JP5848280B2 - Organic thin film solar cell, composition and monomer used therefor, and method for producing film - Google Patents

Description

The present invention relates to an organic thin film solar cell, a composition and a monomer used therefor, and a method for producing a film .

Organic semiconductor polymers have been actively researched in recent years in the electronics field. For example, it is used for an organic electroluminescence element that emits light when electricity is passed, an organic photoelectric conversion element that generates power by light irradiation, an organic thin film transistor element that controls the amount of current and voltage, and the like. In such an element, an organic semiconductor material in which a p-type conductivity / semiconductor material as an electron donating material and an n-type conductivity / semiconductor material as an electron-accepting material are combined is used as in the case of the inorganic semiconductor material.
In recent years, since fossil energy such as petroleum has a problem of releasing carbon dioxide into the atmosphere, demand for solar cells is increasing in order to protect the global environment by suppressing global warming. Known organic solar cells using organic photoelectric conversion elements include wet-type dye-sensitized solar cells (Gretzel cells) and all-solid-state organic thin-film solar cells. Since the latter does not use an electrolytic solution, there is no need to consider evaporation or leakage of the electrolytic solution. Moreover, it is possible to give flexibility, and the structure and manufacture of the solar cell become simpler than the former.

However, the photoelectric conversion efficiency of the organic thin film solar cell is still insufficient. The photoelectric conversion efficiency is calculated by short circuit current density (Jsc) × open circuit voltage (Voc) × fill factor (FF). In order to increase this efficiency, it is necessary to improve the open circuit voltage in addition to the short circuit current density. It becomes. In order to improve the short-circuit current, an organic semiconductor material (for example, a donor-acceptor type thiophene derivative polymer compound) having a narrow band gap that absorbs light in the near infrared region and having a high carrier mobility is used. The open-circuit voltage is said to be related to the difference between the HOMO level of the p-type conductivity / semiconductor material and the LUMO level of the n-type conductivity / semiconductor material. Increasing this difference increases the open-circuit voltage. .
Considering the effects and operating principles of the organic thin-film solar cells as described above, researches on organic semiconductor polymers as p-type conductive / semiconductor materials, which are electron donating materials, are actively conducted. For example, Patent Document 1 proposes a polymer having a specific thienoisothiazole structure. Patent Document 2 and Non-Patent Document 1 disclose thienopyrazine structural units, and Non-Patent Documents 2 and 3 disclose compounds having an isothianaphthene structural unit.

US Patent Application Publication No. 2007/238854 US Patent Application Publication No. 2009/0065059

Chem. Mater. , Vol. 21, no. 15, 2009, pp. 3618-3628 Journal of Polymer Science Polymer Chemistry, Vol. 50, no. 2, 2012, pp. 250-260 Macromolecules, Vol. 45, 2012, 4069-4074

  The present inventors have focused on techniques for stabilizing product quality in view of further improvement in performance as an organic thin-film solar cell as well as mass production and widespread use.

An object of the present invention is to provide an organic thin film solar cell that is excellent in various characteristics relating to photoelectric conversion and has little variation in product quality. Furthermore, an object of the present invention is to provide a composition useful as a semiconductor material used in the solar cell and the like, a monomer for polymer synthesis , and a method for producing a film .

The above-mentioned subject has been achieved by the following means.
[1] An organic thin-film solar cell comprising a first electrode, a second electrode, and a photoelectric conversion layer disposed therebetween, wherein the photoelectric conversion layer has the following formulas (1) , (2), The organic thin-film solar cell containing the polymer which has a structural unit represented by either (3-1)-(3-9) and (4).

[In Formula (1), R ¹¹ represents a hydrogen atom, an acyl group, an alkoxycarbonyl group, an alkyl group, a fluorine atom, an aryl group, a carbamoyl group, a carboxyl group, or a group represented by —CR ^c ═CR ^a R ^b. . R ^a and R ^b each independently represents an alkyl group, a cyano group, an alkoxycarbonyl group or an acyl group, and R ^c represents a hydrogen atom or an alkyl group. However, one of R ^a and R ^b is a cyano group, an alkoxycarbonyl group, or an acyl group. R ¹² represents a hydrogen atom or a substituent. X ^A represents an oxygen atom, a sulfur atom, a selenium atom, SiR ₂ (R is a hydrogen atom or a substituent), a tellurium atom,>C═O,> SO ₂ or> NR ^N ( ^RN is a hydrogen atom or a substituent). Represent. X ¹¹ represents an oxygen atom, a sulfur atom, or> NR ^N ( ^RN is a hydrogen atom or a substituent). X ¹² represents an oxygen atom, a sulfur atom or ═NR ⁿ (R ⁿ is a substituent).
In formula (2), X ²¹ represents an oxygen atom, a sulfur atom, a divalent group represented by ═NR ⁿ or ═CR ²⁰¹ R ²⁰² . R ²⁰¹ and R ²⁰² each independently represent a substituent. R ²⁰¹ and R ²⁰² may be connected to each other to form a ring. Is R ⁿ is as defined in the formula (1). Ring A represents an aromatic ring.
Wherein (3-1) ~ (3-9), X B is as defined above ^{X A.} R ³³ represents a hydrogen atom or a substituent. X ³³ represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or> NR ^N. Is R ^N is as defined in the formula (1). X ³⁴ is a methine group - represents a group or a nitrogen atom (= CR ^M). X ³⁵ represents a divalent group represented by > CR ^b R ^c or> C═CR ^d R ^e . R ^{b to} R ^e each independently represents a hydrogen atom or a substituent. One of X ³⁶ and ^{X 37} represents a nitrogen atom and the other is = CR ^M - represents a. R ^{34 to} R ³⁷ each independently represents a hydrogen atom or a substituent. X ⁶¹ and ^{X 62} each independently methine group - represents a group or a nitrogen atom (= CR ^M). R ^M represents a hydrogen atom or a substituent. R ⁶⁴ and R ⁶⁵ each independently represents an alkoxycarbonyl group or an acyl group. R ^{74 to} R ⁷⁷ each independently represent a hydrogen atom or a substituent.
In the formula (4), the ^{X C} have the same meanings as defined above ^{X A.} R ⁴¹ and R ⁴² are each independently a hydrogen atom, a formyl group, a fluorine atom, a chlorine atom, an alkyl group having 1 to 24 carbon atoms, an acyl group having 2 to 24 carbon atoms, an alkoxycarbonyl group having 3 to 24 carbon atoms, An acyloxy group having 2 to 24 carbon atoms, an alkylsulfonyl group having 1 to 24 carbon atoms, an alkoxysulfonyl group having 1 to 24 carbon atoms, a nitro group, a perfluoroalkyl group having 1 to 24 carbon atoms, and a perfluoroalkyl group having 1 to 24 carbon atoms. Fluoroalkoxy group, carbamoyl group having 1 to 24 carbon atoms, sulfamoyl group having 1 to 24 carbon atoms, perfluoroalkylcarbonyl group having 2 to 24 carbon atoms, perfluoroalkylcarbonyloxy group having 2 to 24 carbon atoms, 2 carbon atoms Represents an alkynyl group of ˜24 or —CR ⁴⁵ ═CR ⁴⁶ R ⁴⁷ . R ⁴⁵ represents a hydrogen atom or an alkyl group. R ⁴⁶ and R ⁴⁷ each independently represents a hydrogen atom, an alkyl group, a cyano group, an alkoxycarbonyl group or an acyl group. However, either one of R ⁴⁶ and R ⁴⁷ is a cyano group, an alkoxycarbonyl group or an acyl group. R ⁴³ represents a substituent. X ⁴¹ represents a nitrogen atom or ═CR ⁴⁴ —. R ⁴⁴ represents a hydrogen atom or a substituent.
Here, definitive each expression * represents a bond to form a polymer backbone. ]
[2] The organic thin film solar cell according to [1], wherein X ¹² in the formula (1) is an oxygen atom.
[3] The organic thin film solar cell according to [1] or [2], wherein X ¹¹ in the formula (1) is an oxygen atom.
[4] The organic thin film solar cell according to any one of X ^A is a sulfur atom in the formula (1) [1] to [3].
[5] The organic thin film solar cell according to [1], wherein the structural unit represented by the formula (2) is a structural unit represented by the following formula (2-1).

[In Formula (2-1), X ²¹ has the same meaning as in Formula (2). X ^E and ^{X F} are each independently a methine group ⁽⁼ CR ^M -: ^R M is a hydrogen atom or a substituent group) or a nitrogen atom. Here, * indicates a bond forming a polymer main chain. ]
[6] The organic thin film solar cell according to [5], wherein the structural unit represented by the formula (2-1) is a structural unit represented by the following formula (2-2).

[In the formula (2-2), R ²² represents> NR ^N or> C═O. R ^{23 to} R ²⁶ each independently represents a hydrogen atom or a substituent. X ^E and ^{X F} are the same meanings as in the formula (2-1). ^RN is synonymous with the formula (1). Here, * indicates a bond forming a polymer main chain. ]

[7] X ^C in Formula (4), an organic thin film solar cell according to a sulfur atom [1].
[8] R ⁴¹ and R ⁴² in the formula (4) are each independently a formyl group, a fluorine atom, a chlorine atom, an acyl group having 2 to 24 carbon atoms, an alkoxycarbonyl group having 3 to 24 carbon atoms, or 2 carbon atoms. To 24 acyloxy groups, alkylsulfonyl groups having 1 to 24 carbon atoms, alkoxysulfonyl groups having 1 to 24 carbon atoms, nitro groups, perfluoroalkyl groups having 1 to 24 carbon atoms, perfluoroalkoxy groups having 1 to 24 carbon atoms Carbamoyl group having 1 to 24 carbon atoms, sulfamoyl group having 1 to 24 carbon atoms, perfluoroalkylcarbonyl group having 2 to 24 carbon atoms, perfluoroalkylcarbonyloxy group having 2 to 24 carbon atoms, 2 to 24 carbon atoms ^{.R 46} and ^{R 47} alkynyl or ^{-CR 45 = CR 46 R 47 (} R 45 represents a hydrogen atom or an alkyl group each To stand, represent a hydrogen atom, an alkyl group, a cyano group, an alkoxycarbonyl group or an acyl group. However, either one of R ⁴⁶ and R ⁴⁷ is a cyano group, an alkoxycarbonyl group or an acyl group.) [1 ] Or the organic thin film solar cell according to [7] .
[9] A composition containing a polymer having a structural unit represented by any one of the following formulas (1) , (2), (3-1) to (3-9) and (4) in an organic solvent.

[In Formula (1), R ¹¹ represents a hydrogen atom, an acyl group, an alkoxycarbonyl group, an alkyl group, a fluorine atom, an aryl group, a carbamoyl group, a carboxyl group, or a group represented by —CR ^c ═CR ^a R ^b. . R ^a and R ^b each independently represents an alkyl group, a cyano group, an alkoxycarbonyl group or an acyl group, and R ^c represents a hydrogen atom or an alkyl group. However, one of R ^a and R ^b is a cyano group, an alkoxycarbonyl group, or an acyl group. R ¹² represents a hydrogen atom or a substituent. X ^A represents an oxygen atom, a sulfur atom, a selenium atom, SiR ₂ (R is a hydrogen atom or a substituent), a tellurium atom,>C═O,> SO ₂ or> NR ^N ( ^RN is a hydrogen atom or a substituent). Represent. X ¹¹ represents an oxygen atom, a sulfur atom, or> NR ^N ( ^RN is a hydrogen atom or a substituent). X ¹² represents an oxygen atom, a sulfur atom or ═NR ⁿ (R ⁿ is a substituent).
In formula (2), X ²¹ represents an oxygen atom, a sulfur atom, a divalent group represented by ═NR ⁿ or ═CR ²⁰¹ R ²⁰² . R ²⁰¹ and R ²⁰² each independently represent a substituent. R ²⁰¹ and R ²⁰² may be connected to each other to form a ring. Is R ⁿ is as defined in the formula (1). Ring A represents an aromatic ring.
Wherein (3-1) ~ (3-9), X B is as defined above ^{X A.} R ³³ represents a hydrogen atom or a substituent. X ³³ represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or> NR ^N. Is R ^N is as defined in the formula (1). X ³⁴ is a methine group - represents a group or a nitrogen atom (= CR ^M). X ³⁵ represents a divalent group represented by > CR ^b R ^c or> C═CR ^d R ^e . R ^{b to} R ^e each independently represents a hydrogen atom or a substituent. One of X ³⁶ and ^{X 37} represents a nitrogen atom and the other is = CR ^M - represents a. R ^{34 to} R ³⁷ each independently represents a hydrogen atom or a substituent. X ⁶¹ and ^{X 62} each independently methine group - represents a group or a nitrogen atom (= CR ^M). R ^M represents a hydrogen atom or a substituent. R ⁶⁴ and R ⁶⁵ each independently represents an alkoxycarbonyl group or an acyl group. R ^{74 to} R ⁷⁷ each independently represent a hydrogen atom or a substituent.
In the formula (4), the ^{X C} have the same meanings as defined above ^{X A.} R ⁴¹ and R ⁴² are each independently a hydrogen atom, a formyl group, a fluorine atom, a chlorine atom, an alkyl group having 1 to 24 carbon atoms, an acyl group having 2 to 24 carbon atoms, an alkoxycarbonyl group having 3 to 24 carbon atoms, An acyloxy group having 2 to 24 carbon atoms, an alkylsulfonyl group having 1 to 24 carbon atoms, an alkoxysulfonyl group having 1 to 24 carbon atoms, a nitro group, a perfluoroalkyl group having 1 to 24 carbon atoms, and a perfluoroalkyl group having 1 to 24 carbon atoms. Fluoroalkoxy group, carbamoyl group having 1 to 24 carbon atoms, sulfamoyl group having 1 to 24 carbon atoms, perfluoroalkylcarbonyl group having 2 to 24 carbon atoms, perfluoroalkylcarbonyloxy group having 2 to 24 carbon atoms, 2 carbon atoms 24 alkynyl group or ^-CR 45 ⁼ represents a ^CR 46 ^{R 47.} R ⁴⁵ represents a hydrogen atom or an alkyl group. R ⁴⁶ and R ⁴⁷ each independently represents a hydrogen atom, a cyano group, an alkoxycarbonyl group or an acyl group. However, either one of R ⁴⁶ and R ⁴⁷ is a cyano group, an alkoxycarbonyl group or an acyl group. R ⁴³ represents a substituent. X ⁴¹ represents a nitrogen atom or ═CR ⁴⁴ —. R ⁴⁴ represents a hydrogen atom or a substituent.
Here, definitive each expression * represents a bond to form a polymer backbone. ]
[10] The composition according to [9] , further comprising an n-type semiconductor component.
[11] The composition according to [10] , wherein the n-type semiconductor component is a fullerene derivative.
[12] The composition according to any one of [9] to [11] , which is for an organic semiconductor material.
[13] A method for producing a film on which the composition according to [12] is applied.
[14] A monomer comprising a compound represented by any one of the following formulas (M1) to (M3-9) .

[In the formula (M1), R ¹¹ represents a hydrogen atom, an acyl group, an alkoxycarbonyl group, an alkyl group, a fluorine atom, an aryl group, a carbamoyl group, a carboxyl group, or a group represented by —CR ^c = CR ^a R ^b. . R ^a and R ^b each independently represents an alkyl group, a cyano group, an alkoxycarbonyl group or an acyl group, and R ^c represents a hydrogen atom or an alkyl group. However, one of R ^a and R ^b is a cyano group, an alkoxycarbonyl group, or an acyl group. R ¹² represents a hydrogen atom or a substituent. X ^A represents an oxygen atom, a sulfur atom, a selenium atom, SiR ₂ (R is a hydrogen atom or a substituent), a tellurium atom,>C═O,> SO ₂ or> NR ^N ( ^RN is a hydrogen atom or a substituent). Represent. X ¹¹ represents an oxygen atom, a sulfur atom, or> NR ^N ( ^RN is a hydrogen atom or a substituent). X ¹² represents an oxygen atom, a sulfur atom or ═NR ⁿ (R ⁿ is a substituent).
Wherein ^{(M2), X 21} represents an oxygen atom, a sulfur atom, a divalent group represented by = NR ⁿ or ⁼ CR ^{201 R 202.} R ²⁰¹ and R ²⁰² each independently represent a substituent. R ²⁰¹ and R ²⁰² may be connected to each other to form a ring. Is R ⁿ is as defined in the formula (1). Ring A represents an aromatic ring.
Wherein (M3-1) ~ (M3-9), X B is as defined above ^{X A.} R ³³ represents a hydrogen atom or a substituent. X ³³ represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or> NR ^N. Is R ^N is as defined in the formula (1). X ³⁴ is a methine group - represents a group or a nitrogen atom (= CR ^M). X ³⁵ represents a divalent group represented by > CR ^b R ^c or> C═CR ^d R ^e . R ^{b to} R ^e each independently represents a hydrogen atom or a substituent. One of X ³⁶ and ^{X 37} represents a nitrogen atom and the other is = CR ^M - represents a. R ^{34 to} R ³⁷ each independently represents a hydrogen atom or a substituent. X ⁶¹ and ^{X 62} each independently methine group - represents a group or a nitrogen atom (= CR ^M). R ^M represents a hydrogen atom or a substituent. R ⁶⁴ and R ⁶⁵ each independently represents an alkoxycarbonyl group or an acyl group. R ^{74 to} R ⁷⁷ each independently represent a hydrogen atom or a substituent.
In formulas (M1) to (M3-9) , Ya and Yb each independently represent a halogen atom, a perfluoroalkanesulfonyloxy group, a trialkyltin group, a boronic ester group, or a boronic acid group. ]

  In this specification, the aromatic ring is used to mean including an aromatic ring and an aromatic heterocyclic ring, and may be monocyclic or bicyclic. An alicyclic ring represents a non-aromatic ring structure which may contain a hetero atom, and may be monocyclic or multicyclic. When there are a plurality of substituents, linking groups, etc. (hereinafter referred to as “substituents”) indicated by a specific symbol, or when a plurality of substituents, etc. are specified simultaneously or alternatively, each substituent, etc. It may be the same or different. The same applies to the definition of the number of substituents and the like. Further, even if not specifically stated, when a plurality of substituents and the like are close to each other, they may be connected to each other or condensed to form a ring.

The organic thin film solar cell of the present invention is excellent in various characteristics relating to photoelectric conversion. Furthermore, there is an excellent effect that there is little variation in quality when considering mass production and actual use. Further, the polymer synthesis monomer of the present invention and the composition containing the same are novel and useful as a semiconductor material used in the solar cell and the like. Furthermore, the present invention can provide a method for producing a film.

It is a side view which shows typically the structure of preferable embodiment of the organic thin-film solar cell of this invention.

  The organic thin film solar cell of the present invention uses a polymer having a structural unit represented by any of the following formulas (1) to (4) in the photoelectric conversion layer. Hereinafter, after explaining the basic structure of the organic thin film solar cell according to the present invention, the characteristics of the polymer will be described.

<Organic thin film solar cell>
FIG. 1 is a side view schematically showing an example of the organic thin film solar cell of the present invention. The solar cell 10 of the present embodiment includes a photoelectric conversion layer (bulk hetero bond layer) 3 including a polymer having the following specific structural unit. Organic thin-film solar cells are generally classified into pin junction organic thin-film solar cells having a p-i-n three-layer structure and bulk heterojunction organic thin-film solar cells, and any of them is used in the present invention. I do not care. Since high power generation efficiency can be easily obtained, it is particularly preferably applied to a bulk heterojunction organic thin film solar cell as shown in FIG.

  In the organic thin film solar cell of this embodiment, the photoelectric conversion layer 3 is composed of a p-type semiconductor phase that is an electron donating compound and an n-type semiconductor phase that is an electron-accepting compound. The photoelectric conversion layer 3 is provided between the first electrode 11 and the second electrode 12. In the present invention, the hole transport layer 21 is preferably provided between the first electrode and the photoelectric conversion layer, and the electron transport layer 22 is preferably provided between the second electrode and the photoelectric conversion layer. By providing these hole transport layer and electron transport layer, it is possible to extract charges generated in the photoelectric conversion layer more efficiently. In the solar cell of the present embodiment, the distinction between the upper and lower sides is not particularly important, but if necessary for convenience, the first electrode 11 side is positioned as the “up” or “top” side, and the second electrode 12 side is defined as “ Position it as “bottom” or “bottom”. Here, in order from the upper layer, the configuration of the substrate, the positive electrode, the hole transport layer, the photoelectric conversion layer, the electron transport layer, and the negative electrode is referred to as the forward configuration, and the substrate, the negative electrode, the electron transport layer, the photoelectric conversion layer, and the hole transport in order from the upper layer. The configuration of the layer and the positive electrode is referred to as a reverse configuration, and in the present invention, both the forward configuration and the reverse configuration are preferably applied.

  In the photoelectric conversion layer, the p-type semiconductor phase and the n-type semiconductor phase are mixed in a specific form as described above, and photoelectric conversion is performed at the interface. The form is not particularly limited, but as an ideal example, a state in which the phases are interdigitated in the order of nanometers as illustrated is preferable. In order to effectively create such a form, the p-type semiconductor polymer preferably has a specific compatibility or incompatibility with the n-type semiconductor polymer. The material that becomes the p-type semiconductor is not determined only by the specific physical properties, but is specified by the relative relationship with the material that becomes the n-type semiconductor. For example, when a typical fullerene is taken as an example of an n-type semiconductor material, a material having a higher electron donating property can be a p-type semiconductor material. According to the following specific polymer, the above requirements can be satisfied satisfactorily.

<Specific polymer>
In this invention, the polymer which has a structural unit (henceforth a specific structural unit) represented by either of following formula (1)-(4) is applied to the photoelectric converting layer of an organic thin-film solar cell.

(Specific structural unit)
[Structural Unit Represented by Formula (1)]

・ R ¹¹ , R ¹²
In Formula (1), R ¹¹ represents a hydrogen atom, an acyl group, an alkoxycarbonyl group, an alkyl group, a fluorine atom, an aryl group, a carbamoyl group, a carboxyl group, or a group represented by —CR ^c ═CR ^a R ^b . R ¹² represents a hydrogen atom or a substituent. Preferable examples of R ¹² include examples of the substituent T described below, and include a hydrogen atom, a fluorine atom, a chlorine atom, an alkyl group (preferably having 1 to 24 carbon atoms), a hydroxyl group, and an acyloxy group (having 2 to 24 carbon atoms). Preferably) or an aryl group (preferably having 6 to 24 carbon atoms), more preferably a hydrogen atom or an alkyl group. R ¹¹ is preferably a hydrogen atom, an alkyl group, an acyl group, an alkoxycarbonyl group, or a group represented by —CR ^c = CR ^a R ^b . R ^a and R ^b each independently represents an alkyl group (preferably having 1 to 24 carbon atoms), a cyano group, an alkoxycarbonyl group (preferably having 2 to 24 carbon atoms), or an acyl group (preferably having 2 to 24 carbon atoms). R ^c represents a hydrogen atom or an alkyl group (preferably having 1 to 24 carbon atoms). However, one of R ^a and R ^b is a cyano group, an alkoxycarbonyl group, or an acyl group.

・ X ^A
X ^A is an oxygen atom, a sulfur atom, a selenium atom, SiR ₂ (R represents a hydrogen atom or a substituent), a tellurium atom,>C═O,> SO ₂ or> NR ^N ( ^RN is a hydrogen atom or a substituent) Represents). When R ^N and R are substituents, preferred examples of the substituent include the examples of substituent T described later, and include a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms), an alkenyl group (carbon number). 2-24 are preferred), an alkynyl group (preferably having 2-24 carbon atoms) is preferred, and an alkyl group is more preferred. A preferable range of the carbon number of the alkyl group and the like exemplified in the substituent T is not particularly specified, but is the same as that described for the substituent T throughout the present specification. X ^A is preferably a sulfur atom, a selenium atom,>C═O,> SO ₂ , or> NR ^{N, and} more preferably a sulfur atom.

・ X ¹¹
X ¹¹ represents an oxygen atom, a sulfur atom or> NR ^N. The R ^N, wherein has the same meaning as R ^N, and their preferable ranges are also the same. X ¹¹ is preferably an oxygen atom.

· ^{X 12}
X ¹² represents an oxygen atom, a sulfur atom or ═NR ⁿ (R ⁿ represents a substituent). Preferable examples of the substituent for R ⁿ include the examples of substituent T described below, and include a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms), and an alkynyl group. (C2-C24 is preferable). X ¹² is preferably an oxygen atom.

  * Indicates a bond forming a polymer main chain. This is the same for other chemical formulas, but it is not neglected.

[Structural Unit Represented by Formula (2)]

・ X ²¹
In formula (2), X ²¹ represents an oxygen atom, a sulfur atom, a divalent group represented by ═NR ⁿ or ═CR ²⁰¹ R ²⁰² . R ²⁰¹ and R ²⁰² represent a substituent. Here, R ⁿ has the same meaning as described above. Examples of the substituent of R ²⁰¹ and R ²⁰² include the examples of substituent T described later, and include an alkyl group (preferably having 1 to 24 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms), an alkynyl group (having carbon numbers). 2-24 are preferred), an acyl group (preferably having 2-24 carbon atoms), an alkoxycarbonyl group (preferably having 2-24 carbon atoms), and a cyano group are preferred. R ²⁰¹ and R ²⁰² may be bonded to each other to form a ring.

Ring A represents an aromatic ring. The aromatic ring includes an aromatic hydrocarbon ring and an aromatic heterocycle, and examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring.
The aromatic heterocycle is preferably a 5- or 6-membered ring, and the ring-constituting heteroatom is preferably a nitrogen atom, oxygen atom, sulfur atom, selenium atom or tellurium atom. For example, a pyrrole ring, thiophene ring, furan ring, pyrazole Ring, imidazole ring, triazole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, thiadiazole ring, selenophene ring, tellurophen ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring. A ring in which a benzene ring is condensed is also preferable.
Preferred aromatic rings include benzene ring, naphthalene ring, benzothiophene ring, benzothiazole ring, benzoisothiazole ring, benzoxazole ring, benzisoxazole ring, pyridine ring, pyridazine ring, among them, benzene ring, pyridine ring A pyridazine ring is preferred. Ring A may be substituted with a substituent T described later.

  The structural unit represented by the formula (2) is preferably a structural unit represented by the following formula (2-1).

・ X ^{21
Wherein, X 21} have the same meanings as those in formula (2).

・ X ^E , X ^F
X ^E and ^{X F} are each independently a methine group ⁽⁼ CR ^M -: ^R M is a hydrogen atom or a substituted group) or a nitrogen atom. Here, when R ^M is a substituent, examples of the substituent include examples described later substituent T, preferably an alkyl group (having 1 to 24 carbon atoms are preferred), alkenyl group (carbon number 2 to 24 ), An alkynyl group (preferably having 2 to 24 carbon atoms), an acyl group (preferably having 2 to 24 carbon atoms), an acyloxy group (preferably having 2 to 24 carbon atoms), an alkoxycarbonyl group (having 2 to 24 carbon atoms). Preferred), a fluorine atom, a chlorine atom, and a cyano group.

  The structural unit represented by the formula (2-1) is preferably a structural unit represented by the following formula (2-2).

・ R ²²
In the formula, R ²² represents> NR ^N or> C═O. ^RN has the same meaning as defined above.

· ^R 23 ~R ²⁶
R ^{23 to} R ²⁶ each independently represent a hydrogen atom or a substituent. X ^E and ^{X F} are the same meanings as in the formula (2-1). Here, when R ^{23 to} R ²⁶ are substituents, examples of the substituent T are given as examples of the substituents, and include a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms), an alkoxy group (carbon number). 1-24 are preferred), an alkoxycarbonyl group (preferably having 2-24 carbon atoms), and an aryl group (preferably having 6-24 carbon atoms) are preferred.

[Structural Unit Represented by Formula (3)]

・ X ^B
Wherein, ^{X B} is as defined above ^{X A.}

・ Ring B
Ring B represents a monocyclic or bicyclic aromatic ring or alicyclic ring. However, when both X ³¹ and X ³² are ═CR ³¹ —, the ring B represents a monocyclic aromatic ring, a monocyclic alicyclic ring containing no nitrogen atom, or a bicyclic aromatic ring or alicyclic ring.
The aromatic ring includes an aromatic hydrocarbon ring and an aromatic heterocycle, and examples of the aromatic hydrocarbon ring include a benzene ring and a naphthalene ring.
The aromatic heterocycle is preferably a 5- or 6-membered ring, and the ring-constituting heteroatom is preferably a nitrogen atom, oxygen atom, sulfur atom, selenium atom or tellurium atom. For example, a pyrrole ring, thiophene ring, furan ring, pyrazole Ring, imidazole ring, triazole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, thiadiazole ring, selenophene ring, tellurophen ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring, and these A ring in which a benzene ring is condensed to the ring is also preferred.

The alicyclic ring is a ring other than an aromatic ring, and includes a cycloalkane or a heterocyclic ring, and a 5- or 6-membered ring is preferable. Examples of the cycloalkane include cyclopentane, cyclopentanone, 1,3-cyclopentanedione, cyclohexane, cyclohexanone, and 1,4-cyclohexanedione, and examples of the heterocyclic ring include pyrrolidinone and 2,5-pyrrolidinedione.
Ring B may be substituted with a substituent T described later.

When at least one of X ³¹ and X ³² is a nitrogen atom, the ring B is benzene, naphthalene, 2,5-pyrrolidinedione, 1,3-cyclopentanedione, thiophene, selenophene, pyrrole, thiazole, isothiazole, imidazole. , Pyrazole, 1,2,3-triazole, oxazole, isoxazole, 1,4-cyclohexanedione, 1,2,5-thiadiazole, pyridine, pyrimidine, pyrazine, pyridazine, benzene, 2,5-pyrrolidinedione 1,3-cyclopentanedione, thiophene, thiazole, isothiazole, imidazole, 1,2,3-triazole, oxazole, isoxazole and 1,4-cyclohexanedione are preferred. When both X ³¹ and X ³² are ═CR ³¹ —, benzene, naphthalene, 1,3-cyclopentanedione, thiophene, selenophene, pyrrole, thiazole, isothiazole, imidazole, pyrazole, 1,2,3-triazole, Oxazole, isoxazole, 1,4-cyclohexanedione, 1,2,5-thiadiazole, pyridine, pyrimidine, pyrazine, pyridazine, benzene, 1,3-cyclopentanedione, thiophene, thiazole, isothiazole, imidazole, 1,2,3-triazole, oxazole, isoxazole and 1,4-cyclohexanedione are preferred.

· ^{X 31, X 32}
X ³¹ and X ³² represent a nitrogen atom or ═CR ³¹ —. Examples of R ³¹ include a substituent T described later, preferably a hydrogen atom, a fluorine atom or a chlorine atom, and more preferably a hydrogen atom or a fluorine atom.

  The structural unit represented by the formula (3) is preferably a structural unit represented by any of the following formulas (3-1) to (3-3).

・ R ³³
In the formula, R ³³ represents a hydrogen atom or a substituent. Examples of the substituent include the substituent T described later, and include a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms), an alkynyl group (having 2 to 24 carbon atoms). Are preferred), an alkoxycarbonyl group (preferably having 2 to 24 carbon atoms), an acyl group (preferably having 2 to 24 carbon atoms), and an alkylsulfonyl group (preferably having 1 to 24 carbon atoms) are preferred.

・ X ³³
X ³³ represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or> NR ^N. X ³³ is preferably a sulfur atom or> NR ^N, more preferably a sulfur atom. ^RN is synonymous with that defined in Formula (1), and the preferred range is also the same.

・ X ³⁴
X ³⁴ is a methine group - represents a group or a nitrogen atom (= CR ^M). R ^M has the same meaning as defined above, and the preferred range is also the same.

・ X ³⁵
X ³⁵ represents a divalent group represented by> CR ^b R ^c ,> C═CR ^d R ^e or> NR ^N. X ³⁵ is preferably> CR ^b R ^c or> NR ^{N. RN} has the same meaning as defined above. R ^{b to} R ^e each independently represents a hydrogen atom or a substituent. When R ^{b to} R ^e are substituents, examples of the substituent T will be given as examples of the substituent, and an alkyl group (preferably having 1 to 24 carbon atoms) and an alkenyl group (preferably having 2 to 24 carbon atoms) are included. An alkynyl group (preferably having 2 to 24 carbon atoms) is preferred, and an alkyl group is more preferred.

· ^R 34 ~R ³⁷
R ^{34 to} R ³⁷ each independently represents a hydrogen atom or a substituent. Examples of the substituent T include examples of the substituent T described below. R ^{34 to} R ³⁷ are each independently an alkyl group (preferably having 1 to 24 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms), or alkynyl. Group (preferably having 2 to 24 carbon atoms), acyl group (preferably having 2 to 24 carbon atoms), alkoxycarbonyl group (preferably having 2 to 24 carbon atoms), acyloxy group (preferably having 2 to 24 carbon atoms), fluorine atom A chlorine atom is preferred. It is preferable that at least one of R ^{34 to} R ³⁷ is an electron withdrawing group. The electron withdrawing group is synonymous with what is defined by R ⁴¹ and R ⁴² later, and the preferred range is also the same. R ³⁴ and R ³⁷ are preferably a halogen atom among the electron-attracting groups, and more preferably a fluorine atom or a chlorine atom. R ³⁵ and R ³⁶ are preferably an alkoxycarbonyl group or an acyl group among electron withdrawing groups.

・ X ^B
X ^B is as defined in the formula (3).

  It is also preferred that the structural unit represented by the formula (3) is a structural unit represented by the following formulas (3-4) to (3-6).

In the formula, R ³³ , X ³³ , X ³⁴ , and X ^B are as defined in formulas (3-1) to (3-3). X ³⁵ represents a> ^CR b ^{R c} or> C = ^CR d ^{R e.} R ^{b to} R ^e have the same meanings as the (3-2) R ^{b to} R ^e . X ⁶¹ and ^{X 62} each independently methine group - represents a group or a nitrogen atom (= CR ^M). R ⁶⁴ and R ⁶⁵ represent a hydrogen atom or a substituent. Both X ^{61, X 62} is a methine group (= CR ^M -) ^{For, R 64,} R ⁶⁵ and ^{R M} is preferably an electron withdrawing group. R ⁶⁴ and R ⁶⁵ is preferably an alkoxycarbonyl group or an acyl group, R ^M is preferably a halogen atom, a fluorine atom or a chlorine atom is more preferable.

  It is also preferred that the structural unit represented by the formula (3) is a structural unit represented by the following formulas (3-7) to (3-9).

In the formula, R ³³ , X ³³ , X ³⁴ , X ³⁵ , and X ^B are as defined in the above formulas (3-1) to (3-3). R ^{74 to} R ⁷⁷ in the formula (3-9) have the same meanings as R ^{34 to} R ^{37 in the} formula (3-3). In addition, in this specification, the notation of a repeating unit means that this includes an isomer having a structure that is horizontally reversed. In other words, the structural unit represented by the structural formula may be introduced into the polymer in an inverted form.

[Structural Unit Represented by Formula (4)]

・ X ^C
Wherein, X ^C has the same meaning as defined above X ^A, the preferred range is also the same.

・ R ⁴¹ , R ⁴²
R ⁴¹ and R ⁴² are each independently a hydrogen atom, a formyl group, a fluorine atom, a chlorine atom, an alkyl group having 1 to 24 carbon atoms (preferably having 4 to 24 carbon atoms, more preferably 6 to 24 carbon atoms), carbon C2-C24 acyl group (C4-C24 is preferable, C6-C24 is more preferable), C3-C25 alkoxycarbonyl group (C5-C25 is preferable, C7-C25 is More preferably), an acyloxy group having 2 to 24 carbon atoms (preferably 4 to 24 carbon atoms, more preferably 6 to 24 carbon atoms), an alkylsulfonyl group having 1 to 24 carbon atoms (preferably 4 to 24 carbon atoms, carbon 6 to 24 are more preferable), an alkoxysulfonyl group having 2 to 24 carbon atoms (4 to 24 carbon atoms are preferable, and 6 to 24 carbon atoms are more preferable), a nitro group, and a perfluoro having 1 to 24 carbon atoms. An alkyl group (preferably having 1 to 16 carbon atoms, more preferably 1 to 6 carbon atoms), a perfluoroalkoxy group having 1 to 24 carbon atoms (preferably having 1 to 16 carbon atoms, more preferably 1 to 6 carbon atoms), A carbamoyl group having 1 to 24 carbon atoms (preferably 4 to 24 carbon atoms, more preferably 6 to 24 carbon atoms), a sulfamoyl group having 1 to 24 carbon atoms (preferably 4 to 24 carbon atoms, and 6 to 24 carbon atoms). More preferably), a perfluoroalkylcarbonyl group having 2 to 24 carbon atoms (preferably 2 to 16 carbon atoms, more preferably 2 to 6 carbon atoms), a perfluoroalkylcarbonyloxy group having 2 to 24 carbon atoms (2 carbon atoms). to 16, and more preferably 2 to 6 carbon atoms), preferably an alkynyl group (24 carbon atoms of 2 to 24 carbon atoms, more preferably 6 to 24 carbon atoms), - ^{CR 45} It represents a CR ⁴⁶ R ^47.

  4-24 are preferable and, as for carbon number of the said group except a perfluoroalkyl group, a perfluoroalkoxy group, a perfluoroalkylcarbonyl group, and a perfluoroalkylcarbonyloxy group among the said groups, 6-24 are more preferable. 1-16 are preferable and, as for carbon number of a perfluoroalkyl group, a perfluoroalkoxy group, and a perfluoroalkylcarbonyl group, 1-6 are more preferable. When the carbon number is in the above range, the solubility of the polymer is improved, and a uniform film can be formed. Therefore, it is considered that the battery characteristics can be improved and the product quality can be suppressed.

R ⁴¹ and R ⁴² are each independently a formyl group, fluorine atom, chlorine atom, acyl group having 4 to 24 carbon atoms, alkoxycarbonyl group having 5 to 25 carbon atoms, alkylsulfonyl group having 4 to 24 carbon atoms, carbon number A perfluoroalkyl group having 1 to 16 carbon atoms, a perfluoroalkoxy group having 1 to 16 carbon atoms, a perfluoroalkylcarbonyl group having 2 to 16 carbon atoms, an alkynyl group having 3 to 24 carbon atoms, -CR ⁴⁵ = CR ⁴⁶ R ⁴⁷ Preferably, a hydrogen atom, a fluorine atom, a chlorine atom, an acyl group having 6 to 24 carbon atoms, an alkoxycarbonyl group having 7 to 25 carbon atoms, a perfluoroalkyl group having 1 to 6 carbon atoms, an alkynyl group having 6 to 24 carbon atoms, -CR ⁴⁵ = ^CR 46 ^{R 47} is more preferable.

R ⁴⁵ represents a hydrogen atom or an alkyl group (preferably having 1 to 24 carbon atoms). R ⁴⁶ and R ⁴⁷ each independently represent a hydrogen atom, a cyano group, an alkoxycarbonyl group (preferably having 2 to 24 carbon atoms) or an acyl group (preferably having 2 to 24 carbon atoms). However, either one of R ⁴⁶ and R ⁴⁷ is a cyano group, an alkoxycarbonyl group or an acyl group.
R ⁴³ represents a hydrogen atom or a substituent. Examples of the substituent include the substituent T described later, and a hydrogen atom and a fluorine atom are preferable.

・ X ⁴¹
X ⁴¹ represents a nitrogen atom or ═CR ⁴⁴ —. R ⁴⁴ represents a hydrogen atom or a substituent. Examples of the substituent include a substituent T described later, a hydrogen atom, a fluorine atom, a chlorine atom, an alkyl group (preferably having 1 to 24 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms), an alkynyl group ( C2-C24 is preferable), and a hydrogen atom or a fluorine atom is more preferable.

(Specific monomer)
The specific structural unit in the specific polymer can be synthesized from a compound represented by any of the following formulas (M1) to (M4).

In the formula, R ¹¹ , R ¹² , R ⁴¹ , R ⁴² , R ⁴³ , X ^A , X ^B , X ^C , X ¹¹ , X ¹² , X ²¹ , X ³¹ , X ³² , X ⁴¹ , Ring A, Ring B Is synonymous with the formulas (1) to (4).

・ Ya, Yb
Ya and Yb each independently represent a halogen atom, a perfluoroalkanesulfonyloxy group, a trialkyltin group, a boronic ester group or a boronic acid group.

(Copolymerization component)
The polymer used in the present invention is preferably a copolymer having the specific structural unit and two or more other copolymer components. As copolymerization components, benzene structural unit, naphthalene structural unit, anthracene structural unit, phenanthrene structural unit, benzodithiophene structural unit, naphthodithiophene structural unit, carbazole structural unit, silacyclopentadithiophene structural unit, cyclopentadithiazole Structural unit, benzothiadiazole structural unit, thiadiazoloquinoxaline structural unit, cyclopentadithiophene structural unit, oxidized cyclopentadithiophene structural unit, benzoisothiazole structural unit, benzothiazole structural unit, oxidized thiophene structural unit, thienothiophene structural unit , Thienothiophene oxide unit, dithienothiophene unit, dithienothiophene oxide unit, tetrahydroisoindole unit, fluorene unit, fluorenone unit, Zole building block, isothiazole building block, selenophene building block, thiophene building block, furan building block, pyrrole building block, silole building block, thiazolothiazole building block, naphthothiadiazole building block, thienopyrazine building block, oxazole building block, isoxazole Constitutional unit, imidazole constitutional unit, pyrazole constitutional unit, triazole constitutional unit, pyridine constitutional unit, pyridazine constitutional unit, pyrimidine constitutional unit, triazine constitutional unit, tetrazine constitutional unit, thiadiazole constitutional unit, oxadiazole constitutional unit, benzoxazole constitutional unit, Examples include a benzimidazole structural unit, a thienothiazole structural unit, and a cyclopentadipyridine structural unit. What condensed the said structural unit is also preferable. The copolymerization mode is not particularly limited, but when the monomer is a two-component, it is preferably an alternating copolymer.

  These structural units are preferably those represented by the following formulas (II-1) to (II-23). * Represents a bond incorporated in the main chain.

・ Xa
Xa in the formulas (II-1) to (II-23) is C (Rb) ₂ , C═C (Rc) ₂ , Si (Rb) ₂ , S, Se, Te, S═O, SO ₂ , C = O, O, NH or NRb is represented.

・ Xb
Xb in the formulas (II-1) to (II-23) represents NH, NRb, O or S. Xc represents CRa or N.

・ Ra
Ra represents a hydrogen atom or a substituent, and may be connected to each other to form a ring. When a plurality of substituents are indicated by a specific code, they may be different from each other. Further, when the substituent Ra is condensed to form an aromatic ring or an aromatic heterocyclic ring, it may have a structure different from the resonance structure shown above. Examples of Ra include a substituent T described later, a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, an alkyl group (preferably having 1 to 24 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms), alkynyl. Group (preferably having 2 to 24 carbon atoms), alkoxy group (preferably having 1 to 24 carbon atoms), acyl group (preferably having 2 to 12 carbon atoms), acyloxy group (preferably having 2 to 24 carbon atoms), alkoxycarbonyl group An alkylsulfonyl group (preferably having 1 to 24 carbon atoms) is preferred (preferably having 2 to 24 carbon atoms).

・ Rb
Rb represents a hydrogen atom or a substituent, and examples of the substituent include the substituent T described later, a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms), and an alkenyl group (preferably having 2 to 24 carbon atoms). ) And alkynyl groups (preferably having 2 to 24 carbon atoms) are preferred. When Rb is a substituent, they may be connected to each other to form a ring.

・ Rc
Rc represents a hydrogen atom substituent, and examples of the substituent include the substituent T described later, a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms), and an alkenyl group (preferably having 2 to 24 carbon atoms). , An alkynyl group (preferably having 2 to 4 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 24 carbon atoms), an acyl group (preferably having 2 to 24 carbon atoms), and a cyano group are preferred.

  The structural units of formulas (II-1) to (II-23) are preferably those represented by formulas (1) to (61).

  In the formulas (1) to (61), Ra and Rb are the same as described above.

  Among these, (2), (3), (5), (9), (10), (11), (16), (21), (25), (26), (27), (30 ), (31), (32), (33), (34), (35), (36), (37), (38), (39), (40), (43), (45), The structural units represented by (46), (47), (48), (49), (50), (51), (56) to (61) are preferred, and (2), (3), (5 ), (9), (25), (26), (30), (31), (32), (34), (35), (36), (37), (38), (45), The structural units represented by (46), (47), (48), (49), (50), (51), (56) to (61) are more preferable.

Examples of the monomer forming the specific structural unit of the present invention include the following examples.
Here, Me represents —CH ₃ , Bu represents —C ₄ H ₉ , and M ⁺ represents a metal ion such as Na ⁺ or K ⁺ .

Examples of the polymer that forms the specific structural unit of the present invention include the following examples.
Here, Me represents a -CH _3.

The polymers of the present invention can be used in coupling reactions such as Chemical Reviews, 2002, 102, 1358, Chemical Reviews, 2011, 111, 1493, Journal of Materials of Chemistry, 2004, 14, 11 and the like. Can be synthesized using the method described in 1. above. That is, Negishi coupling using a zinc reagent using a transition metal catalyst, Ueda-Kosugi-Stille coupling using a tin reagent, Suzuki-Miyaura coupling using a boron reagent, Kumada-tama using a magnesium reagent It can be synthesized by utilizing cross-coupling such as tail-Corriu coupling, Ulsan coupling using a silicon reagent, Ullmann reaction using copper, Yamamoto polymerization using nickel, and the like. As the transition metal catalyst, metals such as palladium, nickel, copper, cobalt, and iron (Journal of the American Chemical Society, 2007, Vol. 129, page 9844) can be used. The metal may have a ligand, such as a phosphorus ligand such as PPh ₃ or P (t-Bu) _3, or an N-heterocyclic carbene ligand (Angewandte Chemie International Edition, 2002, 41, 1290) and the like are preferably used. A method for synthesizing a metal reactant such as a tin reactant and a boron reactant as a raw material is not particularly limited, and can be synthesized according to various known methods. For example, the tin reactant is Journal of the American Chemistry, 2009, 131, 7792, the Journal of the American Chemistry, 2008, 130, 16144, the European Patent Application No. 2407465, and the boron reactant is Journal. It can be synthesized with reference to American Chemistry, pages 2012, 134, 539 and the like. The reaction may be performed under microwave irradiation as described in Macromolecular Rapid Communications, 2007, 28, 387.

  Although the molecular weight of the polymer having the specific structural unit is not particularly limited, the mass average molecular weight (weight average molecular weight) is preferably 5,000 to 50,000, and more preferably 10,000 to 500,000.

  Unless otherwise specified, the molecular weight and the degree of dispersion are values measured using a GPC (gel filtration chromatography) method, and the molecular weight is a polystyrene-reduced mass average molecular weight. 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. It is preferable to use 2 to 6 columns connected together. Examples of the solvent used include ether solvents such as tetrahydrofuran, amide solvents of N-methylpyrrolidone, halogen solvents such as chloroform, and aromatic solvents such as chlorobenzene and 1,2-dichlorobenzene. The measurement is preferably performed at a solvent flow rate in the range of 0.1 to 2 mL / min, and most preferably in the range of 0.5 to 1.5 mL / min. By performing the measurement within this range, the apparatus is not loaded and the measurement can be performed more efficiently. The measurement temperature is preferably 10 to 50 ° C, most preferably 20 to 40 ° C. Measurement can also be performed at 50 ° C. to 200 ° C. using a column having a high usable temperature and a solvent having a high boiling point. The column and carrier to be used can be appropriately selected according to the physical properties of the polymer compound to be measured.

  In the present invention, when the polymer containing the specific structural unit is a copolymer, the copolymerization ratio is not particularly limited, but the specific structural unit is preferably 10 to 90 mol% of the total molar ratio, and 40 to 60 mol%. preferable. In the present invention, the copolymer may be a random copolymer, an alternating copolymer, a block copolymer, or a periodic copolymer, but is preferably an alternating copolymer or a periodic copolymer. More preferably, it is an alternating copolymer.

  In the present specification, a substituent (including a linking group) for which substitution / non-substitution is not specified means that the group may have an arbitrary substituent. This is also the same for compounds and polymers that do not specify substitution / non-substitution. Preferred substituents include the following substituent T.

Examples of the substituent T include the following.
An alkyl group (preferably an alkyl group having 1 to 24 carbon atoms such as methyl, ethyl, isopropyl, n-butyl, t-butyl, sec-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2 -Methylheptyl, 2-ethylhexyl, n-nonyl, n-decyl, 3,7-dimethyloctyl, isodecyl, n-undecyl, n-dodecyl, 2-butyloctyl, n-tridecyl, 3-butylnonyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, 2-hexyldecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, 2-octyldodecyl, n-icosyl, n-heneicosyl, n-docosyl, n-tricosyl, n-tetracosyl, 2-decyltetradecyl etc.), an alkenyl group (preferably having 2 to 24 carbon atoms) A alkenyl group (preferably an alkynyl group having 2 to 24 carbon atoms such as ethynyl, butadiynyl, phenylethynyl, etc.), a cycloalkyl group (preferably having 3 to 20 carbon atoms). A cycloalkyl group such as cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc., an aryl group (preferably an aryl group having 6 to 26 carbon atoms such as phenyl, 1-naphthyl, 4-methoxyphenyl, 2-chlorophenyl) , 3-methylphenyl, etc.),

Heterocyclic group (preferably a heterocyclic group having 2 to 20 carbon atoms, preferably a 5- or 6-membered heterocyclic group having at least one oxygen atom, sulfur atom or nitrogen atom, such as pyridyl, pyrazyl, Pyridazyl, pyrimidyl, triazyl, tetrazyl, pyrrolyl, furyl, thienyl, imidazolyl, pyrazolyl, triazolyl, benzimidazolyl, thiazolyl, thiadiazolyl, isothiazolyl, oxazolyl, isoxazolyl, oxadiazolyl, selenophenyl, etc.), alkoxy group (preferably having 1 to 24 carbon atoms) Alkoxy groups such as methoxy, ethoxy, isopropyloxy, benzyloxy, hexyloxy, 2-ethylhexyloxy, octyloxy, 3,7-dimethyloctyloxy, 2-butyloctyloxy, 2 Hexyldecyloxy, 2-decyltetradecyloxy, etc.), aryloxy groups (preferably aryloxy groups having 6 to 26 carbon atoms, such as phenoxy, 1-naphthyloxy, 3-methylphenoxy, 4-methoxyphenoxy, etc.), An alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 24 carbon atoms such as ethoxycarbonyl, 2-ethylhexyloxycarbonyl, hexyloxycarbonyl, 2-ethylhexyloxycarbonyl, octyloxycarbonyl, 3,7-dimethyloctyloxycarbonyl, 2-butyloctyloxycarbonyl, 2-hexyldecyloxycarbonyl, 2-decyltetradecyloxycarbonyl, etc.), amino group (preferably an amino group having 0 to 20 carbon atoms, alkylamino group, aryl A mino group, for example, amino, N, N-dimethylamino, N, N-diethylamino, N-ethylamino, anilino, etc.), a sulfamoyl group (preferably a sulfonamide group having 0 to 20 carbon atoms, such as N, N-dimethylsulfamoyl, N-phenylsulfamoyl, etc.),

An acyl group (preferably an acyl group having 1 to 24 carbon atoms such as acetyl, propionyl, butyryl, benzoyl, hexanoyl, 2-ethylhexanoyl, octanoyl, 3,7-dimethyloctanoyl, 2-butyloctanoyl, 2- Hexyldecanoyl, 2-decyltetradecanoyl, etc.), acyloxy groups (preferably acyloxy groups having 1 to 24 carbon atoms, such as acetyloxy, benzoyloxy, hexanoyloxy, 2-ethylhexanoyloxy, octanoyloxy, 3,7-dimethyloctanoyloxy, 2-butyloctanoyloxy, 2-hexyldecanoyloxy, 2-decyltetradecanoyloxy, etc.), a carbamoyl group (preferably a carbamoyl group having 1 to 24 carbon atoms, such as N , N-dimethylcarbamoyl, N- Phenylcarbamoyl etc.), acylamino group (preferably acylamino group having 1 to 24 carbon atoms, eg acetylamino, benzoylamino etc.), sulfonamido group (preferably sulfamoyl group having 0 to 24 carbon atoms, eg methanesulfonamide) , Benzenesulfonamide, N-methylmethanesulfonamide, N-ethylbenzenesulfonamide, etc.), alkylthio group (preferably an alkylthio group having 1 to 24 carbon atoms, such as methylthio, ethylthio, isopropylthio, benzylthio, etc.), arylthio group (Preferably an arylthio group having 6 to 26 carbon atoms, such as phenylthio, 1-naphthylthio, 3-methylphenylthio, 4-methoxyphenylthio, etc.), an alkyl or arylsulfonyl group (preferably an arylthio group having 1 to 24 carbon atoms). Kill or arylsulfonyl group such as methanesulfonyl, ethanesulfonyl, benzenesulfonyl, etc., alkyl or arylsulfonyloxy group (preferably alkyl or arylsulfonyloxy group having 1 to 24 carbon atoms such as methanesulfonyloxy, ethanesulfonyloxy) , Benzenesulfonyloxy and the like) alkoxy or aryloxysulfonyl group (preferably an alkoxy or aryloxysulfonyl group having 1 to 24 carbon atoms, such as methoxysulfonyl, ethoxysulfonyl, phenoxysulfonyl, etc.), hydroxyl group, cyano group, nitro group, A carboxyl group, a thiol group, a formyl group, and a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom).
In addition, each of the groups listed as the substituent T may be further substituted with the substituent T described above.

  When the compound or substituent / linking group contains an alkyl group / alkylene group, alkenyl group / alkenylene group, etc., these may be cyclic or chain-like, and may be linear or branched, and substituted as described above. It may be substituted or unsubstituted. Moreover, when an aryl group, a heterocyclic group, etc. are included, they may be monocyclic or condensed and may be similarly substituted or unsubstituted.

<Organic semiconductor polymer>
The polymer having the specific structural unit of the present invention is useful as an organic semiconductor polymer. An organic semiconductor polymer is a polymer of an organic compound capable of exhibiting properties as a semiconductor, and the polymer of the present invention is particularly useful as a p-type organic semiconductor polymer. The p-type organic semiconductor compound containing a polymer is generally a π-electron conjugated compound having a highest occupied orbital (HOMO) level of 4.5 to 6.0 eV.
Organic semiconductor polymers are used in the field of organic electronics, organic electroluminescence elements that emit light when electricity is passed, organic photoelectric conversion elements that generate electricity when irradiated with light, organic thin film transistor elements that control the amount of current and voltage, electrochemical sensors, and printables Used in circuits. In this invention, it is preferable to use with a photovoltaic cell, especially an organic thin-film solar cell.

<Composition for organic semiconductor material>
The composition for organic semiconductor materials of the present invention will be described.
The polymer (specific polymer) having the specific structural unit of the present invention is useful as a p-type organic semiconductor polymer, and the composition for an organic semiconductor material preferably contains the specific polymer in an organic solvent. The composition further preferably contains an n-type semiconductor compound, and particularly preferably contains an n-type organic semiconductor compound. Further, if necessary, a p-type organic semiconductor compound other than a polymer having a specific structural unit, a compound other than a semiconductor (for example, poly-3-hexylthiophene (P3HT), poly [2-HT Methoxy-5- (2-ethylhexyloxy) -1,4-phenylene vinylene (MEH-PPV), poly [2-methoxy-5- (3 ′, 7′-dimethyloctyloxy) -1,4-phenylene vinylene ] (MDMO-PPV), poly [(9,9-di-n-octylfluorenyl-2,7-diyl) -alt- (benzo [2,1,3] thiadiazole-4,8-diyl)] (F8BT) etc. are illustrated, and as a compound other than a semiconductor, other polymers such as a polyester-based resin and a methacrylic resin described later may be contained.

  The organic solvent applied to the composition is not particularly limited, but ether solvents such as tetrahydrofuran, 1,4-dioxane, cyclopentylmethyl ether, benzene, toluene, ethylbenzene, xylene, mesitylene, anisole, thioanisole, pyridine, picoline , Aromatic solvents such as lutidine, halogen solvents such as chloroform, dichloromethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, chlorobenzene, o-dichlorobenzene, 1,3,5-trichlorobenzene, bromo Aromatic halogen solvents such as benzene, iodobenzene, trifluoromethylbenzene, fluorobenzene, difluorobenzene, thioanisole, 1-chloronaphthalene, etc. , Dichloromethane, chlorobenzene, o- dichlorobenzene, etc. 1,3,5-trichlorobenzene are preferred.

  These solvents may be used alone or as a mixed solvent of two or more. Moreover, you may add 0.1 mass%-10 mass% additive to the said solvent for the phase-separation structure control of the below-mentioned p-type semiconductor phase and n-type semiconductor phase. Examples of the additive include diiodoalkane (for example, 1,8-diiodooctane, 1,6-diiodohexane, 1,10-diiododecane, etc.), alkanedithiol (for example, 1,8-octanedithiol, 1,6-hexanedithiol, 1,10-decanedithiol, etc.) and 1-chloronaphthalene.

  The content of the polymer having the specific structural unit is not particularly limited, but when the mass of the total composition is 100, it is preferable to contain 0.01 to 90% by mass of the polymer having the specific structural unit. More preferably, 70% by mass is contained.

  About an n-type organic-semiconductor compound, when the mass of the whole composition is set to 100, it is preferable to contain 0.01-90 mass%, and it is more preferable to contain 0.1-70 mass%. About arbitrary p-type organic-semiconductor compounds other than the polymer which has a specific structural unit, it is preferable to contain 0-50 mass%, and it is more preferable to contain 0-30 mass%. About compounds other than a semiconductor, although it is based also on the component, you may make it contain about 0-50 mass%.

  In the present invention, the composition means that two or more components exist substantially uniformly in a specific composition. Here, “substantially uniform” means that each component may be unevenly distributed within the range where the effects of the invention are exerted. The composition is not particularly limited as long as the above definition is satisfied, is not limited to a fluid liquid or a paste, and includes a solid or powder composed of a plurality of components. Furthermore, even when there is a sediment, it means that the composition maintains a dispersion state for a predetermined time by stirring.

<Components of organic thin-film solar cells>
(N-type organic semiconductor compound)
The n-type organic semiconductor compound is not particularly limited, but is generally a π-electron conjugated compound having a lowest unoccupied orbital (LUMO) level of 3.5 to 4.5 eV, such as fullerene or Perfluoro derivatives (eg, perfluoropentacene or perfluorophthalocyanine) in which hydrogen atoms of p-type organic semiconductor compounds are substituted with fluorine atoms, such as derivatives thereof, octaazaporphyrins, naphthalene tetracarboxylic acid anhydrides, naphthalene tetracarboxylic acid diimides, Examples thereof include aromatic carboxylic acid anhydrides such as perylene tetracarboxylic acid anhydride and perylene tetracarboxylic acid diimide, and polymer compounds containing the imidized product thereof as a skeleton.

Among these n-type organic semiconductor compounds, fullerene or a derivative thereof is preferable because charge separation can be performed at high speed and efficiently from the organic semiconductor polymer (p-type organic semiconductor compound) having the specific structural unit of the present invention.
As fullerenes and derivatives thereof, C ₆₀ fullerene, C ₇₀ fullerene, C ₇₆ fullerene, C ₇₈ fullerene, C ₈₄ fullerene, C ₂₄₀ fullerene, C ₅₄₀ fullerene, mixed fullerene, fullerene nanotube, and some of them are 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.

As the fullerene derivative, 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 are preferable, The carbon number of the alcohol part of the butyric acid ester is preferably 1 to 30, more preferably 1 to 8, still more preferably 1 to 4, and most preferably 1.

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

(P-type organic semiconductor compound)
The composition for an organic semiconductor material of the present invention contains another p-type semiconductor compound (for example, a condensed polycyclic aromatic low molecular weight compound, oligomer or polymer) together with the polymer having the specific structural unit of the present invention. Also good.

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

(Photoelectric conversion layer)
In the present invention, the composition for an organic semiconductor material is preferably used as a coating composition for a photoelectric conversion layer (particularly a bulk hetero layer). The mixing ratio of the p-type organic semiconductor compound that is an electron-donating material and the n-type semiconductor compound that is an electron-accepting material is preferably adjusted so as to increase the photoelectric conversion efficiency. It is selected from the range of ˜90: 10, preferably 20:80 to 80:20. As a method for forming such a mixed layer, for example, a co-evaporation method is used. Or it is also possible to produce by carrying out solvent application | coating using the solvent common to both organic materials. 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.

  Here, for the purpose of promoting the phase separation of the electron donating region (donor) and the electron accepting region (acceptor) in the photoelectric conversion layer, crystallization of the organic material contained in the photoelectric conversion layer, and transparency of the electron transport layer, etc. You may heat-process (anneal) by the method. In the case of a dry film formation method such as vapor deposition, for example, there is a method of heating the substrate temperature during film formation to 50 ° C. to 150 ° C. In the case of a wet film forming method such as printing or coating, there is a method of setting the drying temperature after coating to 50 ° C to 250 ° C. Moreover, you may heat at 50 degreeC-250 degreeC after completion | finish of a subsequent process, for example, formation of a metal negative electrode. By promoting phase separation, carrier mobility may be improved and high photoelectric conversion efficiency may be obtained.

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

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

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

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

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

(Hall transport layer)
In the present invention, it is preferable to provide a hole transport layer between the first electrode and the photoelectric conversion layer. Examples of the conductive polymer that forms the hole transport layer include polythiophene, polypyrrole, polyaniline, polyphenylene vinylene, polyphenylene, polyacetylene, polyquinoxaline, polyoxadiazole, polybenzothiadiazole, and polymers having a plurality of these conductive skeletons. Can be mentioned.
Among these, polythiophene and its derivatives are preferable, and polyethylenedioxythiophene and polythienothiophene are particularly preferable. These polythiophenes are usually partially oxidized in order to obtain conductivity. The electrical conductivity of the conductive polymer can be adjusted by the degree of partial oxidation (doping amount). The larger the doping amount, the higher the electrical conductivity. Since polythiophene becomes cationic by partial oxidation, a counter anion for neutralizing the charge is required. Examples of such polythiophenes include polyethylene dioxythiophene (PEDOT-PSS) with polystyrene sulfonic acid as a counter ion and polyethylene dioxythiophene (PEDOT-TsO) with p-toluenesulfonic acid as a counter anion.

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

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

(Support)
In the present invention, the support constituting the photovoltaic cell includes at least a first electrode (positive electrode), a photoelectric conversion layer, a second electrode (metal negative electrode), and in a more preferred embodiment, a first electrode (positive electrode), a hole. It is not particularly limited as long as it can form and hold a transport layer, a photoelectric conversion layer, an electron transport layer, and a second electrode (metal negative electrode). For example, glass, plastic film, etc. You can choose.

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

  Although photovoltaic cells have been described for polymers having specific building blocks of the present invention (specific polymers), in some embodiments, specific polymers can be used in other devices and systems. For example, field effect transistors, photodetectors (eg, infrared photodetectors), photovoltaic detectors, imaging devices (eg, RGB imaging devices for cameras or medical imaging systems), light emitting diodes (LEDs) (eg, Organic LEDs, or infrared or near-infrared LEDs), laser elements, conversion layers (eg, layers that convert visible emission into infrared emission), amplifiers and radiators for telecommunications (eg, fiber dopants), These polymers can be used in suitable organic semiconductor elements such as storage elements (eg, holographic storage elements), as well as electrochromic elements (eg, electrochromic displays).

  EXAMPLES The present invention will be described more specifically with reference to the following examples. However, the present invention is not construed as being limited thereby.

Example 1
(Polymer synthesis)
The polymer of the present invention was synthesized as follows.

(1) Synthesis of polymer (101) having structural unit of formula (1) Polymer (101) was synthesized by the following reaction scheme.

Compound (1-1) synthesized according to the method described in Journal of Organic Chemistry, 1980, 45, 617-620 is reduced and oxidized according to the method described in International Publication No. 2003/93277 to give compound (1-2 )
Compound (1-2) was reacted with ethyl acetoacetate according to the method described in Tetrahedron Letters, 2011, 52, 6643-6645 to give compound (1-3).
Compound (1-3) was reacted with cyanoacetate ester (1-4) according to the method described in Journal of Medicinal Chemistry, 2008, 51, 6538-6546, to give compound (1-5).
Compound (1-5) was brominated according to the method described in Journal of American Chemical Society, 2009, 131, 7792-7799 to give compound (1-6).
Compound (1-6): MALDI-MS m / z 530.1 (M ⁺ + H)
¹ H-NMR (CDCl ₃ ); δ [ppm] = 0.90 (3H, t) 1.09-1.39 (10H, m), 1.65 (2H, m), 2.51 (3H, s), 4.13 (2H, q), 7.78 (1H, s)

  In a glass reaction vessel, 772 mg (1.00 mmol) of compound (1-7), 531 mg (1.00 mmol) of compound (1-6) and 20 mg of tetrakis (triphenylformin) palladium were taken, and the inside of the vessel was purged with argon. . Toluene (dehydrated) 20 mL and N, N-dimethylformamide (dehydrated) 5 mL were added and reacted at 120 ° C. for 12 hours. The mixture was allowed to cool to room temperature, poured into 500 mL of methanol, and the precipitated solid was collected by filtration. After drying, the solid was dissolved in chloroform, filtered through celite, and concentrated. The concentrate was purified by silica gel column chromatography, crystallized from chloroform-methanol, and collected by filtration. The solid collected by filtration was extracted with acetone for 10 hours by Soxhlet and then dried under reduced pressure to obtain 669 mg (yield 82%) of the polymer (101).

Polymer (101): Mw = 8.3 × 10 ⁴ , Mn = 2.7 × 10 ^4
1 H-NMR (CDCl ₃ ); δ [ppm] = 0.80-2.81 (48H), 3.60-5.00 (6H), 6.70-8.02 (3H)
Tg = 158 ° C

(2) Synthesis of polymer (102) having the structural unit of formula (1) Polymer (102) was synthesized by the following reaction scheme.

The cyanoacetic acid ester (1-4) was changed to the malonic acid ester (2-1) and the same procedure as in the synthesis of the compound (1-5) was performed to obtain the compound (2-2).
The compound (1-5) was changed to the compound (2-2) and the same procedure as in the synthesis of the compound (1-6) was performed to obtain the compound (2-3).

Compound (2-3): MALDI-MS m / z 605.2 (M ⁺ + H)
¹ H-NMR (CDCl ₃ ); δ [ppm] = 0.91 (6H, m), 1.11-1.35 (12H, m), 1.65 (4H, m), 2.47 (3H) , S), 4.15 (4H, m), 7.76 (1H, s)

  The polymer (102) was prepared in the same manner as in the synthesis of the polymer (101) except that the compound (1-7) was replaced with the compound (2-4) and the compound (1-6) was replaced with the compound (2-3). Of 658 mg (yield 79.9%).

Polymer (102): Mw = 8.9 × 10 ⁴ , Mn = 3.0 × 10 ^4
1 H-NMR (CDCl ₃ ); δ [ppm] = 0.75-2.80 (59H), 3.69-4.98 (4H), 6.74-8.02 (3H)
Tg = 151 ° C.

(3) Synthesis of polymer (103) having structural unit of formula (1) Polymer (103) was synthesized by the following reaction scheme.

The cyanoacetic acid ester (1-4) was changed to the acetoacetic acid ester (3-1), and the reaction was performed in the same manner as the synthesis of the compound (1-5) to obtain the compound (3-2).
The compound (1-5) was changed to the compound (3-2), and the same procedure as in the synthesis of the compound (1-6) was performed to obtain a compound (3-3).

Compound (3-3): MALDI-MS m / z 575.1 (M ⁺ + H)
¹ H-NMR (CDCl ₃ ); δ [ppm] = 0.89 (3H, t) 1.10-1.37 (14H, m), 1.65 (2H, m), 2.10 (3H, s), 2.48 (3H, s), 4.18 (2H, q), 7.73 (1H, s)

  The polymer (103) was prepared in the same manner as in the synthesis of the polymer (101) except that the compound (1-7) was changed to the compound (3-4) and the compound (1-6) was changed to the compound (3-3). 643 mg (yield 80.2%) was obtained.

Polymer (103): Mw = 7.1 × 10 ⁴ , Mn = 2.2 × 10 ^4
1 H-NMR (CDCl ₃ ); δ [ppm] = 0.77-2.90 (51H), 3.75-4.87 (2H), 6.70-7.99 (3H)
Tg = 182 ° C

(4) Synthesis of polymer (201) having structural unit of formula (2) Polymer (201) was synthesized by the following reaction scheme.

Compound (4-1) synthesized according to the method described in Journal of Organic Chemistry, 1992, 57, 6749-6755 is reacted with compound (4-2) according to the method described in International Publication No. 2008/143759, Compound (4-3) was obtained.
According to the method described in Journal of Polymer Science Part A, 2011, 49, 369-380, compound (4-3) was oxidized to obtain compound (4-4).

Compound (4-4): MALDI-MS m / z 288.9 (M ⁺ + H)
¹ H-NMR (CDCl ₃ ); δ [ppm] = 7.63 (2H, s)

  Except having replaced the compound (1-6) with the compound (4-4), it carried out similarly to the synthesis | combination of the polymer (101), and obtained 653 mg (yield 86.1%) of polymers (201).

Polymer (201): Mw = 5.0 × 10 ⁴ , Mn = 2.1 × 10 ^4
1 H-NMR (CDCl ₃ ); δ [ppm] = 0.77-2.77 (30H), 3.75-4.87 (4H), 6.82-7.93 (4H)
Tg = 198 ° C

(5) Synthesis of polymer (202) having structural unit of formula (2) Polymer (202) was synthesized by the following reaction scheme.

  According to the method described in US Pat. No. 4,065,572, compound (4-1) and carbon disulfide are reacted to form compound (5-1), and compound (5-1) is oxidized ( 5-2) was obtained.

Compound (5-2) MALDI-MS m / z 305.1 (M + + H)
¹ H-NMR (CDCl ₃ ); δ [ppm] = 7.57 (2H, s)

  Except that the compound (1-7) was replaced with the compound (5-3) and the compound (1-6) was replaced with the compound (5-2), the synthesis was performed in the same manner as in the synthesis of the polymer (101). 613 mg (yield 71.3%) was obtained.

Polymer (202): Mw = 5.4 × 10 ⁴ , Mn = 2.2 × 10 ^4
1 H-NMR (CDCl ₃ ); δ [ppm] = 0.78-2.80 (54H), 6.74-8.10 (4H)
Tg = 187 ° C

(6) Synthesis of polymer (203) having structural unit of formula (2) Polymer (203) was synthesized by the following reaction scheme.

  Compound (4-1) was prepared according to Journal of Fluorine Chemistry, 2007, 128, p. According to the method described in 232-235, the compound (6-1) was reacted to obtain the compound (6-2).

Compound (6-2) was prepared as described in Journal of Organic Chemistry, 1991, 56, p. The compound (6-3) was obtained by reacting with iodooctane according to the method described in 4223-4233. The compound (6-3) was treated with the ion exchange resin Amberlite resin IRA-401 (OH ^- form) according to the method described in the same document to obtain the compound (6-4).

Compound (6-4): MALDI-MS m / z 464.0 (M ⁺ + H)
¹ H-NMR (CDCl ₃ ); δ [ppm] = 0.89 (3H, t), 1.10-1.37 (10H, m), 1.84 (2H, m), 4.26 (2H , T), 7.43 (2H, s), 8.63 (2H, d), 8.82 (2H, d)

Except that the compound (1-6) was replaced with the compound (6-4), it was carried out in the same manner as the synthesis of the polymer (101) to obtain 689 mg (yield: 82.9%) of the polymer (203).
Polymer (203): Mw = 3.9 × 10 ⁴ , Mn = 1.2 × 10 ^4
1 H-NMR (CDCl ₃ ); δ [ppm] = 0.84-2.69 (45H), 3.78-4.79 (6H), 6.71-8.90 (8H)
Tg = 172 ° C

(7) Synthesis of polymer (204) having structural unit of formula (2) Polymer (204) was synthesized by the following reaction scheme.

  Angelwandte Chemie, International Edition, 2010, 49, p. In accordance with the method described in 7992-7995, compound (7-1) was reduced to synthesize compound (7-2). The compound (7-2) and the compound (7-3) were reacted to obtain the compound (7-4), and then the compound (7-5) was synthesized in the same manner as in the case of the polymer (203). .

Compound (7-5): MALDI-MS m / z 465.2 (M ⁺ + H)
¹ H-NMR (CDCl ₃ ); δ [ppm] = 0.92 (6H, t), 1.22-1.63 (20H, m), 1.89 (4H, m), 3.67 (4H) , T), 7.13 (2H, s), 7.77 (1H, s)

  Except having replaced the compound (1-6) with the compound (7-5), the same procedure as in the synthesis of the polymer (101) was carried out to obtain 651 mg (yield: 80.0%) of the polymer (204).

Polymer (204): Mw = 5.9 × 10 ⁴ , Mn = 2.2 × 10 ^4
1 H-NMR (CDCl ₃ ); δ [ppm] = 0.84-2.69 (60H), 3.29-4.79 (8H), 6.67-8.21 (5H)
Tg = 164 ° C.

(8) Synthesis of polymer (301) having structural unit of formula (3) Polymer (301) was synthesized by the following reaction scheme.

  Chemistry-A European Journal, 2000, 6, p. According to the method described in 1007-1016, compound (8-1) and compound (8-2) were reacted to synthesize compound (8-3). Compound (8-7) was synthesized from compound (8-3) according to the method described in Journal of American Chemical Society, 2010, 132, 7595-7597.

Compound (8-7): MALDI-MS m / z 529.9 (M ⁺ + H)
¹ H-NMR (CDCl ₃ ); δ [ppm] = 0.89 (3H, t), 1.28 (10H, m), 1.67 (2H, m), 3.62 (2H, t)

  Except having changed the compound (1-6) into the compound (8-7), it was carried out similarly to the synthesis | combination of the polymer (101), and 599 mg (yield 72.3%) of polymers (301) were obtained.

Polymer (301): Mw = 7.9 × 10 ⁴ , Mn = 3.2 × 10 ^4
1 H-NMR (CDCl ₃ ); δ [ppm] = 0.85-2.71 (45H), 3.22-4.78 (6H), 6.72-7.98 (2H)
Tg = 179 ° C

(9) Synthesis of polymer (302) having structural unit of formula (3) Polymer (302) was synthesized by the following reaction scheme.

Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry (1972-1999), 1980, p. Compound (9-1) was nitrated according to the method described in 1331-1335 to give compound (9-2).
Compound (9-2) was reduced according to the method described in WO 2006/65788 to synthesize compound (9-3).

Chemistry-A European Journal, 2000, 6, p. According to the method described in 1007-1016, compound (9-4) and compound (9-3) were reacted to obtain compound (9-5).
Compound (9-8) was synthesized from compound (9-5) according to the method described in Macromolecules, 2001, 34, 1810-1816. Compound (9-8) was hydrolyzed and esterified, and then compound (9-9) was brominated in the same manner as in polymer (101) to give compound (9-10).

Compound (9-10): MALDI-MS m / z 529.9 (M ^< + ^> + H)
¹ H-NMR (CDCl ₃ ); δ [ppm] = 0.90 (3H, t), 1.69 (2H, m), 1.21-1.49 (10H, m), 4.21 (2H) , T), 7.67 (1H, s)

  The polymer (302) was prepared in the same manner as in the synthesis of the polymer (101) except that the compound (1-6) was replaced with the compound (9-10) and the compound (1-7) was replaced with the compound (9-11). 652 mg (yield 81.9%) was obtained.

Polymer (302): Mw = 8.9 × 10 ⁴ , Mn = 3.7 × 10 ^4
1 H-NMR (CDCl ₃ ); δ [ppm] = 0.85-2.71 (41H), 3.51-4.81 (2H), 6.79-7.89 (3H)
Tg = 162 ° C.

(10) Synthesis of polymer (303) having structural unit of formula (3) Polymer (303) was synthesized by the following reaction scheme.

  Compound (10-1) is reacted with ethyl acetate according to the method described in International Publication No. 2011/28827 to obtain compound (10-2), which is then reacted with iodooctane to give compound (10-3). ) Compound (10-3) was brominated in the same manner as in the case of polymer (101) to give compound (10-4).

Compound (10-4): MALDI-MS m / z 585.1 (M ^< + ^> + H)
¹ H-NMR (CDCl ₃ ); δ [ppm] = 0.90 (6H, t), 1.21-1.49 (20H, m), 1.63 (4H, m), 1.99 (4H) , T)

  The polymer (303) was prepared in the same manner as in the synthesis of the polymer (101) except that the compound (1-6) was replaced with the compound (10-4) and the compound (1-7) was replaced with the compound (10-5). 643 mg (yield 83.1%) was obtained.

Polymer (303): Mw = 8.3 × 10 ⁴ , Mn = 3.6 × 10 ^4
1 H-NMR (CDCl ₃ ); δ [ppm] = 0.85-2.73 (60H), 6.69-7.91 (2H)
Tg = 169 ° C.

(11) Synthesis of polymer (304) having structural unit of formula (3) Polymer (304) was synthesized by the following reaction scheme.

  Organic and Biomolecular Chemistry, 2003, vol. 1, # 4 p. The compound (11-7) was synthesized with reference to the method described in 756-762. Fluorination of compound (11-8) is performed according to the method described in US Pat. No. 4,782,180, and the thiophene ring is prepared according to the method described in Journal of American Chemical Society, 2009, 131, 7792-7799. Compound (11-12) was synthesized by construction and bromination.

Compound (11-12): MALDI-MS m / z 633.2 (M ^< + ^> + H)
¹ H-NMR (CDCl ₃ ); δ [ppm] = 0.90 (6H, t), 1.21-1.49 (12H, m), 1.63 (4H, m), 4.27 (4H) , T), 8.25 (2H, s)

  Except having changed the compound (1-6) into the compound (11-12), it was carried out similarly to the synthesis of the polymer (101) to obtain 666 mg (yield: 87.1%) of the polymer (304).

Polymer (304): Mw = 9.3 × 10 ⁴ , Mn = 4.0 × 10 ^4
1 H-NMR (CDCl ₃ ); δ [ppm] = 0.85-2.73 (52H), 3.47-4.75 (8H), 6.72-8.51 (4H)
Tg = 151 ° C.

(12) Synthesis of polymer (305) having structural unit of formula (3) Polymer (305) was synthesized by the following reaction scheme.

Compound (12-3) was synthesized from compound (11-8) according to the above scheme.
Compound (12-3): MALDI-MS m / z 721.1 (M ⁺ + H)
¹ H-NMR (CDCl ₃ ); δ [ppm] = 0.91 (12H, m), 1.21-1.48 (16H, m) 1.70 (4H, m), 4.23 (4H, m) 8.19 (2H, s)

  The polymer (305) was prepared in the same manner as in the synthesis of the polymer (101) except that the compound (1-6) was replaced with the compound (12-3) and the compound (1-7) was replaced with the compound (2-4). Of 659 mg (yield 80.2%).

Polymer (305): Mw = 8.0 × 10 ⁴ , Mn = 3.3 × 10 ^4
1 H-NMR (CDCl ₃ ); δ [ppm] = 0.88-2.80 (64H), 3.40-4.81 (4H), 6.69-8.39 (4H)
Tg = 167 ° C.

(13) Synthesis of polymer (306) having structural unit of formula (3) Polymer (306) was synthesized by the following reaction scheme.

  Compound (13-6) was synthesized according to the above scheme.

Compound (13-6): MALDI-MS m / z 601.2 (M ⁺ + H)
¹ H-NMR (CDCl ₃ ); δ [ppm] = 0.88 (6H, t), 1.13-1.41 (20H, m), 1.76 (4H, m), 2.98 (4H) , T), 8.28 (2H, s)

  Except having replaced the compound (1-6) with the compound (13-6), it carried out similarly to the synthesis | combination of the polymer (101), and obtained 629 mg (yield 78.2%) of polymers (306).

Polymer (306): Mw = 10.2 × 10 ⁴ , Mn = 4.9 × 10 ^4
1 H-NMR (CDCl ₃ ); δ [ppm] = 0.88-3.32 (64H), 3.51-4.76 (4H), 6.68-8.52 (4H)
Tg = 187 ° C

(14) Synthesis of polymer (307) having structural unit of formula (3) Polymer (307) was synthesized by the following reaction scheme.

  Journal of Chemical Research, Miniprint, 1989, 7, pp. Compound (14-6) was synthesized according to the above scheme using Compound (14-1) synthesized according to the method described in 1501-1523.

Compound (14-6): MALDI-MS m / z 601.2 (M ⁺ + H)
¹ H-NMR (CDCl ₃ ); δ [ppm] = 0.90 (6H, t), 1.63 (4H, m), 1.21-1.49 (20H, m), 1.99 (4H) , T), 8.31 (1H, s)

  Except for changing the compound (1-6) to the compound (14-6), the same procedure as in the synthesis of the polymer (101) was performed to obtain 599 mg (yield: 77.7%) of the polymer (307).

Polymer (307): Mw = 8.2 × 10 ⁴ , Mn = 3.9 × 10 ^4
1 H-NMR (CDCl ₃ ); δ [ppm] = 0.86-2.81 (64H), 3.51-4.76 (4H), 6.72-8.59 (3H)
Tg = 191 ° C.

(15) Synthesis of polymer (308) having structural unit of formula (3) Polymer (308) was synthesized by the following reaction scheme.

  Compound (15-5) was synthesized according to the above scheme.

Compound (15-5): MALDI-MS m / z 601.2 (M ⁺ + H)
¹ H-NMR (CDCl ₃ ); δ [ppm] = 0.90 (3H, t), 1.27 (10H, m), 1.67 (2H, m), 3.60 (2H, t), 8.29 (1H, s)

  Except having changed the compound (1-6) into the compound (15-5), it carried out similarly to the synthesis | combination of the polymer (101), and obtained 638 mg (yield 78.6%) of polymers (308).

Polymer (308): Mw = 7.1 × 10 ⁴ , Mn = 2.9 × 10 ^4
1 H-NMR (CDCl ₃ ); δ [ppm] = 0.82-2.72 (47H), 3.50-4.77 (4H), 6.70-8.54 (3H)
Tg = 180 ° C

(16) Synthesis of polymer (309) having structural unit of formula (3) Polymer (309) was synthesized by the following reaction scheme.

  Compound (15′-7) was synthesized according to the above scheme.

Compound (15′-7): MALDI-MS m / z 599.2 (M ⁺ + H)
¹ H-NMR (CDCl ₃ ); δ [ppm] = 0.90 (6H, t), 1.21-1.49 (12H, m), 1.63 (4H, m), 4.27 (4H) , T), 8.19 (2H, s)

  Except for changing the compound (1-6) to the compound (15′-7), the same procedure as in the synthesis of the polymer (101) was performed to obtain 622 mg (yield: 82.1%) of the polymer (309).

Polymer (309): Mw = 6.0 × 10 ⁴ , Mn = 2.3 × 10 ^4
1 H-NMR (CDCl ₃ ); δ [ppm] = 0.6-2.79 (52H), 3.39-4.79 (8H), 6.59-8.30 (4H)
Tg = 175 ° C

(17) Synthesis of polymer (310) having structural unit of formula (3) Polymer (310) was synthesized by the following reaction scheme.

  Compound (15 ″ -6) was synthesized according to the above scheme.

Compound (15 ″ -6): MALDI-MS m / z 599.2 (M ⁺ + H)
¹ H-NMR (CDCl ₃ ); δ [ppm] = 0.90 (6H, t), 1.21-1.49 (12H, m), 1.63 (4H, m), 4.27 (4H) , T), 8.08 (2H, s)

  Except having replaced the compound (1-6) with the compound (15 ″ -6), the same procedure as in the synthesis of the polymer (101) was performed to obtain 661 mg (yield: 85.1%) of the polymer (310).

Polymer (310): Mw = 6.9 × 10 ⁴ , Mn = 2.4 × 10 ^4
1 H-NMR (CDCl ₃ ); δ [ppm] = 0.6-2.86 (56H), 3.50-4.76 (4H), 6.60-8.32 (4H)
Tg = 149 ° C

(18) Synthesis of polymer (401) having structural unit of formula (4) Polymer (401) was synthesized by the following reaction scheme.

  Compound (16-2) was synthesized according to the above scheme.

Compound (16-2): MALDI-MS m / z 548.2 (M ⁺ + H)
¹ H-NMR (CDCl ₃ ); δ [ppm] = 0.89 (6H, t), 1.18-1.51 (12H, m), 1.64 (4H, m), 4.23 (4H , T), 8.27 (1H, s)

  Except having changed the compound (1-6) into the compound (16-2), it carried out similarly to the synthesis | combination of the polymer (101), and obtained 659 mg (yield 83.2%) of polymers (401).

Polymer (401): Mw = 11.0 × 10 ⁴ , Mn = 5.3 × 10 ^4
1 H-NMR (CDCl ₃ ); δ [ppm] = 0.6-2.79 (52H), 3.39-4.79 (8H), 6.49-8.49 (3H)
Tg = 185 ° C

(19) Synthesis of polymer (402) having structural unit of formula (4) Polymer (402) was synthesized by the following reaction scheme.

  Compound (17-4) was synthesized from compound (14-1) according to the above scheme.

Compound (17-4): MALDI-MS m / z 622.1 (M + + H)
¹ H-NMR (CDCl ₃ ); δ [ppm] = 0.89 (12H, m), 1.22-1.48 (16H, m) 1.71 (4H, m), 4.26 (4H, m)

  Except having changed the compound (1-6) into the compound (17-4), it carried out similarly to the synthesis | combination of the polymer (101), and obtained 642 mg (yield 79.6%) of polymers (402).

Polymer (402): Mw = 8.9 × 10 ⁴ , Mn = 3.8 × 10 ^4
1 H-NMR (CDCl ₃ ); δ [ppm] = 0.6-2.79 (60H), 3.39-4.79 (8H), 6.51-7.91 (2H)
Tg = 164 ° C.

(20) Synthesis of polymer (403) having structural unit of formula (4) Polymer (403) was synthesized by the following reaction scheme.

  Compound (18-5) was synthesized according to the above scheme.

Compound (18-5): MALDI-MS m / z 547.2 (M ⁺ + H)
¹ H-NMR (CDCl ₃ ); δ [ppm] = 0.89 (6H, t), 1.21-1.48 (12H, m), 1.62 (4H, m), 4.27 (4H) , T), 7.88 (2H, s)

  Except having changed the compound (1-6) into the compound (18-5), it was carried out in the same manner as the synthesis of the polymer (101) to obtain 661 mg (yield: 83.5%) of the polymer (403).

Polymer (403): Mw = 9.2 × 10 ⁴ , Mn = 3.8 × 10 ^4
1 H-NMR (CDCl ₃ ); δ [ppm] = 0.6-2.79 (52H), 3.39-4.79 (8H), 6.51-8.31 (4H)
Tg = 173 ° C.

(21) Synthesis of polymer (404) having structural unit of formula (4) Polymer (404) was synthesized by the following reaction scheme.

  Compound (19-1) was synthesized according to the above scheme.

Compound (19-1): MALDI-MS m / z 515.0 (M ⁺ + H)
¹ H-NMR (CDCl ₃ ); δ [ppm] = 0.89 (6H, t), 1.14 to 1.41 (12H, m), 1.76 (4H, m), 2.96 (4H) , T), 7.97 (2H, s)

  Except having replaced the compound (1-6) with the compound (19-1), the same procedure as in the synthesis of the polymer (101) was performed to obtain 643 mg (yield: 81.8%) of the polymer (404).

Polymer (404): Mw = 8.2 × 10 ⁴ , Mn = 3.6 × 10 ^4
1 H-NMR (CDCl ₃ ); δ [ppm] = 0.88-3.32 (56H), 3.51-4.76 (4H), 6.69-8.42 (4H)
Tg = 183 ° C

(22) Synthesis of polymer (405) having structural unit of formula (4) Polymer (405) was synthesized by the following reaction scheme.

  Compound (20-7) was synthesized according to the above scheme.

Compound (20-7): MALDI-MS m / z 326.9 (M ⁺ + H)
¹ H-NMR (CDCl ₃ ) δ [ppm] = 8.24 (2H, s)

  Except having changed the compound (1-6) into the compound (20-7), it carried out similarly to the synthesis | combination of the polymer (101), and obtained 848 mg (yield 81.9%) of polymers (405).

Polymer (405): Mw = 9.3 × 10 ⁴ , Mn = 3.6 × 10 ^4
1 H-NMR (CDCl ₃ ); δ [ppm] = 0.6-2.79 (30H), 3.39-4.79 (4H), 6.71-8.52 (4H)
Tg = 163 ° C.

(23) Synthesis of polymer (406) having structural unit of formula (4) Polymer (406) was synthesized as follows.

  The polymer (406) was synthesized in the same manner as the polymer (405).

Polymer (406): Mw = 7.2 × 10 ⁴ , Mn = 3.1 × 10 ^4
1 H-NMR (CDCl ₃ ); δ [ppm] = 0.83-2.81 (76H), 3.38-4.80 (8H), 6.71-8.32 (4H)
Tg = 141 ° C.

[Comparative polymer]
The following comparative polymers were used.

Comparative polymer (C-1) is a polymer described in Chemistry of Materials, 2009, 21, 3618-3628.
Comparative polymers (C-2) and (C-3) are described in Macromolecules, Vol. 45, 2012, 4069-4074.

(Production of element)
(Sample No. 101)
PEDOT-PSS (HC Stark CleviosP VP AI4083) used as a hole transport layer was spin-coated (3000 rpm) on a glass-ITO substrate that had been cleaned and UV-ozone treated, and dried at 140 ° C. for 30 minutes. A mixture of 10 mg of the polymer (101) and 10 mg of PC ₇₁ BM was dissolved in 2 mL of o-dichlorobenzene containing 3% by mass of 1,8-diiodooctane and filtered through a 0.45 μm polytetrafluoroethylene filter (one The amount and mass ratio of the polymer and the fullerene derivative, and the kind and amount of the solvent were changed for some of the exemplified compounds.) The filtrate was applied onto the PEDOT-PSS layer by spin coating (1000 rpm, 40 seconds) and dried to prepare a photoelectric conversion layer. The operation so far was performed in a glove box under a nitrogen atmosphere / yellow light. Lithium fluoride and aluminum were sequentially deposited on the photoelectric conversion layer to form an upper electrode to obtain a 2 mm square element. This is element A.

  The process was performed in the same manner as the element A, except that the spin coating was changed to 1300 rpm, 1400 rpm, 1600 rpm, and 1700 rpm. Three elements were produced for each number of rotations. In addition, three element elements were produced even at a rotation speed of 1500 rpm, and a total of 15 element B groups were obtained.

  It was performed in the same manner as the element A, except that after the photoelectric conversion layer application, annealing was performed at 80 ° C., 90 ° C., 100 ° C., 110 ° C., and 120 ° C. for 10 minutes. Three elements were produced for each temperature, and a total of 15 element C groups were obtained.

  Except having applied and dried the photoelectric converting layer under air | atmosphere, it carried out similarly to the element A, and obtained 10 element D groups.

  Except that the photoelectric conversion layer was applied and dried under a fluorescent lamp, the same procedure was performed as for element A, and 10 element E groups were obtained.

(Sample Nos. 102 to 406 and comparative sample Nos. C01 to C03)
Sample No. In the same manner as in 101, the polymer (101) is converted into an equal mass of the polymers (102), (103), (201) to (204), (301) to (310), (401) to (406), the comparative polymer ( Sample No. 1 except that C-1) to (C-3) were replaced. In the same manner as in Sample 101, Sample No. 102, 103, 201-204, 301-310, 401-406 and comparative samples C01-C03 were prepared.
The polymer number and sample No. Corresponds.

(Photocell evaluation)
(1) Current density-voltage (JV) characteristics of element A 101-406 and comparative sample no. The performance of the C01-C03 element A was evaluated as follows.
Using the SMU2400 type IV measuring device manufactured by Keithley in an atmosphere of nitrogen (oxygen concentration of 1 ppm or less, moisture concentration of 1 ppm or less), the obtained device was measured for current density-voltage (JV) characteristics. Evaluated. Using a filtered xenon lamp light from Oriel (Oriel) manufactured solar simulator approximated to AM1.5G spectrum of 100 mW / cm ^2. In the above device, the output short-circuit current density (Jsc), open circuit voltage (Voc), fill factor (FF) and photoelectric conversion efficiency [η (%)] are described in “Battery performance of device” in Table 1 below. .

(2) Evaluation of variation in photoelectric conversion efficiency of element B, element C, element D, and element E The element B group, element C group, element D group, and element E group obtained in Examples and Comparative Examples are In the same manner as in 1), the current density-voltage (JV) characteristics of the device were evaluated, and the standard deviation of the conversion efficiency (photoelectric conversion efficiency) was calculated. These results are summarized in “Standard deviation of conversion efficiency” in Table 1 below.

As is clear from the above table, the solar cell using the polymer of the present invention as a p-type semiconductor has high photoelectric conversion efficiency, and the polymers [polymers (201) to (204)] and formulas represented by formula (2) Polymer [Polymer (101) to (103)] represented by (1) and Polymer [Polymer (301) to (310)] represented by Formula (3), Polymer [Polymer represented by Formula (4) The photoelectric conversion ability is improved in the order of (401) to (406)].
Furthermore, all of the polymers (101) to (103) have small variations in photoelectric conversion ability during device fabrication under fluorescent lamp irradiation. All of the polymers (201) to (204) have small variations with respect to the annealing temperature. All of the polymers (301) to (310) have small variations during device fabrication in the atmosphere. All of the polymers (401) to (406) have small variations due to the spin coat rotation speed. As described above, it can be seen that all the polymers of the present invention have high photoelectric conversion ability, small variation in photoelectric conversion ability with respect to fluctuations in production conditions, and high quality stability during production.

7 Transparent Support 10 Bulk Heterojunction Organic Thin Film Solar Cell 11 Transparent Electrode (First Electrode)
12 Counter electrode (second electrode)
21 hole transport layer 22 electron transport layer 3 photoelectric conversion layer 31 p-type semiconductor phase 32 n-type semiconductor phase L light P electric motor (fan)

Claims (14)

An organic thin-film solar cell comprising a first electrode, a second electrode, and a photoelectric conversion layer disposed therebetween, wherein the following formulas (1) , (2), (3- An organic thin-film solar cell containing a polymer having the structural unit represented by any one of 1) to (3-9) and (4).

[In Formula (1), R ¹¹ represents a hydrogen atom, an acyl group, an alkoxycarbonyl group, an alkyl group, a fluorine atom, an aryl group, a carbamoyl group, a carboxyl group, or a group represented by —CR ^c ═CR ^a R ^b. . R ^a and R ^b each independently represents an alkyl group, a cyano group, an alkoxycarbonyl group or an acyl group, and R ^c represents a hydrogen atom or an alkyl group. However, one of R ^a and R ^b is a cyano group, an alkoxycarbonyl group, or an acyl group. R ¹² represents a hydrogen atom or a substituent. X ^A represents an oxygen atom, a sulfur atom, a selenium atom, SiR ₂ (R is a hydrogen atom or a substituent), a tellurium atom,>C═O,> SO ₂ or> NR ^N ( ^RN is a hydrogen atom or a substituent). Represent. X ¹¹ represents an oxygen atom, a sulfur atom, or> NR ^N ( ^RN is a hydrogen atom or a substituent). X ¹² represents an oxygen atom, a sulfur atom or ═NR ⁿ (R ⁿ is a substituent).
In formula (2), X ²¹ represents an oxygen atom, a sulfur atom, a divalent group represented by ═NR ⁿ or ═CR ²⁰¹ R ²⁰² . R ²⁰¹ and R ²⁰² each independently represent a substituent. R ²⁰¹ and R ²⁰² may be connected to each other to form a ring. Is R ⁿ is as defined in the formula (1). Ring A represents an aromatic ring.
Wherein (3-1) ~ (3-9), X B is as defined above ^{X A.} R ³³ represents a hydrogen atom or a substituent. X ³³ represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or> NR ^N. Is R ^N is as defined in the formula (1). X ³⁴ is a methine group - represents a group or a nitrogen atom (= CR ^M). X ³⁵ represents a divalent group represented by > CR ^b R ^c or> C═CR ^d R ^e . R ^{b to} R ^e each independently represents a hydrogen atom or a substituent. One of X ³⁶ and ^{X 37} represents a nitrogen atom and the other is = CR ^M - represents a. R ^{34 to} R ³⁷ each independently represents a hydrogen atom or a substituent. X ⁶¹ and ^{X 62} each independently methine group - represents a group or a nitrogen atom (= CR ^M). R ^M represents a hydrogen atom or a substituent. R ⁶⁴ and R ⁶⁵ each independently represents an alkoxycarbonyl group or an acyl group. R ^{74 to} R ⁷⁷ each independently represent a hydrogen atom or a substituent.
In the formula (4), the ^{X C} have the same meanings as defined above ^{X A.} R ⁴¹ and R ⁴² are each independently a hydrogen atom, a formyl group, a fluorine atom, a chlorine atom, an alkyl group having 1 to 24 carbon atoms, an acyl group having 2 to 24 carbon atoms, an alkoxycarbonyl group having 3 to 24 carbon atoms, An acyloxy group having 2 to 24 carbon atoms, an alkylsulfonyl group having 1 to 24 carbon atoms, an alkoxysulfonyl group having 1 to 24 carbon atoms, a nitro group, a perfluoroalkyl group having 1 to 24 carbon atoms, and a perfluoroalkyl group having 1 to 24 carbon atoms. Fluoroalkoxy group, carbamoyl group having 1 to 24 carbon atoms, sulfamoyl group having 1 to 24 carbon atoms, perfluoroalkylcarbonyl group having 2 to 24 carbon atoms, perfluoroalkylcarbonyloxy group having 2 to 24 carbon atoms, 2 carbon atoms 24 alkynyl group or ^-CR 45 ⁼ represents a ^CR 46 ^{R 47.} R ⁴⁵ represents a hydrogen atom or an alkyl group. R ⁴⁶ and R ⁴⁷ each independently represents a hydrogen atom, an alkyl group, a cyano group, an alkoxycarbonyl group or an acyl group. However, either one of R ⁴⁶ and R ⁴⁷ is a cyano group, an alkoxycarbonyl group or an acyl group. R ⁴³ represents a substituent. X ⁴¹ represents a nitrogen atom or ═CR ⁴⁴ —. R ⁴⁴ represents a hydrogen atom or a substituent.
Here, definitive each expression * represents a bond to form a polymer backbone. ] The organic thin film solar cell according to claim 1, wherein X ¹² in the formula (1) is an oxygen atom. The organic thin-film solar cell according to claim 1, wherein X ¹¹ in the formula (1) is an oxygen atom. The organic thin film solar cell according to any one of claims 1 to 3 X ^A in the formula (1) is a sulfur atom. The organic thin-film solar cell according to claim 1, wherein the structural unit represented by the formula (2) is a structural unit represented by the following formula (2-1).

[In Formula (2-1), X ²¹ has the same meaning as in Formula (2). X ^E and ^{X F} are each independently a methine group ⁽⁼ CR ^M -: ^R M is a hydrogen atom or a substituent group) or a nitrogen atom. Here, * indicates a bond forming a polymer main chain. ] The organic thin-film solar cell according to claim 5, wherein the structural unit represented by the formula (2-1) is a structural unit represented by the following formula (2-2).

[In the formula (2-2), R ²² represents> NR ^N or> C═O. R ^{23 to} R ²⁶ each independently represents a hydrogen atom or a substituent. X ^E and ^{X F} are the same meanings as in the formula (2-1). ^RN is synonymous with the formula (1). Here, * indicates a bond forming a polymer main chain. ] The organic thin film solar cell according to claim 1, wherein X ^C in the formula (4) is a sulfur atom. R ⁴¹ and R ⁴² in the formula (4) are each independently a formyl group, a fluorine atom, a chlorine atom, an acyl group having 2 to 24 carbon atoms, an alkoxycarbonyl group having 3 to 24 carbon atoms, or an alkyl group having 2 to 24 carbon atoms. Acyloxy group, alkylsulfonyl group having 1 to 24 carbon atoms, alkoxysulfonyl group having 1 to 24 carbon atoms, nitro group, perfluoroalkyl group having 1 to 24 carbon atoms, perfluoroalkoxy group having 1 to 24 carbon atoms, carbon number A carbamoyl group having 1 to 24 carbon atoms, a sulfamoyl group having 1 to 24 carbon atoms, a perfluoroalkylcarbonyl group having 2 to 24 carbon atoms, a perfluoroalkylcarbonyloxy group having 2 to 24 carbon atoms, an alkynyl group having 2 to 24 carbon atoms, or ^{-CR 45 = CR 46 R 47 (} R 45 is ^{.R 46} and ^{R 47} represents a hydrogen atom or an alkyl group are each independently Hydrogen atom, an alkyl group, a cyano group, an alkoxycarbonyl group or an acyl group. However, either one of R ⁴⁶ and R ⁴⁷ represents a cyano group, an alkoxycarbonyl group or an acyl group.) A which claim 1 or 7 The organic thin-film solar cell described in 1. The composition which contains the polymer which has a structural unit represented by either of following formula (1) , (2), (3-1)-(3-9) and (4) in the organic solvent.

[In Formula (1), R ¹¹ represents a hydrogen atom, an acyl group, an alkoxycarbonyl group, an alkyl group, a fluorine atom, an aryl group, a carbamoyl group, a carboxyl group, or a group represented by —CR ^c ═CR ^a R ^b. . R ^a and R ^b each independently represents an alkyl group, a cyano group, an alkoxycarbonyl group or an acyl group, and R ^c represents a hydrogen atom or an alkyl group. However, one of R ^a and R ^b is a cyano group, an alkoxycarbonyl group, or an acyl group. R ¹² represents a hydrogen atom or a substituent. X ^A represents an oxygen atom, a sulfur atom, a selenium atom, SiR ₂ (R is a hydrogen atom or a substituent), a tellurium atom,>C═O,> SO ₂ or> NR ^N ( ^RN is a hydrogen atom or a substituent). Represent. X ¹¹ represents an oxygen atom, a sulfur atom, or> NR ^N ( ^RN is a hydrogen atom or a substituent). X ¹² represents an oxygen atom, a sulfur atom or ═NR ⁿ (R ⁿ is a substituent).
In formula (2), X ²¹ represents an oxygen atom, a sulfur atom, a divalent group represented by ═NR ⁿ or ═CR ²⁰¹ R ²⁰² . R ²⁰¹ and R ²⁰² each independently represent a substituent. R ²⁰¹ and R ²⁰² may be connected to each other to form a ring. Is R ⁿ is as defined in the formula (1). Ring A represents an aromatic ring.
Wherein (3-1) ~ (3-9), X B is as defined above ^{X A.} R ³³ represents a hydrogen atom or a substituent. X ³³ represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or> NR ^N. Is R ^N is as defined in the formula (1). X ³⁴ is a methine group - represents a group or a nitrogen atom (= CR ^M). X ³⁵ represents a divalent group represented by > CR ^b R ^c or> C═CR ^d R ^e . R ^{b to} R ^e each independently represents a hydrogen atom or a substituent. One of X ³⁶ and ^{X 37} represents a nitrogen atom and the other is = CR ^M - represents a. R ^{34 to} R ³⁷ each independently represents a hydrogen atom or a substituent. X ⁶¹ and ^{X 62} each independently methine group - represents a group or a nitrogen atom (= CR ^M). R ^M represents a hydrogen atom or a substituent. R ⁶⁴ and R ⁶⁵ each independently represents an alkoxycarbonyl group or an acyl group. R ^{74 to} R ⁷⁷ each independently represent a hydrogen atom or a substituent.
In the formula (4), the ^{X C} have the same meanings as defined above ^{X A.} R ⁴¹ and R ⁴² are each independently a hydrogen atom, a formyl group, a fluorine atom, a chlorine atom, an alkyl group having 1 to 24 carbon atoms, an acyl group having 2 to 24 carbon atoms, an alkoxycarbonyl group having 3 to 24 carbon atoms, An acyloxy group having 2 to 24 carbon atoms, an alkylsulfonyl group having 1 to 24 carbon atoms, an alkoxysulfonyl group having 1 to 24 carbon atoms, a nitro group, a perfluoroalkyl group having 1 to 24 carbon atoms, and a perfluoroalkyl group having 1 to 24 carbon atoms. Fluoroalkoxy group, carbamoyl group having 1 to 24 carbon atoms, sulfamoyl group having 1 to 24 carbon atoms, perfluoroalkylcarbonyl group having 2 to 24 carbon atoms, perfluoroalkylcarbonyloxy group having 2 to 24 carbon atoms, 2 carbon atoms 24 alkynyl group or ^-CR 45 ⁼ represents a ^CR 46 ^{R 47.} R ⁴⁵ represents a hydrogen atom or an alkyl group. R ⁴⁶ and R ⁴⁷ each independently represents a hydrogen atom, a cyano group, an alkoxycarbonyl group or an acyl group. However, either one of R ⁴⁶ and R ⁴⁷ is a cyano group, an alkoxycarbonyl group or an acyl group. R ⁴³ represents a substituent. X ⁴¹ represents a nitrogen atom or ═CR ⁴⁴ —. R ⁴⁴ represents a hydrogen atom or a substituent.
Here, definitive each expression * represents a bond to form a polymer backbone. ] Furthermore, the composition of Claim 9 containing an n-type semiconductor component. The composition according to claim 10 , wherein the n-type semiconductor component is a fullerene derivative. The composition according to any one of claims 9 to 11 , which is used for an organic semiconductor material. The manufacturing method of the film | membrane which apply | coats the composition of Claim 12 . A monomer comprising a compound represented by any of the following formulas (M1) to (M3-9) .

[In the formula (M1), R ¹¹ represents a hydrogen atom, an acyl group, an alkoxycarbonyl group, an alkyl group, a fluorine atom, an aryl group, a carbamoyl group, a carboxyl group, or a group represented by —CR ^c = CR ^a R ^b. . R ^a and R ^b each independently represents an alkyl group, a cyano group, an alkoxycarbonyl group or an acyl group, and R ^c represents a hydrogen atom or an alkyl group. However, one of R ^a and R ^b is a cyano group, an alkoxycarbonyl group, or an acyl group. R ¹² represents a hydrogen atom or a substituent. X ^A represents an oxygen atom, a sulfur atom, a selenium atom, SiR ₂ (R is a hydrogen atom or a substituent), a tellurium atom,>C═O,> SO ₂ or> NR ^N ( ^RN is a hydrogen atom or a substituent). Represent. X ¹¹ represents an oxygen atom, a sulfur atom, or> NR ^N ( ^RN is a hydrogen atom or a substituent). X ¹² represents an oxygen atom, a sulfur atom or ═NR ⁿ (R ⁿ is a substituent).
Wherein ^{(M2), X 21} represents an oxygen atom, a sulfur atom, a divalent group represented by = NR ⁿ or ⁼ CR ^{201 R 202.} R ²⁰¹ and R ²⁰² each independently represent a substituent. R ²⁰¹ and R ²⁰² may be connected to each other to form a ring. Is R ⁿ is as defined in the formula (1). Ring A represents an aromatic ring.
Wherein (M3-1) ~ (M3-9), X B is as defined above ^{X A.} R ³³ represents a hydrogen atom or a substituent. X ³³ represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or> NR ^N. Is R ^N is as defined in the formula (1). X ³⁴ is a methine group - represents a group or a nitrogen atom (= CR ^M). X ³⁵ represents a divalent group represented by > CR ^b R ^c or> C═CR ^d R ^e . R ^{b to} R ^e each independently represents a hydrogen atom or a substituent. One of X ³⁶ and ^{X 37} represents a nitrogen atom and the other is = CR ^M - represents a. R ^{34 to} R ³⁷ each independently represents a hydrogen atom or a substituent. X ⁶¹ and ^{X 62} each independently methine group - represents a group or a nitrogen atom (= CR ^M). R ^M represents a hydrogen atom or a substituent. R ⁶⁴ and R ⁶⁵ each independently represents an alkoxycarbonyl group or an acyl group. R ^{74 to} R ⁷⁷ each independently represent a hydrogen atom or a substituent.
In formulas (M1) to (M3-9) , Ya and Yb each independently represent a halogen atom, a perfluoroalkanesulfonyloxy group, a trialkyltin group, a boronic ester group, or a boronic acid group. ]

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