represent a hydrogen atom or a monovalent substituent. Y ⁹¹ and Y ⁹² have the same meanings as Y ⁸¹ and Y ⁸² in the above formula (8), respectively.
In formula (10), Y ¹⁰¹ and Y ¹⁰² have the same meanings as Y ⁸¹ and Y ^{82 in} formula (8), respectively. Z ¹⁰¹ and Z ¹⁰² are synonymous with Z ⁶¹ and Z ⁶² in the above formula (6), respectively. W ¹⁰¹ is synonymous with W ⁶¹ in the above formula (6).
In formula (11), X ¹¹¹ and X ¹¹² have the same meanings as X ⁵¹ and X ^{52 in} formula (5), respectively. Y ¹¹¹ and Y ¹¹² have the same meanings as Y ⁷¹ and Y ⁷⁴ in the above formula (7), respectively. Y ¹¹³ and Y ¹¹⁴ are synonymous with Y ⁸³ and Y ⁸⁴ in the above formula (8), respectively.
In formula (12), X ¹²¹ has the same meaning as X ⁵¹ in formula (5). Y ¹²¹ and Y ¹²² are synonymous with Y ⁷¹ and Y ⁷⁴ in the above formula (7), respectively. Z ¹²¹ and Z ¹²² are synonymous with Z ⁶¹ and Z ⁶² in the above formula (6), respectively. W ¹²¹ is synonymous with W ⁶¹ in the above formula (6).
The structure represented by each of the formulas (5) to (12) has at least one group selected from an alkyl group, an alkenyl group, and an alkynyl group. Moreover, * shows a connection part in each formula.

[5] The organic semiconductor device according to [4], which satisfies the following (a2) to (h2):
(A2) In the above formula (5), R ⁵¹ is an alkyl group, alkenyl group or alkynyl group having 6 to 24 carbon atoms, and does not have any other aliphatic group having 6 or more carbon atoms,
(B2) In the above formula (6), W ⁶¹ is —NR ⁶² —, —CR ⁶³ R ⁶⁴ — or> C═CR ⁶⁵ R ⁶⁶ , and R ⁶² to R ⁶⁶ are alkyl having 6 to 24 carbon atoms. A group, an alkenyl group or an alkynyl group, and no other aliphatic group having 6 or more carbon atoms,
(C2) In the above formula (7), at least one of Y ⁷² and Y ⁷³ is —C (—L ⁷¹ —R ⁷² ) =, and R ⁷² is an alkyl group, alkenyl group having 6 to 24 carbon atoms, or An alkynyl group that does not have any other aliphatic group having 6 or more carbon atoms,
(D2) In the above formula (8), Y ⁸³ is —C (—L ⁸¹ —R ⁸² ) =, R ⁸² is an alkyl group, alkenyl group or alkynyl group having 6 to 24 carbon atoms, Does not have an aliphatic group having 6 or more carbon atoms,
(E2) In the above formula (9), W ⁹¹ is —NR ⁹¹ — or —CR ⁹² R ⁹³ —, and R ⁹¹ to R ⁹³ are alkyl groups, alkenyl groups, or alkynyl groups having 6 to 24 carbon atoms. There is no other aliphatic group having 6 or more carbon atoms,
(F2) In the above formula (10), W ¹⁰¹ is —NR ⁶² —, —CR ⁶³ R ⁶⁴ — or> C = CR ⁶⁵ R ⁶⁶ , and R ⁶² to R ⁶⁶ are alkyl having 6 to 24 carbon atoms. A group, an alkenyl group or an alkynyl group, and no other aliphatic group having 6 or more carbon atoms,
(G2) In the above formula (11), Y ¹¹³ is —C (—L ⁸¹ —R ⁸² ) =, R ⁸² is an alkyl group, alkenyl group or alkynyl group having 6 to 24 carbon atoms; Does not have an aliphatic group having 6 or more carbon atoms,
(H2) In the above formula (12), W ¹²¹ is —NR ⁶² —, —CR ⁶³ R ⁶⁴ — or> C = CR ⁶⁵ R ⁶⁶ , and R ⁶² to R ⁶⁶ are alkyl having 6 to 24 carbon atoms. A group, an alkenyl group or an alkynyl group, and no other aliphatic group having 6 or more carbon atoms.

[6] The organic semiconductor device according to any one of [1] to [5], wherein the compound is represented by any of the following formulas (13) to (17).

In formula (13), X ¹³¹ , X ¹³² , Y ¹³¹ , L ¹³¹ and R ¹³¹ have the same ^meanings as X ²¹ , X ²² , Y ²¹ , L ²¹ and R ^{21 in} formula (2), respectively. However, when both X ¹³¹ and X ¹³² are sulfur atoms, Y ¹³¹ is —C (—L ¹³³ —R ¹³³ ) =. L ¹³³ and R ¹³³ are synonymous with L ²² and R ²³ in Y ²¹ in the formula (2), respectively. X ¹³³ , X ¹³⁴ , Y ¹³² , L ¹³² and R ¹³² have the same ^meanings as X ⁵¹ , X ⁵² , Y ⁵¹ , L ⁵¹ and R ^{51 in the} formula (5), respectively. p is synonymous with p in the above formula (1).
In formula (14), X ¹⁴¹ , X ¹⁴² , Y ¹⁴¹ , L ^141, and R ¹⁴¹ have the same ^meanings as X ²¹ , X ²² , Y ²¹ , L ^21, and R ^{21 in} formula (2), respectively. However, when both X ¹⁴¹ and X ¹⁴² are sulfur atoms, Y ¹⁴¹ is -C (-L ¹⁴² -R ¹⁴² ) =. L ¹⁴² and R ¹⁴² are synonymous with L ²² and R ²³ in Y ²¹ in Formula (2), respectively. X ¹⁴³ and Y ¹⁴² to Y ¹⁴⁵ have the same ^meanings as X ⁷¹ and Y ⁷¹ to Y ^{74 in} formula (7), respectively. p is synonymous with p in the above formula (1).
In the formula (15), X ¹⁵¹ , X ¹⁵² , Y ¹⁵¹ , L ¹⁵¹ and R ¹⁵¹ have the same ^meanings as X ²¹ , X ²² , Y ²¹ , L ²¹ and R ^{21 in the} formula (2), respectively. However, when both X ¹⁵¹ and X ¹⁵² are sulfur atoms, Y ¹⁵¹ is -C (-L ¹⁵² -R ¹⁵² ) =. L ¹⁵² and R ¹⁵² are synonymous with L ²² and R ²³ in Y ²¹ in Formula (2), respectively. X ^{^153,} ^W ^{151, Z} 151 and ^{Z 152} are each synonymous with ^X ^{^61,} W ^61, ^Z 61 and ^{Z 62} in the formula (6). p is synonymous with p in the above formula (1).
In the formula (16), X ¹⁶¹ , X ¹⁶² , Y ¹⁶¹ , L ¹⁶¹ and R ¹⁶¹ have the same ^meanings as X ²¹ , X ²² , Y ²¹ , L ²¹ and R ^{21 in the} formula (2), respectively. However, when both X ¹⁶¹ and X ¹⁶² are sulfur atoms, Y ¹⁶¹ is —C (—L ¹⁶³ —R ¹⁶³ ) =. L ¹⁶³ and R ¹⁶³ have the same ^{meanings as} L ²² and R ²³ in Y ²¹ in formula (2), respectively. X ¹⁶³ , Y ¹⁶² , Y ¹⁶³ , Y ¹⁶⁴ and Y ¹⁶⁵ are synonymous with X ⁸¹ , Y ⁸¹ , Y ⁸² , Y ⁸³ and Y ^{84 in the} above formula (8), respectively. p is synonymous with p in the above formula (1).
In the formula (17), X ¹⁷¹ , X ¹⁷² , Y ¹⁷¹ , L ¹⁷¹ and R ¹⁷¹ have the same ^meaning as X ²¹ , X ²² , Y ²¹ , L ²¹ and R ^{21 in the} above formula (2), respectively. However, when both X ¹⁷¹ and X ¹⁷² are sulfur atoms, Y ¹⁷¹ is -C (-L ¹⁷² -R ¹⁷² ) =. L ¹⁷² and R ¹⁷² have the same ^{meanings as} L ²² and R ²³ in Y ²¹ in formula (2), respectively. Y ¹⁷² , Y ¹⁷³ and W ¹⁷¹ have the same ^meanings as Y ⁹¹ , Y ⁹² and W ^{91 in the} above formula (9), respectively. p is synonymous with p in the above formula (1).
In each of the formulas (13) to (17), the fused aromatic ring having two condensed rings in the side chain direction linked by a single bond is at least one group selected from an alkyl group, an alkenyl group and an alkynyl group. Have

[7] The number of carbon atoms of at least one group selected from the alkyl group, alkenyl group, and alkynyl group included in the donor structural unit and the acceptor structural unit is 6 to 24, The organic semiconductor device in any one.
[8] The organic semiconductor device according to [6], which satisfies the following (a) to (e):
(A) In the above formula ^(13), an alkyl group, an alkenyl group of ^{R 131} and ^{R 132} is 6 to 24 carbon atoms are alkynyl groups, no aliphatic group having 6 or more carbon atoms other,
(B) In the above formula (14), at least one of Y ¹⁴³ and Y ¹⁴⁴ is-(CL ⁷¹ -R ⁷² ) =, and R ¹⁴¹ and R ⁷² are alkyl groups having 6 to 24 carbon atoms, An alkenyl group or an alkynyl group, which has no other aliphatic group having 6 or more carbon atoms,
(C) In the above formula (15), W ¹⁵¹ is —NR ¹⁵³ —, CR ¹⁵⁴ R ¹⁵⁵ —, or> C = CR ¹⁵⁶ R ¹⁵⁷ , and R ¹⁵¹ and R ¹⁵³ to R ¹⁵⁷ have 6 to 24 carbon atoms. An alkyl group, an alkenyl group or an alkynyl group, and having no other aliphatic group having 6 or more carbon atoms,
(D) In the above formula (16), Y ¹⁶⁴ is the above-(CL ⁸¹ -R ⁸² ) =, and R ¹⁶¹ and R ⁸² are an alkyl group, alkenyl group or alkynyl group having 6 to 24 carbon atoms. There is no other aliphatic group having 6 or more carbon atoms,
(E) In the above formula (17), W ¹⁷¹ is —NR ¹⁷³ or —CR ¹⁷⁴ R ¹⁷⁵ —, and R ¹⁷¹ and R ¹⁷³ to R ¹⁷⁵ are an alkyl group, alkenyl group or alkynyl group having 6 to 24 carbon atoms. And no other aliphatic groups having 6 or more carbon atoms.

[9] The organic semiconductor device according to any one of [1] to [8], wherein the compound has a weight average molecular weight of 5,000 to 1,000,000.
[10] The organic semiconductor device according to any one of [1] to [9], wherein the organic semiconductor device is an organic thin film transistor.
[11] The organic semiconductor device according to any one of [1] to [9], wherein the organic semiconductor device is an organic photoelectric conversion device.
[12] The organic semiconductor device according to [11], wherein the semiconductor layer containing the compound contains an n-type semiconductor.
[13] The organic semiconductor device according to [12], wherein the semiconductor layer containing the compound is composed of a mixed layer of the compound and an n-type semiconductor.
[14] The organic semiconductor device according to any one of [1] to [9], wherein the organic semiconductor device is a thermoelectric conversion device.
[15] A compound represented by the following formula (1).

In formula (1), D represents a donor structural unit represented by formula (2) or formula (3). A represents an acceptor structural unit composed of an aromatic ring having a side-chain direction condensed ring structure. S ¹ and S ² represent ethenylene, ethynylene, arylene group, heteroarylene group, azo group, or —C═N—. l and n are integers of 1 to 4, and m1 and m2 are integers of 0 to 2. p represents an integer of 2 to 2000. However, D and A have at least one group selected from an alkyl group, an alkenyl group, and an alkynyl group.
In the formula (2), X ²¹ and X ²² represent a sulfur atom, an oxygen atom, a selenium atom or —NR ²² —, and Y ²¹ represents a nitrogen atom or —C (—L ²² —R ²³ ) ═. However, when both X ²¹ and X ²² are sulfur atoms, Y ²¹ is —C (—L ²² —R ²³ ) =. L ²¹ and L ²² are a single bond, —O—, —S—, —NR ⁵ —, —Si (R ⁵ ) ₂ —, —C (═O) O—, —C (═S) O—, -C (= O) S-, -SC (= O)-, -OC (= O)-, -OC (= S)-, -C (= O)-, -C (= S)-,- C (═O) NR ⁵ —, —NR ⁵ C (═O) —, —S (═O) —, —S (═O) ₂ —, —S (═O) ₂ O—, —OS (= O) ₂ —, —S (═O) ₂ NR ⁵ —, —NR ⁵ S (═O) ₂ —, an arylene group, a heteroarylene group, an alkenylene group or an alkynylene group, or an arylene group, a heteroarylene group A group formed by combining two or more groups selected from a group, an alkenylene group, an alkynylene group, a carbonyl group, and an acyloxy group. R ²¹ to R ²³ represent a hydrogen atom or a monovalent substituent. R ⁵ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group.
In the formula (3), X ³¹ represents a sulfur atom, an oxygen atom, a selenium atom or —NR ³¹ —. Y ³¹ to Y ³⁴ represent a nitrogen atom or —C (—L ³¹ —R ³² ) ═. L ³¹ of Y ³¹ and Y ^{34 has} the same meaning as L ^22, and R ³² of Y ³¹ and Y ^{34 has} the same ^meaning as R ²³ . L ³¹ of Y ³² and Y ^{33 has} the same meaning as L ^21, and R ³² of Y ³² and Y ^{33 has} the same ^meaning as R ²¹ . R ³¹ has the same meaning as R ²² described above.
In formulas (1) to (3), * represents a linking site.

[16] A composition comprising the compound according to [15] and an organic solvent.
[17] The composition according to [16], which is used for forming a semiconductor layer of an organic semiconductor device.
[18] A coating film formed using the composition according to [16] or [17].

In this specification, when there are a plurality of substituents, linking groups, ring structures, repeating units, etc. (hereinafter referred to as “substituents”, etc.) indicated by a specific symbol, or a plurality of substituents are simultaneously or alternatively selected. When specified, unless otherwise specified, each substituent may be the same as or different from each other. The same applies to the definition of the number of substituents and the like. Further, when a plurality of substituents and the like are adjacent to each other, they may be connected to each other to form a ring unless otherwise specified.
In the present specification, each substituent may further have a substituent unless otherwise specified.

In the present specification, “donor property” and “acceptor property” in the donor structural unit and the acceptor structural unit are the at least two types of divalent aromatic ring groups present in one molecular chain length of the organic semiconductor compound. , Indicating a relative electronic relationship. Specifically, those having relatively high electron donating properties are donor properties, and those having relatively high electron accepting properties are acceptor properties. In other words, the higher the HOMO (highest occupied orbital) energy level of the two aromatic rings to be compared is the donor property, and conversely the lower the LUMO (lowest orbital energy level) energy level is the acceptor property. It is. Even with the same aromatic ring structure, if it has an electron-withdrawing group as a substituent, it can be acceptor, and if it has an electron-donating group as a substituent, it can be donor.

In the present specification, an aromatic ring is a ring satisfying the Hückel rule that is a 4n + 2 π-electron system (n is an integer of 0 or more), and includes an aromatic hydrocarbon ring (an aryl group in the case of a group) and an aromatic ring. Group heterocycles (in the case of groups, heteroaryl groups). Further, in this specification, an aliphatic group is a group that collectively refers to an alkyl group, an alkenyl group, and an alkynyl group.

The organic semiconductor device of the present invention has a semiconductor layer exhibiting excellent hole mobility, and can be suitably used as an organic thin film transistor, an organic photoelectric conversion device, an organic thermoelectric conversion device, and the like. For example, when the organic semiconductor device of the present invention is applied to an organic thin film transistor, the transistor can have a high hole mobility and a small change in threshold voltage after repeated driving. Moreover, if the organic-semiconductor device of this invention is applied to an organic photoelectric conversion device, it can be set as the organic photoelectric conversion device excellent in the conversion efficiency of the light energy to the electric power. Furthermore, if the organic semiconductor device of this invention is applied to an organic thermoelectric conversion device, it can be set as the thermoelectric conversion device which is excellent in the conversion efficiency of the heat energy to the electric power.
Since the compound of the present invention has high crystallinity (packing property), the carrier mobility and the solubility can be compatible at a high level, and a semiconductor layer exhibiting excellent hole mobility can be formed.
The composition of the present invention contains the compound of the present invention and an organic solvent, has good coating characteristics, and can form a semiconductor layer with excellent hole mobility.
The coating film of the present invention is formed by applying the composition of the present invention, and is suitable as a semiconductor layer of an organic semiconductor device.
The above and other features and advantages of the present invention will become more apparent from the following description and accompanying drawings.

FIG. 1 is a schematic sectional view showing an example of the organic thin film transistor of the present invention. FIG. 2 is a schematic cross-sectional view of an organic thin film transistor manufactured as an FET characteristic measurement substrate in an example of the present invention. FIG. 3 is a side view schematically showing a preferred embodiment of the organic photoelectric conversion device of the present invention. FIG. 4 is a diagram schematically showing a cross section of an example of the organic thermoelectric conversion device of the present invention. The arrows in FIG. 4 indicate the direction of the temperature difference applied when the element is used. FIG. 5 is a diagram schematically showing a cross section of another example of the organic thermoelectric conversion device of the present invention. The arrows in FIG. 5 indicate the direction of the temperature difference applied when the element is used.

[Organic semiconductor compounds]
The compound of the present invention (hereinafter also referred to as “the organic semiconductor compound of the present invention”) is suitably used in the organic semiconductor layer provided in the organic semiconductor device. Moreover, the organic-semiconductor device of this invention which has the organic-semiconductor compound of this invention in a semiconductor layer is used suitably for an organic thin-film transistor, an organic photoelectric conversion device, and an organic thermoelectric conversion device.
First, the organic semiconductor compound of the present invention will be described below.

The organic semiconductor compound of the present invention is represented by the following formula (1).

(D, A)
In the formula (1), D represents a donor structural unit represented by the above formula (2) or the above formula (3). A represents an acceptor structural unit composed of an aromatic ring having a side-chain direction condensed ring structure.

The “side chain direction condensed ring structure” is a structural unit of a condensed ring structure in which two or more monocycles are condensed that constitutes an organic semiconductor compound, and includes two connecting sites for incorporation into the main chain of the organic semiconductor compound Each means that it exists in one ring among two or more condensed monocycles. For example, the structure represented by the above formula (2) is a form in which two monocycles are condensed, and two linking sites (*) for constituting the main chain of the organic semiconductor compound have two monocyclic condensed rings. Since it exists only in the ring containing X ²¹ among them, it is a “side chain direction condensed ring structure”. Similarly, the structure represented by the above formula (3) is a form in which two monocycles are condensed, and two connecting sites (*) with the main chain of the organic semiconductor compound are among the two monocycles condensed. Since it exists only in the ring containing X ³¹ , it is a “side chain direction condensed ring structure”.
On the other hand, in this specification, the term “main chain direction condensed ring structure” is sometimes used as a concept different from “side chain direction condensed ring structure”. “Main chain direction condensed ring structure” is a structural unit of a condensed ring structure in which two or more monocycles constituting a compound are fused, and one of two linking sites for incorporation into the main chain of an organic semiconductor compound is Means that it is present in one of two or more condensed monocycles, and another linking site is present in another ring.

In the above formula (2) representing D, X ²¹ and X ²² represent a sulfur atom, an oxygen atom, a selenium atom or —NR ²² —. X ²¹ and X ²² are preferably a sulfur atom, an oxygen atom or —NR ²² —, more preferably X ²¹ is a sulfur atom, X ²² is a sulfur atom or an oxygen atom, and X ²¹ and X ²² are It is more preferable that both are sulfur atoms.

Y ²¹ represents a nitrogen atom or —C (—L ²² —R ²³ ) ═. However, when both X ²¹ and X ²² are sulfur atoms, Y ²¹ is —C (—L ²² —R ²³ ) =.
R ²¹ to R ²³ represent a hydrogen atom or a monovalent substituent.

R ²¹ is an alkyl group (preferably a branched or straight chain alkyl group having 1 to 30 carbon atoms, more preferably 3 to 28 carbon atoms, still more preferably 6 to 24 carbon atoms, and particularly preferably 8 to 24 carbon atoms). An alkenyl group (preferably a branched or straight chain alkenyl group having 2 to 30 carbon atoms, more preferably 3 to 28 carbon atoms, still more preferably 6 to 24 carbon atoms, and particularly preferably 8 to 24 carbon atoms), or alkynyl A group (preferably a branched or straight-chain alkynyl group having 2 to 30 carbon atoms, more preferably 3 to 28 carbon atoms, still more preferably 6 to 24 carbon atoms, and particularly preferably 8 to 24 carbon atoms). More preferably, it is a branched or straight chain alkyl group having 6 to 24 carbon atoms, more preferably 8 to 24 carbon atoms.

R ²² is a hydrogen atom or an alkyl group (preferably a branched or straight chain alkyl group having 1 to 30 carbon atoms), an alkenyl group (preferably a branched or straight chain alkenyl group having 2 to 30 carbon atoms), or an alkynyl group. (Preferably a branched or straight chain alkynyl group having 2 to 30 carbon atoms), more preferably a hydrogen atom, or a branched or straight chain alkyl group having 1 to 30 carbon atoms, still more preferably hydrogen. Is an atom.
R ²³ is a hydrogen atom, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group (preferably a branched or straight chain alkyl group having 1 to 30 carbon atoms), an alkenyl group (preferably A branched or straight chain alkenyl group having 2 to 30 carbon atoms) or an alkynyl group (preferably a branched or straight chain alkynyl group having 2 to 30 carbon atoms), more preferably a hydrogen atom, a fluorine atom, A chlorine atom, or a branched or straight chain alkyl group having 1 to 30 carbon atoms, more preferably a hydrogen atom or a fluorine atom, and particularly preferably a hydrogen atom.

L ²¹ and L ²² are a single bond, —O—, —S—, —NR ⁵ —, —Si (R ⁵ ) ₂ —, —C (═O) O—, —C (═S) O—, -C (= O) S-, -SC (= O)-, -OC (= O)-, -OC (= S)-, -C (= O)-, -C (= S)-,- C (═O) NR ⁵ —, —NR ⁵ C (═O) —, —S (═O) —, —S (═O) ₂ —, —S (═O) ₂ O—, —OS (= O) ₂ —, —S (═O) ₂ NR ⁵ —, —NR ⁵ S (═O) ₂ —, an arylene group (preferably an arylene group having 6 to 15 carbon atoms, more preferably 6 to 12 carbon atoms). A heteroarylene group (preferably a heteroarylene group having 3 to 14 carbon atoms, more preferably 5 to 12 carbon atoms), an alkenylene group (preferably an alkenylene group having 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms). ), Or an alkynylene group (preferably an alkynylene group having 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms), or an arylene group (preferably having 6 to 15 carbon atoms, more preferably 6 to 6 carbon atoms). 12 arylene groups), heteroarylene groups (preferably 3 to 14 carbon atoms, more preferably heteroarylene groups having 5 to 12 carbon atoms), alkenylene groups (preferably 2 to 10 carbon atoms, more preferably 2 to 2 carbon atoms). 5 alkenylene groups), alkynylene groups (preferably having 2 to 10 carbon atoms, more preferably alkynylene groups having 2 to 5 carbon atoms), carbonyl groups, and acyloxy groups (preferably having 2 to 10 carbon atoms, more preferably carbon numbers). A group formed by combining two or more groups selected from 2 to 5 acyloxy groups).

Examples of the group formed by combining two or more groups selected from the above arylene group, heteroarylene group, alkenylene group, alkynylene group, carbonyl group, and acyloxy group include groups represented by the following L1 to L39. A group represented by L1, L3, L6, L7, L8, L10, L13, L14, L15, L16, L17 or L18 is preferred, and a group represented by L3, L6, L7, L10, L13 or L14 is more preferred. . The two linking sites possessed by L1 to L39 below are any of the sites indicated by * (one when there are two *) and the ring-constituting atoms in the arylene group or heteroarylene group in L1 to L39. There is no particular limitation on the position of the ring-constituting atom of the arylene group or heteroarylene group that is one and serves as a linking site.

R ⁵ represents a hydrogen atom, an alkyl group (preferably a branched or straight chain alkyl group having 1 to 30 carbon atoms, more preferably 1 to 24 carbon atoms), an alkenyl group (preferably 2 to 30 carbon atoms, more preferably a carbon atom). A branched or linear alkenyl group having 3 to 24 carbon atoms) or an alkynyl group (preferably a branched or straight chain alkynyl group having 2 to 30 carbon atoms, more preferably 3 to 24 carbon atoms), an aryl group, or a heteroaryl group Indicates. R ⁵ is more preferably a hydrogen atom or an alkyl group.

L ²¹ represents a single bond, —O—, —S—, —NR ⁵ —, —Si (R ⁵ ) ₂ —, an arylene group (preferably an arylene group having 6 to 15 carbon atoms, more preferably an arylene group having 6 to 12 carbon atoms). ), A heteroarylene group (preferably a heteroarylene group having 3 to 14 carbon atoms, more preferably 5 to 12 carbon atoms), an alkenylene group (preferably an alkenylene group having 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms). ), An alkynylene group (preferably an alkynylene group having 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms), or L1, L3, L6, L7, L8, L10, L13, L14, L15, L16, L17, And a group selected from L18, a single bond, —O—, —S—, —NR ⁵ —, —Si (R ⁵ ) ₂ —, a heteroarylene group (preferably having 3 to 14 carbon atoms, More preferably, it is a heteroarylene group having 5 to 12 carbon atoms), L3, or L10.

L ²² represents a single bond, —O—, —S—, —NR ⁵ —, —Si (R ⁵ ) ₂ —, an arylene group (preferably an arylene group having 6 to 15 carbon atoms, more preferably an arylene group having 6 to 12 carbon atoms). ), A heteroarylene group (preferably a heteroarylene group having 3 to 14 carbon atoms, more preferably 5 to 12 carbon atoms), an alkenylene group (preferably an alkenylene group having 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms). ), An alkynylene group (preferably an alkynylene group having 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms), or L1, L3, L6, L7, L8, L10, L13, L14, L15, L16, L17, And a group selected from L18, a single bond, —O—, —S—, —NR ⁵ —, —Si (R ⁵ ) ₂ —, a heteroarylene group (preferably having 3 to 14 carbon atoms, More preferably, it is more preferably a heteroarylene group having 5 to 12 carbon atoms), L3 or L10, and particularly preferably a single bond.

When L ²¹ and L ²² are other than a single bond, it is preferable that L ²¹ and L ²² form an electron donating group in a state of being linked to R ²¹ and R ²³ , respectively (that is, -L ²¹ -R ²¹ and It is preferred that -L ²² -R ²³ is an electron donating group). Examples of the electron donating group include branched or straight-chain alkoxy groups having 1 to 30 carbon atoms (preferably 6 to 24 carbon atoms, more preferably 8 to 24 carbon atoms), and 1 to 30 carbon atoms (preferably carbon atoms). A branched or straight-chain alkylthio group having 6 to 24, more preferably 8 to 24 carbon atoms, an alkylamino group having 1 to 30 carbon atoms (preferably 6 to 24 carbon atoms, more preferably 8 to 24 carbon atoms), A dialkylamino group having 1 to 30 carbon atoms (preferably 6 to 24 carbon atoms, more preferably 8 to 24 carbon atoms) or a trialkylsilyl group (preferably 3 to 72 carbon atoms, more preferably 6 to 72 carbon atoms). ) Is preferred.

In the structure represented by the formula (2), an alkyl group (preferably having a carbon number of 1 to 30, more preferably a carbon number of 3 to 28, and still more preferably a carbon number within the above-defined range of the formula (2). A branched or straight chain alkyl group having 6 to 24 carbon atoms, particularly preferably 8 to 24 carbon atoms), an alkenyl group (preferably 2 to 30 carbon atoms, more preferably 3 to 28 carbon atoms, and further preferably 6 to 24 carbon atoms). Particularly preferably a branched or straight-chain alkenyl group having 8 to 24 carbon atoms) and an alkynyl group (preferably having 2 to 30 carbon atoms, more preferably 3 to 28 carbon atoms, still more preferably 6 to 24 carbon atoms, particularly Preferably, at least one group selected from a branched or straight chain alkynyl group having 8 to 24 carbon atoms is included. In the structure represented by the formula (2), R ²¹ is preferably an alkyl group, an alkenyl group, or an alkynyl group. In the structure represented by the formula (2), R ²¹ is an alkyl group, an alkenyl group, or More preferably, it is an alkynyl group and does not have an aliphatic group having 6 or more carbon atoms at a site other than R ²¹ .

In the above formula (3), X ³¹ represents a sulfur atom, an oxygen atom, a selenium atom or —NR ³¹ —. R ³¹ has the same meaning as R ²² described above, and the preferred range is also the same. X ³¹ is preferably a sulfur atom or an oxygen atom, and more preferably a sulfur atom. Y ³¹ to Y ³⁴ represent a nitrogen atom or —C (—L ³¹ —R ³² ) ═. When Y ³¹ and Y ³⁴ are -C (-L ³¹ -R ³² ) =, L ³¹ and R ³² have the same meanings as L ²² and R ²³ described above. When Y ³² and Y ³³ are -C (-L ³¹ -R ³² ) =, L ³¹ and R ³² have the same meanings as L ²¹ and R ²¹ above.
More preferably, in the formula (3), Y ³¹ and Y ³⁴ are a nitrogen atom or —CH═. Further, when one or both of Y ³² and Y ³³ is —C (—L ³¹ —R ³² ) = and L ³¹ is other than a single bond, L ³¹ is connected to R ³² (− It is preferable to constitute an electron donating group (in the state of L ³¹ -R ³² ). Examples of the electron donating group include branched or straight chain alkoxy groups having 1 to 30 carbon atoms (preferably 6 to 24 carbon atoms), branched or straight chain groups having 1 to 30 carbon atoms (preferably 6 to 24 carbon atoms). An alkylthio group having 1 to 30 carbon atoms (preferably 6 to 24 carbon atoms), a dialkylamino group having 1 to 30 carbon atoms (preferably 6 to 24 carbon atoms), or a trialkylsilyl group (preferably C3-C72, more preferably C6-C72) is preferred.

In the structure represented by the formula (3), an alkyl group (preferably having a carbon number of 1 to 30, more preferably a carbon number of 3 to 28, and still more preferably a carbon number of 6 within the above-defined range of the formula (3). To 24, particularly preferably a branched or straight chain alkyl group having 8 to 24 carbon atoms), an alkenyl group (preferably having 2 to 30 carbon atoms, more preferably 3 to 28 carbon atoms, still more preferably 6 to 24 carbon atoms, Particularly preferably a branched or straight chain alkenyl group having 8 to 24 carbon atoms) and an alkynyl group (preferably having 2 to 30 carbon atoms, more preferably 3 to 28 carbon atoms, still more preferably 6 to 24 carbon atoms, particularly preferably Includes at least one group selected from a branched or straight chain alkynyl group having 8 to 24 carbon atoms.
In the above formula (3), Y ³² and Y ³³ may be linked to form a ring. Examples of the case where Y ³² and Y ³³ are linked to form a ring include the following formulas (31) and (32). Or group represented by (33) is mention | raise | lifted.

In formula (31) to formula (33), X ^{31 ′} is synonymous with X ^{31 in} formula (3), and the preferred range is also the same. Y ^{31 ′} and Y ^{34 ′} have the same meanings as Y ³¹ and Y ^{34 in} formula (3), respectively, and the preferred ranges are also the same. In formula (31), Y ^{32 ′} and Y ^{33 ′} have the same meanings as Y ³² and Y ^{33 in} formula (3), respectively, and the preferred ranges are also the same. In the formula (32), X ^{32 ′} , L ^{31 ′} , R ^{31 ′} , and Y ^{36 ′} have the same meanings as X ²² , L ²¹ , R ²¹ , and Y ^{21 in the} formula (2), respectively, and preferred ranges are also included. The same. However, when both X ^{31 ′} and X ^{32 ′} are sulfur atoms, Y ^{36 ′} may be a nitrogen atom.
In formula (33), Z ^{31 ′} and Z ^{32 ′} represent an oxygen atom or a sulfur atom, and more preferably an oxygen atom. W ^{31 'is} -NR ^32' -, - shows ^{^{or> C = CR 35 'R 36}} ' - CR 33 'R 34'. R ^{32 ′} to R ^{36 ′ each} represent a hydrogen atom or a monovalent substituent. This substituent is an alkyl group (preferably a linear or branched alkyl group having 1 to 30 carbon atoms, more preferably 3 to 28 carbon atoms, still more preferably 6 to 24 carbon atoms), an alkenyl group (preferably 2 carbon atoms). A branched or straight chain alkynyl group having 2 to 24 carbon atoms, more preferably a branched or straight chain alkynyl group having 2 to 24 carbon atoms, or an alkynyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 24 carbon atoms). Group, preferably an alkyl group (preferably a linear or branched alkyl group having 1 to 30 carbon atoms, more preferably 3 to 28 carbon atoms, still more preferably 6 to 24 carbon atoms). preferable.
In the above formula (3), one or both of Y ³² and Y ³³ is —C (—L ³¹ —R ³² ) =, and R ³² is an alkyl group having 6 to 24 carbon atoms, It is preferably an alkenyl group having 24 carbon atoms or an alkynyl group having 6 to 24 carbon atoms, and no other aliphatic group having 6 or more carbon atoms.
In the above formula (31), one or both of Y ^{32 ′} and Y ^{33 ′} is the above —C (—L ³¹ —R ³² ) =, and R ³² is an alkyl group having 6 to 24 carbon atoms, It is preferably an alkenyl group having 6 to 24 carbon atoms or an alkynyl group having 6 to 24 carbon atoms and having no other aliphatic group having 6 or more carbon atoms.
In the above formula (32), R ^{31 ′} is an alkyl group having 6 to 24 carbon atoms, an alkenyl group having 6 to 24 carbon atoms, or an alkynyl group having 6 to 24 carbon atoms, and other aliphatic groups having 6 or more carbon atoms It is preferable not to have.
In the above formula (33), R ^{32 ′} to R ^{36 ′ of} W ^{31 ′} are an alkyl group having 6 to 24 carbon atoms, an alkenyl group having 6 to 24 carbon atoms, or an alkynyl group having 6 to 24 carbon atoms, It preferably has no aliphatic group having 6 or more carbon atoms.

* In the formulas (2) and (3) represents a linking site in the organic semiconductor compound. Here, in the formulas (2) and (3), there is no particular limitation on the direction in which the two linking sites represented by * are incorporated into the main chain of the organic semiconductor compound. For example, the connecting part * shown on the right side in the formula (2) may face the A side in the formula (1). Or the connection part * shown on the left side in Formula (2) may face the A side in Formula (1). The same applies to the structural units of other organic semiconductor compounds shown in the present specification, and the same applies to the structural units of organic semiconductor compounds shown in a form incorporated in the organic semiconductor compound. . For example, in each of the organic semiconductor compounds represented by the above formulas (13) to (17), there are four variations of the connection between the donor structural unit shown on the left side and the acceptor structural unit shown on the right side. Each of the formulas (13) to (17) is used as a notation including any of these four linked forms. Furthermore, in this specification, the connection form of a donor-type structural unit and an acceptor-type structural unit may be the same or different among the repeating units constituting one organic semiconductor compound.

In the above formula (1), l representing the number of D represents an integer of 1 to 4, more preferably 1 or 2, and even more preferably 1. In the above formula (1), n representing the number of A represents an integer of 1 to 4, more preferably 1 or 2, and even more preferably 1. In the above formula (1), the number of D and the number of A are preferably the same.

The groups represented by formulas (2) and (3) exhibit weak donor properties as monomers before being incorporated into the polymer, but exhibit strong donor properties when incorporated into the polymer. The reason for this will be described below.

Here, the concept of an aromatic structure and a pseudoquinoid structure is important. An aromatic structure shows a structure like the ring II of Formula (2) and Formula (3). The pseudoquinoid structure indicates a quinone-like structure such as ring I. The reason why the groups represented by the formulas (2) and (3) of the present invention function as a strong donor in the polymer originates from the fact that Ring I has a quinoid structure.
The π-conjugated polymer can have a limit structure A having an aromatic structure as a main chain and a limit structure B having a pseudoquinoid structure as a main chain (in the following formula, thienopyrrole dione is used as an acceptor). When ring I has a quinoid structure, in limit structure B, ring I has an aromatic structure. That is, due to the aromatization of ring I, the limit structure B is stabilized, and as a result, the contribution of the limit structure B is increased. The limit structure B has a polyene-like π-conjugated structure, and the conjugation extends in the main chain direction as compared with the limit structure A. Therefore, the HOMO level of the polymer becomes shallow. This is the reason why the group represented by the formula (2) or the formula (3) exhibits strong donor properties when incorporated in a polymer. Furthermore, the conjugation expansion in the main chain direction by stabilizing the ultimate structure B of the polymer makes it easier for the carriers to move in the main chain direction, which is considered advantageous for improving the carrier mobility. The concept of conjugate expansion by stabilizing the pseudoquinoid structure (extreme structure B) of a polymer has been known so far. However, it is known that the side chain aromatic condensed ring unit represented by the formula (2) or the formula (3) that has been used as an acceptor conventionally functions as a strong donor due to the effect of stabilizing the ultimate structure B. There wasn't.

As shown in the lower part of the following example, when a conventional aromatic ring condensed in the direction of the main chain (dithienosilol in the following example) is used as a donor structural unit, the aromatization of the donor unit does not occur in the limit structure B Therefore, the stabilization of the limit structure B as described above does not appear. The values of the HOMO and LUMO levels in the following formulas are calculated values obtained by molecular orbital calculation software Gaussian 09 (manufactured by Gaussian) using the basis function system 6-31G (d) in the B3LYP method. The donor properties of thieno [3,4-b] thiophene and dithienosilol are stronger in the latter state in the monomer state (shallow HOMO), but when polymerized, both HOMO levels are reversed. For the reasons described above, it can be seen that the former (thieno [3,4-b] thiophene) functions as a stronger donor in the polymer.

In formula (1), A is selected from benzene, pyridine, pyrazine, pyrimidine, pyridazine, triazine, tetrazine, thiophene, furan, pyrrole, selenophene, thiazole, oxazole, imidazole, pyrazole, oxadiazole, thiadiazole, and triazole. A divalent group in which two or more monocycles are condensed in the side chain direction, or benzene, pyridine, pyrazine, pyrimidine, pyridazine, triazine, tetrazine, thiophene, furan, pyrrole, selenophene, thiazole, oxazole, imidazole 1,3-cyclopentadione for a single ring selected from benzene, pyrazole, oxadiazole, thiadiazole, and triazole, or for a condensed ring in which two or more of these single rings are condensed in the side chain direction 1,4- It is preferable black hexa-dione, or 2,5-pyrrole-dione is a divalent group of the fused structure in a side chain direction. The group represented by A has both a HOMO level and a LUMO level of a compound in which two bonds of A are substituted with hydrogen atoms, and both are deeper than a compound in which the bond of the group represented by D is substituted with a hydrogen atom. It is a group.

In the formula (1), A is preferably an aromatic ring having a side chain direction condensed ring structure represented by the following formulas (5) to (12).

In the formula (5), X ⁵¹ and X ⁵² represent a sulfur atom, an oxygen atom, a selenium atom or —NR ⁵² —. X ⁵¹ and X ⁵² are preferably a sulfur atom, an oxygen atom or —NR ⁵² —, and more preferably a sulfur atom. Y ⁵¹ represents a nitrogen atom or —C (—L ⁵² —R ⁵³ ) ═.
R ⁵¹ to R ⁵³ represent a hydrogen atom or a monovalent substituent.

R ⁵¹ is an alkyl group (preferably a branched or straight chain alkyl group having 1 to 30 carbon atoms, more preferably 3 to 28 carbon atoms, still more preferably 6 to 24 carbon atoms, and particularly preferably 8 to 24 carbon atoms). An alkenyl group (preferably a branched or straight chain alkenyl group having 2 to 30 carbon atoms, more preferably 3 to 28 carbon atoms, still more preferably 6 to 24 carbon atoms, and particularly preferably 8 to 24 carbon atoms), or alkynyl And a group (preferably a branched or straight chain alkynyl group having 2 to 30 carbon atoms, more preferably 3 to 28 carbon atoms, still more preferably 6 to 24 carbon atoms, and particularly preferably 8 to 24 carbon atoms). More preferably, it is a branched or straight chain alkyl group having 6 to 24 carbon atoms, more preferably 8 to 24 carbon atoms.

R ⁵² represents a hydrogen atom or an alkyl group (preferably a branched or straight chain alkyl group having 1 to 30 carbon atoms, more preferably 1 to 24 carbon atoms), an alkenyl group (preferably 2 to 30 carbon atoms, more preferably A branched or linear alkenyl group having 2 to 24 carbon atoms) or an alkynyl group (preferably a branched or straight chain alkynyl group having 2 to 30 carbon atoms, more preferably 2 to 24 carbon atoms), A hydrogen atom or a branched or straight chain alkyl group having 1 to 30 carbon atoms, more preferably 1 to 24 carbon atoms is more preferable, and a hydrogen atom is still more preferable.

R ⁵³ is a hydrogen atom, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), a cyano group, a nitro group, a formyl group, or an alkyl group (preferably having a carbon number of 1 to 30, more preferably a carbon number). 1 to 24 branched or straight chain alkyl groups), alkenyl groups (preferably 2 to 30 carbon atoms, more preferably 2 to 24 carbon branched or straight chain alkenyl groups), or alkynyl groups (preferably carbon numbers). A branched or straight-chain alkynyl group having 2 to 24 carbon atoms, more preferably a hydrogen atom, a fluorine atom, a chlorine atom, or a cyano group, and still more preferably a hydrogen atom. Or it is a fluorine atom.

L ⁵¹ and L ⁵² are a single bond, —O—, —S—, —NR ⁵ —, —Si (R ⁵ ) ₂ —, —C (═O) O—, —C (═S) O—, — C (= O) S-, -SC (= O)-, -OC (= O)-, -OC (= S)-, -C (= O)-, -C (= S)-, -C (═O) NR ⁵ —, —NR ⁵ C (═O) —, —S (═O) —, —S (═O) ₂ —, —S (═O) ₂ O—, —OS (═O ) ₂ —, —S (═O) ₂ NR ⁵ —, —NR ⁵ S (═O) ₂ —, an arylene group (preferably an arylene group having 6 to 15 carbon atoms, more preferably an arylene group having 6 to 12 carbon atoms), A heteroarylene group (preferably an arylene group having 4 to 14 carbon atoms, more preferably an arylene group having 5 to 12 carbon atoms), an alkenylene group (preferably an alkenylene group having 2 to 10 carbon atoms, more preferably an alkenylene group having 2 to 5 carbon atoms), Or an alkynylene group (preferably an alkynylene group having 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms), or an arylene group (preferably 6 to 15 carbon atoms, more preferably 6 to 12 carbon atoms). Arylene groups), heteroarylene groups (preferably 4-14 carbon atoms, more preferably arylene groups having 5-12 carbon atoms), alkenylene groups (preferably 2-10 carbon atoms, more preferably 2-5 carbon atoms). Alkenylene group), an alkynylene group (preferably an alkynylene group having 2 to 10 carbon atoms, more preferably an alkynylene group having 2 to 5 carbon atoms), a carbonyl group, and an acyloxy group (preferably 2 to 10 carbon atoms, more preferably 2 to 2 carbon atoms). A group formed by combining two or more groups selected from 5 acyloxy groups). R ⁵ has the same meaning as R ⁵ in L ²¹ of the above formula (2), and the preferred embodiment is also the same.

L ⁵¹ is a single bond, —C (═O) O—, —C (═S) O—, —C (═O) S—, —SC (═O) —, —OC (═O) —, — OC (= S)-, -C (= O)-, -C (= S)-, -C (= O) NR ^5- , -S (= O)-, -S (= O) _2- , _{_{-S (= O) 2 O -}} , - OS (= O) 2 -, - S (= O) 2 NR 5 -, - NR 5 S (= O) 2 -, or alkynylene group (preferably 2 carbon atoms To 10 and more preferably an alkynylene group having 2 to 5 carbon atoms).

L ⁵² represents a single bond, —C (═O) O—, —C (═S) O—, —C (═O) S—, —SC (═O) —, —OC (═O) —, — OC (= S)-, -C (= O)-, -C (= S)-, -C (= O) NR ^5- , -S (= O)-, -S (= O) _2- , _{_{-S (= O) 2 O -}} , - OS (= O) 2 -, - S (= O) 2 NR 5 -, - NR 5 S (= O) 2 -, or alkynylene group (preferably 2 carbon atoms To 10 and more preferably an alkynylene group having 2 to 5 carbon atoms, and more preferably a single bond.

In addition to the above embodiment, when L ⁵¹ and L ⁵² are other than a single bond, it is also preferable that L ⁵¹ and L ⁵² constitute an electron-withdrawing group together with R ⁵¹ and R ^53, respectively. Preferred examples of the electron withdrawing group include a 1-alkynyl group (preferably a 1-alkynyl group having 2 to 24 carbon atoms, more preferably a 1-alkynyl group having 6 to 24 carbon atoms), an acyl group (preferably Is an acyl group having 2 to 30 carbon atoms, more preferably 4 to 28 carbon atoms, still more preferably 6 to 24 carbon atoms, an alkoxycarbonyl group (preferably 2 to 30 carbon atoms, more preferably 4 to 28 carbon atoms, More preferably, it is an alkoxycarbonyl group having 6 to 24 carbon atoms, an aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 30 carbon atoms, more preferably an aryloxycarbonyl group having 7 to 20 carbon atoms), an acyloxy group (preferably having 2 carbon atoms). To 30 and more preferably an acyloxy group having 6 to 24 carbon atoms), an arylcarbonyloxy group (preferably having 7 to 30 carbon atoms, more preferably Or an arylcarbonyloxy group having 7 to 20 carbon atoms), a carbamoyl group (preferably 1 to 49 carbon atoms, more preferably a carbamoyl group having 3 to 49 carbon atoms), a sulfamoyl group (preferably having 0 to 48 carbon atoms, Preferably a sulfamoyl group having 2 to 48 carbon atoms), an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 30, more preferably 4 to 28 carbon atoms, more preferably 6 to 24 carbon atoms), an arylsulfonyl group (Preferably an arylsulfonyl group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms), an alkylsulfinyl group (preferably 1 to 30 carbon atoms, more preferably 4 to 28 carbon atoms, still more preferably 6 carbon atoms). To 24 alkylsulfinyl groups) and sulfonyloxy groups (preferably having 1 to 30 carbon atoms, more preferably Ku is 4-28 carbon atoms, more preferably include sulfonyloxy group) having 6 to 24 carbon atoms.

In formula (6), X ⁶¹ has the same meaning as X ⁵¹ in formula (5), and the preferred embodiment is also the same.
Z ⁶¹ and Z ^{62 each} represents an oxygen atom or a sulfur atom, preferably an oxygen atom.
W ⁶¹ represents —NR ⁶² —, —CR ⁶³ R ⁶⁴ —, or> C = CR ⁶⁵ R ⁶⁶ . R ⁶² to R ⁶⁶ represent a hydrogen atom or a monovalent substituent. This substituent is an alkyl group (preferably a linear or branched alkyl group having 1 to 30 carbon atoms, more preferably 1 to 24 carbon atoms), an alkenyl group (preferably 2 to 30 carbon atoms, more preferably 2 carbon atoms). To 24 branched or straight chain alkenyl groups) or alkynyl groups (preferably 2 to 30 carbon atoms, more preferably branched or straight chain alkynyl groups having 2 to 24 carbon atoms). A linear or branched alkyl group having 1 to 30 carbon atoms, more preferably 1 to 24 carbon atoms is more preferable.

Wherein ^{(7), X 71} has the same meaning as ^{X 51} in the formula (5), preferred embodiments are also the same. Y ⁷¹ to Y ^{74 each} represents a nitrogen atom or —C (—L ⁷¹ —R ⁷² ) ═.
When Y ⁷¹ and Y ⁷⁴ are -C (-L ⁷¹ -R ⁷² ) =, L ⁷¹ is synonymous with L ⁵² in the above formula (5), and R ⁷² is synonymous with R ⁵³ in the above formula (5). The preferred embodiments are also the same.
When Y ⁷² and Y ⁷³ are -C (-L ⁷¹ -R ⁷² ) =, L ⁷¹ is synonymous with L ⁵¹ in the above formula (5), and R ⁷² is synonymous with R ⁵¹ in the above formula (5). The preferred embodiments are also the same.
More preferably, in formula (7), Y ⁷¹ and Y ⁷⁴ are a nitrogen atom or —CH═. Further, when Y ⁷² and Y ⁷³ are —C (—L ⁷¹ —R ⁷² ) = and L ⁷¹ is other than a single bond, L ⁷¹ is linked to R ⁷² (in the form of —L ⁷¹ —R ⁷² It is preferred (in the state) to constitute an electron withdrawing group. As said electron withdrawing group, what was mentioned as an example of an electron withdrawing group in description of the said Formula (5) is employable, for example.

Wherein ^{(8), X 81} has the same meaning as ^{X 52} in the formula (5), preferred embodiments are also the same. Y ⁸¹ to Y ^{84 each} represents a nitrogen atom or —C (—L ⁸¹ —R ⁸² ) ═.
When Y ⁸³ is -C (-L ⁸¹ -R ⁸² ) =, L ⁸¹ is synonymous with L ⁵¹ in the above formula (5), and R ⁸² is synonymous with R ⁵¹ in the above formula (5). When Y ⁸¹ , Y ⁸² , and Y ⁸⁴ are —C (—L ⁸¹ -R ⁸² ) =, L ⁸¹ is L ⁵² in the above formula (5), and R ⁸² is R ⁵³ in the above formula (5). It is synonymous.
When Y ⁸³ is —C (—L ⁸¹ —R ⁸² ) = and L ⁸¹ is other than a single bond, it is preferable that —L ⁸¹ —R ⁸² is an electron withdrawing group. As this electron withdrawing group, for example, those exemplified as examples of the electron withdrawing group in the description of the above formula (5) can be adopted.

In Formula (9), W ⁹¹ represents —NR ⁹¹ — or —CR ⁹² R ⁹³ —, and R ⁹¹ to R ⁹³ represent a hydrogen atom or a monovalent substituent. Examples of the substituent include an alkyl group (preferably a linear or branched alkyl group having 1 to 30 carbon atoms, more preferably 3 to 28 carbon atoms, and still more preferably 6 to 24 carbon atoms), an alkenyl group (preferably a carbon atom). A linear or branched alkenyl group having 2 to 30 carbon atoms, more preferably 6 to 28 carbon atoms, still more preferably 8 to 24 carbon atoms), an alkynyl group, preferably 2 to 30 carbon atoms, more preferably 6 to 28 carbon atoms. And more preferably a linear or branched alkynyl group having 8 to 24 carbon atoms.
Y ⁹¹ and Y ⁹² are synonymous with Y ⁸¹ and Y ^{82 in} formula (8), respectively, and preferred embodiments are also the same.

In formula (10), Y ¹⁰¹ and Y ¹⁰² are synonymous with Y ⁸¹ and Y ^{82 in} formula (8), respectively, and preferred embodiments are also the same. Z ¹⁰¹ and Z ¹⁰² are synonymous with Z ⁶¹ and Z ⁶² in the above formula (6), respectively, and preferred embodiments are also the same. W ¹⁰¹ is synonymous with W ⁶¹ in the above formula (6), and a preferred embodiment is also the same.

In formula (11), X ¹¹¹ and X ¹¹² have the same meanings as X ⁵¹ and X ^{52 in} formula (5), respectively, and preferred embodiments are also the same. Y ¹¹¹ and Y ¹¹² are synonymous with Y ⁷¹ and Y ^{74 in} the above formula (7), respectively, and preferred embodiments are also the same. Y ¹¹³ is synonymous with Y ^{83 in the} above formula (8), and the preferred embodiment is also the same. Y ¹¹⁴ is synonymous with Y ^{84 in the} above formula (8), and the preferred embodiment is also the same.

In formula (12), X ¹²¹ has the same meaning as X ⁵¹ in formula (5), and the preferred embodiment is also the same. Y ¹²¹ and Y ¹²² are synonymous with Y ⁷¹ and Y ⁷⁴ in the above formula (7), respectively, and preferred embodiments are also the same. Z ¹²¹ and Z ¹²² are synonymous with Z ⁶¹ and Z ⁶² in the above formula (6), respectively, and preferred embodiments are also the same. W ¹²¹ is synonymous with W ⁶¹ in the above formula (6), and the preferred embodiment is also the same.

In the structures represented by the formulas (5) to (12), an alkyl group (preferably having a carbon number of 1 to 30, more preferably a carbon number of 3 to 28, and still more preferably within the range defined by each formula. Is a branched or straight chain alkyl group having 6 to 24 carbon atoms, particularly preferably 8 to 24 carbon atoms, or an alkenyl group (preferably 2 to 30 carbon atoms, more preferably 3 to 28 carbon atoms, still more preferably carbon atoms). A branched or straight-chain alkenyl group having 6 to 24 carbon atoms, particularly preferably 8 to 24 carbon atoms, and an alkynyl group (preferably 2 to 30 carbon atoms, more preferably 3 to 28 carbon atoms, still more preferably 6 to 6 carbon atoms). 24, particularly preferably a branched or straight-chain alkynyl group having 8 to 24 carbon atoms). Moreover, * shows a connection part in each formula.

In the structure represented by formula (5), R ⁵¹ is preferably the alkyl group, alkenyl group, or alkynyl group. In the structure represented by formula (5), R ⁵¹ is an alkyl group, alkenyl group, Or it is an alkynyl group, and it is more preferable not to have an aliphatic group having 6 or more carbon atoms in addition to R ⁵¹ .

In the structure represented by the formula (6), the R ⁶² to R ⁶⁶ are preferably the alkyl group, alkenyl group, or alkynyl group. In the structure represented by the formula (6), the R ⁶² to R More preferably, ⁶⁶ is an alkyl group, an alkenyl group, or an alkynyl group, and does not have an aliphatic group having 6 or more carbon atoms in addition to the above R ⁶² to R ⁶⁶ .

In the structure represented by formula (7), at least one of Y ⁷² and Y ⁷³ is the above-C (L ⁷¹ -R ⁷² ), and R ⁷² is the above alkyl group, alkenyl group, or alkynyl group. Preferably, in the structure represented by formula (7), at least one of Y ⁷² and Y ⁷³ is the above-C (L ⁷¹ -R ⁷² ), R ⁷² is an alkyl group, an alkenyl group, or an alkynyl group, It is more preferable not to have an aliphatic group having 6 or more carbon atoms.

Structure represented by the formula ^{(8), Y 83} is the ^{^{-C (-L 81 -R 82) =}} , it is preferred that ^{R 82} is the above alkyl group, alkenyl group, or alkynyl ^{group, Y 83} Is more preferably —C (—L ⁸¹ —R ⁸² ) =, R ⁸² is the above alkyl group, alkenyl group, or alkynyl group, and no other aliphatic group having 6 or more carbon atoms. .

In the structure represented by formula (9), R ⁹¹ to R ⁹³ are preferably the alkyl group, alkenyl group, or alkynyl group, and R ⁹¹ to R ⁹³ are preferably the alkyl group, alkenyl group, or alkynyl. It is more preferable that it is a group and does not have an aliphatic group having 6 or more carbon atoms.

In the structure represented by the formula (10), the R ⁶² to R ⁶⁶ in the referenced formula (6) are preferably the alkyl group, alkenyl group, or alkynyl group, and the structure represented by the formula (10) Among them, it is more preferable that R ⁶² to R ⁶⁶ in the formula (6) to be referred to are an alkyl group, an alkenyl group, or an alkynyl group, and no other aliphatic group having 6 or more carbon atoms.

In the structure represented by the formula (11), Y ¹¹³ is preferably —C (—L ⁸¹ —R ⁸² ) ═, and R ⁸² is preferably the above alkyl group, alkenyl group, or alkynyl group. More preferably, it does not have an aliphatic group having 6 or more carbon atoms.

In the structure represented by the formula (12), the R ⁶² to R ⁶⁶ in the referenced formula (6) are preferably the alkyl group, alkenyl group, or alkynyl group, and other aliphatic groups having 6 or more carbon atoms. More preferably, it has no group.

^(S ^{1, S} 2)
In the above formula (1), S ¹ and S ² represent ethenylene, ethynylene, arylene group, heteroarylene group, azo group, or —C═N—.
The arylene group preferably has 6 to 20 carbon atoms, and more preferably 6 to 15 carbon atoms. The arylene group is preferably phenylene or naphthylene.

The carbon number of the heteroarylene group is preferably 2 to 20, and more preferably 3 to 12. Preferred examples of the heteroarylene group include a divalent thiophene ring, a divalent thiazole ring, a divalent oxazole ring, a divalent furan ring, a divalent pyrrole ring, a divalent selenophene ring, and a divalent thiazole ring. Divalent oxazole ring, divalent thiadiazole ring, divalent oxadiazole ring, divalent pyrazole ring, divalent imidazole ring, divalent pyridine ring, divalent pyrazine ring, divalent pyridazine ring Examples thereof include a divalent pyrimidine ring, a divalent triazine ring, a divalent triazole ring, and a divalent tetrazine ring.
M1 representing the number of S ¹ is an integer of 0 to 2, preferably 0 or 1, and more preferably 0. M2 representing the number of S ² is an integer of 0 to 2, preferably 0 or 1, and more preferably 0. m1 and m2 are preferably the same.

In the formula (1), p represents an integer of 2 to 2000, more preferably an integer of 10 to 2000.

The compound represented by the above formula (1) is preferably represented by the following formula (4).

In the formula (4), D, A, l, n and p have the same meanings as D, A, l, n and p in the formula (1), respectively, and preferred embodiments are also the same.

The compound represented by the above formula (1) or (4) is preferably represented by any of the following formulas (13) to (17).

In formula (13), X ¹³¹ , X ¹³² , Y ¹³¹ , L ¹³¹ and R ¹³¹ have the same meaning as X ²¹ , X ²² , Y ²¹ , L ²¹ and R ^{21 in} formula (2), respectively, and are preferable. The aspect is also the same. However, when both X ¹³¹ and X ¹³² are sulfur atoms, Y ¹³¹ is —C (—L ¹³³ —R ¹³³ ) =. L ¹³³ and R ¹³³ are synonymous with L ²² and R ²³ in Y ²¹ in the formula (2), respectively, and preferred embodiments are also the same.
X ¹³³ , X ¹³⁴ , Y ¹³² , L ¹³² and R ¹³² are the same as X ⁵¹ , X ⁵² , Y ⁵¹ , L ⁵¹ and R ^{51 in the} above formula (5), respectively, and preferred embodiments are also the same. p is synonymous with p of the said Formula (1), and its preferable aspect is also the same.

In formula (14), X ¹⁴¹ , X ¹⁴² , Y ¹⁴¹ , L ¹⁴¹ and R ¹⁴¹ have the same meaning as X ²¹ , X ²² , Y ²¹ , L ²¹ and R ^{21 in} formula (2), respectively, and are preferable. The aspect is also the same. However, when both X ¹⁴¹ and X ¹⁴² are sulfur atoms, Y ¹⁴¹ is -C (-L ¹⁴² -R ¹⁴² ) =. L ¹⁴² and R ¹⁴² are respectively synonymous with L ²² and R ²³ in Y ²¹ in the formula (2), and preferred embodiments are also the same.
X ¹⁴³ and Y ¹⁴² to Y ¹⁴⁵ have the same ^meanings as X ⁷¹ and Y ⁷¹ to Y ^{74 in} formula (7), respectively, and preferred embodiments are also the same. p is synonymous with p of the said Formula (1), and its preferable aspect is also the same.

In formula (15), X ¹⁵¹ , X ¹⁵² , Y ¹⁵¹ , L ¹⁵¹ and R ¹⁵¹ have the same ^meanings as X ²¹ , X ²² , Y ²¹ , L ²¹ and R ^{21 in} formula (2), respectively, and are preferable. The aspect is also the same. However, when both X ¹⁵¹ and X ¹⁵² are sulfur atoms, Y ¹⁵¹ is -C (-L ¹⁵² -R ¹⁵² ) =.
L ¹⁵² and R ¹⁵² have the same definitions as L ²² and R ²³ described for Y ²¹ in formula (2), respectively, and preferred embodiments are also the same.
X ^{^153,} ^W ^{151, Z} 151 and ^{Z 152} are each synonymous with ^X ^{^61,} W ^61, ^Z 61 and ^{Z 62} in the formula (6), a preferred embodiment is also the same. p is synonymous with p of the said Formula (1), and its preferable aspect is also the same.

In the formula (16), X ¹⁶¹ , X ¹⁶² , Y ¹⁶¹ , L ¹⁶¹ and R ¹⁶¹ are respectively synonymous with X ²¹ , X ²² , Y ²¹ , L ²¹ and R ²¹ in the formula (2), and are preferable. The aspect is also the same. However, when both X ¹⁶¹ and X ¹⁶² are sulfur atoms, Y ¹⁶¹ is —C (—L ¹⁶³ —R ¹⁶³ ) =. L ¹⁶³ and R ¹⁶³ have the same meanings as L ²² and R ²³ described for Y ²¹ in formula (2), respectively, and preferred embodiments are also the same.
X ¹⁶³ , Y ¹⁶² , Y ¹⁶³ , Y ¹⁶⁴ and Y ¹⁶⁵ are synonymous with X ⁸¹ , Y ⁸¹ , Y ⁸² , Y ⁸³ and Y ^{84 in the} above formula (8), respectively, and preferred embodiments are also the same. p is synonymous with p of the said Formula (1), and its preferable aspect is also the same.

In the formula (17), X ¹⁷¹ , X ¹⁷² , Y ¹⁷¹ , L ¹⁷¹ and R ¹⁷¹ are the same as X ²¹ , X ²² , Y ²¹ , L ²¹ and R ^{21 in the} above formula (2), respectively. The aspect is also the same. However, when both X ¹⁷¹ and X ¹⁷² are sulfur atoms, Y ¹⁷¹ is -C (-L ¹⁷² -R ¹⁷² ) =. L ¹⁷² and R ¹⁷² have the same meanings as L ²² and R ²³ described for Y ²¹ in formula (2), respectively, and preferred embodiments are also the same. Y ¹⁷² , Y ¹⁷³ and W ¹⁷¹ have the same ^meanings as Y ⁹¹ , Y ⁹² and W ^{91 in the} above formula (9), respectively, and preferred embodiments are also the same. p is synonymous with p of the said Formula (1), and its preferable aspect is also the same.

In the structures represented by the formulas (13) to (17), any of the two condensed aromatic rings linked by a single bond may be an alkyl group (preferably having a carbon number of 1 to 30, more preferably 3 to 28 carbon atoms, more preferably 6 to 24 carbon atoms, particularly preferably a branched or straight chain alkyl group having 8 to 24 carbon atoms, an alkenyl group (preferably 2 to 30 carbon atoms, more Preferably, it has 3 to 28 carbon atoms, more preferably 6 to 24 carbon atoms, particularly preferably a branched or straight chain alkenyl group having 8 to 24 carbon atoms, and an alkynyl group (preferably 2 to 30 carbon atoms, more preferably A branched or straight-chain alkynyl group having 3 to 28 carbon atoms, more preferably 6 to 24 carbon atoms, particularly preferably 8 to 24 carbon atoms, and at least one group. At least one group selected from the alkyl group, alkenyl group, and alkynyl group that the condensed aromatic ring has may be directly linked to a ring member atom or may be bonded via a linking group.

When the organic semiconductor compound used in the present invention takes any one of the above formulas (13) to (17), the following (a) to (e) corresponding to each of the above formulas (13) to (17) It is more preferable to take the form.
(A) In the above formula (13), R ¹³¹ and R ¹³² are alkyl groups, alkenyl groups, or alkynyl groups having 6 to 24 carbon atoms, and have no other aliphatic groups having 6 or more carbon atoms (b ) In the above formula (14), at least one of Y ¹⁴³ and Y ¹⁴⁴ is-(CL ⁷¹ -R ⁷² ) = in the formula (7) to be referred to, and R ¹⁴¹ and R ⁷² have 6 carbon atoms. An alkyl group, an alkenyl group or an alkynyl group having ˜24 and no other aliphatic group having 6 or more carbon atoms (c) In the above formula (15), W ¹⁵¹ is —NR ¹⁵³ —, CR ¹⁵⁴ R ¹⁵⁵ -, ^or> a ^{C =} CR ^{156 R ^157,} an alkyl group of ^{R 151} and ^R 153 ^{~ R 157} is from 6 to 24 carbon atoms, alkenyl or alkynyl group having 6 or more aliphatic carbons is otherwise In embodiments without (d) is the formula ^{(16), Y 164} is, in the reference to Equation ^{(8) - (C-L} 81 -R 82) = a ^A, carbon atoms ^{R 161} and ^{R 82} is 6 An alkyl group, an alkenyl group or an alkynyl group having from 24 to 24 and no other aliphatic group having 6 or more carbon atoms (e) In the above formula (17), W ¹⁷¹ is —NR ¹⁷³ or —CR ¹⁷⁴ R ^175- , wherein R ¹⁷¹ and R ¹⁷³ to R ¹⁷⁵ are an alkyl group, alkenyl group or alkynyl group having 6 to 24 carbon atoms and no other aliphatic group having 6 or more carbon atoms

The organic semiconductor compounds in the forms (a) to (e) described above are an alkyl group, alkenyl group or alkynyl group (hereinafter referred to as an alkyl chain or the like) having a specific carbon number or more in a direction perpendicular to the main chain direction of the organic semiconductor compound Said). Furthermore, the organic semiconductor compound of the present invention has high structural regularity because both the donor structural unit and the acceptor structural unit have a side-chain direction condensed ring structure. As a result, as shown in the following examples, in addition to the main chain portion, alkyl chains and the like can also be closely overlapped (packing) (see the packing form shown on the right side of the arrow in the following examples). Thereby, it is considered that the organic semiconductor compound of the present invention has high crystallinity and improved carrier mobility. As a result, it is considered that carrier mobility and solubility can be achieved at a high level.

The side chain represented by R represents a soluble group such as an alkyl group, an alkenyl group, or an alkynyl group. In the packing form shown on the right side of the above example, R is a straight chain extending vertically. p represents the number of repeating units. In addition, R does not need to be a straight chain and may be a branched chain.

On the other hand, in an organic semiconductor compound having an aromatic ring having a main chain direction condensed ring structure as a donor structural unit, as shown in the following example, the donor structural unit has a main chain direction condensed ring structure, and acceptor properties The structural unit is a side chain direction condensed ring structure. For this reason, structural regularity is low and soluble groups, such as an alkyl group, cannot overlap closely (refer to the form on the right side of the arrow in the following examples).

The weight average molecular weight of the organic semiconductor compound used in the present invention is preferably from 5,000 to 1,000,000, and more preferably from 10,000 to 1,000,000. The weight average molecular weight is measured using a GPC (gel filtration chromatography) method. The molecular weight is a weight average molecular weight in terms of polystyrene. The gel packed in the column used in the GPC method is preferably a gel having an aromatic compound as a repeating unit, and examples thereof include a gel made of a styrene-divinylbenzene copolymer. Two to six columns are preferably connected and used. Solvents used include halogen solvents such as chloroform, aromatic solvents such as toluene, chlorobenzene, 1,2-dichlorobenzene and trichlorobenzene, ether solvents such as tetrahydrofuran, and amide solvents such as N-methylpyrrolidone. An aromatic solvent is preferable from the viewpoint of the solubility of the compound. The measurement is preferably performed at a solvent flow rate in the range of 0.1 to 2 mL / min, and more preferably in the range of 0.5 to 1.5 mL / min. The measurement temperature is appropriately changed depending on the boiling point of the solvent, but it is preferably 10 to 200 ° C., more preferably 20 to 150 ° C. The column and carrier to be used can be selected according to the physical properties of the polymer compound to be measured. In the present invention, the column: TSK-GEL SUPER H-RC 6.0 * 150 + TSK-GEL BMHHR-H (20) 7.8 * 300 (two), solvent: 1,2-dichlorobenzene, temperature: 145 ° C. Flow rate: sample side: 1 mL / min, reference side: determined at 0.5 mL / min.

Specific examples of the organic semiconductor compound represented by the above formula (1) are shown below, but the present invention is not limited thereto. In the following formula, p represents the number of repeating units. Me represents methyl.

The method for synthesizing the compound of the present invention is not particularly limited, and can be synthesized with reference to various known methods. For example, the compound represented by the formula (1) or the formula (4) is a coupling reaction of the compounds represented by (M1) to (M6) as in the following formula (for example, Chemical Reviews, 2002, Volume 102). 1359, Chemical Reviews, 2011, 111, 1493, Journal of Materials of Chemistry, 2004, 14, 11, etc.).

Specifically, Negishi coupling using transition metal catalyst, zinc reactive agent, right-Kosugi-Still coupling using tin reactant, Suzuki-Miyaura coupling using boron reactant, magnesium reactant It can be synthesized using Kumada-Tamao-Coriu coupling, cross coupling such as Ulsan coupling using a silicon reagent, Ullmann reaction using copper, Yamamoto polymerization using nickel, and the like. In the present invention, it is more preferable to use the Ueda-Kosugi-Still coupling and the Suzuki-Miyaura coupling. As the transition metal catalyst, metals such as palladium, nickel, copper, cobalt, and iron (Journal of the American Chemical Society, 2007, Vol. 129, page 9844) can be used. The metal may have a ligand, such as PPh ₃ , P (t-Bu) ₃ , P (o-tol) ₃ , P (2-furyl) ₃ , S-Phos, X-Phos, etc. A phosphorus ligand, an N-heterocyclic carbene ligand (Angewandte Chemie International Edition, 2002, 41, 1290) and the like are preferably used. The reaction may be performed under microwave irradiation as described in Macromolecular Rapid Communications, 2007, 28, 387.
Here, when M ¹ and M ² are a trialkyltin group, a trialkylsilyl group, or —B (OR ^α ) ₂ , M ³ and M ⁴ are a halogen atom or a perfluoroalkanesulfonyloxy group. When M ¹ and M ² are a halogen atom or a perfluoroalkanesulfonyloxy group, M ³ and M ⁴ are a trialkyltin group, a trialkylsilyl group, or —B (OR ^α ) ₂ . R ^α represents a hydrogen atom or an alkyl group. R ^α may be linked to form a ring.

The terminal group of the organic semiconductor compound of the present invention is a hydrogen atom, or a trialkyltin group, a trialkylsilyl group, -B (OR ^α ) ₂ derived from the monomer used for synthesis (where R ^α is a hydrogen atom or An alkyl group), a halogen atom, or a perfluoroalkanesulfonyloxy group. Alternatively, an aryl group or a heteroaryl group may be used as a terminal group by performing capping described below.
In addition, capping may be performed by adding a compound represented by Ar—V ¹ after polymerization and reacting with a polymer terminal. Here, Ar represents an aryl group (for example, phenyl group, naphthyl group, tolyl group, etc.) or a heteroaryl group (for example, thienyl group, thiazolyl group, furyl group, pyridyl group, etc.). Ar may have a substituent such as an alkyl group, an alkenyl group, an alkynyl group, an acyl group, an alkoxycarbonyl group, an acyloxy group, or a halogen atom.
V ¹ is a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), perfluoroalkanesulfonyloxy group (eg, trifluoromethanesulfonyloxy group, nonafluorobutanesulfonyloxy group), trialkyltin A group (for example, trimethylstannyl group, tributylstannyl group, etc.), a trialkylsilyl group (for example, trimethylsilyl group, triethylsilyl group, etc.), and —B (OR ^x ) ₂ . Here, R ^x represents a hydrogen atom or an alkyl group. R ^x may be linked to form a ring.

There are no particular limitations on the method of synthesizing the metal reactants and halides such as tin reactants and boron reactants represented by (M1) to (M6), which are the raw materials, and they are synthesized according to various arbitrary methods. Can do. For example, the tin reactant is Journal of the American Chemistry, 2009, 131, 7792, the Journal of the American Chemistry, 2008, 130, 16144, the European Patent Application No. 2407465, and the boron reactant is Journal. American Chemistry, 2012, 134, 539 and the like, and halogenated compounds can be synthesized with reference to Journal of American Chemical Society 2009, 131, 7792-7799 and the like.
The method for synthesizing the compound in which the bond of the group represented by A in Formula (2), Formula (3), or Formula (1) and (4) is replaced with a hydrogen atom is not particularly limited, and various arbitrary methods Can be synthesized.
Compounds in which the bond of the group represented by the formula (2) is changed to a hydrogen atom include, for example, Journal of Polymer Science, part A; Polymer Chemistry, 2011, 49, 3260-3271, Tetrahedron Letters 2010, 50, 2089- It can be synthesized with reference to the method described on page 2091.
Compounds in which the bond of the group represented by formula (3) is changed to a hydrogen atom include, for example, Journal of Materials Chemistry 2012, 22, 23514-23524, Journal of Organic Chemistry 2002, 67, 9073-9076, Chemist of Materials 2012, 45, 4069-4074, Tetrahedron 1998, 54, 7075-7080, and the like.
Examples of the compound in which the bond of the group represented by A is changed to a hydrogen atom or a halogen atom include, for example, Journal of American Chemical Society 2010, 132, 5330-5331 (imide), JP 2012-214621 A, Macromolecules 2011. , 44, 7184-7187 (thienothiazole), Chemistry of Materials 2010, 22, 2978-2987 (triazole), Journal of American Chemical Society 2009, 131, 7206-7207, pyrrole of benzene, ul 20 45, 4069-4074, Dyes and Pigments 2013, 96, 61. -625 pages, the method described in international patent 2011/28827 can be synthesized with reference.

[Organic semiconductor devices]
The organic semiconductor device of the present invention is not particularly limited as long as the semiconductor layer contains the organic semiconductor compound of the present invention. For example, transistors, photoelectric conversion devices, organic thermoelectric conversion devices, photodetectors (for example, infrared photodetectors), photovoltaic detectors, imaging devices (for example, RGB imaging devices for cameras or medical imaging systems), light emission Diodes (LEDs) (eg, organic LEDs, or infrared or near infrared LEDs), laser elements, conversion layers (eg, layers that convert visible emission to infrared emission), telecommunications amplifiers and radiators (eg, , Fiber dopants), storage elements (eg holographic storage elements), and electrochromic elements (eg electrochromic displays). Especially, it is preferable that they are an organic thin-film transistor, an organic photoelectric conversion device, or an organic thermoelectric conversion device.

(Organic thin film transistor)
The organic thin film transistor of the present invention has a semiconductor layer containing the organic semiconductor compound of the present invention.
The organic thin film transistor of the present invention may further include other layers in addition to the semiconductor layer.
The organic thin film transistor of the present invention is preferably used as an organic field effect transistor (FET), and more preferably used as an insulated gate FET in which a gate-channel is insulated.
Hereinafter, although the aspect of the preferable structure of the organic thin-film transistor of this invention is demonstrated in detail using drawing, this invention is not limited to these aspects.

<Laminated structure>
There is no restriction | limiting in particular as a laminated structure of an organic field effect transistor, It can be set as the thing of arbitrary various structures.
As an example of the structure of the organic thin film transistor of the present invention, there is a structure (bottom gate / top contact type) in which an electrode, an insulator layer, an organic semiconductor layer, and two electrodes are sequentially arranged on the upper surface of the lowermost substrate. it can. In this structure, the electrode disposed on the upper surface of the lowermost substrate is disposed on a part of the substrate, and the insulator layer is disposed so as to be in contact with the substrate at a portion other than the portion where the electrode is disposed. Further, the two electrodes provided on the upper surface of the semiconductor layer are arranged separately from each other.
The structure of the bottom-gate / top-contact transistor is shown in FIG. FIG. 1 is a schematic view showing a cross section of an example of the structure of the organic thin film transistor of the present invention. The organic thin film transistor of FIG. 1 has a substrate 11 disposed in the lowermost layer, an electrode 12 is provided on a part of the upper surface thereof, and further covers the electrode 12 and is in contact with the substrate 11 at a portion other than the electrode 12. 13 is provided. Further, a semiconductor layer 14 is provided on the upper surface of the insulator layer 13, and the two

electrodes

15a and 15b are disposed separately on a part of the upper surface.
In the organic thin film transistor 1 shown in FIG. 1, the electrode 12 is a gate, and the

electrodes

15a and 15b are drains or sources, respectively. The organic thin film transistor 1 shown in FIG. 1 is an insulated gate FET in which a channel that is a current path between a drain and a source is insulated from a gate.

Another example of the structure of the organic thin film transistor of the present invention is a bottom gate / bottom contact type element.
The structure of the bottom gate / bottom contact transistor is shown in FIG. FIG. 2 is a schematic view showing a cross section of the structure of an organic thin film transistor manufactured as a substrate for measuring FET characteristics in an example of the present invention. In the organic thin film transistor of FIG. 2, the substrate 21 is disposed in the lowermost layer, the electrode 22 is provided on a part of the upper surface thereof, the electrode 22 is further covered, and the insulating layer is in contact with the substrate 21 at a portion other than the electrode 22. 23 is provided. Further, the semiconductor layer 24 is provided on the upper surface of the insulator layer 23, and the

electrodes

25 a and 25 b are below the semiconductor layer 24.
In the organic thin film transistor 2 shown in FIG. 2, the electrode 22 is a gate, and the electrode 25a and the electrode 25b are a drain or a source, respectively. The organic thin film transistor 2 shown in FIG. 2 is an insulated gate FET in which a channel that is a current path between a drain and a source is insulated from a gate.

The structure of the organic thin film transistor of the present invention is preferably a top gate / top contact type element having an insulator and a gate electrode above the semiconductor layer, or a top gate / bottom contact type element in addition to the above example.

<Thickness>
When the organic thin film transistor of the present invention needs to be a thinner transistor, it is preferable that the thickness of the entire transistor is, for example, 0.1 to 0.5 μm.

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

<Board>
-material-
The organic thin film transistor of the present invention preferably includes a substrate.
There is no restriction | limiting in particular as a material of the said board | substrate, Arbitrary materials can be used. For example, polyester films such as polyethylene naphthoate (PEN) and polyethylene terephthalate (PET), cycloolefin polymer films, polycarbonate films, triacetyl cellulose (TAC) films, polyimide films, and these polymer films were bonded to ultrathin glass. Can be mentioned, ceramic, silicon, quartz, glass, etc., with silicon being preferred.

<Electrode>
-material-
The organic thin film transistor of the present invention preferably includes an electrode.
Examples of the constituent material of the electrode include metal materials such as Cr, Al, Ta, Mo, Nb, Cu, Ag, Au, Pt, Pd, In, Ni, and Nd, alloy materials thereof, carbon materials, and conductive materials. Any known conductive material such as a conductive polymer can be used without particular limitation.

-thickness-
The thickness of the electrode is not particularly limited, but is preferably 10 to 50 nm.
There is no particular limitation on the gate width (or channel width) W and the gate length (or channel length) L. These ratios W / L are preferably 10 or more, and more preferably 20 or more.

<Insulator layer>
-material-
The material constituting the insulator layer is not particularly limited as long as a necessary insulating effect is obtained. For example, fluoropolymer insulating materials such as silicon dioxide, silicon nitride, PTFE, CYTOP, polyester insulating materials, polycarbonate insulating materials, acrylic polymer insulating materials, epoxy resin insulating materials, polyimide insulating materials, polyvinylphenol resin insulating materials, Examples include polyparaxylylene resin-based insulating materials.
The top surface of the insulator layer may be surface-treated. For example, an insulator layer in which the surface of silicon dioxide is surface-treated by application of hexamethyldisilazane (HMDS) or octadecyltrichlorosilane (OTS) can be preferably used.

-thickness-
There is no particular limitation on the thickness of the insulator layer. When thinning is required, the thickness is preferably 10 to 400 nm, more preferably 20 to 200 nm, and particularly preferably 50 to 200 nm.

<Semiconductor layer>
-material-
The organic thin film transistor of the present invention is characterized in that the semiconductor layer contains the organic semiconductor compound of the present invention.
The semiconductor layer may be a layer made of the organic semiconductor compound of the present invention. Or in addition to the organic-semiconductor compound of this invention, the layer further contained the below-mentioned low molecular organic semiconductor and the below-mentioned polymer may be sufficient. Moreover, the residual solvent at the time of film-forming may be contained.
Examples of the low molecular organic semiconductor include compounds in which a benzene ring, a thiophene ring, a furan ring, a pyrrole ring, a thiazole ring, a selenophene ring, a thiadiazole ring, an oxadiazole ring, and the like are condensed or connected. For example, anthracene, tetracene, pentacene, hexacene, heptacene, chrysene, picene, fluorene, pyrene, peropyrene, perylene, terylene, quaterylene, coronene, ovalene, circumcamanthracene, bisanthene, zestrene, heptazesulene, pyranthrene, violanthene, isoviolanthene, Polycyclic aromatic hydrocarbons such as circobiphenyl, polycyclic heteroaromatic hydrocarbon compounds such as anthradithiophene, benzodithiophene, naphthodithiophene, benzothienobenzothiophene, dinaphthothienothiophene, porphyrin and copper phthalocyanine, and these And derivatives and precursors thereof.

Examples of the polymer include insulating polymers such as polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyimide, polyurethane, polysiloxane, polysulfone, polymethyl methacrylate, polymethyl acrylate, cellulose, polyethylene, and polypropylene, and their co-polymers. Examples thereof include photoconductive polymers such as coalescence, polyvinyl carbazole, and polysilane, conductive polymers such as polythiophene, polypyrrole, polyaniline, and polyparaphenylene vinylene, and semiconductor polymers.
The above low molecular organic semiconductors and polymers may be used alone or in combination of two or more.
In addition, the organic semiconductor compound of the present invention and the polymer may be homogeneously mixed, or a part or all of them may be phase separated. The organic semiconductor compound and the polymer are preferably phase-separated in the film thickness direction. The phase separation can prevent the charge transfer of the organic semiconductor from being hindered by the polymer.
There is no restriction | limiting in particular in content of the low molecular organic semiconductor and polymer in the said semiconductor layer. It is preferably used in the range of 0 to 95% by mass, more preferably 10 to 90% by mass, further preferably 20 to 80% by mass, and particularly preferably 30 to 70% by mass.

-thickness-
There is no particular limitation on the thickness of the semiconductor layer. When thinning is required, the thickness is preferably 10 to 400 nm, more preferably 10 to 200 nm, and particularly preferably 10 to 100 nm.

<Film formation method>
In order to form a semiconductor layer, the organic semiconductor compound of the present invention is preferably formed on the surface of a substrate or the like. Any film forming method may be used.
During film formation, a substrate to be formed may be heated or cooled. By changing the temperature of the substrate or the like, the film quality and molecular packing in the film can be controlled to some extent. There is no restriction | limiting in particular as temperature of the board | substrate etc. which form into a film. It is preferably between 0 ° C. and 200 ° C., more preferably between 15 ° C. and 100 ° C., and particularly preferably between 20 ° C. and 95 ° C.
When the organic semiconductor compound of the present invention is formed on the surface of a substrate or the like, it is preferably formed by a vacuum process or a solution process.

Examples of film formation by a vacuum process include vacuum vapor deposition, sputtering, ion plating, physical vapor deposition such as molecular beam epitaxy (MBE), or chemical vapor deposition (CVD) such as plasma polymerization. It is particularly preferable to use a vacuum deposition method.

Here, film formation by solution process refers to a method of preparing a composition in which the organic semiconductor compound of the present invention is dissolved in an organic solvent, applying the composition, and forming the film. Specifically, coating methods such as casting method, dip coating method, die coater method, roll coater method, bar coater method (bar coating method), spin coating method, ink jet method, screen printing method, gravure printing method, flexography Various printing methods such as a printing method, an offset printing method, a microcontact printing method, and a normal method such as a Langmuir-Blodgett (LB) method can be used. It is particularly preferable to use a casting method, a bar coater method, a spin coating method, an ink jet method, a gravure printing method, a flexographic printing method, an offset printing method, or a microcontact printing method.
When the semiconductor layer of the organic thin film transistor of the present invention contains a polymer, this semiconductor layer is obtained by dissolving or dispersing at least the organic semiconductor compound of the present invention and the polymer in an appropriate organic solvent ( The coating solution is preferably formed by various coating methods.
Hereinafter, the coating solution that can be used for film formation by a solution process will be described.

-Coating solution-
Examples of the organic solvent used in the coating solution include hydrocarbon solvents such as hexane, octane, decane, toluene, xylene, mesitylene, ethylbenzene, decalin, and 1-methylnaphthalene, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Ketone solvents such as dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene, chlorotoluene, trichlorobenzene, 1-chloronaphthalene and other halogenated hydrocarbon solvents, ethyl acetate, Esters such as butyl acetate and amyl acetate, methanol, propanol, butanol, pentanol, hexanol, cyclohexanol, methyl cellosolve, Alcohol solvents such as tilcellosolve, ethylene glycol, ether solvents such as dibutyl ether, tetrahydrofuran, dioxane, anisole, N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone, 1-methyl Examples include amide / imide solvents such as -2-imidazolidinone, sulfoxide solvents such as dimethyl sulfoxide, and nitrile solvents such as acetonitrile and benzonitrile. A solvent may be used individually by 1 type and may be used in combination of multiple types. Among these, hydrocarbon solvents, halogenated hydrocarbon solvents or ether solvents are preferred, and toluene, xylene, mesitylene, tetralin, chloroform, chlorobenzene, dichlorobenzene or trichlorobenzene are more preferred. The concentration of the organic semiconductor compound in the coating solution is preferably 0.1 to 80% by mass, more preferably 0.1 to 10% by mass, and particularly preferably 0.5 to 10% by mass.

(Organic photoelectric conversion device)
FIG. 3 is a side view schematically showing an example of the organic photoelectric conversion device of the present invention. The photoelectric conversion device 3 of this embodiment includes a photoelectric conversion layer 33 containing the organic semiconductor compound of the present invention. The photoelectric conversion layer of an organic photoelectric conversion device generally includes a p-type organic semiconductor and an n-type organic semiconductor, and a pn two-layer junction or a pin three-layer junction type and a bulk heterojunction type depending on the junction form. are categorized. The photoelectric conversion layer of the organic photoelectric conversion device of the present invention may be in any of these forms. FIG. 3 shows a bulk heterojunction photoelectric conversion layer 33. By providing a bulk heterojunction photoelectric conversion layer, higher power generation efficiency can be obtained more easily.

The organic photoelectric conversion device of the present invention contains the organic semiconductor compound of the present invention as a p-type organic semiconductor in the photoelectric conversion layer 33 (semiconductor layer). The photoelectric conversion layer 33 is provided between the first electrode 35 and the second electrode 31.
In the present invention, it is preferable to provide the hole transport layer 34 between the first electrode 35 and the photoelectric conversion layer 33. In addition, it is preferable to provide the electron transport layer 32 between the second electrode 31 and the photoelectric conversion layer 33. By providing the hole transport layer 34 and the electron transport layer 32, it is possible to more efficiently take out the charges generated in the photoelectric conversion layer 33. In the photoelectric conversion element of the present invention, the distinction between the upper and lower sides is not particularly important, but the first electrode 35 side is positioned as “up” or “top” side and the second electrode 31 side is “ Position it as “bottom” or “bottom”.

Here, in order from the upper layer, the configuration of the substrate, the positive electrode, the hole transport layer, the photoelectric conversion layer, the electron transport layer, and the negative electrode is referred to as the forward configuration, and the substrate, the negative electrode, the electron transport layer, the photoelectric conversion layer, and the hole transport in order from the upper layer The configuration of the layer and the positive electrode is referred to as a reverse configuration. In the present invention, both forward and reverse configurations are preferably applied.

In the photoelectric conversion layer 33, it is preferable that the p-type organic semiconductor and the n-type organic semiconductor phase are mixed in a specific form as described above. In this case, photoelectric conversion (charge separation) is performed at the interface between the p-type organic semiconductor and the n-type organic semiconductor. In the bulk heterojunction photoelectric conversion layer, as shown in FIG. 3, the phases are interdigitated in a nanometer order. In order to effectively create such a form, it is preferable that the p-type organic semiconductor has a specific compatibility or incompatibility with the n-type organic semiconductor. The material that becomes the p-type semiconductor is not determined only by the specific physical properties, but is specified by the relative relationship with the material that becomes the n-type semiconductor. For example, when a typical fullerene is taken as an example of an n-type semiconductor material, a material having a higher electron donating property can be a p-type semiconductor material.
The organic photoelectric conversion device of the present invention is preferably used as an organic thin film solar cell.

<Members of organic photoelectric conversion device>
-N-type organic semiconductor-
The n-type organic semiconductor is not particularly limited. In general, it is a π-electron conjugated compound having a lowest unoccupied orbital (LUMO) level of −3.5 to −4.5 eV. For example, fullerene or a derivative thereof, octaazaporphyrin, etc., a perfluoro compound in which a hydrogen atom of a p-type organic semiconductor is substituted with a fluorine atom (for example, perfluoropentacene or perfluorophthalocyanine), naphthalenetetracarboxylic anhydride, naphthalenetetracarboxylic Examples thereof include aromatic carboxylic acid anhydrides such as acid diimide, perylene tetracarboxylic acid anhydride, and perylene tetracarboxylic acid diimide, and polymer compounds containing an imidized product thereof as a skeleton.

Among these n-type organic semiconductors, fullerene or a derivative thereof is preferable because charge separation can be performed at high speed and efficiently from the organic semiconductor compound of the present invention.
The fullerene or its _{derivatives, C 60} _{fullerene, C 70} _{fullerene, C 76} _{fullerene, C 78} _{fullerene, C 84} _{fullerene, C 240} _{fullerenes, C 540} fullerenes, mixed fullerenes, fullerene nanotubes, and some of these hydrogen atoms , Fullerene derivatives substituted by halogen atoms, substituted or unsubstituted alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroaryl groups, cycloalkyl groups, silyl groups, ether groups, thioether groups, amino groups, silyl groups, etc. Can be mentioned.

Preferred fullerene derivatives are phenyl-C ₆₁ -butyric acid ester, diphenyl-C ₆₂ -bis (butyric acid ester), phenyl-C ₇₁ -butyric acid ester, phenyl-C ₈₅ -butyric acid ester or thienyl-C ₆₁ -butyric acid ester, The preferred number of carbon atoms in the alcohol portion of the butyric acid ester is 1-30, more preferably 1-8, still more preferably 1-4, and most preferably 1.

Examples of preferred fullerene derivatives include phenyl-C ₆₁ -butyric acid methyl ester ([60] PCBM), phenyl-C ₆₁ -butyric acid n-butyl ester ([60] PCBnB), phenyl-C ₆₁ -butyric acid isobutyl ester ([60 PCBiB), phenyl-C ₆₁ -butyric acid n-hexyl ester ([60] PCBH), phenyl-C ₆₁ -butyric acid n-octyl ester ([60] PCBO), diphenyl-C ₆₂ -bis (butyric acid methyl ester) ( Bis [60] PCBM), phenyl-C ₇₁ -butyric acid methyl ester ([70] PCBM), phenyl-C ₈₅ -butyric acid methyl ester ([84] PCBM), thienyl-C ₆₁ -butyric acid methyl ester ([60] ThCBM) _{), C 60} pyrrolidine tris _{acids, C 60} pyrrolidine tris San'e Glycol ester, N- methyl hula b pyrrolidine _(MP-C 60), (1,2 methanofullerene _C 60) -61- carboxylic acid, (1,2-methanofullerene _C 60) -61- carboxylic acid t- butyl ester And fullerene having a cyclic ether group such as US Pat. No. 7,329,709, and the like.

-P-type organic semiconductor-
The organic semiconductor compound of the present invention is used for the photoelectric conversion layer of the photoelectric conversion device of the present invention. Other p-type organic semiconductors (for example, condensed polycyclic aromatic low molecular weight compounds, oligomers or polymers) may be contained.

Examples of the condensed polycyclic aromatic low-molecular compound that is a p-type organic semiconductor include, for example, anthracene, tetracene, pentacene, hexacene, heptacene, chrysene, picene, fluorene, pyrene, peropyrene, perylene, terylene, quaterylene, coronene, ovalene, circumcam Compounds such as anthracene, bisanthene, zeslen, heptazesulene, pyranthrene, violanthene, isoviolanthene, sacobiphenyl, anthradithiophene, porphyrin, copper phthalocyanine, tetrathiafulvalene (TTF) -tetracyanoquinodimethane (TCNQ) complex, bis Examples thereof include ethylenetetrathiafulvalene (BEDTTTTF) -perchloric acid complex, and derivatives and precursors thereof.

-Photoelectric conversion layer-
In the present invention, it is preferable that the photoelectric conversion layer (semiconductor layer) contains a p-type organic semiconductor as an electron donating material and an n-type organic semiconductor as an electron accepting material in a ratio showing a desired photoelectric conversion efficiency. Usually, the content of both is selected from the range of mass ratio, p-type: n-type = 10: 90 to 90:10, preferably 20:80 to 80:20. There is no restriction | limiting in particular in the formation method of a photoelectric converting layer, The film-forming method demonstrated in the above-mentioned organic thin-film transistor is employable. A coating method is preferable in order to increase the area of the interface where holes and electrons are separated by charge and to have high photoelectric conversion efficiency. As a coating solution used for the coating method, it is preferable to use a composition in which at least the organic semiconductor compound of the present invention and an n-type organic semiconductor are dissolved or dispersed in an organic solvent. The organic solvent used in the coating solution, the content of the organic semiconductor compound of the present invention in the coating solution is the organic solvent that can be used in the coating solution described in the organic thin film transistor and the organic semiconductor compound in the coating solution described in the organic thin film transistor. The content of can be adopted.

Here, for the purpose of promoting the phase separation of the electron donating region (donor) and the electron accepting region (acceptor) in the photoelectric conversion layer, crystallization of the organic material contained in the photoelectric conversion layer, and transparency of the electron transport layer, etc. You may heat-process (anneal) by the method. In the case of a dry film formation method such as vapor deposition, for example, there is a method in which the substrate temperature during film formation is heated to 30 ° C. to 150 ° C. In the case of a wet film forming method such as printing or coating, there is a method of setting the drying temperature after coating to 30 ° C. to 250 ° C. Further, it may be heated to 30 ° C. to 250 ° C. after the subsequent step, for example, the formation of the metal negative electrode is completed. By promoting phase separation, a charge transport path may be formed, and the photoelectric conversion efficiency may be improved. The thickness of the photoelectric conversion layer is preferably 30 to 1000 nm, and more preferably 50 to 600 nm.
In the present invention, a plurality of photoelectric conversion layers may be provided, but the photoelectric conversion layer is preferably a single layer.

-electrode-
The organic photoelectric conversion device according to the present invention has at least a first electrode and a second electrode. One of the first electrode and the second electrode is a positive electrode, and the rest is a negative electrode. Further, when a tandem configuration is adopted, the tandem configuration can be achieved by using an intermediate electrode. In the present invention, an electrode through which holes mainly flow is referred to as a positive electrode, and an electrode through which electrons mainly flow is referred to as a negative electrode. From the functional aspect of whether or not there is translucency, an electrode having translucency is referred to as a transparent electrode, and an electrode having no translucency is referred to as a counter electrode or a metal electrode. In the forward configuration of the present invention, the positive electrode is a translucent transparent electrode, and the negative electrode is a non-translucent counter electrode or metal electrode. In the reverse configuration, the negative electrode is a translucent transparent electrode, and the positive electrode is a non-translucent counter electrode or metal electrode. Both the first electrode and the second electrode can be transparent electrodes.

--First electrode--
The first electrode is a positive electrode. In the case of a photoelectric conversion device having a forward configuration, it is preferably a transparent electrode that transmits light from visible light to near infrared light (380 to 800 nm). Examples of the material include transparent conductive metal oxides such as indium tin oxide (ITO), indium zinc oxide (IZO), indium tungsten oxide (IWO), tin oxide, zinc oxide, and indium oxide, magnesium, aluminum, calcium, For example, ultrathin films of metal and metal alloys such as titanium, chromium, manganese, iron, copper, zinc, strontium, silver, indium, tin, barium, and bismuth, metal nanowires, and carbon nanotubes can be used. It is also possible to use a mesh electrode in which a metal such as silver is meshed to ensure light transmission. Also, a conductive material selected from the group consisting of polypyrrole, polyaniline, polythiophene, polythienylene vinylene, polyazulene, polyisothianaphthene, polycarbazole, polyacetylene, polyphenylene, polyphenylene vinylene, polyacene, polyphenylacetylene, polydiacetylene and polynaphthalene. A functional polymer can also be used. In addition, a plurality of these conductive compounds can be combined to form a positive electrode. In the case of a transparent electrode with a forward configuration, the transmittance of the positive electrode is the thickness used for solar cells (for example, 0.2 μm thickness), and the average light transmittance in the wavelength region of 380 nm to 800 nm is 75% or more. It is preferably some 85% or more. If light transmittance is not required in the reverse configuration, metals such as chromium, cobalt, nickel, copper, molybdenum, palladium, silver, tantalum, tungsten, platinum, gold, alloys thereof, transparent conductive oxide, polyaniline The positive electrode can be formed of a conductive polymer such as polythiophene or polypyrrole. Details of suitable conductive polymer layers are disclosed in JP 2012-43835 A, polythiophene derivatives are preferable, and polyethylenedioxythiophene-polystyrene sulfonic acid (PEDOT-PSS) is more preferable. These metals, transparent conductive oxides, and conductive polymers may be used alone, or two or more kinds may be mixed or laminated.

--Second electrode--
In the present invention, the second electrode is a negative electrode. The negative electrode may be a conductive material single layer. Or in addition to the material which has electroconductivity, you may use together resin which hold | maintains these. As the conductive material for the negative electrode, a material having a small work function (4 eV or less) metal, alloy, electrically conductive compound, and a mixture thereof as an electrode material is used. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like. Among these, from the viewpoint of electron extraction performance and durability against oxidation, etc., a mixture of these metals and a second metal which is a stable metal having a larger work function value than this, for example, a magnesium / silver mixture, magnesium / Aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred. The negative electrode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The film thickness is usually selected in the range of 10 nm to 5 μm, preferably 50 to 200 nm.

In the case of the reverse configuration, the second electrode is a transparent electrode. A transparent electrode that transmits light from visible light to near infrared light (380 to 800 nm) is preferable, and examples thereof include metals, metal oxides, conductive polymers, mixtures thereof, and laminated structures. Specific examples include transparent conductive oxides such as tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), and indium tungsten oxide (IWO), magnesium, aluminum, calcium, titanium, Examples thereof include ultrathin films of metals and metal alloys such as chromium, manganese, iron, copper, zinc, strontium, silver, indium, tin, barium, and bismuth, and conductive polymers such as polyaniline, polythiophene, and polypyrrole. Particularly preferable materials for the transparent conductive oxide are ITO, IZO, tin oxide, antimony-doped tin oxide (ATO), fluorine-doped tin oxide (FTO), zinc oxide, antimony-doped zinc oxide (AZO), and gallium-doped oxide. Zinc (GZO) can be used. In the case of a transparent electrode with a reverse configuration, the transmittance of the negative electrode is the thickness used for solar cells (eg, 0.2 μm thickness), and the average light transmittance in the wavelength region of 380 nm to 800 nm is 75% or more. It is preferably some 85% or more.

If a metal material is used as the negative electrode conductive material of the forward configuration and the positive electrode conductive material of the reverse configuration, the light reaching the metal electrode is reflected and reflected to the photoelectric conversion layer side, and the reflected light is absorbed again. Is preferable. The metal electrode may be a metal (eg, gold, silver, copper, platinum, rhodium, ruthenium, aluminum, magnesium, indium, etc.), carbon nanoparticle, nanowire, or nanostructure. A dispersion is preferable because a transparent and highly conductive negative electrode can be formed by a coating method.
Further, when the metal electrode side is made light transmissive, for example, a conductive material suitable for the negative electrode such as aluminum and aluminum alloy, silver and silver compound is formed in a thin film thickness of about 1 to 20 nm, and then the positive electrode is formed. A light-transmitting negative electrode can be obtained by providing the conductive light-transmitting material film mentioned in the description.

-Hole transport layer-
In the present invention, it is preferable to provide a hole transport layer between the first electrode and the photoelectric conversion layer. Examples of the conductive polymer that forms the hole transport layer include polythiophene, polypyrrole, polyaniline, polyphenylene vinylene, polyphenylene, polyacetylene, polyquinoxaline, polyoxadiazole, polybenzothiadiazole, and polymers having a plurality of these conductive skeletons. Can be mentioned.
Among these, polythiophene and its derivatives are preferable, and polyethylenedioxythiophene and polythienothiophene are particularly preferable. These polythiophenes are usually partially oxidized in order to obtain conductivity. The electrical conductivity of the conductive polymer can be adjusted by the degree of partial oxidation (doping amount). The larger the doping amount, the higher the electrical conductivity. Since polythiophene becomes cationic by partial oxidation, a counter anion for neutralizing the charge is required. Examples of such polythiophenes include polyethylene dioxythiophene (PEDOT-PSS) with polystyrene sulfonic acid as a counter ion and polyethylene dioxythiophene (PEDOT-TsO) with p-toluenesulfonic acid as a counter anion.
The thickness of the hole transport layer is usually from 0.1 to 500 nm, preferably from 0.5 to 300 nm. The hole transport layer can be suitably formed by any of a wet film formation method by coating or the like, a dry film formation method by PVD method such as vapor deposition or sputtering, a transfer method, or a printing method.

-Electron transport layer-
In the present invention, it is preferable to provide an electron transport layer between the second electrode and the photoelectric conversion layer, a hole transport layer is provided between the first electrode and the photoelectric conversion layer, and the photoelectric conversion layer and the second It is particularly preferable to provide an electron transport layer between the electrodes.
Examples of the electron transport material that can be used for the electron transport layer include an n-type semiconductor compound that is the electron accepting material mentioned in the photoelectric conversion layer, and Electron in Chemical Review, Vol. 107, pages 953 to 1010 (2007). -Listed as Transporting and Hole-Blocking Materials. In the present invention, it is preferable to use an inorganic salt or an inorganic oxide. As the inorganic salt, alkali metal compounds such as lithium fluoride, sodium fluoride, and cesium fluoride are preferable. Various metal oxides are preferably used as materials for electron transport layers having high stability. For example, lithium oxide, magnesium oxide, aluminum oxide, calcium oxide, titanium oxide, zinc oxide, strontium oxide, niobium oxide, ruthenium oxide, indium oxide Zinc oxide and barium oxide. Of these, relatively stable aluminum oxide, titanium oxide, and zinc oxide are more preferable. The thickness of the electron transport layer is usually from 0.1 to 500 nm, preferably from 0.5 to 300 nm. The electron transport layer can be suitably formed by any of a wet film formation method such as coating, a dry film formation method such as vapor deposition and sputtering, a transfer method, and a printing method.

Note that holes generated in the photoelectric conversion layer do not flow to the negative electrode side in the electron transport layer having a HOMO level deeper than the HOMO level of the p-type organic semiconductor used in the photoelectric conversion layer. A hole blocking function having a rectifying effect is provided. More preferably, a material deeper than the HOMO level of the n-type organic semiconductor is used as the electron transport layer. Moreover, it is preferable to use a compound with high electron mobility from the characteristic of transporting electrons. Such an electron transport layer is also referred to as a hole block layer, and it is preferable to use an electron transport layer having such a function. Such materials include phenanthrene compounds such as bathocuproine, n-type semiconductor compounds such as naphthalene tetracarboxylic acid anhydride, naphthalene tetracarboxylic acid diimide, perylene tetracarboxylic acid anhydride, perylene tetracarboxylic acid diimide, and titanium oxide. N-type inorganic oxides such as zinc oxide and gallium oxide, and alkali metal compounds such as lithium fluoride, sodium fluoride, and cesium fluoride can be used. Moreover, the layer which consists of a n-type organic semiconductor single-piece | unit used for the photoelectric converting layer can also be used.

-Support-
In the present invention, the support constituting the photoelectric conversion device includes at least a first electrode (positive electrode), a photoelectric conversion layer, a second electrode (metal negative electrode), and in a more preferred embodiment, the first electrode (positive electrode). , A hole transport layer, a photoelectric conversion layer, an electron transport layer, and a second electrode (metal negative electrode) are not particularly limited as long as they can be formed and held. For example, glass, plastic film, etc. Can be selected as appropriate.

In addition, a conventional layer may be applied to provide an easy adhesion layer / undercoat layer, functional layer, recombination layer, other semiconductor layer, protective layer, gas barrier layer, UV absorption layer, antireflection layer, etc. Good.

(Organic thermoelectric conversion device)
The organic thermoelectric conversion device of this invention has a 1st electrode, an organic thermoelectric conversion layer, and a 2nd electrode on a base material, and a thermoelectric conversion layer contains the organic-semiconductor compound of this invention at least.

The organic thermoelectric conversion device of this invention should just have a 1st electrode, a thermoelectric conversion layer, and a 2nd electrode on a base material, A 1st electrode, a 2nd electrode, and a thermoelectric conversion layer There are no particular limitations on other configurations such as the positional relationship. In the organic thermoelectric conversion device of the present invention, the thermoelectric conversion layer may be disposed on at least one surface so as to be in contact with the first electrode and the second electrode. For example, the aspect in which the thermoelectric conversion layer is sandwiched between the first electrode and the second electrode, that is, the organic thermoelectric conversion device of the present invention has the first electrode, the thermoelectric conversion layer, and the second electrode in this order on the substrate. The aspect which has may be sufficient. Further, the thermoelectric conversion layer is disposed on one surface so as to be in contact with the first electrode and the second electrode, that is, the organic thermoelectric conversion device of the present invention is formed on the substrate so as to be separated from each other. The aspect which has the thermoelectric conversion layer laminated | stacked on the 1st electrode and the 2nd electrode may be sufficient.
As an example of the structure of the organic thermoelectric conversion device of the present invention, the structure of the device shown in FIGS. 4 and 5, the arrows indicate the direction of the temperature difference when using the thermoelectric conversion device.
The thermoelectric conversion device 4 shown in FIG. 4 includes a pair of electrodes including the first electrode 43 and the second electrode 45 on the first base material 42, and the organic semiconductor compound of the present invention between the

electrodes

43 and 45. The thermoelectric conversion layer 44 formed using is provided. A second substrate 46 is disposed on the other surface of the second electrode 45, and the

metal plates

41 and 47 are opposed to each other on the outside of the first substrate 42 and the second substrate 46. Is arranged.
In the organic thermoelectric conversion device of the present invention, a thermoelectric conversion layer containing the organic semiconductor compound of the present invention is provided on a base material via an electrode, and this base material functions as a first base material. Is preferred. That is, the thermoelectric conversion device 4 is provided with the first electrode 43 or the second electrode 45 on the surface of the two base materials 42 and 46 (formation surface of the thermoelectric conversion layer 44), and between these

electrodes

43 and 45. It is preferable that the structure has a thermoelectric conversion layer 44 containing the organic semiconductor compound of the present invention.

In the thermoelectric conversion device 5 shown in FIG. 5, a first electrode 52 and a second electrode 53 are disposed on a first base 51, and a thermoelectric conversion layer 54 containing the organic semiconductor compound of the present invention thereon. Is provided.

One surface of the thermoelectric conversion layer 44 of the thermoelectric conversion device 4 is covered with the first base material 42 via the first electrode 43, and the thermoelectric conversion layer 54 of the thermoelectric conversion device 5 is The surface is covered with the first electrode 52, the second electrode 53, and the first base material 51. From the viewpoint of protecting the thermoelectric conversion layers 44 and 54, it is preferable that the

second substrate

46 or 55 is also bonded to the other surface via the second electrode 45 or without the electrode. That is, it is preferable that the second electrode 45 is formed in advance on the surface of the second substrate 46 used in the thermoelectric conversion device 4 (the pressure contact surface of the thermoelectric conversion layer 44). Further, in the thermoelectric conversion devices 4 and 5, it is preferable to press the electrode and the thermoelectric conversion layer by heating to about 100 ° C. to 200 ° C. from the viewpoint of improving adhesion.

The base material of the organic thermoelectric conversion device of the present invention, the first base material 42 and the second base material 46 in the thermoelectric conversion device 4 may be a base material such as glass, transparent ceramics, metal, or plastic film. In the organic thermoelectric conversion device of the present invention, it is preferable that the substrate has flexibility. Specifically, the flexibility is such that the number of bending resistances MIT by a measurement method prescribed in ASTM D2176 is 10,000 cycles or more. It is preferable to have a tee. The substrate having such flexibility is preferably a plastic film. Specifically, polyethylene terephthalate, polyethylene isophthalate, polyethylene naphthalate, polybutylene terephthalate, poly (1,4-cyclohexylenedimethylene terephthalate), Polyethylene-2,6-naphthalene dicarboxylate, polyester film such as polyester film of bisphenol A and iso and terephthalic acid, ZEONOR film (trade name, manufactured by Nippon Zeon), ARTON film (trade name, manufactured by JSR), Sumilite Polycycloolefin films such as FS1700 (trade name, manufactured by Sumitomo Bakelite), Kapton (trade name, manufactured by Toray DuPont), Apical (trade name, manufactured by Kaneka), Upilex (trade name, Ube) Sumilite FS1100 (product), polyimide film such as Pomilan (trade name, manufactured by Arakawa Chemical Co., Ltd.), polycarbonate film such as Pure Ace (trade name, manufactured by Teijin Chemicals), Elmec (trade name, manufactured by Kaneka) Name, a polyether ether ketone film such as Sumitomo Bakelite Co., Ltd.), and a polyphenyl sulfide film such as Torelina (trade name, manufactured by Toray Industries, Inc.). These are appropriately selected depending on use conditions and environment. Commercially available polyethylene terephthalate, polyethylene naphthalate, various polyimides, polycarbonate films, and the like are preferable from the viewpoints of availability, preferably heat resistance of 100 ° C. or higher, economy, and effects.

In particular, it is preferable to use a base material in which an electrode is provided on the pressure contact surface with the thermoelectric conversion layer. As electrode materials for forming the first electrode and the second electrode provided on the base material, transparent electrodes such as ITO and ZnO, metal electrodes such as silver, copper, gold and aluminum, CNT (carbon nanotube), graphene Carbon materials such as PODOT / PSS, conductive pastes in which conductive fine particles such as silver and carbon are dispersed, and conductive pastes containing metal nanowires such as silver, copper, and aluminum can be used. Among these, a metal material is preferable, and aluminum, gold, silver, or copper is more preferable.
At this time, the thermoelectric conversion device 4 is configured in the order of the first base material 42, the first electrode 43, the thermoelectric conversion layer 44, and the second electrode 45. Even if the base materials 46 are adjacent to each other, the second electrode 45 may be exposed to air as the outermost surface without providing the second base material 46. The thermoelectric conversion element 5 includes a first base 51, a first electrode 52, a second electrode 53, and a thermoelectric conversion layer 54, and a second substrate is disposed outside the thermoelectric conversion layer 54. Even if the material 55 is adjacent, the thermoelectric conversion layer 44 may be exposed to air as the outermost surface without providing the second substrate 55.

The thickness of the substrate is preferably from 30 to 3000 μm, more preferably from 50 to 1000 μm, still more preferably from 100 to 1000 μm, particularly preferably from 200 to 800 μm from the viewpoints of handleability and durability. If the substrate is too thick, the thermal conductivity may decrease, and if it is too thin, the film may be easily damaged by external impact.

The layer thickness of the thermoelectric conversion layer is preferably 0.1 to 1000 μm, and more preferably 1 to 100 μm. If the layer thickness is thin, it is not preferable because it is difficult to provide a temperature difference and the resistance in the layer increases.

The method for forming the thermoelectric conversion layer is not particularly limited. For example, spin coating, extrusion die coating, blade coating, bar coating, screen printing, stencil printing, roll coating, curtain coating, spray coating, dip coating, ink jet printing, etc. A known coating method can be used.
Among these, screen printing is preferable from the viewpoint of excellent adhesion of the thermoelectric conversion layer to the electrode.
Ink jet printing is also preferable because it is easy to handle the apparatus and has a high degree of freedom in selecting an element pattern shape.

When applying a thermoelectric conversion material and forming a film, at least the organic semiconductor compound of the present invention is used as a coating solution. It is preferable to appropriately adjust the amount of the dispersion medium so that the coating solution has a desired solid content concentration and viscosity.

The organic solvent used in the coating solution, the content of the organic semiconductor compound of the present invention in the coating solution is the organic solvent that can be used in the coating solution described in the organic thin film transistor and the organic semiconductor compound in the coating solution described in the organic thin film transistor. The content of can be adopted.
The organic thermoelectric conversion device of the present invention can be suitably used as a power generation device for an article for thermoelectric power generation. Specific examples of such power generation devices include power generators such as hot spring thermal generators, solar thermal generators, and waste heat generators, wristwatch power supplies, semiconductor drive power supplies, and (small) sensor power supplies.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not construed as being limited to the following examples.

[Example 1] Production of organic semiconductor device using polymer P1 (1) Synthesis of polymer P1 (synthesis of monomer (1-2))

Method described in Macromolecules 2012, 45, 6390-6395, compound (1-1) (synthesized according to the method described in Journal of Polymer Science, Part A: Polymer Chemistry, 2011, vol. 49, p. 3260-3271) The monomer (1-2) was synthesized by tin formation with reference to

(Synthesis of polymer P1)

Compound (1-2) 190 mg (0.300 mmol), Compound (1-3) 159 mg (0.300 mmol), Tris (dibenzylideneacetone) dipalladium (0) chloroform adduct 6.21 mg (6.00 μmol), o- 14.6 mg (0.0480 mmol) of tolylphosphine was placed in a glass reaction vessel, and the inside of the vessel was replaced with argon. Chlorobenzene (6.0 mL, dehydrated) was added, and the mixture was reacted at 140 ° C. for 12 hours under an argon atmosphere. After allowing to cool, the reaction solution was poured into methanol for crystallization, and the solid was collected by filtration. The obtained solid was sequentially extracted by Soxhlet extraction (methanol 12 hours, acetone 3 hours, hexane 3 hours) to remove impurities, and then extracted with chlorobenzene. The chlorobenzene extracted solution was concentrated, dissolved in chlorobenzene, crystallized with methanol, filtered and dried to obtain 163 mg (yield: 80.0%) of polymer P1.
Polymer P1:
GPC (o-dichlorobenzene) Mw = 86 × 10 ³ , Mn = 36 × 10 ³

(2) Production of Organic Thin Film Transistor 3 mg of polymer P1 and 1 mL of toluene were mixed and dissolved by heating to 100 ° C. to obtain a coating solution for organic semiconductor devices. This coating solution is spin-coated on a substrate for FET property measurement heated to 90 ° C. in a nitrogen atmosphere, and then annealed at 130 ° C. for 10 minutes to form an organic semiconductor thin film having a thickness of 50 nm. A thin film transistor was obtained. As a substrate for measuring FET characteristics, a bottom provided with chromium / gold (gate width W = 100 mm, gate length L = 100 μm) arranged in a comb shape as source and drain electrodes, and SiO ₂ (thickness 200 nm) as an insulating film A silicon substrate having a gate / bottom contact structure was used.

(3) Preparation of organic photoelectric conversion device PEDOT-PSS (CLEVIOS P VP.AI4083 (trade name) manufactured by Heraeus Precision Material) used as a hole transport layer is spin-coated on a glass-ITO substrate that has been cleaned and UV-ozone-treated. (3000 rpm) and heated at 140 ° C. for 30 minutes. A mixture of 10 mg of polymer P1 and 10 mg of PC ₇₁ BM ([6,6] -phenyl-C71-butyric acid methyl ester) was dissolved in 1 mL of chlorobenzene containing 1% by volume of 1.8-diiodooctane. This solution was applied onto the PEDOT-PSS layer by spin coating (1000 rpm) and dried to prepare a photoelectric conversion layer having a thickness of 80 nm. LiF (1 nm) and aluminum (100 nm) were sequentially deposited on the photoelectric conversion layer to form an upper electrode, thereby obtaining an organic photoelectric conversion device.

(4) Preparation of organic thermoelectric conversion device After dissolving 6 mg of polymer P1 in 4.0 ml of orthodichlorobenzene, this solution was used as the first electrode 43 to have gold (thickness 20 nm, width: 5 mm) on one side surface. It apply | coated to the electrode 43 surface on the base material 42 (thickness: 0.8 mm) by the screen printing method, and it heated for 30 minutes at 80 degreeC, and removed the solvent. Subsequently, it was doped by immersing in an acetonitrile solution of iron (III) chloride. Thereafter, the thermoelectric conversion layer 44 having a film thickness of 3.1 μm and a size of 8 mm × 8 mm was formed by drying at room temperature under vacuum for 10 hours. Thereafter, a glass substrate 46 in which gold is deposited as the second electrode 45 on the thermoelectric conversion layer 44 (the thickness of the electrode 45: 20 nm, the width of the electrode 45: 5 mm, the thickness of the glass substrate 46: 0.8 mm). Were bonded at 80 ° C. so that the second electrode 45 was in contact with the thermoelectric conversion layer 44, and the thermoelectric conversion device 4 shown in FIG. 4 was produced.

[Example 2] Production of organic semiconductor device using polymer P2 (1) Synthesis of polymer P2

The same procedure as in Example 1 was carried out except that 207 mg (0.300 mmol) of compound (2-1) and 157 mg (0.300 mmol) of compound (2-2) were used, and 174 mg of polymer P2 (yield 79.9%) )Obtained.
Polymer P2:
GPC (o-dichlorobenzene) Mw = 93 × 10 ³ , Mn = 40 × 10 ³

(2) Production of Organic Thin Film Transistor An organic thin film transistor was obtained in the same manner as in Example 1 except that the polymer P1 was changed to the polymer P2.

(3) Production of organic photoelectric conversion device An organic photoelectric conversion device was obtained in the same manner as in Example 1 except that the polymer P1 was changed to the polymer P2 and diiodooctane was changed from 1% by volume to 1.5% by volume.

[Example 3] Production of organic semiconductor device using polymer P3 (1) Synthesis of polymer P3

The same procedure as in Example 1 was conducted, except that 191 mg (0.300 mmol) of compound (3-1) and 159 mg (0.300 mmol) of compound (3-2) were used, and 169 mg of polymer P3 (yield: 80.2%) )Obtained.
Polymer P3:
GPC (o-dichlorobenzene) Mw = 80 × 10 ³ , Mn = 32 × 10 ³

(2) Production of Organic Thin Film Transistor An organic thin film transistor was obtained in the same manner as in Example 1 except that the polymer P1 was changed to the polymer P3.

(3) Preparation of organic photoelectric conversion device An organic photoelectric conversion device was obtained in the same manner as in Example 1 except that the polymer P1 was changed to the polymer P3 and the diiodooctane was changed from 1% by volume to 1.5% by volume. It was.

[Example 4] Production of organic semiconductor device using polymer P4 (1) Synthesis of polymer P4

179 mg (yield: 85.0%) of polymer P4 was obtained in the same manner as in Example 1 except that 196 mg (0.300 mmol) of compound (4-1) and 163 mg (0.300 mmol) of compound (4-2) were used. It was.
Polymer P4:
GPC (o-dichlorobenzene) Mw = 69 × 10 ³ , Mn = 28 × 10 ³

(2) Production of Organic Thin Film Transistor An organic thin film transistor was obtained in the same manner as in Example 1 except that the polymer P1 was changed to the polymer P4.

(3) Preparation of organic photoelectric conversion device An organic photoelectric conversion device was obtained in the same manner as in Example 1 except that the polymer P1 was changed to the polymer P4.

[Example 5] Production of organic semiconductor device using polymer P5 (1) Synthesis of polymer P5

134 mg (yield: 82.4%) of polymer P5 was obtained in the same manner as in Example 1 except that 182 mg (0.300 mmol) of compound (5-1) and 127 mg (0.300 mmol) of compound (5-2) were used. It was.
Polymer P5:
GPC (o-dichlorobenzene) Mw = 41 × 10 ³ , Mn = 19 × 10 ³

(2) Production of Organic Thin Film Transistor An organic thin film transistor was obtained in the same manner as in Example 1 except that the polymer P1 was changed to the polymer P5.

(3) Production of Organic Photoelectric Conversion Device An organic photoelectric conversion device was obtained in the same manner as in Example 1 except that the polymer P1 was changed to the polymer P5 and diiodooctane was changed from 1% by volume to 3% by volume.

[Example 6] Production of organic semiconductor device using polymer P6 (1) Synthesis of polymer P6

The same procedure as in Example 1 was carried out except that 190 mg (0.300 mmol) of compound (6-1) and 139 mg (0.300 mmol) of compound (6-2) were used, and 143 mg of polymer P6 (yield 78.1%) )Obtained.
Polymer P6:
GPC (o-dichlorobenzene) Mw = 37 × 10 ³ , Mn = 20 × 10 ³

(2) Production of Organic Thin Film Transistor An organic thin film transistor was obtained in the same manner as in Example 1 except that the polymer P1 was changed to the polymer P6.

(3) Production of Organic Photoelectric Conversion Device An organic photoelectric conversion device was obtained in the same manner as in Example 1 except that the polymer P1 was changed to the polymer P6 and diiodooctane was changed from 1% by volume to 3% by volume.

[Example 7] Production of organic semiconductor device using polymer P7 (1) Synthesis of polymer P7

The same procedure as in Example 1 was conducted, except that 199 mg (0.300 mmol) of compound (7-1) and 159 mg (0.300 mmol) of compound (7-2) were used, and 170 mg of polymer P7 (yield 86.3%) )Obtained.
Polymer P7:
GPC (o-dichlorobenzene) Mw = 98 × 10 ³ , Mn = 37 × 10 ³

(2) Production of Organic Thin Film Transistor An organic thin film transistor was obtained in the same manner as in Example 1 except that the polymer P1 was changed to the polymer P7.

(3) Production of organic photoelectric conversion device An organic photoelectric conversion device was obtained in the same manner as in Example 1 except that the polymer P1 was changed to the polymer P7 and diiodooctane was changed from 1% by volume to 2% by volume.

(4) Production of organic thermoelectric conversion device A thermoelectric conversion device was produced in the same manner as in Example 1 except that the polymer P1 was changed to P7.

[Example 8] Production of organic semiconductor device using polymer P8 (1) Synthesis of polymer P8

The same procedure as in Example 1 was conducted, except that 173 mg (0.300 mmol) of compound (8-1) and 160 mg (0.300 mmol) of compound (8-2) were used, and 166 mg of polymer P8 (yield: 88.8%) )Obtained.
Polymer P8:
GPC (o-dichlorobenzene) Mw = 79 × 10 ³ , Mn = 38 × 10 ³

(2) Production of Organic Thin Film Transistor An organic thin film transistor was obtained in the same manner as in Example 1 except that the polymer P1 was changed to the polymer P8.

(3) Preparation of organic photoelectric conversion device An organic photoelectric conversion device was obtained in the same manner as in Example 1 except that the polymer P1 was changed to the polymer P8.

[Example 9] Production of organic semiconductor device using polymer P9 (1) Synthesis of polymer P9

The same procedure as in Example 1 was conducted, except that 173 mg (0.300 mmol) of compound (9-1) and 189 mg (0.300 mmol) of (9-2) were used, and 176 mg of polymer P9 (yield 81.3%) Obtained.
Polymer P9:
GPC (o-dichlorobenzene) Mw = 77 × 10 ³ , Mn = 33 × 10 ³

(2) Production of Organic Thin Film Transistor An organic thin film transistor was obtained in the same manner as in Example 1 except that the polymer P1 was changed to the polymer P9.

(3) Preparation of organic photoelectric conversion device An organic photoelectric conversion device was obtained in the same manner as in Example 1 except that the polymer P1 was changed to the polymer P9.

(4) Production of organic thermoelectric conversion device A thermoelectric conversion device was produced in the same manner as in Example 1 except that the polymer P1 was changed to P9.

[Example 10] Production of organic semiconductor device using polymer P10 (1) Synthesis of polymer P10

The same procedure as in Example 1 was carried out, except that 190 mg (0.300 mmol) of compound (10-1) and 199 mg (0.300 mmol) of (10-2) were used, and 204 mg of polymer P10 (yield 83.9%) Obtained.
Polymer P10:
GPC (o-dichlorobenzene) Mw = 72 × 10 ³ , Mn = 31 × 10 ³

(2) Production of Organic Thin Film Transistor An organic thin film transistor was obtained in the same manner as in Example 1 except that the polymer P1 was changed to the polymer P10.

(3) Production of Organic Photoelectric Device An organic photoelectric conversion device was obtained in the same manner as in Example 1 except that the polymer P1 was changed to the polymer P10 and the diiodooctane was changed from 1% by volume to 2.5% by volume.

[Example 11] Production of organic semiconductor device using polymer P11 (1) Synthesis of polymer P11

The same procedure as in Example 1 was conducted, except that 182 mg (0.300 mmol) of compound (11-1) and 198 mg (0.300 mmol) of (11-2) were used, and 178 mg of polymer P11 (yield 75.9%) Obtained.
Polymer P11:
GPC (o-dichlorobenzene) Mw = 79 × 10 ³ , Mn = 31 × 10 ³
(2) Production of Organic Thin Film Transistor An organic thin film transistor was obtained in the same manner as in Example 1 except that the polymer P1 was changed to the polymer P11.

(3) Production of organic photoelectric conversion device An organic photoelectric conversion device was obtained in the same manner as in Example 1 except that the polymer P1 was changed to the polymer P11 and the diiodooctane was changed from 1% by volume to 4% by volume.

[Example 12] Production of organic semiconductor device using polymer P12 (1) Synthesis of polymer P12

The same procedure as in Example 1 was conducted, except that 241 mg (0.300 mmol) of compound (12-1) and 164 mg (0.300 mmol) of (12-2) were used, and 208 mg of polymer P12 (yield 80.3%) Obtained.
Polymer P12:
GPC (o-dichlorobenzene) Mw = 51 × 10 ³ , Mn = 21 × 10 ³

(2) Production of Organic Thin Film Transistor An organic thin film transistor was obtained in the same manner as in Example 1 except that the polymer P1 was changed to the polymer P12.

(3) Production of Organic Photoelectric Conversion Device An organic photoelectric conversion device was obtained in the same manner as in Example 1 except that the polymer P1 was changed to the polymer P12 and the diiodooctane was changed from 1% by volume to 1.5% by volume.

[Example 13] Production of organic semiconductor device using polymer P13 (1) Synthesis of polymer P13

151 mg (yield 77.7%) of polymer P13 was obtained in the same manner as in Example 1 except that 199 mg (0.300 mmol) of compound (13-1) and 142 mg (0.300 mmol) of (13-2) were used. .
Polymer P13:
GPC (o-dichlorobenzene) Mw = 40 × 10 ³ , Mn = 18 × 10 ³

(2) Production of Organic Thin Film Transistor An organic thin film transistor was obtained in the same manner as in Example 1 except that the polymer P1 was changed to the polymer P13.

(3) Production of Organic Photoelectric Conversion Device An organic photoelectric conversion device was obtained in the same manner as in Example 1 except that the polymer P1 was changed to the polymer P13 and diiodooctane was changed from 1% by mass to 2% by mass.

[Example 14] Production of organic semiconductor device using polymer P14 (1) Synthesis of polymer P14

The same procedure as in Example 1 was conducted, except that 173 mg (0.300 mmol) of compound (14-1) and 167 mg (0.300 mmol) of (14-2) were used, and 173 mg of polymer P14 (yield: 89.0%) Obtained.
Polymer P14:
GPC (o-dichlorobenzene) Mw = 65 × 10 ³ , Mn = 25 × 10 ³

(2) Production of Organic Thin Film Transistor An organic thin film transistor was obtained in the same manner as in Example 1 except that the polymer P1 was changed to the polymer P14.

(3) Preparation of organic photoelectric conversion device An organic photoelectric conversion device was obtained in the same manner as in Example 1 except that the polymer P1 was changed to the polymer P14 and diiodooctane was not used.

[Example 15] Production of organic semiconductor device using polymer P15 (1) Synthesis of polymer P15

The same procedure as in Example 1 was carried out except that 182 mg (0.300 mmol) of compound (15-1) and 149 mg (0.300 mmol) of (15-2) were used, and 185 mg of polymer P15 (yield: 75.6%) Obtained.
Polymer P15:
GPC (o-dichlorobenzene) Mw = 32 × 10 ³ , Mn = 16 × 10 ³

(2) Production of Organic Thin Film Transistor An organic thin film transistor was obtained in the same manner as in Example 1 except that the polymer P1 was changed to the polymer P15.

(3) Preparation of organic photoelectric conversion device An organic photoelectric conversion device was obtained in the same manner as in Example 1 except that the polymer P1 was changed to the polymer P15.

[Example 16] Production of organic semiconductor device using polymer P16 (1) Synthesis of polymer P16

The same procedure as in Example 1 was carried out except that 207 mg (0.300 mmol) of compound (16-1) and 150 mg (0.300 mmol) of (16-2) were used, and 180 mg of polymer P16 (yield 84.9%) Obtained.
Polymer P16:
GPC (o-dichlorobenzene) Mw = 39 × 10 ³ , Mn = 14 × 10 ³

(2) Production of Organic Thin Film Transistor An organic thin film transistor was obtained in the same manner as in Example 1 except that the polymer P1 was changed to the polymer P16.

(3) Production of organic photoelectric conversion device An organic photoelectric conversion device was obtained in the same manner as in Example 1 except that the polymer P1 was changed to the polymer P16 and the diiodooctane was changed from 1% by volume to 3.5% by volume.

[Example 17] Production of organic semiconductor device using polymer P17 (1) Synthesis of polymer P17

The same procedure as in Example 1 was carried out, except that 206 mg (0.300 mmol) of compound (17-1) and 161 mg (0.300 mmol) of (17-2) were used, and 661 mg of polymer P17 (yield 90.1%) Obtained.
Polymer P17:
GPC (o-dichlorobenzene) Mw = 70 × 10 ³ , Mn = 25 × 10 ³
(2) Production of Organic Thin Film Transistor An organic thin film transistor was obtained in the same manner as in Example 1 except that the polymer P1 was changed to the polymer P17.
(3) Production of organic photoelectric conversion device An organic photoelectric conversion device was obtained in the same manner as in Example 1 except that the polymer P1 was changed to the polymer P17 and the diiodooctane was changed from 1% by volume to 6% by volume.

[Comparative Example 1]
P18 described in WO2013 / 056355 A1 was used as a comparative example.

Polymer P18:
GPC (o-dichlorobenzene) Mw = 49 × 10 ³ , Mn = 20 × 10 ³

(1) Production of Organic Thin Film Transistor An organic thin film transistor was obtained in the same manner as in Example 1 except that the polymer P1 was changed to P18.

(2) Preparation of organic photoelectric conversion device An organic photoelectric conversion device was obtained in the same manner as in Example 1 except that the polymer P1 was changed to P18.

(3) Preparation of organic thermoelectric conversion device A thermoelectric conversion device was obtained in the same manner as in Example 1 except that the polymer P1 was changed to P18.

[Comparative Example 2]
J. et al. Phys. Chem. P19 described in C 2009, 113, p21928-21936 was used as a comparative example.

Polymer P19:
GPC (o-dichlorobenzene) Mw = 12 × 10 ³ , Mn = 4.9 × 10 ³

(1) Production of Organic Thin Film Transistor An organic thin film transistor was obtained in the same manner as in Example 1 except that the polymer P1 was changed to P19.

(2) Production of organic photoelectric conversion device An organic photoelectric conversion device was obtained in the same manner as in Example 1 except that the polymer P1 was changed to P19.

(3) Preparation of organic thermoelectric conversion device A thermoelectric conversion device was obtained in the same manner as in Example 1 except that the polymer P1 was changed to P19.

<Evaluation of organic photoelectric conversion device>
Current Density-Voltage (JV) Characteristics The performance of each organic photoelectric conversion device prepared in Examples and Comparative Examples was evaluated as follows. The obtained device was evaluated for current density-voltage (JV) characteristics of the device using a SMU2400 type IV measuring apparatus manufactured by Keithley under a nitrogen atmosphere. Using a filtered xenon lamp light from Oriel (Oriel) manufactured solar simulator approximated to AM1.5G spectrum of 100 mW / cm ^2. The photoelectric conversion efficiency output by the above apparatus is shown in Table 1 below.

Moreover, in order to compare the photoelectric conversion performance by changing the coating method of the photoelectric conversion layer, the photoelectric conversion efficiency of an organic photoelectric conversion device in which the photoelectric conversion layer is formed by spin coating or bar coating (hereinafter also simply referred to as conversion efficiency). Evaluated.
The obtained results were evaluated according to the following criteria.
A: (conversion efficiency of bar coating method) / (conversion efficiency of spin coating method) 0.9 or more B: (conversion efficiency of bar coating method) / (conversion efficiency of spin coating method) 0.8 or more to 0.9 Less than C: (conversion efficiency of bar coating method) / (conversion efficiency of spin coating method) 0.7 or more and less than 0.8 D: (conversion efficiency of bar coating method) / (conversion efficiency of spin coating method) 0. Less than 7

<Evaluation of organic thin film transistor>
The FET characteristics of the organic thin film transistor are measured using a semiconductor parameter analyzer (Agilent, 4156C (trade name)) connected to a semi-auto prober (Vector Semicon, AX-2000 (trade name)) under normal pressure and nitrogen atmosphere. Mobility was evaluated.
The obtained results are shown in Table 1 below.
(A) Hole Mobility A voltage of −80 V was applied between the source electrode and the drain electrode of each organic thin film transistor (FET element), and the gate voltage was changed in the range of 20 V to −100 V. Formula I _d = (w / 2L) μC _i (V _g −V _th ) ² representing drain current I _d (where L is the gate length, W is the gate width, and C _i is the capacitance per unit area of the insulating layer) , V _g is a gate voltage, and V _th is a threshold voltage) to calculate the carrier mobility μ.

(B) Threshold voltage change after repeated driving A voltage of −80 V is applied between the source electrode and the drain electrode of each organic thin film transistor (FET element), and the gate voltage is repeated 100 times in the range of +20 V to −100 V. (a) The difference between the threshold voltage V _{before the} repeated driving and the threshold voltage V _after the repeated driving ( _after | V− _before V |) was evaluated in the following three stages. The smaller this value, the higher the repeated driving stability of the transistor, which is preferable.
A: | _{after the} V -V _before | ≦ 5V
B: 5V <| V _after -V _before | ≦ 10V
C: | _After V- _Before V |> 10V

As described above, the organic semiconductor compound of the present invention has very high structural regularity including not only the main chain but also the side chain structure. Therefore, the organic semiconductor compound of the present invention has a highly crystalline structure (packing property) that is spontaneously arranged during film formation by π-π interaction in the main chain portion and van der Waals interaction (fastener effect) in the side chain portion. High structure). Therefore, the change in conversion efficiency when the coating method is changed is small. Further, since the organic semiconductor compound of the present invention has high crystallinity, it is considered that the change in molecular arrangement due to repeated driving in the organic thin film transistor is small, and the change in threshold voltage is also reduced.

<Measurement of thermoelectric characteristic value (thermoelectromotive force S)>
The first electrode of the thermoelectric conversion device was placed on a hot plate maintained at a constant temperature, and a Peltier element for temperature control was placed on the second electrode. While maintaining the temperature of the hot plate constant (100 ° C.), the temperature of the Peltier element was lowered to give a temperature difference (over 0K to 10K or less) between both electrodes. At this time, the thermoelectromotive force S (μV / K) per unit temperature difference is obtained by dividing the thermoelectromotive force (μV) generated between both electrodes by the specific temperature difference (K) generated between both electrodes. This value was calculated as the thermoelectric characteristic value of the thermoelectric conversion device. The calculated thermoelectric characteristic values are shown in Table 2 as relative values to the calculated values of the thermoelectric conversion device using the comparative polymer P19.

From the above results, it was found that the thermoelectric conversion device using the semiconductor layer of the organic semiconductor compound of the present invention is excellent in thermoelectric conversion efficiency.

DESCRIPTION OF SYMBOLS 1 Bottom gate top contact type transistor 11 Substrate 12 Electrode 13 Insulator layer 14 Semiconductor layer (organic semiconductor layer)
15a electrode 15b electrode

2 Bottom Gate / Bottom Contact Type Transistor 21 Substrate 22 Electrode 23 Insulator Layer 24 Semiconductor Layer (Organic Semiconductor Layer)
25a electrode 25b electrode

3 Photoelectric conversion devices (bulk heterojunction organic thin film solar cells)
31 Counter electrode (second electrode)
32 Electron transport layer 33 Photoelectric conversion layer 33a n-type semiconductor phase 33b p-type semiconductor phase 34 hole transport layer 35 transparent electrode (first electrode)
36 Transparent support L Light P Electric motor (winding machine)

4

Thermoelectric Conversion Device

41, 47 Metal Plate 42 First Base Material 43 First Electrode 44 Thermoelectric Conversion Layer 45 Second Electrode 46 Second Base Material

5 Thermoelectric Conversion Device 51 First Base Material 52 First Electrode 53 Second Electrode 54 Thermoelectric Conversion Layer 55 Second Base Material

While this invention has been described in conjunction with its embodiments, we do not intend to limit our invention in any detail of the description unless otherwise specified and are contrary to the spirit and scope of the invention as set forth in the appended claims. I think it should be interpreted widely.

This application claims priority based on Japanese Patent Application No. 2013-179321 filed in Japan on August 30, 2013, the contents of which are hereby incorporated by reference. Capture as part.

Claims

The organic-semiconductor device which contains the compound represented by following formula (1) in a semiconductor layer.

In formula (1), D represents a donor structural unit represented by formula (2) or formula (3). A represents an acceptor structural unit composed of an aromatic ring having a side-chain direction condensed ring structure. S 1 and S 2 represent ethenylene, ethynylene, arylene group, heteroarylene group, azo group, or —C═N—. l and n are integers of 1 to 4, and m1 and m2 are integers of 0 to 2. p represents an integer of 2 to 2000.
In the formula (2), X 21 and X 22 represent a sulfur atom, an oxygen atom, a selenium atom or —NR 22 —, and Y 21 represents a nitrogen atom or —C (—L 22 —R 23 ) ═. However, when both X 21 and X 22 are sulfur atoms, Y 21 is —C (—L 22 —R 23 ) =. L 21 and L 22 are a single bond, —O—, —S—, —NR 5 —, —Si (R 5 ) 2 —, —C (═O) O—, —C (═S) O—, -C (= O) S-, -SC (= O)-, -OC (= O)-, -OC (= S)-, -C (= O)-, -C (= S)-,- C (═O) NR 5 —, —NR 5 C (═O) —, —S (═O) —, —S (═O) 2 —, —S (═O) 2 O—, —OS (= O) 2 —, —S (═O) 2 NR 5 —, —NR 5 S (═O) 2 —, an arylene group, a heteroarylene group, an alkenylene group or an alkynylene group, or an arylene group, a heteroarylene group A group formed by combining two or more groups selected from a group, an alkenylene group, an alkynylene group, a carbonyl group, and an acyloxy group. R 21 to R 23 represent a hydrogen atom or a monovalent substituent. R 5 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group.
In the formula (3), X 31 represents a sulfur atom, an oxygen atom, a selenium atom or —NR 31 —. Y 31 to Y 34 represent a nitrogen atom or —C (—L 31 —R 32 ) ═. L 31 of Y 31 and Y 34 has the same meaning as L 22, and R 32 of Y 31 and Y 34 has the same meaning as R 23 . L 31 of Y 32 and Y 33 has the same meaning as L 21, and R 32 of Y 32 and Y 33 has the same meaning as R 21 . R 31 has the same meaning as R 22 described above.
In formulas (2) and (3), * indicates a linking site.
However, D and A have at least one group selected from an alkyl group, an alkenyl group, and an alkynyl group.
The organic semiconductor device according to claim 1, wherein the compound represented by the formula (1) is represented by the following formula (4).

In formula (4), D, A, l, n and p have the same meanings as D, A, l, n and p in formula (1), respectively.
The organic semiconductor device according to claim 1 or 2, which satisfies the following (a1) to (b1):
(A1) In the formula (2), R 21 is an alkyl group having 6 to 24 carbon atoms, an alkenyl group, or an alkynyl group, and has no other aliphatic group having 6 or more carbon atoms.
(B1) In the formula (3), one or both of Y 32 and Y 33 is —C (—L 31 —R 32 ) =, and R 32 is an alkyl group having 6 to 24 carbon atoms, alkenyl Group or alkynyl group, and has no other aliphatic group having 6 or more carbon atoms.
The organic semiconductor device according to any one of claims 1 to 3, wherein the acceptor structural unit A is represented by any one of the following formulas (5) to (12).

In the formula (5), X 51 and X 52 represent a sulfur atom, oxygen atom, selenium atom or —NR 52 —, and Y 51 represents a nitrogen atom or —C (—L 52 —R 53 ) ═. L 51 and L 52 are a single bond, —O—, —S—, —NR 5 —, —Si (R 5 ) 2 —, —C (═O) O—, —C (═S) O—, — C (= O) S-, -SC (= O)-, -OC (= O)-, -OC (= S)-, -C (= O)-, -C (= S)-, -C (═O) NR 5 —, —NR 5 C (═O) —, —S (═O) —, —S (═O) 2 —, —S (═O) 2 O—, —OS (═O ) 2 —, —S (═O) 2 NR 5 —, —NR 5 S (═O) 2 —, an arylene group, a heteroarylene group, an alkenylene group or an alkynylene group, or an arylene group, a heteroarylene group , A group formed by combining two or more groups selected from an alkenylene group, an alkynylene group, a carbonyl group, and an acyloxy group. R 5 has the same meaning as R 5 in L 21 in the formula (2). R 51 to R 53 represent a hydrogen atom or a monovalent substituent.
In formula (6), X 61 has the same meaning as X 51 in formula (5). Z 61 and Z 62 represent an oxygen atom or a sulfur atom. W 61 represents —NR 62 —, —CR 63 R 64 —, or> C = CR 65 R 66 . R 62 to R 66 represent a hydrogen atom or a monovalent substituent.
Wherein (7), X 71 has the same meaning as X 51 in formula (5). Y 71 to Y 74 each represents a nitrogen atom or —C (—L 71 —R 72 ) ═. L 71 in Y 71 and Y 74 has the same meaning as L 52 in the formula (5), and L 71 in Y 72 and Y 73 has the same meaning as L 51 in the formula (5). R 72 represents a hydrogen atom or a monovalent substituent.
Wherein (8), X 81 has the same meaning as X 52 in formula (5). Y 81 to Y 84 each represents a nitrogen atom or —C (—L 81 —R 82 ) ═. L 81 of Y 83 has the same meaning as L 51 in the formula (5), L 81 of Y 81, Y 82 and Y 84 have the same meanings as L 52 in the formula (5) in, R 82 is hydrogen An atom or a monovalent substituent is shown.
In Formula (9), W 91 represents —NR 91 — or —CR 92 R 93 —, and R 91 to R 93 represent a hydrogen atom or a monovalent substituent. Y 91 and Y 92 have the same meanings as Y 81 and Y 82 in Formula (8), respectively.
In formula (10), Y 101 and Y 102 have the same meanings as Y 81 and Y 82 in formula (8), respectively. Z 101 and Z 102 are synonymous with Z 61 and Z 62 in the formula (6), respectively. W 101 has the same meaning as W 61 in formula (6).
In formula (11), X 111 and X 112 have the same meanings as X 51 and X 52 in formula (5), respectively. Y 111 and Y 112 have the same meanings as Y 71 and Y 74 in the formula (7), respectively. Y 113 and Y 114 are synonymous with Y 83 and Y 84 in the formula (8), respectively.
In formula (12), X 121 has the same meaning as X 51 in formula (5). Y 121 and Y 122 are synonymous with Y 71 and Y 74 in the formula (7), respectively. Z 121 and Z 122 are synonymous with Z 61 and Z 62 in the formula (6), respectively. W 121 is synonymous with W 61 in the formula (6).
The structure represented by each of the formulas (5) to (12) has at least one group selected from an alkyl group, an alkenyl group, and an alkynyl group. Moreover, * shows a connection part in each formula.
The organic semiconductor device according to claim 4, which satisfies the following (a2) to (h2):
(A2) In the formula (5), R 51 is an alkyl group, alkenyl group or alkynyl group having 6 to 24 carbon atoms, and does not have any other aliphatic group having 6 or more carbon atoms.
(B2) In the formula (6), W 61 is —NR 62 —, —CR 63 R 64 — or> C═CR 65 R 66 , and R 62 to R 66 are alkyl having 6 to 24 carbon atoms. A group, an alkenyl group or an alkynyl group, and no other aliphatic group having 6 or more carbon atoms,
(C2) In the formula (7), at least one of Y 72 and Y 73 is —C (—L 71 —R 72 ) =, and R 72 is an alkyl group, alkenyl group having 6 to 24 carbon atoms, or An alkynyl group that does not have any other aliphatic group having 6 or more carbon atoms,
(D2) In the formula (8), Y 83 is —C (—L 81 —R 82 ) =, R 82 is an alkyl group, alkenyl group, or alkynyl group having 6 to 24 carbon atoms; Does not have an aliphatic group having 6 or more carbon atoms,
(E2) In the above formula (9), W 91 is —NR 91 — or —CR 92 R 93 —, and R 91 to R 93 are alkyl groups, alkenyl groups, or alkynyl groups having 6 to 24 carbon atoms. There is no other aliphatic group having 6 or more carbon atoms,
(F2) In the formula (10), W 101 is —NR 62 —, —CR 63 R 64 — or> C═CR 65 R 66 , and R 62 to R 66 are alkyl having 6 to 24 carbon atoms. A group, an alkenyl group or an alkynyl group, and no other aliphatic group having 6 or more carbon atoms,
(G2) In the formula (11), Y 113 is —C (—L 81 —R 82 ) =, R 82 is an alkyl group, alkenyl group, or alkynyl group having 6 to 24 carbon atoms; Does not have an aliphatic group having 6 or more carbon atoms,
(H2) In the formula (12), W 121 is —NR 62 —, —CR 63 R 64 — or> C═CR 65 R 66 , and R 62 to R 66 are alkyl having 6 to 24 carbon atoms. A group, an alkenyl group or an alkynyl group, and no other aliphatic group having 6 or more carbon atoms.
The organic semiconductor device according to any one of claims 1 to 5, wherein the compound is represented by any one of the following formulas (13) to (17).

In formula (13), X 131 , X 132 , Y 131 , L 131 and R 131 have the same meanings as X 21 , X 22 , Y 21 , L 21 and R 21 in formula (2), respectively. However, when both X 131 and X 132 are sulfur atoms, Y 131 is —C (—L 133 —R 133 ) =. L 133 and R 133 are synonymous with L 22 and R 23 in Y 21 in the formula (2), respectively. X 133 , X 134 , Y 132 , L 132 and R 132 have the same meanings as X 51 , X 52 , Y 51 , L 51 and R 51 in the formula (5), respectively. p has the same meaning as p in the formula (1).
In formula (14), X 141 , X 142 , Y 141 , L 141 and R 141 have the same meanings as X 21 , X 22 , Y 21 , L 21 and R 21 in formula (2), respectively. However, when both X 141 and X 142 are sulfur atoms, Y 141 is -C (-L 142 -R 142 ) =. L 142 and R 142 are synonymous with L 22 and R 23 in Y 21 in Formula (2), respectively. X 143 and Y 142 to Y 145 have the same meanings as X 71 and Y 71 to Y 74 in formula (7), respectively. p has the same meaning as p in the formula (1).
In formula (15), X 151 , X 152 , Y 151 , L 151 and R 151 have the same meanings as X 21 , X 22 , Y 21 , L 21 and R 21 in formula (2), respectively. However, when both X 151 and X 152 are sulfur atoms, Y 151 is -C (-L 152 -R 152 ) =. L 152 and R 152 are synonymous with L 22 and R 23 in Y 21 in Formula (2), respectively. X 153, W 151, Z 151 and Z 152 are each synonymous with X 61, W 61, Z 61 and Z 62 in the formula (6) in. p has the same meaning as p in the formula (1).
In the formula (16), X 161 , X 162 , Y 161 , L 161 and R 161 are respectively synonymous with X 21 , X 22 , Y 21 , L 21 and R 21 in the formula (2). However, when both X 161 and X 162 are sulfur atoms, Y 161 is —C (—L 163 —R 163 ) =. L 163 and R 163 have the same meanings as L 22 and R 23 in Y 21 in formula (2), respectively. X 163 , Y 162 , Y 163 , Y 164 and Y 165 have the same meanings as X 81 , Y 81 , Y 82 , Y 83 and Y 84 in the formula (8), respectively. p has the same meaning as p in the formula (1).
In the formula (17), X 171 , X 172 , Y 171 , L 171 and R 171 have the same meaning as X 21 , X 22 , Y 21 , L 21 and R 21 in the formula (2), respectively. However, when both X 171 and X 172 are sulfur atoms, Y 171 is -C (-L 172 -R 172 ) =. L 172 and R 172 have the same meanings as L 22 and R 23 in Y 21 in formula (2), respectively. Y 172 , Y 173 and W 171 have the same meanings as Y 91 , Y 92 and W 91 in the formula (9), respectively. p has the same meaning as p in the formula (1).
In each of the formulas (13) to (17), the fused aromatic ring having two condensed rings in the side chain direction linked by a single bond is at least one group selected from an alkyl group, an alkenyl group and an alkynyl group. Have
The carbon number of at least one group selected from the alkyl group, alkenyl group, and alkynyl group of the donor structural unit and the acceptor structural unit is 6 to 24. The organic semiconductor device described.
The organic semiconductor device according to claim 6, which satisfies the following (a) to (e):
(A) In the formula (13), R 131 and R 132 are an alkyl group, an alkenyl group, or an alkynyl group having 6 to 24 carbon atoms, and no other aliphatic group having 6 or more carbon atoms.
(B) In the formula (14), at least one of Y 143 and Y 144 is the above-(CL 71 -R 72 ) =, and R 141 and R 72 are alkyl groups having 6 to 24 carbon atoms, An alkenyl group or an alkynyl group, which has no other aliphatic group having 6 or more carbon atoms,
(C) In the formula (15), W 151 is —NR 153 —, CR 154 R 155 —, or> C = CR 156 R 157 , and R 151 and R 153 to R 157 have 6 to 24 carbon atoms. An alkyl group, an alkenyl group or an alkynyl group, and having no other aliphatic group having 6 or more carbon atoms,
(D) In the formula (16), Y 164 is — (CL 81 —R 82 ) =, and R 161 and R 82 are alkyl groups, alkenyl groups, or alkynyl groups having 6 to 24 carbon atoms. There is no other aliphatic group having 6 or more carbon atoms,
(E) In the above formula (17), W 171 is —NR 173 or —CR 174 R 175 —, and R 171 and R 173 to R 175 are an alkyl group, alkenyl group or alkynyl group having 6 to 24 carbon atoms. And no other aliphatic groups having 6 or more carbon atoms.
The organic semiconductor device according to any one of claims 1 to 8, wherein the compound has a weight average molecular weight of 5,000 to 1,000,000.
The organic semiconductor device according to any one of claims 1 to 9, wherein the organic semiconductor device is an organic thin film transistor.
The organic semiconductor device according to any one of claims 1 to 9, wherein the organic semiconductor device is an organic photoelectric conversion device.
The organic semiconductor device according to claim 11, wherein the semiconductor layer containing the compound contains an n-type semiconductor.
The organic semiconductor device according to claim 12, wherein the semiconductor layer containing the compound is a mixed layer of the compound and an n-type semiconductor.
The organic semiconductor device according to any one of claims 1 to 9, wherein the organic semiconductor device is a thermoelectric conversion device.
A compound represented by the following formula (1).

In formula (1), D represents a donor structural unit represented by formula (2) or formula (3). A represents an acceptor structural unit composed of an aromatic ring having a side-chain direction condensed ring structure. S 1 and S 2 represent ethenylene, ethynylene, arylene group, heteroarylene group, azo group, or —C═N—. l and n are integers of 1 to 4, and m1 and m2 are integers of 0 to 2. p represents an integer of 2 to 2000. However, D and A have at least one group selected from an alkyl group, an alkenyl group, and an alkynyl group.
In the formula (2), X 21 and X 22 represent a sulfur atom, an oxygen atom, a selenium atom or —NR 22 —, and Y 21 represents a nitrogen atom or —C (—L 22 —R 23 ) ═. However, when both X 21 and X 22 are sulfur atoms, Y 21 is —C (—L 22 —R 23 ) =. L 21 and L 22 are a single bond, —O—, —S—, —NR 5 —, —Si (R 5 ) 2 —, —C (═O) O—, —C (═S) O—, -C (= O) S-, -SC (= O)-, -OC (= O)-, -OC (= S)-, -C (= O)-, -C (= S)-,- C (═O) NR 5 —, —NR 5 C (═O) —, —S (═O) —, —S (═O) 2 —, —S (═O) 2 O—, —OS (= O) 2 —, —S (═O) 2 NR 5 —, —NR 5 S (═O) 2 —, an arylene group, a heteroarylene group, an alkenylene group or an alkynylene group, or an arylene group, a heteroarylene group A group formed by combining two or more groups selected from a group, an alkenylene group, an alkynylene group, a carbonyl group, and an acyloxy group. R 21 to R 23 represent a hydrogen atom or a monovalent substituent. R 5 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group.
In the formula (3), X 31 represents a sulfur atom, an oxygen atom, a selenium atom or —NR 31 —. Y 31 to Y 34 represent a nitrogen atom or —C (—L 31 —R 32 ) ═. L 31 of Y 31 and Y 34 has the same meaning as L 22, and R 32 of Y 31 and Y 34 has the same meaning as R 23 . L 31 of Y 32 and Y 33 has the same meaning as L 21, and R 32 of Y 32 and Y 33 has the same meaning as R 21 . R 31 has the same meaning as R 22 described above.
In formulas (1) to (3), * represents a linking site.
A composition comprising the compound according to claim 15 and an organic solvent.
The composition according to claim 16, which is used for forming a semiconductor layer of an organic semiconductor device.
A coating film formed using the composition according to claim 16 or 17.