JP5643735B2 - Organic thin film solar cell, organic semiconductor polymer and organic semiconductor material composition used therefor - Google Patents

Description

  The present invention relates to an organic thin film solar cell, an organic semiconductor polymer used for the organic thin film solar cell, and a composition for an organic semiconductor material.

In recent years, organic semiconductor polymers have been actively studied in the field of organic electronics. 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 releases 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, it is not necessary to consider the evaporation and leakage of the electrolytic solution, and it is possible to provide flexibility, and the structure and production of the solar cell becomes 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 (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. . In order to improve the short-circuit current, organic semiconductor materials with high solubility and carrier mobility (for example, compounds having a fluorene structure or a silafluorene structure) should be used, and the open circuit voltage is HOMO level of p-type conductive / semiconductor materials. It is said that this is related to the difference between the level and the LUMO level of the n-type conductive / semiconductor material. Increasing this difference increases the open circuit voltage. Furthermore, in the case of an organic solar cell, in order to improve efficiency, it is efficient to absorb a lot of light from a longer wavelength region (650 to 800 nm) of sunlight. For this reason, a narrow band gap is desired. In the case of an organic electroluminescence element, further improvement in luminous efficiency, that is, power efficiency of organic electroluminescence illumination is expected.
On the other hand, research on organic semiconductor polymers as p-type conductive / semiconductor materials, which are electron donating materials, has been actively conducted. For example, Patent Document 1 proposes a polymer having a specific cyclopentadithiazole structure.

International Publication No. 2008/067023 Pamphlet

  Even if the chemical substance of Patent Document 1 is useful as an organic semiconductor polymer, according to the present inventors' confirmation, its performance is not always sufficient when used in an organic thin film solar cell (see Comparative Examples below). Improvement in performance was desired.

  An object of the present invention is to provide an organic thin-film solar cell that is excellent in photoelectric conversion efficiency and durability (particularly durability in the presence of oxygen), and has a small decrease in photoelectric conversion efficiency even when the cell size is increased. Furthermore, an object of the present invention is to provide a composition and a polymer useful as a semiconductor material used for the solar cell and the like.

  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 is represented by the following formula (I) An organic thin film solar cell containing a polymer having a structural unit.

（式中、Ｘ^１、Ｘ^２は各々、ＮまたはＣＲ^３を表す。但しＸ^１およびＸ^２の少なくとも一方はＮである。Ｚ^１、Ｚ^２は各々、ＳまたはＳｉを表す。但しＺ^１およびＺ^２の少なくとも一方はＳである。Ｒ^１、Ｒ^２は各々、１価の置換基を表す。Ｒ^１、Ｒ^２は互いに結合して環を形成してもよい。Ｒ^３は水素原子又は置換基を表す。）
（２）前記ポリマーが共重合体である（１）に記載の有機薄膜太陽電池。
（３）前記ポリマーの置換基Ｒ^１及びＲ^２ハメットの置換基定数σｐ値の合計が０以上１．３以下である（１）又は（２）に記載の有機薄膜太陽電池。
（４）前記式（Ｉ）で表されるポリマーをｐ型有機半導体ポリマーとして用い、前記光電変換層にさらにｎ型有機半導体化合物を含有させた（１）〜（３）のいずれか１項に記載の有機薄膜太陽電池。
（５）前記ｎ型有機半導体化合物が、フラーレンもしくはその誘導体である（４）に記載の有機薄膜太陽電池。
（６）前記フラーレンもしくはその誘導体が、フェニル−Ｃ_６１−酪酸エステル、ジフェニル−Ｃ_６２−ビス（酪酸エステル）、フェニル−Ｃ_７１−酪酸エステル、フェニル−Ｃ_８５−酪酸エステルまたはチエニル−Ｃ_６１−酪酸エステルである（５）に記載の有機薄膜太陽電池。
（７）前記第一の電極と前記光電変換層との間にホール輸送層を有する（１）〜（６）のいずれか１項に記載の有機薄膜太陽電池。
（８）前記第二の電極と前記光電変換層との間に電子輸送層を有する（１）〜（７）のいずれか１項に記載の有機薄膜太陽電池。
（９）前記第一の電極が透明電極である（１）〜（８）のいずれか１項に記載の有機薄膜太陽電池。
（１０）前記第二の電極が金属電極である（１）〜（９）のいずれか１項に記載の有機薄膜太陽電池。
（１１）下記式（Ｉ’）で表される構造単位を有するポリマー。

(Wherein X ¹ and X ² each represent N or CR ³ , provided that at least one of X ¹ and X ² is N. Z ¹ and Z ² each represent S or Si, provided that Z ¹ And at least one of Z ² is S. R ¹ and R ² each represent a monovalent substituent, R ¹ and R ² may combine with each other to form a ring, and R ³ represents a hydrogen atom. Or represents a substituent.)
(2) The organic thin film solar cell according to (1), wherein the polymer is a copolymer.
(3) The organic thin film solar cell according to (1) or (2), wherein the sum of substituent constants σp values of substituents R ¹ and R ² Hammett of the polymer is 0 or more and 1.3 or less.
(4) In any one of (1) to (3), the polymer represented by the formula (I) is used as a p-type organic semiconductor polymer, and the photoelectric conversion layer further contains an n-type organic semiconductor compound. The organic thin film solar cell described.
(5) The organic thin film solar cell according to (4), wherein the n-type organic semiconductor compound is fullerene or a derivative thereof.
(6) the fullerene or its derivatives, phenyl _{-C 61} - butyric acid ester, diphenyl _{-C 62} - bis (butyrate), phenyl _{-C 71} - butyrate, phenyl _{-C 85} - acid ester or thienyl _{-C 61} - The organic thin-film solar cell according to (5), which is a butyric acid ester.
(7) The organic thin-film solar cell according to any one of (1) to (6), wherein a hole transport layer is provided between the first electrode and the photoelectric conversion layer.
(8) The organic thin-film solar cell according to any one of (1) to (7), having an electron transport layer between the second electrode and the photoelectric conversion layer.
(9) The organic thin-film solar cell according to any one of (1) to (8), wherein the first electrode is a transparent electrode.
(10) The organic thin film solar cell according to any one of (1) to (9), wherein the second electrode is a metal electrode.
(11) A polymer having a structural unit represented by the following formula ( I ′ ).

（式中、Ｘ^１、Ｘ^２は各々、ＮまたはＣＲ^３を表す。但しＸ^１およびＸ^２の少なくとも一方はＮである。Ｚ^１、Ｚ^２は各々、ＳまたはＳｉを表す。但しＺ^１およびＺ^２の少なくとも一方はＳである。Ｒ^１ は１価の置換基を表す。Ｒ ^２ ’はアルキルスルホニル基を表す。Ｒ^１、Ｒ ^２ ’は互いに結合して環を形成してもよい。Ｒ^３は水素原子又は置換基を表す。）
（１２）下記式（Ｉ）で表される構造単位と下記式（ＩＩ−１）、（ＩＩ−５）または（ＩＩＡ）で表される構造単位を有するか、または下記ｅｘ−６で表される共重合体であるポリマー。

（式中、Ｘ ^１ 、Ｘ ^２ は各々、ＮまたはＣＲ ^３ を表す。但しＸ ^１ およびＸ ^２ の少なくとも一方はＮである。Ｚ ^１ 、Ｚ ^２ は各々、ＳまたはＳｉを表す。但しＺ ^１ およびＺ ^２ の少なくとも一方はＳである。Ｒ ^１ 、Ｒ ^２ は各々、１価の置換基を表す。Ｒ ^１ 、Ｒ ^２ は互いに結合して環を形成してもよい。Ｒ ^３ は水素原子又は置換基を表す。ＸａはＳｉ（Ｒａ） _２ 、Ｓ、Ｓｅ、ＳＯ、ＳＯ _２ またはＣＯを表す。ＸｃはＮを表す。Ｒａは水素原子または置換基を表し、互いに連結してあるいは縮環して環を形成してもよい。また置換基Ｒａが縮環して芳香族環もしくは芳香族複素環を形成するとき、上記で示した共鳴構造と異なる構造をとってもよい。Ｚ ^１ ’およびＺ ^２ ’は各々独立に、Ｓ、Ｏ、ＳｅまたはＴｅを表す。ＹはＮを表す。ｍおよびｎは共重合比（モル比）を表す。Ｒは水素原子または置換基を表す。）
（１３）前記共重合体が、下記ｅｘ−３、ｅｘ−５または前記ｅｘ−６で表される請求項１２に記載のポリマー。

（式中、Ｒ ^１ 、Ｒ ^２ 、Ｒ ^３ 、ｍおよびｎは、前記ｅｘ−６と同義である。Ｒ ^４ は水素原子または置換基を表す。）
（１４）下記式（Ｉ）で表される構造単位を有するポリマーとフラーレンもしくはその誘導体とを含有する有機半導体材料用組成物。

（式中、Ｘ ^１ 、Ｘ ^２ は各々、ＮまたはＣＲ ^３ を表す。但しＸ ^１ およびＸ ^２ の少なくとも一方はＮである。Ｚ ^１ 、Ｚ ^２ は各々、ＳまたはＳｉを表す。但しＺ ^１ およびＺ ^２ の少なくとも一方はＳである。Ｒ ^１ 、Ｒ ^２ は各々、１価の置換基を表す。Ｒ ^１ 、Ｒ ^２ は互いに結合して環を形成してもよい。Ｒ ^３ は水素原子又は置換基を表す。）

(Wherein X ¹ and X ² each represent N or CR ³ , provided that at least one of X ¹ and X ² is N. Z ¹ and Z ² each represent S or Si, provided that Z ¹ and at least one of Z ² are S .R ¹ represents a monovalent substituent. R 2 ^'represents an alkylsulfonyl group. R ^1, R ^2' may be bonded to each other to form a ring R ³ represents a hydrogen atom or a substituent.
(12) It has a structural unit represented by the following formula (I) and a structural unit represented by the following formula (II-1), (II-5) or (IIA), or represented by the following ex-6 A polymer that is a copolymer.

(Wherein X ¹ and X ² each represent N or CR ³ , provided that at least one of X ¹ and X ² is N. Z ¹ and Z ² each represent S or Si, provided that Z ¹ And at least one of Z ² is S. R ¹ and R ² each represent a monovalent substituent, R ¹ and R ² may combine with each other to form a ring, and R ³ represents a hydrogen atom. Or Xa represents Si (Ra) ₂ , S, Se, SO, SO ₂ or CO. Xc represents N. Ra represents a hydrogen atom or a substituent which is connected to each other or condensed. may form a ring. also, when forming an aromatic ring or aromatic heterocyclic substituent Ra is condensed, it may take a resonance structure different from the structure shown in the above .Z 1 ^'and Z ² 'each independently your .m represents S, O, a .Y is N representing a Se or Te Fine n is .R representing a copolymerization ratio (molar ratio) represents a hydrogen atom or a substituent.)
(13) The polymer according to claim 12, wherein the copolymer is represented by the following ex-3, ex-5, or ex-6.

(In the formula, R ¹ , R ² , R ³ , m and n have the same meanings as ex-6. R ⁴ represents a hydrogen atom or a substituent.)
(14) A composition for an organic semiconductor material comprising a polymer having a structural unit represented by the following formula (I) and fullerene or a derivative thereof.

(Wherein X ¹ and X ² each represent N or CR ³ , provided that at least one of X ¹ and X ² is N. Z ¹ and Z ² each represent S or Si, provided that Z ¹ And at least one of Z ² is S. R ¹ and R ² each represent a monovalent substituent, R ¹ and R ² may combine with each other to form a ring, and R ³ represents a hydrogen atom. Or represents a substituent.)

  The organic thin-film solar cell of the present invention is excellent in photoelectric conversion efficiency and durability (particularly durability in the presence of oxygen). Furthermore, even when the cell size is increased as necessary, there is an excellent effect that the decrease in photoelectric conversion efficiency is small. In addition, the polymer of the present invention and a composition containing the polymer are novel and useful as a semiconductor material used in the solar cell and the like.

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

  The present inventors paid attention to the HOMO level of an n-type organic semiconductor polymer applied thereto in order to improve the photoelectric conversion efficiency and durability of the organic thin film solar cell. By examining various compounds of the polymer structure, the HOMO level of the organic semiconductor polymer is related to the Voc (open voltage) of the solar cell, and the lower the HOMO level, the higher the Voc is. In general, it tends to be oxidized and easily deteriorated, but it was confirmed that lowering its energy level improves the oxidation stability due to oxygen in the atmosphere. On the other hand, it was thought that if the energy level of LUMO was kept low to maintain the conversion efficiency and the narrow band gap was maintained, it was possible to simultaneously achieve longer absorption wavelength and improved durability. Based on the above idea, the present inventors searched for a polymer that achieves this, ascertained this, and incorporated it into the photoelectric conversion layer of an organic thin film solar cell, thereby completing the present invention. Hereinafter, the present invention will be described in detail.

<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-coupling layer) 3 containing a polymer represented by the following formula (I). 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”.

  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 p-type semiconductor material can have a higher electron donating property. According to the polymer represented by the following formula (I), the above requirements can be satisfied satisfactorily.

<Polymer having structural unit represented by formula (I)>
In the present invention, a polymer having a structural unit represented by the formula (I) is used.

· ^X 1, ^{X 2}
In the formula, each of X ¹ and X ² represents N or CR ³ . However, at least one of X ¹ and X ² is N. R ³ represents a hydrogen atom or a substituent. Preferred examples of the substituent include examples of the substituent T described later.

・ Z ¹ , Z ²
Z ¹ and Z ² each represent S or Si. However, at least one of Z ¹ and Z ² is S.

・ R ¹ , R ²
R ¹ and R ² each represent a monovalent substituent. R ¹ and R ² may combine with each other to form a ring. This ring may be either saturated or unsaturated, and may be an aliphatic ring composed of carbon atoms, an aromatic ring, an aliphatic heterocyclic ring or an aromatic heterocyclic ring.

In the present invention, it is preferable that the sum of Hammett's substituent constant σp values of R ¹ and R ² is 0 or more and 1.3 or less.
Hammett's substituent constant σ value will be described. Hammett's rule is a method described in 1935 by L. E. in order to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants determined by Hammett's rule include σp value and σm value, and these values can be found in many general books. For example, J. et al. A. Dean, “Lange's Handbook of Chemistry”, 12th edition, 1979 (McGraw-Hill), “Areas of Chemistry”, No. 122, 96-103, 1979 (Nankodo), Chem. Rev. 1991, 91, 165-195. The combination of substituents having a total Hammett's substituent constant σp value of 0 or more and 1.3 or less in the present invention indicates a combination exhibiting moderate electron withdrawing properties.
The total σp value (Σσp) is more preferably 0 or more and 1.2 or less, further preferably 0 or more and 0.9 or less, further preferably 0.1 or more and 0.7 or less, and It is particularly preferably 25 or more and 0.6 or less.

Examples of combinations of substituents having a total Hammett's substituent constant σp value of 0 or more and 1 or less include an alkoxycarbonyl group (—COOCH ₃ ) and an ethyl group (0.45 + (− 0.15) = 0.30), Cyano group and methyl group (0.66 + (− 0.17) = 0.49), alkylsulfonyl group (—SO ₂ CH ₃ ) and hydrogen atom (0.72 + 0 = 0.72), alkoxycarbonyl group and alkoxycarbonyl A group (0.45 + 0.45 = 0.90), an alkylcarbonyl group (—CO 2 CH ₃ ), an alkylcarbonyl group (0.50 + 0.50 = 1.00), and the like. The values in parentheses are the σp values of typical substituents in Chem. Rev. 1991, Vol. 91, pp. 165-195. Moreover, in the substituent in which σp value is not described, it can be estimated from the value of a similar substituent having similar properties. For example, although the value of the n-octyl group is not described in the above-mentioned document, it can be estimated that it is approximately −0.15 from the methyl group (−0.17) and ethyl group (−0.15) described. .

When R ¹ and R ² are bonded to each other to form a ring, the σp value of R ¹ and R ² cannot be defined. However, in the present invention, R ¹ and R ² are each substituted with a ring partial structure. Σp value in the case of ring formation is defined. For example, when a 1,3-indandione ring is formed, it is considered that R ¹ and R ² are each substituted with a benzoyl group.

R ¹ and R ² are preferably a hydrogen atom, halogen, an alkyl group having 1 to 20 carbon atoms, a cyano group, an alkoxycarbonyl group having 2 to 21 carbon atoms, an alkylsulfonyl group having 1 to 20 carbon atoms, or 2 to 2 carbon atoms. 21 alkylcarbonyl groups, aminocarbonyl groups, C2-C21 alkylaminocarbonyl groups, C3-C41 dialkylaminocarbonyl groups, aminosulfonyl groups, C1-20 alkylaminosulfonyl groups, C2 -40 dialkylaminosulfonyl group, a C1-C20 alkoxy group, a C6-C22 aryl group, and a C1-C20 heteroaryl group are mentioned. These may further have a substituent and may have an unsaturated bond.
More preferably, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cyano group, an alkoxycarbonyl group having 2 to 21 carbon atoms, an alkylsulfonyl group having 1 to 20 carbon atoms, an alkylcarbonyl group having 2 to 21 carbon atoms, carbon These are an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 22 carbon atoms, and a heteroaryl group having 1 to 20 carbon atoms. Hydrogen atom, alkyl group having 1 to 20 carbon atoms, cyano group, alkoxycarbonyl group having 2 to 21 carbon atoms, alkylsulfonyl group having 1 to 20 carbon atoms, alkylcarbonyl group having 2 to 21 carbon atoms, 6 to 22 carbon atoms The aryl group is more preferable. A hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cyano group, an alkoxycarbonyl group having 2 to 21 carbon atoms, and an alkylsulfonyl group having 1 to 20 carbon atoms are particularly preferable.

-Copolymerization component The polymer used in the present invention is preferably a homopolymer comprising the structural unit represented by the formula (I), but may be a copolymer having other copolymerization components. The copolymer components include silacyclopentadithiophene structural unit, cyclopentadithiazole structural unit, benzothiadiazole structural unit, thiadiazoloquinoxaline structural unit, cyclopentadithiophene structural unit, oxidized cyclopentadithiophene structural unit, benzoiso Thiazole structural unit, benzothiazole structural unit, thiophene oxide structural unit, thienothiophene structural unit, oxidized thienothiophene structural unit, dithienothiophene structural unit, oxidized dithienothiophene structural unit, tetrahydroisoindole structural unit, fluorene structural unit, fluorenone structure Unit, thiazole structural unit, selenophene or thiophene structural unit, silole structural unit, thiazolothiazole moiety, thienothiophene structural unit, naphthothiadiazole structural unit, thieno Rajin structural units, oxazole structural unit having an imidazole structure unit, pyrimidine structural units, benzoxazole structural units, benzimidazole structural units include thienothiazole structural units and cyclopentadienyl pyridine structural units. 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-7).

In the formula, Xa represents C (Ra) ₂ , Si (Ra) ₂ , S, Se, SO, SO ₂ , or CO. Xb represents NH or O. Xc represents CRa or N. Ra represents a hydrogen atom or a substituent, and may be connected to each other or condensed to form a ring. When a plurality of substituents are indicated by one symbol, 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. When Ra represents a substituent, examples of Ra include the substituent T described later, and the preferred range is also the same.

  The structural unit of the formula (II) is preferably further represented by the formulas (1) to (36).

In the formulas (1) to (36), R ^{11 to} R ¹⁸ each independently represents a hydrogen atom or a substituent T described later, among which a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an alkoxy group Group, aryloxy group, cyano group, hydroxyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, and alkyl or arylsulfonyl group are preferred. R ^{13 to} R ¹⁷ are more preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an alkoxy group, or an aryloxy group. Preferable examples of each group include examples of the substituent T described later.

X ² and Y ¹ each independently represent CH ₂ , O or S.

Y ² represents S or Se.

  Among these, structural units represented by (1), (2), (3), (12), (14), (20), (22), (25), (27), (35) and the following The structural unit represented by the formula (IIA) shown below is preferred, the structural unit represented by (1), (20), (25) and the structural unit represented by the following formula (II) are more preferred.

  Examples of the copolymer component include a structural unit represented by the following formula (IIA).

・ Z ¹ ′ , Z ² ′
In the formula, Z ¹ ′ and Z ² ′ each independently represent S, O, Se or Te, S or O is more preferable, and S is most preferable.

・ Y
Y represents C (R ²¹ ) or N.

・ R, R ²¹
R and R ²¹ each independently represents a hydrogen atom or a substituent. Examples of the substituent in R and R ²¹ include examples of the substituent T described later. Especially, the substituent which an alkyl group, a cycloalkyl group, an aryl group, and an aromatic heterocyclic group may have is mentioned.

R is preferably an alkyl group, —SO _p X ¹ , —CN, —NO ₂ , —P (═O) (OR ²² ) (OR ²³ ) or —C (R ²⁴ ) ═C (CN) ₂ There, more preferably ^{_{-SO p X 1, -CN, -NO}} 2, a ^{-P (= O) (oR 22} ) (oR 23) or ^{-C (R 24) = C (} CN) 2. Here, X ¹ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aromatic heterocyclic group, or —NR ²⁵ (R ²⁶ ). R ^{22 to} R ²⁶ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aromatic heterocyclic group. R ²⁵ and R ²⁶ may be bonded to each other to form a ring. p represents 1 or 2. p is preferably 2.

The alkyl group, cycloalkyl group, aryl group, and aromatic heterocyclic group in R ^{21 to} R ^{26 have} the same meanings as the alkyl group, cycloalkyl group, aryl group, and aromatic heterocyclic group in the substituent T, and preferred ranges Is the same.

R ^{21 to} R ²⁶ and X ¹ are excellent in thermal stability of the obtained polymer film, and thus do not contain a double bond such as a vinyl group or an allyl group, or a cyclic ether such as an acetylene group, an epoxy group or an oxetane group. More preferred.

  In the present invention, it is also preferable to use a copolymer component of the following formula (a) for the copolymer having the structural unit of the formula (I).

^{· X 1, X 2, X} 3, X 4
In the formula, X ¹ , X ² , X ³ and X ⁴ each independently represent Si, S, S═O, O, N, NR ^a , P, Se, Te, CR or CR ₂ . ^One of the bond set of X ¹ -C and C—X ^{2 and} the bond set of X ³ —C and C—X ⁴ represents a combination of one single bond and the other a double bond. Therefore, an atom (group) in which the above relationship is established between X ¹ and X ² and between X ³ and X ⁴ is selected as a combination of X ¹ , X ² , X ³ , and X ⁴ .

· ^A 1, ^{A 2}
A ¹ and A ² each independently represent CR, CR ₂ , SiR ^a , SiR ^a ₂ , N, NR ^a , O, or S. The bond of A ¹ -A ² represents a single bond or a double bond.

R is independently a hydrogen atom, alkyl group, cycloalkyl group, aryl group, aromatic heterocyclic group, hydroxy group, alkoxy group, aryloxy group, cyano group, amino group, nitro group, alkoxycarbonyl group, aminocarbonyl Represents a group, an alkylsulfonyl group, an arylsulfonyl group, an aminosulfonyl group or a halogen. R ^a each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aromatic heterocyclic group. When two R's are bonded to the same atom, they may be bonded to each other to form a ring, and may represent = O, = S, = CR ₂ , = NR ^a representing the same atom. . When two R ^a are bonded to the same atom, they may be bonded to each other to form a ring. R or R ^a bonded to different atoms may be bonded to each other to form a ring.

  Examples of the structural unit represented by the formula (a) are given below, but the present invention is not construed as being limited thereby.

  In the present invention, it is also preferable to use a copolymer component of the following formula (b) for the copolymer having the structural unit of the formula (I).

^{· X 1, X 2, X} 3, X 4
In the formula, X ¹ , X ² , X ³ and X ⁴ each independently represent Si, S, S═O, O, N, NR ^a , P, Se, Te, CR or CR ₂ . ^One of the bond set of X ¹ -C and C—X ^{2 and} the bond set of X ³ —C and C—X ⁴ represents a combination of one single bond and the other a double bond. Therefore, an atom (group) in which the above relationship is established between X ¹ and X ² and between X ³ and X ⁴ is selected as a combination of X ¹ , X ² , X ³ , and X ⁴ .

· ^A 1, ^{A 2}
A ¹ and A ² each independently represent CR, CR ₂ , SiR ^a , SiR ^a ₂ , N, NR ^a , O, or S. Each bond of the 6-membered ring including A ¹ and A ² represents a single bond or a double bond.

R and ^Ra are as defined in the above formula (a).

  Examples of the structural unit represented by the formula (b) are given below, but the present invention is not construed as being limited thereto.

  In the present invention, it is also preferred to use a copolymer component of the following formula (c) for the copolymer having the structural unit of the formula (I).

^{· X 1, X 2, X} 3, X 4
In the formula, X ¹ , X ² , X ³ and X ⁴ each independently represent Si, S, S═O, O, N, NR ^a , P, Se, Te, CR or CR ₂ . ^One of the bond set of X ¹ -C and C—X ^{2 and} the bond set of X ³ —C and C—X ⁴ represents a combination of one single bond and the other a double bond. Therefore, an atom (group) in which the above relationship is established between X ¹ and X ² and between X ³ and X ⁴ is selected as a combination of X ¹ , X ² , X ³ , and X ⁴ .

・ A ¹
A ¹ CR ₂ , SiR ^a ₂ , NR ^a , O, S are represented.
・ A ² , A ³
A ² and A ³ each independently represent CR, CR ₂ , SiR ^a , SiR ^a ₂ , N, NR ^a , O, or S. The bond between A ² and A ³ represents a single bond or a double bond.

R and ^Ra are as defined in the above formula (a).

  Examples of the structural unit represented by the formula (c) are given below, but the present invention is not construed as being limited thereto.

  In the present invention, it is also preferable to use a copolymer component of the following formula (d) for the copolymer having the structural unit of the formula (I).

^{· X 1, X 2, X} 3, X 4, X 5, X 6, X 7, X 8
In the formula, X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ and X ⁸ are each independently Si, S, S═O, O, N, NR ^a , P, Se, Te, represents CR or CR _2. Each bond of the 6-membered ring containing X ¹ , X ² , X ³ and X ⁴ and the 6-membered ring containing X ⁵ , X ⁶ , X ⁷ and X ⁸ represents a single bond or a double bond. However, ^one of X ¹ , X ² , X ³ and X ⁴ and one of X ⁵ , X ⁶ , X ⁷ and X ⁸ each have a single bond for bonding to another structural unit. ing.

・ A
A represents CR ₂ , SiR ^a ₂ , NR ^a , O, or S.

R and ^Ra are as defined in the above formula (a).

  Examples of the structural unit represented by the formula (d) will be given below, but the present invention is not construed as being limited thereto.

  In the present invention, it is also preferable to use a copolymer component of the following formula (e) for the copolymer having the structural unit of the formula (I).

^{· X 1, X 2, X} 3, X 4, X 5, X 6, X 7, X 8
In the formula, X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ and X ⁸ are each independently Si, S, S═O, O, N, NR ^a , P, Se, Te, represents CR or CR _2. Each bond of the 6-membered ring containing X ¹ , X ² , X ³ and X ⁴ and the 6-membered ring containing X ⁵ , X ⁶ , X ⁷ and X ⁸ represents a single bond or a double bond. However, ^one of X ¹ , X ² , X ³ and X ⁴ and one of X ⁵ , X ⁶ , X ⁷ and X ⁸ each have a single bond for bonding to another structural unit. ing.

A ¹ and A ²
A ¹ and A ² each independently represent CR ₂ , SiR ^a ₂ , NR ^a , O, or S.

R and ^Ra are as defined in the above formula (a).

  Examples of the structural unit represented by the formula (c) are given below, but the present invention is not construed as being limited thereto.

R and ^Ra are as defined in the above formula (a).

  Examples of the structural unit represented by the formula (e) are given below, but the present invention is not construed as being limited thereby.

  In the present invention, it is also preferable to use a copolymer component of the following formula (f) for the copolymer having the structural unit of the formula (I).

・Ｘ^１、Ｘ^２、Ｘ^３、Ｘ^４
式中、Ｘ^１、Ｘ^２、Ｘ^３およびＸ^４はそれぞれ独立してＳｉ、Ｓ、Ｓ＝Ｏ、Ｏ、Ｎ、ＮＲ^ａ、Ｐ、Ｓｅ、Ｔｅ、ＣＲまたはＣＲ_２を表す。Ｘ^１−ＣとＣ−Ｘ^２の結合の組およびＸ^３−ＣとＣ−Ｘ^４の結合の組は、いずれか一方が単結合で他方が二重結合の組み合わせを表す。したがって、Ｘ^１とＸ^２との間、Ｘ^３とＸ^４との間に前記の関係が成立する原子（群）がＸ^１、Ｘ^２、Ｘ^３、Ｘ^４の組合せとして選定される。

^{· X 1, X 2, X} 3, X 4
In the formula, X ¹ , X ² , X ³ and X ⁴ each independently represent Si, S, S═O, O, N, NR ^a , P, Se, Te, CR or CR ₂ . ^One of the bond set of X ¹ -C and C—X ^{2 and} the bond set of X ³ —C and C—X ⁴ represents a combination of one single bond and the other a double bond. Therefore, an atom (group) in which the above relationship is established between X ¹ and X ² and between X ³ and X ⁴ is selected as a combination of X ¹ , X ² , X ³ , and X ⁴ .

R and ^Ra are as defined in the above formula (a).

  Examples of the structural unit represented by the formula (f) will be given below, but the present invention is not construed as being limited thereto.

  In the present invention, it is also preferred to use a copolymer component of the following formula (g) for the copolymer having the structural unit of the formula (I).

^{· X 1, X 2, X} 3, X 4, X 5, X 6
In the formula, X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ are each independently Si, S, S═O, O, N, NR ^a , P, Se, Te, CR or CR _2. Represents. ^One of the bond set of X ¹ -C and C—X ^{2 and} the bond set of X ³ —C and C—X ⁴ represents a combination of one single bond and the other a double bond. Each bond of the 6-membered ring including X ³ , X ⁴ , X ⁵ and X ⁶ represents a single bond or a double bond. Therefore, an atom (group) in which the above relationship is established between X ¹ and X ² is selected as a combination of X ¹ and X ² .

R and ^Ra are as defined in the above formula (a).

  Examples of the structural unit represented by the formula (g) will be given below, but the present invention is not construed as being limited thereto.

  In the present invention, it is also preferable to use a copolymer component of the following formula (h) for the copolymer having the structural unit of the formula (I).

^{· X 1, X 2, X} 3, X 4
In the formula, X ¹ , X ² , X ³ and X ⁴ each independently represent Si, S, S═O, O, N, NR ^a , P, Se, Te, CR or CR ₂ . ^One of the bond set of X ¹ -C and C—X ^{2 and} the bond set of X ³ —C and C—X ⁴ represents a combination of one single bond and the other a double bond. Therefore, an atom (group) in which the above relationship is established between X ¹ and X ² and between X ³ and X ⁴ is selected as a combination of X ¹ , X ² , X ³ , and X ⁴ .

· ^A 1, ^{A 2}
A ¹ and A ² each independently represent CR ₂ , SiR ^a ₂ , NR ^a , O, or S.

R and ^Ra are as defined in the above formula (a).

  Examples of the structural unit represented by the formula (h) will be given below, but the present invention is not construed as being limited thereto.

  Preferred examples of the homopolymer and copolymer containing the structural unit of the formula (I) are shown below, but the present invention is not construed as being limited thereto.

R ¹ and R ² are as defined in the above formula (I). Examples of R ³ and R ⁴ include R ¹ and R ² . n and m represent a copolymerization ratio (molar ratio).

The polymer having the structural unit represented by the formula (I) of the present invention can be synthesized using a coupling reaction, for example, a method described in Chemical Reviews, 2002, 102, 1358. That is, Negishi coupling using a zinc reagent using transition metal catalyst, Ueda-Kosugi-Stille coupling using tin reagent, Suzuki-Miyaura coupling using boron reagent, Kumada-Tamao using magnesium reagent -Corriu coupling, cross coupling such as Ulsan coupling using a silicon reagent, Ullmann reaction using copper, Yamamoto polymerization using nickel, etc. can be used for the synthesis. As the transition metal catalyst, metals such as palladium, nickel, copper, cobalt, and iron (described in 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 and 1290 pages) are preferably used. Metal reactants such as tin reactant and boron reactant as raw materials are Organic Synthesis Collective Volume, 11, 2009, page 393, Vol. 9, 1998, page 553, Tetrahedron, 1997, 53, 1925. Page, Journal of Organic Chemistry, 1993, Vol. 58, page 904, Japanese Patent Application Laid-Open No. 2005-290001, Japanese Translation of PCT International Publication No. 2010-526853, 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 which has a structural unit represented by the said formula (I) is not specifically limited, 5000-500000 are preferable at a weight average molecular weight, and 10000-100,000 are more preferable.

  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 weight 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 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. The column and carrier to be used can be appropriately selected depending on the physical properties of the polymer compound to be measured.

In the present invention, when the polymer containing the structural unit represented by the formula (I) is a copolymer, the copolymerization ratio is not particularly limited, but the structural unit represented by the formula (I) is 10 in terms of molar ratio. It is preferable that it is -90 mol%, and it is preferable that it is 45-55 mol%.
In the formula (I) of the present invention, when any ^one of R ¹ and R ² , X ¹ and X ² , Z ¹ and Z ² represents different from each other, that is, the structural unit represented by the formula (I) When is asymmetric, the polymer containing it has regioregularity due to the difference in bonding mode. In the present invention, only one typical binding mode is described, but the present invention is not construed as being limited thereto.
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 a coalescence.

  In the present specification, the term “compound” or “polymer” (polymer) is used to mean that the compound or polymer itself, its salt, complex, or its ionic state. Moreover, it is the meaning including the derivative modified with the predetermined form in the range with the desired effect. Further, 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 20 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.), alkenyl A group (preferably an alkenyl group having 2 to 20 carbon atoms, such as vinyl, allyl, oleyl, etc.), an alkynyl group (preferably an alkynyl group having 2 to 20 carbon atoms, such as ethynyl, butadiynyl, phenylethynyl, etc.), A cycloalkyl group (preferably a cycloalkyl group having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc.), an aryl group (preferably an aryl group having 6 to 26 carbon atoms, for example, Phenyl, 1-naphthyl, 4-methoxyphenyl, -Chlorophenyl, 3-methylphenyl, etc.), heterocyclic groups (preferably heterocyclic groups having 2 to 20 carbon atoms, such as 2-pyridyl, 4-pyridyl, 2-imidazolyl, 2-benzimidazolyl, 2-thiazolyl, 2 -Oxazolyl etc.), an alkoxy group (preferably an alkoxy group having 1 to 20 carbon atoms, such as methoxy, ethoxy, isopropyloxy, benzyloxy etc.), an aryloxy group (preferably an aryloxy group having 6 to 26 carbon atoms) , For example, phenoxy, 1-naphthyloxy, 3-methylphenoxy, 4-methoxyphenoxy, etc.), alkoxycarbonyl groups (preferably C2-C20 alkoxycarbonyl groups such as ethoxycarbonyl, 2-ethylhexyloxycarbonyl, etc.) ), Amino group (preferably carbon Amino group having 0 to 20 children, such as amino, N, N-dimethylamino, N, N-diethylamino, N-ethylamino, anilino, etc.), sulfonamide group (preferably sulfonamide having 0 to 20 carbon atoms) A group such as N, N-dimethylsulfonamide, N-phenylsulfonamide, etc., an acyloxy group (preferably an acyloxy group having 1 to 20 carbon atoms such as acetyloxy, benzoyloxy, etc.), a carbamoyl group (preferably A carbamoyl group having 1 to 20 carbon atoms, such as N, N-dimethylcarbamoyl, N-phenylcarbamoyl, etc.), an acylamino group (preferably an acylamino group having 1 to 20 carbon atoms, such as acetylamino, benzoylamino, etc.) , A cyano group, or a halogen atom (eg, fluorine atom, chlorine atom, bromine atom) More preferably an alkyl group, alkenyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, alkoxycarbonyl group, amino group, acylamino group, cyano group or halogen atom, Particularly preferred are an alkyl group, an alkenyl group, a heterocyclic group, an alkoxy group, an alkoxycarbonyl group, an amino group, an acylamino group, and a cyano group.

<Organic semiconductor polymer>
The polymer having the structural unit represented by the formula (I) 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 having the structural unit represented by the formula (I) of the present invention is useful as a p-type organic semiconductor polymer, and the composition for an organic semiconductor material of the present invention has a structure represented by the formula (I). Although it contains a polymer having a unit and an n-type semiconductor compound, it is particularly preferred in the present invention to contain an n-type organic semiconductor compound. If necessary, a p-type organic semiconductor compound other than the polymer having the structural unit represented by the formula (I), a compound other than a semiconductor (for example, other p-type semiconductor compounds such as poly-3-hexylthiophene (P3HT ), Poly [2-methoxy-5- (2-ethylhexyloxy) -1,4-phenylenevinylene (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) and the like, 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 content of the polymer having the structural unit represented by the formula (I) is not particularly limited, but when the total mass of the composition is 100, the polymer having the structural unit represented by the formula (I) is 10 to 90. It is preferable to make it contain by mass%, and it is more preferable to make it contain 30-70 mass%.

  About an n-type organic-semiconductor compound, when the mass of the composition whole quantity is set to 100, it is preferable to contain 10-90 mass%, and it is more preferable to contain 30-70 mass%. About arbitrary p-type organic-semiconductor compounds other than the polymer which has a structural unit represented by Formula (I), 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, fullerenes or derivatives thereof can be efficiently and efficiently separated from an organic semiconductor polymer (p-type organic semiconductor compound) having a structural unit represented by the formula (I) of the present invention. Is preferable, and fullerene or a derivative thereof is more preferable.
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 includes, in addition to the polymer having the structural unit represented by the above formula (I) of the present invention, other p-type semiconductor compounds (for example, condensed polycyclic aromatic low molecular weight compounds, oligomers). Or a polymer).

  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)
The composition for organic semiconductor materials of the present invention is preferably used as a coating composition for a photoelectric conversion layer (particularly a bulk hetero-bonding 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 adjusted so that the photoelectric conversion efficiency is the highest. Usually, the mass ratio is 10:90 to 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 150 ° C. Moreover, you may heat at 50 degreeC-150 degreeC after completion | finish of 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, and in the case of a solar cell, it is preferably a transparent electrode that transmits light from visible light to near infrared light (380 to 800 nm). As the material, for example, transparent conductive metal oxides such as indium tin oxide (ITO), SnO ₂ and ZnO, metal nanowires, carbon nanotubes and the like can be used. 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. Note that when light transmittance is not required, the positive electrode may be formed using a metal material such as nickel, molybdenum, silver, tungsten, or gold. In the case of a transparent solar cell, the transmittance of the positive electrode is the thickness used for the solar cell (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 85% or more.

(Second electrode)
The second electrode of the present invention is a negative electrode and a metal negative electrode having a positive standard electrode potential.
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.

If a metal material is used as the conductive material for the negative electrode, the light reaching the negative electrode side is reflected and reflected to the first electrode side, and this light can be reused and absorbed again by the photoelectric conversion layer. Improved and preferable. The negative electrode may be a metal (for example, gold, silver, copper, platinum, rhodium, ruthenium, aluminum, magnesium, indium, etc.), carbon nanoparticle, nanowire, or nanostructure. If it is a thing, a transparent and highly conductive negative electrode can be formed by the apply | coating method, and it is preferable.
In addition, when the negative electrode side is made light transmissive, for example, a conductive material suitable for the negative electrode such as aluminum and aluminum alloy, silver and silver compound is thinly formed with a film thickness of about 1 to 20 nm, and then the positive electrode is formed. A light-transmitting negative electrode can be obtained by providing the conductive light-transmitting material film mentioned in the description.

(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. Such materials include phenanthrene compounds such as bathocuproine, n-type semiconductor compounds such as naphthalene tetracarboxylic acid anhydride, naphthalene tetracarboxylic acid diimide, perylene tetracarboxylic acid anhydride, perylene tetracarboxylic acid diimide, and titanium oxide. N-type inorganic oxides such as zinc oxide and gallium oxide, and alkali metal compounds such as lithium fluoride, sodium fluoride, and cesium fluoride can be used. Moreover, the layer which consists of a n-type semiconductor compound single-piece | unit used for the photoelectric converting layer can also be used.

(Support)
The support constituting the photovoltaic cell of the present invention comprises 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 commonly used layer may be applied to dispose an easy adhesion layer / undercoat layer, a functional layer, a recombination layer, other semiconductor layers, a protective layer, a gas barrier layer, and the like.

  Although the photovoltaic cell has been described with respect to the polymer having the structural unit represented by the formula (I) of the present invention, in some embodiments, the polymer having the structural unit represented by the formula (I) of the present invention is used. Can be used for 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 to 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.

(Synthesis example)
Synthesis of Polymer 3 Compound B was synthesized according to the following scheme. Compound A was synthesized by the method described in US Patent Application Publication No. 2010 / 0301314A1.

  A homopolymer (Polymer 3) using Compound B as a monomer was synthesized with reference to the method described in Macromolecules, 1992, Vol. 25, pages 1214-1223.

  Polymers 1, 2 and 4-7 were synthesized in the same manner. The corresponding monomer was synthesized from Compound A in the same manner as Compound B using any method of Wittig reaction, Horner-Wadsworth-Emmons reaction, and Knoevenagel reaction.

Synthesis of Polymer 8 A copolymer (Polymer 8) using Compound C and Compound D as monomers was synthesized with reference to a method described in JP 2011-116961 A. Compound C was synthesized from Compound B by the method described in Japanese Patent Application No. 2011-80813 with reference to the method described in Journal of Organic Chemistry, 1995, Vol. 60, pages 7508-7510.

Synthesis of Polymer 9 A copolymer (Polymer 9) using Compound B and Compound E as monomers was synthesized with reference to the method described in Journal of the American Chemical Society, 2008, 130, 7670-7865. Compound E was synthesized by the method described in Journal of the American Chemical Society, 2009, Vol. 131, pages 7792-7799.

Synthesis of Polymer 10 A copolymer (Polymer 10) using Compound B and Compound F as monomers was synthesized in the same manner as Polymer 8. Compound F was synthesized by the method described in Japanese Patent Application No. 2011-80999.

Synthesis of Polymer 11 A copolymer (Polymer 11) using Compound C and Compound G as monomers was synthesized in the same manner as Polymer 8. Compound G was synthesized with reference to the method described in Japanese Patent No. 4414881.

Synthesis of Polymer 12 A copolymer (Polymer 12) using Compound B and Compound H as monomers was synthesized in the same manner as Polymer 8. Compound H was synthesized by the method described in International Publication No. 2003/077453.

The sum (Σσp) of σp of R ¹ and R ^{2 in} the formula (I) corresponding to each polymer was as follows. Note that Chem. Rev. , 1991, Vol. 91, pages 165 to 195, the value of a substituent not described in parentheses was deduced from similar substituents and expressed in parentheses.

-Synthesis | combination of the comparison polymer A The following comparison polymer A was synthesize | combined with reference to the method as described in international publication 2008/067023 pamphlet (p12-13).

-Synthesis | combination of the comparison polymer B The following comparison polymer B was synthesize | combined with reference to the method as described in the international publication 93/05077 pamphlet (p26 and 34-36).

-Synthesis | combination of the comparison polymer C The following comparison polymer C was synthesize | combined with reference to the method as described in international publication 2008/067023 pamphlet (p12-13).

Synthesis of Comparative Polymer D The following comparative polymer D was synthesized with reference to the method described in Macromolecules, 2010, Vol. 43, pages 7864-7867.

(Create photovoltaic cell)
Using the polymers shown in Table 1 below, photovoltaic cells were formed on a glass ITO substrate by the following procedure.
A PEDOT: PSS (HC Star CleviosP VP AI4083) layer used as a hole transport layer was spin-coated on a clean and UV ozone-treated ITO glass substrate and dried at 120 ° C. for 15 minutes.
Subsequently, a mixture (mass ratio 1: 1) of each p-type semiconductor polymer and PC61BM (Solenne [60] PCBM) was dissolved in o-dichlorobenzene, and then spin-coated on the PEDOT: PSS layer. And dried at 120 ° C. for 15 minutes to form a photoelectric conversion layer.
Further, a dehydrated ethanol solution (2% by mass) of titanium isopropoxide (manufactured by Sigma Aldrich) was spin-coated on this photoelectric conversion layer, and dried at room temperature for 1 hour to form an electron transport layer of a titanium oxide layer.
Thereafter, an upper electrode was formed by high vacuum vapor deposition of aluminum to obtain a photovoltaic cell element.
At this time, by changing the size of the glass ITO substrate to be used and the pattern size of ITO and vapor-deposited aluminum, two types of elements of 2 mm □ and 20 mm □ were prepared.

(Photocell evaluation)
(1) Element Current Density-Voltage (JV) Characteristics The performance of each 2 mm □ element and 20 mm □ element produced as described above 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. The short-circuit current (Jsc), open-circuit voltage (Voc), fill factor (FF), and power generation efficiency (η) output by the above apparatus are shown in Table 1 below.

(2) Retention rate of power generation efficiency when left in the atmosphere The 2 mm square element obtained above is exposed to light-shielded atmosphere (23 ° C., 50% RH) for 72 hours, and then the current of the element is the same as in 1) above. Density-voltage (JV) characteristics were evaluated. The retention rate was calculated by the following formula.
These results are summarized in Table 1 below.
[Formula A] Power generation efficiency retention ratio (%) = (power generation efficiency after being left in the atmosphere) / (initial power generation efficiency) × 100

(3) Element Size Dependence The initial power generation efficiency of the 2 mm square element and the 20 mm square element obtained above were compared, and the difference in power generation efficiency due to the increase in element size was calculated using the following equation.
[Formula B] Ratio (%) = (20 mm □ element power generation efficiency) / (2 mm □ element power generation efficiency) × 100

As a result, the solar cell element using the organic semiconductor polymer of the present invention has a high power generation efficiency η, a high power generation efficiency retention ratio after being left in the atmosphere, and a small decrease in power generation efficiency when the element size is increased. I understand that.
On the other hand, the solar cell element using the organic semiconductor polymer of the comparative example has a low conversion efficiency η, the conversion efficiency η tends to decrease after being left in the atmosphere, and the decrease in power generation efficiency when the element size is increased is large. Recognize.

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 (winding machine)

Claims (14)

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 a structural unit represented by the following formula (I): An organic thin film solar cell containing a polymer having the same.

(Wherein X ¹ and X ² each represent N or CR ³ , provided that at least one of X ¹ and X ² is N. Z ¹ and Z ² each represent S or Si, provided that Z ¹ And at least one of Z ² is S. R ¹ and R ² each represent a monovalent substituent, R ¹ and R ² may combine with each other to form a ring, and R ³ represents a hydrogen atom. Or represents a substituent.)   The organic thin film solar cell according to claim 1, wherein the polymer is a copolymer. 3. The organic thin-film solar cell according to claim 1, wherein a sum of substituent constants σp values of substituents R ¹ and R ² Hammett of the polymer is 0 or more and 1.3 or less.   The organic thin film solar according to any one of claims 1 to 3, wherein the polymer represented by the formula (I) is used as a p-type organic semiconductor polymer, and the photoelectric conversion layer further contains an n-type organic semiconductor compound. battery.   The organic thin film solar cell according to claim 4, wherein the n-type organic semiconductor compound is fullerene or a derivative thereof. The fullerene or its derivatives, phenyl _{-C 61} - butyric acid ester, diphenyl _{-C 62} - bis (butyrate), phenyl _{-C 71} - butyrate, phenyl _{-C 85} - butyric acid ester - acid ester or thienyl _{-C 61} The organic thin film solar cell according to claim 5.   The organic thin-film solar cell of any one of Claims 1-6 which has a hole transport layer between said 1st electrode and said photoelectric conversion layer.   The organic thin-film solar cell of any one of Claims 1-7 which has an electron carrying layer between said 2nd electrode and said photoelectric conversion layer.   The organic thin-film solar cell according to any one of claims 1 to 8, wherein the first electrode is a transparent electrode.   The organic thin-film solar cell according to any one of claims 1 to 9, wherein the second electrode is a metal electrode. A polymer having a structural unit represented by the following formula (I ′) .

(Wherein X ¹ and X ² each represent N or CR ³ , provided that at least one of X ¹ and X ² is N. Z ¹ and Z ² each represent S or Si, provided that Z ¹ and at least one of Z ² is S .R ¹ represents a monovalent substituent. R 2 ^'represents an alkylsulfonyl group. R ^1, R ^2' may be bonded to each other to form a ring R ³ represents a hydrogen atom or a substituent. The structural unit represented by the following formula (I) and the structural unit represented by the following formula (II-1), (II-5) or (IIA), or the coexistence represented by the following ex-6 A polymer that is a coalescence.

(Wherein X ¹ and X ² each represent N or CR ³ , provided that at least one of X ¹ and X ² is N. Z ¹ and Z ² each represent S or Si, provided that Z ¹ And at least one of Z ² is S. R ¹ and R ² each represent a monovalent substituent, R ¹ and R ² may combine with each other to form a ring, and R ³ represents a hydrogen atom. Or Xa represents Si (Ra) ₂ , S, Se, SO, SO ₂ or CO. Xc represents N. Ra represents a hydrogen atom or a substituent which is connected to each other or condensed. may form a ring. also, when forming an aromatic ring or aromatic heterocyclic substituent Ra is condensed, it may take a resonance structure different from the structure shown in the above .Z 1 ^'and Z ² 'each independently your .m represents S, O, a .Y is N representing a Se or Te Fine n is .R representing a copolymerization ratio (molar ratio) represents a hydrogen atom or a substituent.) The polymer according to claim 12, wherein the copolymer is represented by ex-3, ex-5, or ex-6.

(Wherein R ¹ , R ² , R ³ , M, and n have the same meanings as ex-6. R ⁴ Represents a hydrogen atom or a substituent. ) The composition for organic-semiconductor materials containing the polymer which has a structural unit represented by following formula (I), and fullerene or its derivative (s) .

(Wherein X ¹ and X ² each represent N or CR ³ , provided that at least one of X ¹ and X ² is N. Z ¹ and Z ² each represent S or Si, provided that Z ¹ And at least one of Z ² is S. R ¹ and R ² each represent a monovalent substituent, R ¹ and R ² may combine with each other to form a ring, and R ³ represents a hydrogen atom. Or represents a substituent.)

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