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WO2015029910A1 - Dispositif à semi-conducteur organique, et composé, composition, et film de revêtement pour celui-ci - Google Patents

Dispositif à semi-conducteur organique, et composé, composition, et film de revêtement pour celui-ci Download PDF

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WO2015029910A1
WO2015029910A1 PCT/JP2014/072052 JP2014072052W WO2015029910A1 WO 2015029910 A1 WO2015029910 A1 WO 2015029910A1 JP 2014072052 W JP2014072052 W JP 2014072052W WO 2015029910 A1 WO2015029910 A1 WO 2015029910A1
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carbon atoms
organic semiconductor
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寛記 杉浦
野村　公篤
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Fujifilm Corp
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Definitions

  • 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 ⁇ -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 ⁇ -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.
  • Done-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
  • It has a repeating unit (see Non-Patent Document 1, for example).
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • HOMO deepest maximum occupied orbital
  • the knowledge which showed the donor property equivalent to or more than a ring structure was acquired.
  • 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.
  • 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
  • m1 and m2 are integers of 0 to 2.
  • p represents an integer of 2 to 2000.
  • 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 ) ⁇ .
  • 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.
  • 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.
  • * indicates a linking site.
  • D and A have at least one group selected from an alkyl group, an alkenyl group, and an alkynyl group.
  • D, A, l, n and p have the same meanings as D, A, l, n and p in the above formula (1), respectively.
  • X 51 and X 52 represent a sulfur atom, oxygen atom, selenium atom or —NR 52 —
  • Y 51 represents a nitrogen atom or —C (—L 52 —R 53 ) ⁇ .
  • 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.
  • 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.
  • R 62 to R 66 represent a hydrogen atom or a monovalent substituent.
  • 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)
  • 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.
  • 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.
  • 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.
  • 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).
  • 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.
  • 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.
  • 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
  • W 61 is —NR 62 —, —CR 63 R 64 — or> C ⁇ CR 65 R 66
  • R 62 to R 66 are alkyl having 6 to 24 carbon atoms.
  • W 91 is —NR 91 — or —CR 92 R 93 —, and R 91 to R 93 are alkyl groups, alken
  • 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.
  • 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).
  • 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.
  • 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).
  • 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.
  • 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).
  • 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.
  • 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).
  • 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.
  • 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).
  • 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.
  • 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.
  • 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
  • W 171 is —NR 173 or —CR 174 R 175 —
  • R 171 and R 173 to R 175 are an alkyl group, alkenyl group or alkynyl group having 6 to 24 carbon atoms.
  • no other aliphatic groups having 6 or more carbon atoms are no other aliphatic groups having 6 or more carbon atoms.
  • 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.
  • D and A have at least one group selected from an alkyl group, an alkenyl group, and an alkynyl group.
  • 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 ) ⁇ .
  • 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.
  • 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.
  • * represents a linking site.
  • composition comprising the compound according to [15] and an organic solvent.
  • composition according to [16] which is used for forming a semiconductor layer of an organic semiconductor device.
  • composition according to [16] which is used for forming a semiconductor layer of an organic semiconductor device.
  • coating film formed using the composition according to [16] or [17].
  • substituents 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.
  • 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.
  • substituents and the like 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.
  • each substituent may further have a substituent unless otherwise specified.
  • 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.
  • an aromatic ring is a ring satisfying the Hückel rule that is a 4n + 2 ⁇ -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).
  • 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.
  • the transistor 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.
  • 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.
  • 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.
  • 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.
  • 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 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.
  • 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”.
  • 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.
  • 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.
  • 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).
  • 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
  • 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.
  • a halogen atom a fluorine atom, a chlorine atom, a bromine atom, an iodine atom
  • an alkyl group preferably
  • 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
  • an arylene group preferably having 6 to 15 carbon atoms, more preferably 6 to 6 carbon atoms.
  • 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).
  • 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.
  • L 21 and L 22 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).
  • 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).
  • 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).
  • R 21 is preferably an alkyl group, an alkenyl group, or an alkynyl group.
  • 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 .
  • 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.
  • 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 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).
  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • Y 36 ′ may be a nitrogen atom.
  • Z 31 ′ and Z 32 ′ represent an oxygen atom or a sulfur atom, and more preferably an oxygen atom.
  • 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).
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • l representing the number of D represents an integer of 1 to 4, more preferably 1 or 2, and even more preferably 1.
  • n representing the number of A represents an integer of 1 to 4, more preferably 1 or 2, and even more preferably 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.
  • 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 ⁇ -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).
  • ring I has a quinoid structure
  • 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 ⁇ -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.
  • 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.
  • 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.
  • 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.
  • A is selected from benzene, pyridine, pyrazine, pyrimidine, pyridazine, triazine, tetrazine, thiophene, furan, pyrrole, selenophene, thiazole, oxazole, imidazole, pyrazole, oxadiazole, thiadiazole, and triazole.
  • 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.
  • A is preferably an aromatic ring having a side chain direction condensed ring structure represented by the following formulas (5) to (12).
  • 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).
  • 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
  • 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.
  • an alkenyl group preferably 2 to 30 carbon atoms, more preferably A branched or linear alkenyl group having 2 to 24 carbon atoms
  • an alkynyl group preferably a branched or straight chain alkynyl group having 2 to 30 carbon
  • 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.
  • 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.
  • alkynylene group preferably 2 carbon atoms To 10 and more preferably an alkynylene group having 2 to 5 carbon atoms, and more
  • L 51 and L 52 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.
  • 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
  • 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 (
  • alkylsulfinyl 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.
  • 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.
  • 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).
  • alkynyl groups preferably 2 to 30 carbon atoms, more preferably branched or straight chain alkynyl groups having 2 to 24 carbon atoms.
  • 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 ) ⁇ .
  • the preferred embodiments are also the same.
  • Y 71 and Y 74 are a nitrogen atom or —CH ⁇ .
  • 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.
  • 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 ) ⁇ .
  • —L 81 —R 82 is an electron withdrawing group.
  • 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.
  • W 91 represents —NR 91 — or —CR 92 R 93 —
  • R 91 to R 93 represent a hydrogen atom or a monovalent substituent.
  • 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).
  • an alkynyl group preferably 2 to 30 carbon atoms, more preferably 6 to 28 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • * shows a connection part in each formula.
  • R 51 is preferably the alkyl group, alkenyl group, or alkynyl group.
  • 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 .
  • the R 62 to R 66 are preferably the alkyl group, alkenyl group, or alkynyl group.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 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.
  • 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.
  • 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).
  • 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).
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • W 171 is —NR 173 or
  • 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.
  • R is a straight chain extending vertically.
  • p represents the number of repeating units.
  • R does not need to be a straight chain and may be a branched chain.
  • 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.
  • 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.
  • 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.
  • the method for synthesizing the compound of the present invention is not particularly limited, and can be synthesized with reference to various known methods.
  • 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.).
  • 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.
  • the transition metal catalyst metals such as palladium, nickel, copper, cobalt, and iron (Journal of the American Chemical Society, 2007, Vol.
  • 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.
  • M 1 and M 2 are a trialkyltin group, a trialkylsilyl group, or —B (OR ⁇ ) 2
  • M 3 and M 4 are a halogen atom or a perfluoroalkanesulfonyloxy group.
  • 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 ⁇ ) 2
  • R ⁇ represents a hydrogen atom or an alkyl group.
  • R ⁇ 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 ⁇ ) 2 derived from the monomer used for synthesis (where R ⁇ is a hydrogen atom or An alkyl group), a halogen atom, or a perfluoroalkanesulfonyloxy group.
  • R ⁇ is a hydrogen atom or An alkyl group
  • a halogen atom or a perfluoroalkanesulfonyloxy group.
  • an aryl group or a heteroaryl group may be used as a terminal group by performing capping described below.
  • capping may be performed by adding a compound represented by Ar—V 1 after polymerization and reacting with a polymer terminal.
  • 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 .
  • R x represents a hydrogen atom or an alkyl group.
  • R x may be linked to form a ring.
  • tin reactants and boron reactants represented by (M1) to (M6), which are the raw materials, and they are synthesized according to various arbitrary methods.
  • 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.
  • 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.
  • transistors 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).
  • transistors for example, 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) (e
  • 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.
  • FET organic field effect transistor
  • ⁇ Laminated structure> There is no restriction
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the electrode 22 is a gate
  • 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.
  • the thickness of the entire transistor is, for example, 0.1 to 0.5 ⁇ m.
  • 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.
  • 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.
  • the organic thin film transistor of the present invention preferably includes a substrate.
  • substrate Arbitrary materials can be used.
  • 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.
  • PEN polyethylene naphthoate
  • PET polyethylene terephthalate
  • TAC triacetyl cellulose
  • polyimide films and these polymer films were bonded to ultrathin glass.
  • the organic thin film transistor of the present invention preferably includes an electrode.
  • 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.
  • the thickness of the electrode is not particularly limited, but is preferably 10 to 50 nm.
  • the gate width (or channel width) W and the gate length (or channel length) L are preferably 10 or more, and more preferably 20 or more.
  • the material constituting the insulator layer is not particularly limited as long as a necessary insulating effect is obtained.
  • 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.
  • 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.
  • the thickness of the insulator layer is preferably 10 to 400 nm, more preferably 20 to 200 nm, and particularly preferably 50 to 200 nm.
  • 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.
  • the layer further contained the below-mentioned low molecular organic semiconductor and the below-mentioned polymer may be sufficient.
  • 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.
  • anthracene 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.
  • Polycyclic aromatic hydrocarbons such as circ
  • polystyrene examples 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.
  • 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.
  • 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
  • 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.
  • the thickness of the semiconductor layer is preferably 10 to 400 nm, more preferably 10 to 200 nm, and particularly preferably 10 to 100 nm.
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • the coating solution that can be used for film formation by a solution process will be described.
  • organic solvent used in the coating solution examples 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.
  • 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
  • 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.
  • 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.
  • 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.
  • 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”.
  • 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
  • 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.
  • the p-type organic semiconductor and the n-type organic semiconductor phase are mixed in a specific form as described above.
  • photoelectric conversion charge separation
  • the phases are interdigitated in a nanometer order.
  • 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.
  • 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.
  • n-type organic semiconductor is not particularly limited. In general, it is a ⁇ -electron conjugated compound having a lowest unoccupied orbital (LUMO) level of ⁇ 3.5 to ⁇ 4.5 eV.
  • LUMO lowest unoccupied orbital
  • 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 for example, naphthalenetetracarboxylic
  • 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.
  • 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 (
  • 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.
  • condensed polycyclic aromatic low-molecular compound that is a p-type organic semiconductor examples 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
  • the photoelectric conversion 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.
  • p-type: n-type 10: 90 to 90:10, preferably 20:80 to 80:20.
  • 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.
  • 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.
  • the method 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.
  • a dry film formation method such as vapor deposition
  • the substrate temperature during film formation is heated to 30 ° C. to 150 ° C.
  • 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.
  • 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.
  • the organic photoelectric conversion device 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.
  • the tandem configuration can be achieved by using an intermediate electrode.
  • an electrode through which holes mainly flow is referred to as a positive electrode
  • an electrode through which electrons mainly flow is referred to as a negative electrode.
  • an electrode having translucency is referred to as a transparent electrode
  • an electrode having no translucency is referred to as a counter electrode or a metal electrode.
  • the positive electrode is a translucent transparent electrode
  • the negative electrode is a non-translucent counter electrode or metal electrode.
  • the negative electrode is a translucent transparent electrode
  • the positive electrode is a non-translucent counter electrode or metal electrode.
  • Both the first electrode and the second electrode can be transparent electrodes.
  • the first electrode is a positive electrode.
  • it is preferably a transparent electrode that transmits light from visible light to near infrared light (380 to 800 nm).
  • 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,
  • 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
  • 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.
  • a mesh electrode in which a metal such as silver is meshed to ensure light transmission.
  • 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.
  • a plurality of these conductive compounds can be combined to form a positive electrode.
  • the transmittance of the positive electrode is the thickness used for solar cells (for example, 0.2 ⁇ m 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.
  • 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.
  • PEDOT-PSS polyethylenedioxythiophene-polystyrene sulfonic acid
  • These metals, transparent conductive oxides, and conductive polymers may be used alone, or two or more kinds may be mixed or laminated.
  • 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
  • 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.
  • 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 ⁇ m, preferably 50 to 200 nm.
  • 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.
  • 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
  • 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
  • ultrathin films of metals and metal alloys such as chromium, manganese, iron, copper, zinc, strontium, silver, indium, tin, barium, and bismuth
  • conductive polymers such as polyaniline, polythiophene, and polypyrrole.
  • the transparent conductive oxide is 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.
  • the transmittance of the negative electrode is the thickness used for solar cells (eg, 0.2 ⁇ m 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • a material deeper than the HOMO level of the n-type organic semiconductor is used as the electron transport layer.
  • 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 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.
  • 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.
  • glass, plastic film, etc. Can be selected as appropriate.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • stacked on the 1st electrode and the 2nd electrode may be sufficient.
  • 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.
  • 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.
  • 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.
  • 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.
  • thermoelectric conversion device 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.
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • a base material in which an electrode is provided on the pressure contact surface with the thermoelectric conversion layer.
  • 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.
  • a metal material is preferable, and aluminum, gold, silver, or copper is more preferable.
  • 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 ⁇ m, more preferably from 50 to 1000 ⁇ m, still more preferably from 100 to 1000 ⁇ m, particularly preferably from 200 to 800 ⁇ m 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 ⁇ m, and more preferably 1 to 100 ⁇ m. 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.
  • thermoelectric conversion layer is not particularly limited.
  • 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.
  • 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.
  • thermoelectric conversion material 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.
  • SiO 2 thickness 200 nm
  • 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.
  • 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.
  • thermoelectric conversion layer 44 having a film thickness of 3.1 ⁇ m 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.
  • thermoelectric conversion device was produced in the same manner as in Example 1 except that the polymer P1 was changed to P7.
  • thermoelectric conversion device was produced in the same manner as in Example 1 except that the polymer P1 was changed to P9.
  • Example 2 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.
  • Example 2 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.
  • Example 2 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.
  • 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.
  • 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.
  • 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
  • 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 ⁇ - ⁇ 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.
  • thermoelectric characteristic value thermoelectric conversion device.
  • 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.
  • the thermoelectromotive force S ( ⁇ V / K) per unit temperature difference is obtained by dividing the thermoelectromotive force ( ⁇ V) 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.
  • thermoelectric conversion device using the semiconductor layer of the organic semiconductor compound of the present invention is excellent in thermoelectric conversion efficiency.
  • Photoelectric conversion devices Bulk heterojunction organic thin film solar cells
  • Counter electrode second electrode
  • 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)

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Abstract

L'objet de la présente invention est de pourvoir à un composé semi-conducteur organique qui augmente la cristallinité (propriétés d'encapsulation) d'un polymère semi-conducteur organique, permet d'obtenir à la fois une mobilité et une solubilité de porteur de charge à un niveau élevé, présente une mobilité de porteur de charge en cas d'utilisation dans une couche semi-conductrice, et dont les propriétés d'application sont également bonnes. L'objet de la présente invention est également de pourvoir à une composition utilisant ledit composé, à un film de revêtement, et à un dispositif à semi-conducteur organique pour lequel le composé est inclus dans une couche semi-conductrice. La présente invention porte ainsi sur un dispositif à semi-conducteur organique pour lequel une couche semi-conductrice contient un composé représenté par la formule (1). Dans la formule (1), D représente un motif structural donneur représenté par la formule (2) ou par la formule (3). Les symboles de la formule (2) et de la formule (3) représentent des groupes ou des atomes spécifiques. A représente un motif structural accepteur comprenant un cycle aromatique d'une structure cyclique condensée de direction de chaîne latérale. S1 et S2 représentent des groupes ou des liaisons spécifiques. l, n, m1, m2, et p représentent des nombres entiers spécifiques. En outre, D et A comprennent au moins un groupe parmi un groupe alkyle, un groupe alcényle, et un groupe alcynyle.
PCT/JP2014/072052 2013-08-30 2014-08-22 Dispositif à semi-conducteur organique, et composé, composition, et film de revêtement pour celui-ci Ceased WO2015029910A1 (fr)

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WO2016148169A1 (fr) * 2015-03-16 2016-09-22 富士フイルム株式会社 Élément à semi-conducteur organique et son procédé de fabrication, composé, composition semi-conductrice organique, et film semi-conducteur organique et son procédé de fabrication
JPWO2015129877A1 (ja) * 2014-02-28 2017-03-30 国立大学法人 奈良先端科学技術大学院大学 熱電変換材料および熱電変換素子
US20180175299A1 (en) * 2015-09-02 2018-06-21 Fujifilm Corporation Organic thin film transistor, method of manufacturing organic thin film transistor, organic semiconductor composition, organic semiconductor film, and method of manufacturing organic semiconductor film

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