JP5869420B2 - Organic thin film solar cell, composition used therefor, monomer and method for producing semiconductor film - Google Patents

Description

The present invention relates to an organic thin film solar cell, set Narubutsu that used to a process for the preparation of the monomer and the semiconductor 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 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, 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 (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.
Considering the effects and operating principles of the organic thin-film solar cell as described above, research on organic semiconductor polymers as p-type conductive / semiconductor materials that are electron donating materials has been conducted. For example, Patent Documents 1 and 2 propose a polymer having a repeating unit having a structure in which a plurality of thiophenes are condensed. Patent Document 3 proposes a polymer having a polycyclic monomer structure in which thiadiazole units are condensed, Patent Document 4 proposes a polymer having an indacenodithiophene structure, and Patent Document 5 proposes a polymer having a naphthodithiophene structure. Has been.

Chinese Patent Application No. 1022886013 International Publication No. 2008/106019 Pamphlet US Patent Application Publication No. 2011/178236 US Patent Application Publication No. 2011/226999 PCT International Publication No. 2011/078246 Specification

  The present inventor has paid attention to the technology for improving the suitability and durability in view of the future commercialization and widespread use as well as the performance improvement in the organic thin film solar cell.

  An object of the present invention is to provide an organic thin-film solar cell that is excellent in various characteristics and manufacturability relating to photoelectric conversion, and that is excellent in durability against heat and moisture. 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, and a monomer for polymer synthesis.

The above-mentioned subject has been achieved by the following means.
[1] An organic thin-film solar cell including a first electrode, a second electrode, and a photoelectric conversion layer disposed therebetween, wherein the photoelectric conversion layer includes the following formulas (1a) and (1b): And an organic thin film solar cell containing a polymer having a structural unit represented by any one of formulas (2a) to (2f) .

Ｘ^１：Ｃ（Ｒ^２）_２，Ｎ（Ｒ^３），Ｏ，Ｓ，Ｓｉ（Ｒ^３）_２から選ばれる。
Ｘ^２：Ｃ（Ｒ^２）_２，Ｎ（Ｒ^３），Ｏ，Ｓｉ（Ｒ^３）_２から選ばれる。
Ｘ^３：Ｃ（Ｒ^２）_２，Ｓから選ばれる。
Ｘ^４：Ｎ（Ｒ^３），Ｏ，Ｓ，Ｓｉ（Ｒ^３）_２から選ばれる。ただし、Ｘ ^３ がＳである場合、Ｘ ^４ はＯ，Ｓｉ（Ｒ ^３ ） _２ から選ばれる。
Ｒ^１、Ｒ^２：水素原子、ハロゲン原子、アルキル基、シクロアルキル基、アリール基、または芳香族へテロ環基を表す。
Ｒ^３：水素原子、アルキル基、シクロアルキル基、アリール基、または芳香族へテロ環基を表す。

前記式（２ａ）および式（２ｆ）において、
Ｘ ^２１ ：Ｃ（Ｒ ^２ ） _２ ，Ｎ（Ｒ ^３ ），Ｏ，Ｓ，Ｓｉ（Ｒ ^３ ） _２ から選ばれる。
Ｘ ^２２ ：Ｃ（Ｒ ^２ ） _２ ，Ｎ（Ｒ ^３ ），Ｏ，Ｓ，Ｓｉ（Ｒ ^３ ） _２ から選ばれる。
前記式（２ｂ）および式（２ｄ）において、
Ｘ ^２１ ：Ｃ（Ｒ ^２ ） _２ ，Ｎ（Ｒ ^３ ），Ｏ，Ｓから選ばれる。
Ｘ ^２２ ：Ｃ（Ｒ ^２ ） _２ ，Ｎ（Ｒ ^３ ），Ｏ，Ｓ，Ｓｉ（Ｒ ^３ ） _２ から選ばれる。
前記式（２ｃ）において、
Ｘ ^２２ ：Ｃ（Ｒ ^２ ） _２ ，Ｎ（Ｒ ^３ ），Ｏ，Ｓ，Ｓｉ（Ｒ ^３ ） _２ から選ばれる。
Ｘ ^２３ ：Ｎ（Ｒ ^３ ），Ｏ，Ｓから選ばれる。
前記式（２ｅ）において、
Ｘ ^２１ ：Ｃ（Ｒ ^２ ） _２ ，Ｓｉ（Ｒ ^３ ） _２ から選ばれる。
Ｘ ^２２ ：Ｃ（Ｒ ^２ ） _２ ，Ｓｉ（Ｒ ^３ ） _２ から選ばれる。
Ｒ ^１ 、Ｒ^２、Ｒ^３は、式（１ａ）と同義である。
＊は主鎖に組み込まれる結合手である。
ただし、前記式（２ａ）が下記式（ｃ−１）の場合、Ｘ^８は、Ｃ（Ｒ^２）_２，Ｏ，Ｎ（Ｒ^３），Ｓｉ（Ｒ^３）_２から選ばれ、Ｘ^９は、Ｃ（Ｒ^２）_２，Ｏ，Ｎ（Ｒ^３），Ｓ，Ｓｉ（Ｒ^３）_２から選ばれる。前記式（２ｃ）で表される構造単位は式（ｃ−２）で表される構造単位を除く。Ｒ^４は、水素原子、ハロゲン原子、アルキル基、シクロアルキル基、アリール基、または芳香族へテロ環基を表す。Ｒ^１、Ｒ^２は、前記式（１ａ）と同義である。

［２］前記ポリマーが、前記式（１ａ）または（１ｂ）で表される構造単位を有する［１］に記載の有機薄膜太陽電池。
［３］式（１ａ）のＸ^２が、Ｃ（Ｒ^２）_２、Ｎ（Ｒ^３）、またはＳｉ（Ｒ^３）_２であり、式（１ｂ）のＸ^４が、Ｎ（Ｒ^３）、Ｏ、またはＳｉ（Ｒ^３）_２ 、ただし、Ｘ ^３ がＳである場合、ＯまたはＳｉ（Ｒ ^３ ） _２ である［１］に記載の有機薄膜太陽電池。
［４］前記ポリマーが、下記式（ＩＩ−１）〜（ＩＩ−２３）で表される構造単位を有する［１］〜［３］のいずれか１項に記載の有機薄膜太陽電池。

（式中、ＸａはＣ（Ｒａ）_２、Ｃ＝Ｃ（Ｒａ）_２、Ｓｉ（Ｒａ）_２、Ｓ、Ｓｅ、Ｓ＝Ｏ、ＳＯ_２、Ｃ＝Ｏ、ＮＨ又はＮＲｂを表す。ＸｂはＮＨ、Ｏ又はＳを表す。ＸｃはＣＲａ又はＮを表す。Ｒａは水素原子又は置換基を表す。Ｒｂは、水素原子または置換基を表す。複数のＲａまたはＲｂが置換基のとき、それぞれ互いに連結してあるいは縮環して環を形成していてもよい。）
［５］前記光電変換層に、ｎ型有機半導体化合物を含有させた［１］〜［４］のいずれか１項に記載の有機薄膜太陽電池。
［６］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［５］に記載の有機薄膜太陽電池。
［７］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［６］に記載の有機薄膜太陽電池。
［８］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］〜［７］のいずれか１項に記載の有機薄膜太陽電池。
［９］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］〜［８］のいずれか１項に記載の有機薄膜太陽電池。
［１０］前記第一の電極が透明電極である［１］〜［９］のいずれか１項に記載の有機薄膜太陽電池。
［１１］前記第二の電極が金属電極である［１］〜［１０］のいずれか１項に記載の有機薄膜太陽電池。
［１２］下記式（１ａ）、式（１ｂ）、および式（２ａ）〜（２ｆ）のいずれかで表される構造単位を有するポリマーを有機溶媒中に含有させた組成物。

X ¹ : selected from C (R ² ) ₂ , N (R ³ ), O, S, Si (R ³ ) ₂ .
X ^{2 is selected from} C (R ² ) ₂ , N (R ³ ), O, Si (R ³ ) ₂ .
X ³ is selected from C (R ² ) ₂ and S.
X ⁴ is selected from N (R ³ ), O, S, Si (R ³ ) ₂ . However, when X ³ is S, X ⁴ is selected from O, Si (R ³ ) ₂ .
R ¹ and R ^{2 represent a} hydrogen atom, a halogen atom , an alkyl group, a cycloalkyl group, an aryl group, or an aromatic heterocyclic group.
R ^{3 represents a} hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aromatic heterocyclic group.

In the formula (2a) and the formula (2f),
X ^{21 is selected from} C (R ² ) ₂ , N (R ³ ), O, S, Si (R ³ ) ₂ .
X ²² : selected from C (R ² ) ₂ , N (R ³ ), O, S, Si (R ³ ) ₂ .
In the formula (2b) and the formula (2d),
X ²¹ is selected from C (R ² ) ₂ , N (R ³ ), O, and S.
X ²² : selected from C (R ² ) ₂ , N (R ³ ), O, S, Si (R ³ ) ₂ .
In the formula (2c),
X ²² : selected from C (R ² ) ₂ , N (R ³ ), O, S, Si (R ³ ) ₂ .
X ²³ is selected from N (R ³ ), O, and S.
In the formula (2e),
X ²¹ is selected from C (R ² ) ₂ and Si (R ³ ) ₂ .
X ²² is selected from C (R ² ) ₂ and Si (R ³ ) ₂ .
R ¹ , R ² and R ³ have the same meanings as in formula (1a).
* Is a bond incorporated in the main chain.
However, if the above formula (2a) is represented by the following formula (c-1), ^{X 8 _{is, C (R 2) 2,}} O, N (R 3), is selected from _{^{Si (R 3) 2, X}} 9 is , C (R ² ) ₂ , O, N (R ³ ), S, Si (R ³ ) ₂ . The structural unit represented by the formula (2c) excludes the structural unit represented by the formula (c-2). R ⁴ represents a hydrogen atom, a halogen atom , an alkyl group, a cycloalkyl group, an aryl group, or an aromatic heterocyclic group. R ¹ and R ² have the same meaning as in the formula (1a).

[2] The organic thin-film solar cell according to [1], wherein the polymer has a structural unit represented by the formula (1a) or (1b).
[3] X ^{2 in} formula (1a) is C (R ² ) ₂ , N (R ³ ), or Si (R ³ ) ₂ , and X ^{4 in} formula (1b) is N (R ³ ), O or Si (R ³ ) ₂ , provided that when X ³ is S, the organic thin-film solar cell according to [1] , which is O or Si (R ³ ) ₂ .
[ 4 ] The organic thin-film solar cell according to any one of [1] to [ 3 ], wherein the polymer has structural units represented by the following formulas (II-1) to (II-23).

(In the formula, Xa represents C (Ra) ₂ , C═C (Ra) ₂ , Si (Ra) ₂ , S, Se, S═O, SO ₂ , C═O, NH, or NRb. Xb represents NH. , O or S. Xc represents CRa or N. Ra represents a hydrogen atom or a substituent.Rb represents a hydrogen atom or a substituent. When a plurality of Ra or Rb are substituents, they are linked to each other. Or may be condensed to form a ring.)
[ 5 ] The organic thin film solar cell according to any one of [1] to [ 4 ], wherein the photoelectric conversion layer contains an n-type organic semiconductor compound.
[ 6 ] The organic thin-film solar cell according to [ 5 ], wherein the n-type organic semiconductor compound is fullerene or a derivative thereof.
[7] 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 [ 6 ], which is a butyric acid ester.
[ 8 ] The organic thin-film solar cell according to any one of [1] to [ 7 ], which has a hole transport layer between the first electrode and the photoelectric conversion layer.
[ 9 ] The organic thin-film solar cell according to any one of [1] to [ 8 ], having an electron transport layer between the second electrode and the photoelectric conversion layer.
[ 10 ] The organic thin-film solar cell according to any one of [1] to [ 9 ], wherein the first electrode is a transparent electrode.
[ 11 ] The organic thin-film solar cell according to any one of [1] to [ 10 ], wherein the second electrode is a metal electrode.
[ 12 ] A composition comprising a polymer having a structural unit represented by any of the following formulas (1a), (1b), and (2a) to (2f) in an organic solvent.

Ｘ^１：Ｃ（Ｒ^２）_２，Ｎ（Ｒ^３），Ｏ，Ｓ，Ｓｉ（Ｒ^３）_２から選ばれる。
Ｘ^２：Ｃ（Ｒ^２）_２，Ｎ（Ｒ^３），Ｏ，Ｓｉ（Ｒ^３）_２から選ばれる。
Ｘ^３：Ｃ（Ｒ^２）_２，Ｓから選ばれる。
Ｘ^４：Ｎ（Ｒ^３），Ｏ，Ｓ，Ｓｉ（Ｒ^３）_２から選ばれる。ただし、Ｘ ^３ がＳである場合、Ｘ ^４ はＯ，Ｓｉ（Ｒ ^３ ） _２ から選ばれる。
Ｒ^１、Ｒ^２：水素原子、ハロゲン原子、アルキル基、シクロアルキル基、アリール基、または芳香族へテロ環基を表す。
Ｒ^３：水素原子、アルキル基、シクロアルキル基、アリール基、または芳香族へテロ環基を表す。

前記式（２ａ）および式（２ｆ）において、
Ｘ ^２１ ：Ｃ（Ｒ ^２ ） _２ ，Ｎ（Ｒ ^３ ），Ｏ，Ｓ，Ｓｉ（Ｒ ^３ ） _２ から選ばれる。
Ｘ ^２２ ：Ｃ（Ｒ ^２ ） _２ ，Ｎ（Ｒ ^３ ），Ｏ，Ｓ，Ｓｉ（Ｒ ^３ ） _２ から選ばれる。
前記式（２ｂ）および式（２ｄ）において、
Ｘ ^２１ ：Ｃ（Ｒ ^２ ） _２ ，Ｎ（Ｒ ^３ ），Ｏ，Ｓから選ばれる。
Ｘ ^２２ ：Ｃ（Ｒ ^２ ） _２ ，Ｎ（Ｒ ^３ ），Ｏ，Ｓ，Ｓｉ（Ｒ ^３ ） _２ から選ばれる。
前記式（２ｃ）において、
Ｘ ^２２ ：Ｃ（Ｒ ^２ ） _２ ，Ｎ（Ｒ ^３ ），Ｏ，Ｓ，Ｓｉ（Ｒ ^３ ） _２ から選ばれる。
Ｘ ^２３ ：Ｎ（Ｒ ^３ ），Ｏ，Ｓから選ばれる。
前記式（２ｅ）において、
Ｘ ^２１ ：Ｃ（Ｒ ^２ ） _２ ，Ｓｉ（Ｒ ^３ ） _２ から選ばれる。
Ｘ ^２２ ：Ｃ（Ｒ ^２ ） _２ ，Ｓｉ（Ｒ ^３ ） _２ から選ばれる。
Ｒ ^１ 、Ｒ^２、Ｒ^３は、式（１ａ）と同義である。
＊は主鎖に組み込まれる結合手である。
ただし、前記式（２ａ）が下記式（ｃ−１）の場合、Ｘ^８は、Ｃ（Ｒ^２）_２，Ｏ，Ｎ（Ｒ^３），Ｓｉ（Ｒ^３）_２から選ばれ、Ｘ^９は、Ｃ（Ｒ^２）_２，Ｏ，Ｎ（Ｒ^３），Ｓ，Ｓｉ（Ｒ^３）_２から選ばれる。前記式（２ｃ）で表される構造単位は式（ｃ−２）で表される構造単位を除く。Ｒ^４は、水素原子、ハロゲン原子、アルキル基、シクロアルキル基、アリール基、または芳香族へテロ環基を表す。Ｒ^１、Ｒ^２は、前記式（１ａ）と同義である。

X ¹ : selected from C (R ² ) ₂ , N (R ³ ), O, S, Si (R ³ ) ₂ .
X ^{2 is selected from} C (R ² ) ₂ , N (R ³ ), O, Si (R ³ ) ₂ .
X ³ is selected from C (R ² ) ₂ and S.
X ⁴ is selected from N (R ³ ), O, S, Si (R ³ ) ₂ . However, when X ³ is S, X ⁴ is selected from O, Si (R ³ ) ₂ .
R ¹ and R ^{2 represent a} hydrogen atom, a halogen atom , an alkyl group, a cycloalkyl group, an aryl group, or an aromatic heterocyclic group.
R ^{3 represents a} hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aromatic heterocyclic group.

In the formula (2a) and the formula (2f),
X ^{21 is selected from} C (R ² ) ₂ , N (R ³ ), O, S, Si (R ³ ) ₂ .
X ²² : selected from C (R ² ) ₂ , N (R ³ ), O, S, Si (R ³ ) ₂ .
In the formula (2b) and the formula (2d),
X ²¹ is selected from C (R ² ) ₂ , N (R ³ ), O, and S.
X ²² : selected from C (R ² ) ₂ , N (R ³ ), O, S, Si (R ³ ) ₂ .
In the formula (2c),
X ²² : selected from C (R ² ) ₂ , N (R ³ ), O, S, Si (R ³ ) ₂ .
X ²³ is selected from N (R ³ ), O, and S.
In the formula (2e),
X ²¹ is selected from C (R ² ) ₂ and Si (R ³ ) ₂ .
X ²² is selected from C (R ² ) ₂ and Si (R ³ ) ₂ .
R ¹ , R ² and R ³ have the same meanings as in formula (1a).
* Is a bond incorporated in the main chain.
However, if the above formula (2a) is represented by the following formula (c-1), ^{X 8 _{is, C (R 2) 2,}} O, N (R 3), is selected from _{^{Si (R 3) 2, X}} 9 is , C (R ² ) ₂ , O, N (R ³ ), S, Si (R ³ ) ₂ . The structural unit represented by the formula (2c) excludes the structural unit represented by the formula (c-2). R ⁴ represents a hydrogen atom, a halogen atom , an alkyl group, a cycloalkyl group, an aryl group, or an aromatic heterocyclic group. R ¹ and R ² have the same meaning as in the formula (1a).

［１３］有機半導体材料用である［１２］に記載の組成物。
［１４］［１３］に記載の組成物を用い塗布形成する、光電変換能を有する半導体膜の製造方法。
［１５］下記式（１ａ’）、式（１ｂ’）、および式（２ａ’）〜（２ｆ’）のいずれかで表される化合物からなる単量体。

Ｘ^１：Ｃ（Ｒ^２）_２，Ｎ（Ｒ^３），Ｏ，Ｓ，Ｓｉ（Ｒ^３）_２から選ばれる。
Ｘ^２：Ｃ（Ｒ^２）_２，Ｎ（Ｒ^３），Ｏ，Ｓｉ（Ｒ^３）_２から選ばれる。
Ｘ^３：Ｃ（Ｒ^２）_２，Ｓから選ばれる。
Ｘ^４：Ｎ（Ｒ^３），Ｏ，Ｓ，Ｓｉ（Ｒ^３）_２から選ばれる。ただし、Ｘ ^３ がＳである場合、Ｘ ^４ はＯ，Ｓｉ（Ｒ ^３ ） _２ から選ばれる。
Ｒ^１、Ｒ^２：水素原子、ハロゲン原子、アルキル基、シクロアルキル基、アリール基、または芳香族へテロ環基を表す。
Ｒ^３：水素原子、アルキル基、シクロアルキル基、アリール基、または芳香族へテロ環基を表す。

前記式（２ａ’）および式（２ｆ’）において、
Ｘ ^２１ ：Ｃ（Ｒ ^２ ） _２ ，Ｎ（Ｒ ^３ ），Ｏ，Ｓ，Ｓｉ（Ｒ ^３ ） _２ から選ばれる。
Ｘ ^２２ ：Ｃ（Ｒ ^２ ） _２ ，Ｎ（Ｒ ^３ ），Ｏ，Ｓ，Ｓｉ（Ｒ ^３ ） _２ から選ばれる。
前記式（２ｂ’）および式（２ｄ’）において、
Ｘ ^２１ ：Ｃ（Ｒ ^２ ） _２ ，Ｎ（Ｒ ^３ ），Ｏ，Ｓから選ばれる。
Ｘ ^２２ ：Ｃ（Ｒ ^２ ） _２ ，Ｎ（Ｒ ^３ ），Ｏ，Ｓ，Ｓｉ（Ｒ ^３ ） _２ から選ばれる。
前記式（２ｃ’）において、
Ｘ ^２２ ：Ｃ（Ｒ ^２ ） _２ ，Ｎ（Ｒ ^３ ），Ｏ，Ｓ，Ｓｉ（Ｒ ^３ ） _２ から選ばれる。
Ｘ ^２３ ：Ｎ（Ｒ ^３ ），Ｏ，Ｓから選ばれる。
前記式（２ｅ’）において、
Ｘ ^２１ ：Ｃ（Ｒ ^２ ） _２ ，Ｓｉ（Ｒ ^３ ） _２ から選ばれる。
Ｘ ^２２ ：Ｃ（Ｒ ^２ ） _２ ，Ｓｉ（Ｒ ^３ ） _２ から選ばれる。
Ｒ ^１ 、Ｒ^２、Ｒ^３は、式（１ａ）と同義である。
＊は主鎖に組み込まれる結合手である。
ただし、前記式（２ａ’）が下記式（ｃ−１’）の場合、Ｘ^８は、Ｃ（Ｒ^２）_２，Ｏ，Ｎ（Ｒ^３），Ｓｉ（Ｒ^３）_２から選ばれ、Ｘ^９は、Ｃ（Ｒ^２）_２，Ｏ，Ｎ（Ｒ^３），Ｓ，Ｓｉ（Ｒ^３）_２から選ばれる。前記式（２ｃ’）で表される構造単位は式（ｃ−２’）で表される構造単位を除く。Ｒ^４は、水素原子、ハロゲン原子、アルキル基、シクロアルキル基、アリール基、または芳香族へテロ環基を表す。Ｒ^１、Ｒ^２は、前記式（１ａ）と同義である。

［上記式中、Ｙａ、Ｙｂは、ハロゲン原子、トリフルオロメタンスルホニルオキシ基、トリアルキルスズ基、ホウ酸エステル基、またはホウ酸基を示す。］

[ 13 ] The composition according to [ 12 ], which is for an organic semiconductor material.
[ 14 ] A method for producing a semiconductor film having photoelectric conversion ability, which is formed by coating using the composition according to [ 13 ].
[ 15 ] A monomer comprising a compound represented by any of the following formulas (1a ′), (1b ′), and formulas (2a ′) to (2f ′) .

X ¹ : selected from C (R ² ) ₂ , N (R ³ ), O, S, Si (R ³ ) ₂ .
X ^{2 is selected from} C (R ² ) ₂ , N (R ³ ), O, Si (R ³ ) ₂ .
X ³ is selected from C (R ² ) ₂ and S.
X ⁴ is selected from N (R ³ ), O, S, Si (R ³ ) ₂ . However, when X ³ is S, X ⁴ is selected from O, Si (R ³ ) ₂ .
R ¹ and R ^{2 represent a} hydrogen atom, a halogen atom , an alkyl group, a cycloalkyl group, an aryl group, or an aromatic heterocyclic group.
R ^{3 represents a} hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aromatic heterocyclic group.

In the formula (2a ′) and the formula (2f ′),
X ^{21 is selected from} C (R ² ) ₂ , N (R ³ ), O, S, Si (R ³ ) ₂ .
X ²² : selected from C (R ² ) ₂ , N (R ³ ), O, S, Si (R ³ ) ₂ .
In the formula (2b ′) and the formula (2d ′),
X ²¹ is selected from C (R ² ) ₂ , N (R ³ ), O, and S.
X ²² : selected from C (R ² ) ₂ , N (R ³ ), O, S, Si (R ³ ) ₂ .
In the formula (2c ′),
X ²² : selected from C (R ² ) ₂ , N (R ³ ), O, S, Si (R ³ ) ₂ .
X ²³ is selected from N (R ³ ), O, and S.
In the formula (2e ′),
X ²¹ is selected from C (R ² ) ₂ and Si (R ³ ) ₂ .
X ²² is selected from C (R ² ) ₂ and Si (R ³ ) ₂ .
R ¹ , R ² and R ³ have the same meanings as in formula (1a).
* Is a bond incorporated in the main chain.
However, in the aforesaid formula (2a ') is the following formula ^{(c-1'), X} 8 _{^{is, C (R 2) 2,}} O, N (R 3), is selected from Si ^(R _{3) 2,} X ⁹ is selected from C (R ² ) ₂ , O, N (R ³ ), S, Si (R ³ ) ₂ . The structural unit represented by the formula (2c ′) excludes the structural unit represented by the formula (c-2 ′ ). R ⁴ represents a hydrogen atom, a halogen atom , an alkyl group, a cycloalkyl group, an aryl group, or an aromatic heterocyclic group. R ¹ and R ² have the same meaning as in the formula (1a).

[In the above formula, Ya and Yb represent a halogen atom, a trifluoromethanesulfonyloxy group, a trialkyltin group, a boric acid ester group, or a boric acid group. ]

［上記式中、Ｙａ、Ｙｂは、ハロゲン原子、トリフルオロメタンスルホニルオキシ基、トリアルキルスズ基、ホウ酸エステル基、またはホウ酸基を示す。］

[In the above formula, Ya and Yb represent a halogen atom, a trifluoromethanesulfonyloxy group, a trialkyltin group, a boric acid ester group, or a boric acid group. ]

  In the present specification, when there are a plurality of substituents, linking groups, and the like (hereinafter referred to as substituents) indicated by specific symbols, or when a plurality of substituents are specified simultaneously or alternatively, The substituents and the like may be the same as or different from each other. The same applies to the definition of the number of substituents and the like. Further, 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 and manufacturing suitability (prevention of coating unevenness), and is excellent in durability against heat and moisture. 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.

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 one of the following formulas (1a), (1b), and (2) 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”.

  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>
(Specific structural unit)
The specific polymer used in the present invention has a structural unit (specific structural unit) represented by any of the following formulas (1a), (1b), and (2).

~ Structural Units Represented by Formulas (1a) and (1b) ~

・ X ¹
X ¹ is selected from C (R ² ) ₂ , N (R ³ ), O, S, Si (R ³ ) ₂ . Among these, N (R ³ ), O, or S is preferable. R ² and R ³ will be described later.

・ X ²
X ² is selected from C (R ² ) ₂ , N (R ³ ), O, Si (R ³ ) ₂ . Among these, X ² is preferably C (R ² ) ₂ , N (R ³ ), or Si (R ³ ) ₂ . R ² and R ³ will be described later.

・ X ³
X ³ is selected from C (R ² ) ₂ and S. Among these, S is preferable. R ² will be described later.

・ X ⁴
X ⁴ is selected from N (R ³ ), O, S, Si (R ³ ) ₂ . Among these, X ⁴ is preferably N (R ³ ), O, or Si (R ³ ) ₂ . R ² and R ³ will be described later.

・ R ¹ , R ²
R ¹ and R ² represent a hydrogen atom, a halogen, an alkyl group, a cycloalkyl group, an aryl group, or an aromatic heterocyclic group. As the alkyl group, cycloalkyl group, aryl group, or aromatic heterocyclic group, examples of the substituent T described later are preferable. Among them, the alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, such as methyl group, ethyl group, n-propyl group, n-butyl group, t-butyl group, n-hexyl group, n-octyl, 2-ethylhexyl. Group, n-dodecyl group and the like are preferable. The cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms, more preferably a cycloalkyl group having 6 to 10 carbon atoms, and particularly preferably a cyclohexyl group. The aryl group is preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms. Among them, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms is preferable, and further, a 6 to 12 carbon atom is preferable. A substituted or unsubstituted aryl group is preferable, and for example, a phenyl group, a p-tolyl group, a naphthyl group, an m-chlorophenyl group, an o-hexadecanoylaminophenyl group, and the like are preferable. The aromatic heterocyclic group is preferably an aromatic heterocyclic group having 4 to 12 carbon atoms, and examples thereof include a pyridyl group, a furyl group, a thienyl group, a pyridyl group or a furyl group is preferable, and a pyridyl group is more preferable. preferable.

・ R ³
R ^{3 represents a} hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aromatic heterocyclic group. As the alkyl group, cycloalkyl group, aryl group, or aromatic heterocyclic group, examples of the substituent T described later are preferable. Among them, the alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, for example, methyl group, ethyl group, n-propyl group, n-butyl group, t-butyl group, n-hexyl group, n-octyl, 2 -An ethylhexyl group, n-dodecyl group, etc. are preferable. The cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms, more preferably a cycloalkyl group having 6 to 10 carbon atoms, and particularly preferably a cyclohexyl group. The aryl group is preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms. Among them, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms is preferable, and further, a 6 to 12 carbon atom is preferable. A substituted or unsubstituted aryl group is preferable, and for example, a phenyl group, a p-tolyl group, a naphthyl group, an m-chlorophenyl group, an o-hexadecanoylaminophenyl group, and the like are preferable. The aromatic heterocyclic group is preferably an aromatic heterocyclic group having 4 to 12 carbon atoms, and examples thereof include a pyridyl group, a furyl group, a thienyl group, a pyridyl group or a furyl group is preferable, and a pyridyl group is more preferable. preferable.

Note that X ^{1 to} X ⁴ are premised on being independently defined, and may or may not overlap. X ¹ and X ² are preferably not a structure in which all of them are C (R ² ) ₂ , N (R ³ ), or O. Preferably, X ¹ and X ² are different from each other. Further, it is preferable that the structure does not satisfy X ₃ = X ₄ = S. Preferably, X ₃ and X ₄ are different from each other, or X ₃ = S, and X ₄ is a different combination. When all of X ¹ and X ² are C (R ² ) ₂ , N (R ³ ), or O, or X ₃ = X ₄ = S, the obtained polymer Since the polarity of the liquid crystal is reduced, the solubility in a solvent is reduced, coating becomes impossible or difficult, and the thickness of the obtained photoelectric conversion layer is not uniform, so that Voc and FF in the case of an element tend to decrease. It is in.

~ Structural Unit Represented by Formula (2) ~

Ａ、Ｂ、Ｃ、Ｂ’、Ａ’は各々単環であり、縮環している状態を表す。

A, B, C, B ′ and A ′ are each monocyclic and represent a condensed state.

・ A, A ', C, B, B'
A and A ′ are aromatic 5-membered rings represented by the formula (a), and A and A ′ may be the same or different. X ^A is selected from C (R ² ) ₂ , O, N (R ³ ), S, Si (R ³ ) ₂ . R ² and R ³ have the same meaning as in the formula (1a).
B and B ′ are aromatic 5-membered rings represented by the formula (b), and B and B ′ may be the same or different. X ^B is selected from C (R ² ) ₂ , O, N (R ³ ), S, Si (R ³ ) ₂ . R ² and R ³ have the same meaning as in the formula (1a).

  C is a benzene ring or a heteroaromatic 6-membered ring. Preferred examples of the heteroaromatic 6-membered ring include pyridine, pyrazine, and pyridazine.

However, if the expression (2) is the formula (c-1), ^{X 8 _{is, C (R 2) 2,}} O, N (R 3), is selected from Si ^(R _{3) 2,} ^{X 9} is, C (R ² ) ₂ , O, N (R ³ ), S, Si (R ³ ) _{2 are} selected. The compound represented by Formula (c-2) is excluded. R ⁴ represents a hydrogen atom, a halogen, an alkyl group, a cycloalkyl group, an aryl group, or an aromatic heterocyclic group. R ¹ and R ² have the same meaning as in the formula (1a).

  The structural unit represented by the formula (2) is preferably represented by any one of the following formulas (2a) to (2f).

Ｘ^２１：Ｃ（Ｒ^２）_２，Ｎ（Ｒ^３），Ｏ，Ｓ，Ｓｉ（Ｒ^３）_２から選ばれる。
Ｘ^２２：Ｃ（Ｒ^２）_２，Ｎ（Ｒ^３），Ｏ，Ｓ，Ｓｉ（Ｒ^３）_２から選ばれる。
Ｘ^２３：Ｎ（Ｒ^３），Ｏ，Ｓ，Ｓｉ（Ｒ^３）_２から選ばれる。
Ｒ^２、Ｒ^３は、式（１ａ）と同義である。
＊は主鎖に組み込まれる結合手である。
Ｒ^１は式（１ａ）と同義である。

X ^{21 is selected from} C (R ² ) ₂ , N (R ³ ), O, S, Si (R ³ ) ₂ .
X ²² : selected from C (R ² ) ₂ , N (R ³ ), O, S, Si (R ³ ) ₂ .
X ²³ is selected from N (R ³ ), O, S, Si (R ³ ) ₂ .
R ² and R ³ have the same meaning as in formula (1a).
* Is a bond incorporated in the main chain.
R ¹ has the same meaning as in formula (1a).

  In the formula (2a), the following formula (2a ′) is preferable, and in the formula (2b), it is preferable that the following formula (2b ′) or (2b ″) is not satisfied.

  The specific polymer can be suitably synthesized using a monomer composed of a compound represented by any of the following formulas (1a ′), (1b ′), and (2 ′).

Ｘ^１、Ｘ^２、Ｘ^３、Ｘ^４、Ｒ^１は前記と同義である。

X ¹ , X ² , X ³ , X ⁴ and R ¹ are as defined above.

  A, B, C, B ′, and A ′ are as defined in the above formula (2).

However, when Formula (2 ′) is Formula (c-1 ′), X ⁸ is selected from C (R ² ) ₂ , O, N (R ³ ), Si (R ³ ) ₂ , and X ⁹ is , C (R ² ) ₂ , O, N (R ³ ), S, Si (R ³ ) ₂ . The compound represented by the formula (c-2 ′) is excluded. R ⁴ represents a hydrogen atom, a halogen, an alkyl group, a cycloalkyl group, an aryl group or an aromatic heterocyclic group. R ² and R ³ have the same meaning as in the formula (1a ′).

  In the above formula, Ya and Yb represent a halogen atom, a trifluoromethanesulfonyloxy group, a trialkyltin group, a boric acid ester group, or a boric acid group.

  The preferable thing of the said monomer is synonymous with the said structural unit formula (1a), Formula (1b), and Formula (2) in the mother structure. For example, with respect to the formulas (2a) to (2f), compounds in which the bond * is changed to the above-mentioned Ya and Yb are mentioned as preferable monomers.

(Copolymerization component)
The polymer used in the present invention is preferably a copolymer having the specific structural unit and another copolymer component. As copolymer components, benzene structural unit, naphthalene structural unit, anthracene unit, phenanthrene 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, oxidized Thienothiophene structural unit, dithienothiophene structural unit, oxidized dithienothiophene structural unit, tetrahydroisoindole structural unit, fluorene structural unit, fluorenone structural unit, thiazole Structural unit, selenophene or thiophene structural unit, silole structural unit, thiazolothiazole moiety, thienothiophene structural unit, naphthothiadiazole structural unit, thienopyrazine structural unit, oxazole structural unit, imidazole structural unit, pyrimidine structural unit, benzoxazole structural unit, benzo Examples include imidazole structural units, thienothiazole structural units, and cyclopentadipyridine structural units. 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 formula (II) represents C (Ra) ₂ , C═C (Ra) ₂ , Si (Ra) ₂ , S, Se, S═O, SO ₂ , C═O, NH, or NRb.
・ Xb
Xb in the formula (II) represents NH, O, or S.
・ Xc
Xc in the formula (II) represents CRa or N.
・ Ra
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 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.
・ Rb
Rb includes a hydrogen atom or a substituent T described later. A hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkylthio group, a dialkylamino group, a diarylamino group, an arylamino group, an alkylamino group, an acyl Group, an alkoxycarbonyl group, and an acyloxy group are preferable, and a hydrogen atom, an alkyl group, and an alkoxy group are more preferable. When R ^b represents a substituent, examples of Rb include the substituent T described later, preferably an alkyl group, an alkenyl group, and an alkynyl group, and more preferably an alkyl group. When Rb is a substituent, they may be connected to each other or condensed to form a ring.

  The structural unit of the formula (II) is preferably further represented by the formulas (1) to (61).

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

  Among these, (1), (2), (3), (5), (6), (9), (11), (12), (14), (15), (17), (20 ), (21), (25), (30), (31), (32), (35), (36), (37), (43), (45), (48), (49), The structural units represented by (50), (51), (53), (54) are preferred, and (1), (2), (5), (6), (9), (12), (15 ), (53), and structural units represented by (54) are more preferable.

式（１ｂ）の構成単位

式（２）の構成単位

＊ は主鎖に組み込まれる結合手を表す。 Examples of the specific structural unit include the following.
Structural unit of formula (1a)

Structural unit of formula (1b)

Unit of formula (2)

* Represents a bond incorporated in the main chain.

The polymer (specific polymer) having a specific structural unit 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 having the specific structural unit is not particularly limited, the weight average molecular weight is preferably 5,000 to 500,000, and more preferably 10,000 to 100,000.

  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 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 o-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 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 whole in terms of molar ratio. More preferably, it is mol%. 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, 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.), a heterocyclic group (preferably a heterocyclic group having 2 to 20 carbon atoms, preferably a 5- or 6-membered heterocycle having at least one oxygen atom, sulfur atom, nitrogen atom) A cyclic group is preferable, for example, 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, for example, Methoxy, ethoxy, isopropyloxy, benzyloxy, 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 having 2 to 20 carbon atoms) Nyl groups such as ethoxycarbonyl, 2-ethylhexyloxycarbonyl, etc., amino groups (preferably including amino groups having 0 to 20 carbon atoms, alkylamino groups, arylamino groups, such as amino, N, N-dimethyl Amino, N, N-diethylamino, N-ethylamino, anilino, etc.), sulfamoyl groups (preferably sulfonamido groups having 0 to 20 carbon atoms, such as N, N-dimethylsulfamoyl, N-phenylsulfamoyl) Etc.), an acyl group (preferably an acyl group having 1 to 20 carbon atoms, such as acetyl, propionyl, butyryl, benzoyl, etc.), an acyloxy group (preferably an acyloxy group having 1 to 20 carbon atoms, such as acetyloxy, Benzoyloxy, etc.), carbamoyl groups (preferably C 1-20 carbon atoms) Rubamoyl groups such as N, N-dimethylcarbamoyl and N-phenylcarbamoyl), acylamino groups (preferably having 1 to 20 carbon atoms, such as acetylamino and benzoylamino), sulfonamido groups (preferably Is a sulfamoyl group having 0 to 20 carbon atoms, such as methanesulfonamide, benzenesulfonamide, N-methylmethanesulfonamide, N-ethylbenzenesulfonamide, etc., an alkylthio group (preferably an alkylthio having 1 to 20 carbon atoms). Groups such as methylthio, ethylthio, isopropylthio, benzylthio, etc., arylthio groups (preferably arylthio groups having 6 to 26 carbon atoms, such as phenylthio, 1-naphthylthio, 3-methylphenylthio, 4-methoxyphenylthio ), An alkyl or arylsulfonyl group (preferably an alkyl or arylsulfonyl group having 1 to 20 carbon atoms, such as methylsulfonyl, ethylsulfonyl, benzenesulfonyl, etc.), a hydroxyl group, a cyano group, a halogen atom (for example, a fluorine atom, chlorine) Atoms, bromine atoms, iodine atoms, etc.), more preferably alkyl groups, alkenyl groups, aryl groups, heterocyclic groups, alkoxy groups, aryloxy groups, alkoxycarbonyl groups, amino groups, acylamino groups, hydroxyl groups or halogen atoms. And particularly preferably an alkyl group, an alkenyl group, a heterocyclic group, an alkoxy group, an alkoxycarbonyl group, an amino group, an acylamino group or a hydroxyl group.
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.

  Although the organic solvent applied to the said composition is not specifically limited, Toluene, tetrahydrofuran, chloroform, chlorobenzene, o-dichlorobenzene, nitrobenzene etc. are mentioned, Toluene, chlorobenzene, o-dichlorobenzene etc. are especially preferable.

  The content of the polymer having a specific structural unit is not particularly limited, but when the total mass of the composition is 100, it is preferable to contain 10 to 90% by weight of a polymer having a specific structural unit, and 30 to 70% by weight is contained. More preferably.

  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 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 it can perform charge separation at high speed and efficiently from the organic semiconductor polymer (p-type organic semiconductor compound) having the specific structural unit of the present invention. 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 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 bond 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 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)
In the present invention, the second electrode 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)
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 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 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.

Synthesis of each polymer

［化合物（１ａ−ｍ１）：融点１４８℃、ＭＳ（ｍ／ｚ）８８１．５（Ｍ^＋＋Ｈ）］
引き続き、下記ポリマー１ａ−１を下記ＳｃｈｅｍｅのようにＪｏｕｒｎａｌ ｏｆ ｔｈｅ Ａｍｅｒｉｃａｎ Ｃｈｅｍｉｃａｌ Ｓｏｃｉｅｔｙ，２００８年，１３０巻，７６７０〜７６８５ページに記載の方法を参考にして合成した。ｏ−ジクロロベンゼン（１４０℃）溶媒でのＧＰＣ測定の結果、重量平均分子量４５，０００、数平均分子量２３，０００であった。

〔ポリマー１ａ−２の合成〕
下記のＳｃｈｅｍｅのように単量体（１ａ−ｍ２）を合成した。

［化合物（１ａ−ｍ２）：融点１７３℃、ＭＳ（ｍ／ｚ）１２４８．４（Ｍ^＋＋Ｈ）］
引き続き、下記ポリマー１ａ−２をポリマー１ａ−１と同様に下記Ｓｃｈｅｍｅのように重合を行い、ｏ−ジクロロベンゼン（１４０℃）溶媒でのＧＰＣ測定の結果、重量平均分子量３８，０００、数平均分子量２０，０００であった。

〔ポリマー１ａ−３の合成〕
下記のＳｃｈｅｍｅのように単量体（１ａ−ｍ３）を合成した。

［化合物（１ａ−ｍ３）：融点１５７℃、ＭＳ（ｍ／ｚ）９５９．７（Ｍ^＋＋Ｈ）］
引き続き、下記ポリマー１ａ−３をポリマー１ａ−１と同様に下記Ｓｃｈｅｍｅのように重合を行い、ｏ−ジクロロベンゼン（１４０℃）溶媒でのＧＰＣ測定の結果、重量平均分子量４９，０００、数平均分子量２６，０００であった。

〔ポリマー１ａ−４の合成〕
下記のＳｃｈｅｍｅのように単量体（１ａ−ｍ４）を合成した。

［化合物（１ａ−ｍ４）：融点１７１℃、ＭＳ（ｍ／ｚ）８６１．３（Ｍ＋＋Ｈ）］
引き続き、下記ポリマー１ａ−４をポリマー１ａ−１と同様に下記Ｓｃｈｅｍｅのように重合を行い、ｏ−ジクロロベンゼン（１４０℃）溶媒でのＧＰＣ測定の結果、重量平均分子量３１，０００、数平均分子量１５，０００であった。

〔ポリマー１ｂ−１の合成〕
下記のＳｃｈｅｍｅのように単量体（１ｂ−ｍ１）を合成した。

［化合物（１ｂ−ｍ１）：融点１８０℃、ＭＳ（ｍ／ｚ）９３７．６（Ｍ^＋＋Ｈ）］
引き続き、下記ポリマー１ｂ−１をポリマー１ａ−１と同様に下記Ｓｃｈｅｍｅのように重合を行い、ｏ−ジクロロベンゼン（１４０℃）溶媒でのＧＰＣ測定の結果、重量平均分子量３５，０００、数平均分子量２０，０００であった。

〔ポリマー１ｂ−２の合成〕
下記のＳｃｈｅｍｅのように単量体（１ｂ−ｍ２）を合成した。

［化合物（１ｂ−ｍ２）：融点１５７℃、ＭＳ（ｍ／ｚ）８０８．４（Ｍ^＋＋Ｈ）］
引き続き、下記ポリマー１ｂ−２をポリマー１ａ−１と同様に下記Ｓｃｈｅｍｅのように重合を行い、ｏ−ジクロロベンゼン（１４０℃）溶媒でのＧＰＣ測定の結果、重量平均分子量２９，０００、数平均分子量１６，０００であった。

〔ポリマー１ｂ−３の合成〕
下記のＳｃｈｅｍｅのように単量体（１ｂ−ｍ３）を合成した。

［化合物（１ｂ−ｍ３）：融点１６２℃、ＭＳ（ｍ／ｚ）９６７．８（Ｍ^＋＋Ｈ）］
引き続き、下記ポリマー１ｂ−３をポリマー１ａ−１と同様に下記Ｓｃｈｅｍｅのように重合を行い、ｏ−ジクロロベンゼン（１４０℃）溶媒でのＧＰＣ測定の結果、重量平均分子量３６，０００、数平均分子量１９，０００であった。

〔ポリマー２ａ−１の合成〕
下記のＳｃｈｅｍｅのように単量体（２ａ−ｍ１）を合成した。

［化合物（２ａ−ｍ１）：融点１５９℃、ＭＳ（ｍ／ｚ）９３１．６（Ｍ^＋＋Ｈ）］
引き続き、下記ポリマー２ａ−１をポリマー１ａ−１と同様に下記Ｓｃｈｅｍｅのように重合を行い、ｏ−ジクロロベンゼン（１４０℃）溶媒でのＧＰＣ測定の結果、重量平均分子量５１，０００、数平均分子量３３，０００であった。

〔ポリマー２ａ−２の合成〕
下記のＳｃｈｅｍｅのように単量体（２ａ−ｍ２）を合成した。

［化合物（２ａ−ｍ２）：融点１５７℃、ＭＳ（ｍ／ｚ）９６１．８（Ｍ^＋＋Ｈ）］
引き続き、下記２ａ−２をポリマー１ａ−１と同様に下記Ｓｃｈｅｍｅのように重合を行い、ｏ−ジクロロベンゼン（１４０℃）溶媒でのＧＰＣ測定の結果、重量平均分子量４０，０００、数平均分子量２１，０００であった。

〔ポリマー２ｂ−１の合成〕
下記のＳｃｈｅｍｅのように単量体（２ｂ−ｍ１）を合成した。

［化合物（２ｂ−ｍ１）：融点１３３℃、ＭＳ（ｍ／ｚ）９７９．７（Ｍ^＋＋Ｈ）］
引き続き、下記ポリマー２ｂ−１をポリマー１ａ−１と同様に下記Ｓｃｈｅｍｅのように重合を行い、ｏ−ジクロロベンゼン（１４０℃）溶媒でのＧＰＣ測定の結果、重量平均分子量２９，０００、数平均分子量１６，０００であった。

〔ポリマー２ｃ−１の合成〕
下記のＳｃｈｅｍｅのように単量体（２ｃ−ｍ１）を合成した。

［化合物（２ｃ−ｍ１）：融点１５５℃、ＭＳ（ｍ／ｚ）９３１．６（Ｍ^＋＋Ｈ）］
引き続き、下記ポリマー２ｃ−１をポリマー１ａ−１と同様に下記Ｓｃｈｅｍｅのように重合を行い、ｏ−ジクロロベンゼン（１４０℃）溶媒でのＧＰＣ測定の結果、重量平均分子量３６，０００、数平均分子量１７，０００であった。

〔ポリマー２ｃ−２の合成〕
下記のＳｃｈｅｍｅのように単量体（２ｃ−ｍ２）を合成した。

［化合物（２ｃ−ｍ２）：融点１６０℃、ＭＳ（ｍ／ｚ）９６１．８（Ｍ^＋＋Ｈ）］
引き続き、下記ポリマー２ｃ−２をポリマー１ａ−１と同様に下記Ｓｃｈｅｍｅのように重合を行い、ｏ−ジクロロベンゼン（１４０℃）溶媒でのＧＰＣ測定の結果、重量平均分子量５２，０００、数平均分子量２８，０００であった。

〔ポリマー２ｄ−１の合成〕
下記のＳｃｈｅｍｅのように単量体（２ｄ−ｍ１）を合成した。

［化合物（２ｄ−ｍ１）：融点１６１℃、ＭＳ（ｍ／ｚ）９７７．７（Ｍ^＋＋Ｈ）］
引き続き、下記ポリマー２ｄ−１をポリマー１ａ−１と同様に下記Ｓｃｈｅｍｅのように重合を行い、ｏ−ジクロロベンゼン（１４０℃）溶媒でのＧＰＣ測定の結果、重量平均分子量３６，０００、数平均分子量１７，０００であった。

〔ポリマー２ｄ−２の合成〕
下記のＳｃｈｅｍｅのように単量体（２ｄ−ｍ２）を合成した。

［化合物（２ｄ−ｍ２）：融点１５６℃、ＭＳ（ｍ／ｚ）９６１．８（Ｍ^＋＋Ｈ）］
引き続き、下記ポリマー２ｄ−２をポリマー１ａ−１と同様に下記Ｓｃｈｅｍｅのように重合を行い、ｏ−ジクロロベンゼン（１４０℃）溶媒でのＧＰＣ測定の結果、重量平均分子量５１，０００、数平均分子量２７，０００であった。

[Synthesis of Polymer 1a-1]
Monomers (1a-m1) were synthesized as shown in the following scheme.

[Compound (1a-m1): melting point 148 ° C., MS (m / z) 881.5 (M ⁺ + H)]
Subsequently, the following polymer 1a-1 was synthesized by referring to the method described in Journal of the American Chemical Society, 2008, Vol. 130, pages 7670-7865 as shown in the following scheme. As a result of GPC measurement using o-dichlorobenzene (140 ° C.) solvent, the weight average molecular weight was 45,000 and the number average molecular weight was 23,000.

[Synthesis of Polymer 1a-2]
Monomers (1a-m2) were synthesized as shown in the following scheme.

[Compound (1a-m2): melting point 173 ° C., MS (m / z) 1248.4 (M ⁺ + H)]
Subsequently, the following polymer 1a-2 was polymerized in the same manner as in the following Scheme similarly to polymer 1a-1, and as a result of GPC measurement in an o-dichlorobenzene (140 ° C.) solvent, the weight average molecular weight was 38,000, the number average molecular weight. It was 20,000.

[Synthesis of Polymer 1a-3]
Monomers (1a-m3) were synthesized as shown in the following scheme.

[Compound (1a-m3): melting point 157 ° C., MS (m / z) 959.7 (M ⁺ + H)]
Subsequently, the following polymer 1a-3 was polymerized in the same manner as in the following Scheme similarly to polymer 1a-1, and as a result of GPC measurement in an o-dichlorobenzene (140 ° C.) solvent, the weight average molecular weight was 49,000 and the number average molecular weight. 26,000.

[Synthesis of Polymer 1a-4]
A monomer (1a-m4) was synthesized as shown in the following scheme.

[Compound (1a-m4): melting point 171 ° C., MS (m / z) 861.3 (M ++ H)]
Subsequently, the following polymer 1a-4 was polymerized in the same manner as in the following Scheme in the same manner as the polymer 1a-1, and as a result of GPC measurement using an o-dichlorobenzene (140 ° C.) solvent, the weight average molecular weight was 31,000, and the number average molecular weight. 15,000.

[Synthesis of Polymer 1b-1]
A monomer (1b-m1) was synthesized as shown in the following scheme.

[Compound (1b-m1): melting point 180 ° C., MS (m / z) 937.6 (M ⁺ + H)]
Subsequently, the following polymer 1b-1 was polymerized in the same manner as in the following Scheme in the same manner as the polymer 1a-1, and as a result of GPC measurement using an o-dichlorobenzene (140 ° C.) solvent, the weight average molecular weight was 35,000 and the number average molecular weight was It was 20,000.

[Synthesis of Polymer 1b-2]
A monomer (1b-m2) was synthesized as shown in the following scheme.

[Compound (1b-m2): melting point 157 ° C., MS (m / z) 808.4 (M ⁺ + H)]
Subsequently, the following polymer 1b-2 was polymerized in the same manner as in the following Scheme similarly to the polymer 1a-1, and as a result of GPC measurement using an o-dichlorobenzene (140 ° C.) solvent, the weight average molecular weight was 29,000 and the number average molecular weight was 16,000.

[Synthesis of Polymer 1b-3]
A monomer (1b-m3) was synthesized as shown in the following scheme.

[Compound (1b-m3): melting point 162 ° C., MS (m / z) 967.8 (M ⁺ + H)]
Subsequently, the following polymer 1b-3 was polymerized in the same manner as in the following Scheme similarly to the polymer 1a-1, and as a result of GPC measurement using an o-dichlorobenzene (140 ° C.) solvent, the weight average molecular weight was 36,000, and the number average molecular weight was It was 19,000.

[Synthesis of Polymer 2a-1]
A monomer (2a-m1) was synthesized as shown in the following scheme.

[Compound (2a-m1): melting point 159 ° C., MS (m / z) 931.6 (M ⁺ + H)]
Subsequently, the following polymer 2a-1 was polymerized in the same manner as in the following Scheme similarly to the polymer 1a-1, and as a result of GPC measurement using an o-dichlorobenzene (140 ° C.) solvent, the weight average molecular weight was 51,000 and the number average molecular weight was 33,000.

[Synthesis of Polymer 2a-2]
Monomers (2a-m2) were synthesized as shown in the following scheme.

[Compound (2a-m2): melting point 157 ° C., MS (m / z) 961.8 (M ⁺ + H)]
Subsequently, the following 2a-2 was polymerized as in the following Scheme similarly to the polymer 1a-1, and as a result of GPC measurement using an o-dichlorobenzene (140 ° C.) solvent, the weight average molecular weight was 40,000 and the number average molecular weight was 21. 000.

[Synthesis of Polymer 2b-1]
A monomer (2b-m1) was synthesized as shown in the following scheme.

[Compound (2b-m1): melting point 133 ° C., MS (m / z) 979.7 (M ⁺ + H)]
Subsequently, the following polymer 2b-1 was polymerized in the same manner as in the following scheme as in the case of the polymer 1a-1, and as a result of GPC measurement using an o-dichlorobenzene (140 ° C.) solvent, the weight average molecular weight was 29,000 and the number average molecular weight was 16,000.

[Synthesis of Polymer 2c-1]
A monomer (2c-m1) was synthesized as shown in the following scheme.

[Compound (2c-m1): melting point 155 ° C., MS (m / z) 931.6 (M ⁺ + H)]
Subsequently, the following polymer 2c-1 was polymerized in the same manner as in the following Scheme similarly to the polymer 1a-1, and as a result of GPC measurement using an o-dichlorobenzene (140 ° C.) solvent, the weight average molecular weight was 36,000, and the number average molecular weight was 17,000.

[Synthesis of Polymer 2c-2]
A monomer (2c-m2) was synthesized as shown in the following scheme.

[Compound (2c-m2): melting point 160 ° C., MS (m / z) 961.8 (M ⁺ + H)]
Subsequently, the following polymer 2c-2 was polymerized in the same manner as in the following Scheme similarly to the polymer 1a-1, and as a result of GPC measurement in an o-dichlorobenzene (140 ° C.) solvent, the weight average molecular weight was 52,000 and the number average molecular weight was 28,000.

[Synthesis of Polymer 2d-1]
A monomer (2d-m1) was synthesized as shown in the following scheme.

[Compound (2d-m1): melting point 161 ° C., MS (m / z) 977.7 (M ⁺ + H)]
Subsequently, the following polymer 2d-1 was polymerized in the same manner as in the following Scheme similarly to the polymer 1a-1, and as a result of GPC measurement in an o-dichlorobenzene (140 ° C.) solvent, the weight average molecular weight was 36,000, the number average molecular weight. 17,000.

[Synthesis of Polymer 2d-2]
A monomer (2d-m2) was synthesized as shown in the following scheme.

[Compound (2d-m2): melting point 156 ° C., MS (m / z) 961.8 (M ⁺ + H)]
Subsequently, the following polymer 2d-2 was polymerized in the same manner as in the following Scheme similarly to the polymer 1a-1, and as a result of GPC measurement using an o-dichlorobenzene (140 ° C.) solvent, the weight average molecular weight was 51,000 and the number average molecular weight was 27,000.

［化合物（２ｅ−ｍ１）：融点１５９℃、ＭＳ（ｍ／ｚ）９３１．６（Ｍ^＋＋Ｈ）］
引き続き、下記ポリマー２ｅ−１をポリマー１ａ−１と同様に下記Ｓｃｈｅｍｅのように重合を行い、ｏ−ジクロロベンゼン（１４０℃）溶媒でのＧＰＣ測定の結果、重量平均分子量３６，０００、数平均分子量１７，０００であった。

[Synthesis of Polymer 2e-1]
A monomer (2e-m1) was synthesized as shown in the following scheme.

[Compound (2e-m1): melting point 159 ° C., MS (m / z) 931.6 (M ⁺ + H)]
Subsequently, the following polymer 2e-1 was polymerized in the same manner as in the following Scheme similarly to the polymer 1a-1, and as a result of GPC measurement using an o-dichlorobenzene (140 ° C.) solvent, the weight average molecular weight was 36,000, and the number average molecular weight was 17,000.

〔比較用ポリマーＣ２の合成〕
中国公開特許ＣＮ１０２２８６０１３号公報に記載の方法で下記単量体１および単量体２を合成し、下記Ｓｃｈｅｍｅに従って比較用ポリマーＣ２を合成した。ｏ−ジクロロベンゼン（１４０℃）溶媒でのＧＰＣ測定の結果、重量平均分子量３１，０００、数平均分子量１９，０００であった。

〔比較用ポリマーＣ３の合成〕
米国公開特許ＵＳ２０１１／０１７８２３６号公報に記載の方法で下記比較用ポリマーＣ３を合成した。ｏ−ジクロロベンゼン（１４０℃）溶媒でのＧＰＣ測定の結果、重量平均分子量１８，０００、数平均分子量１４，０００であった。

〔比較用ポリマーＣ４の合成〕
米国公開特許ＵＳ２０１１／０２２６９９９号公報に記載の方法で下記比較用ポリマーＣ４を合成した。ｏ−ジクロロベンゼン（１４０℃）溶媒でのＧＰＣ測定の結果、重量平均分子量６５，０００、数平均分子量３７，０００であった。

〔比較用ポリマーＣ５の合成〕
国際公開特許ＷＯ２０１１／０７８２４６号公報に記載の方法で下記比較用ポリマーＣ５を合成した。ｏ−ジクロロベンゼン（１４０℃）溶媒でのＧＰＣ測定の結果、重量平均分子量１６，０００、数平均分子量８，０００であった。

[Synthesis of Comparative Polymer C1]
The following comparative polymer C1 was synthesized by the method described in published patent application WO2008 / 106019, p41. As a result of GPC measurement using an o-dichlorobenzene (140 ° C.) solvent, the weight average molecular weight was 31,000 and the number average molecular weight was 19,000.

[Synthesis of Comparative Polymer C2]
The following monomer 1 and monomer 2 were synthesized by the method described in Chinese Patent Publication CN10228613, and a comparative polymer C2 was synthesized according to the following scheme. As a result of GPC measurement using an o-dichlorobenzene (140 ° C.) solvent, the weight average molecular weight was 31,000 and the number average molecular weight was 19,000.

[Synthesis of Comparative Polymer C3]
The following comparative polymer C3 was synthesized by the method described in US Published Patent No. US2011 / 0178236. As a result of GPC measurement using an o-dichlorobenzene (140 ° C.) solvent, the weight average molecular weight was 18,000 and the number average molecular weight was 14,000.

[Synthesis of Comparative Polymer C4]
The following comparative polymer C4 was synthesized by the method described in US Published Patent No. US2011 / 0226999. As a result of GPC measurement using an o-dichlorobenzene (140 ° C.) solvent, the weight average molecular weight was 65,000 and the number average molecular weight was 37,000.

[Synthesis of Comparative Polymer C5]
The following comparative polymer C5 was synthesized by the method described in International Patent Publication No. WO2011 / 078246. As a result of the GPC measurement using an o-dichlorobenzene (140 ° C.) solvent, the weight average molecular weight was 16,000 and the number average molecular weight was 8,000.

(Create photovoltaic cell)
Using each polymer, a photovoltaic cell was formed on a glass ITO substrate by the following procedure.
PEDOT: PSS (HC Star CleviosP VP AI4083) used as a hole transport layer on a clean and UV ozone-treated 100 mm square glass ITO substrate having 25 (5 rows × 5 columns) element patterns The layer was spin coated and dried at 120 ° C. for 15 minutes.
Subsequently, after dissolving a mixture (mass ratio 1: 1) of each p-type semiconducting polymer of each polymer and PC ₆₁ BM ([60] PCBM manufactured by Solenne) in o-dichlorobenzene using an automatic coater, A PEDOT: PSS layer was spin-coated and dried at 120 ° C. for 15 minutes to form a photoelectric conversion layer. Unnecessary portions were removed with a cotton swab with ethanol so that there were 25 elements of 10 mm □ at 10 mm intervals. Thereafter, the same processing as described above was performed to produce 10 photovoltaic cell elements in which 25 elements were formed (a total of 250 elements).
The thickness of the photoelectric conversion layer was measured for each of these elements, and the standard deviation of the thickness was obtained.
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 having an element size of 10 mm □.

(Photocell evaluation)
(1) Element Current Density-Voltage (JV) Characteristics The obtained element was subjected to a SMU2400 type IV measuring device manufactured by Keithley in a nitrogen atmosphere (oxygen concentration: 1 ppm or less, moisture concentration: 1 ppm or less). The current density-voltage (J-V) characteristics of the device were 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 apparatus, the open circuit voltage (Voc), fill factor (FF), and power generation efficiency (η) are shown in Table 1 below.

(2) Evaluation of Thermal Durability of Element The 10 mm square element obtained above was exposed to a nitrogen atmosphere and a temperature of 80 ° C. for 72 hours, and then the current density-voltage (J− V) The characteristics were evaluated (average of 5 elements extracted at random).
[Thermal durability efficiency retention rate (%)] = (Power generation efficiency after thermal durability test) / (Power generation efficiency before durability test) × 100
These results are summarized in Table 1 below.

(3) Humidity durability evaluation of the element The 10 mm square element obtained above was exposed to a 0.1% moisture concentration environment in a nitrogen atmosphere for 72 hours, and then the current density of the element in the same manner as in 1) above. The voltage (JV) characteristics were evaluated (average of 5 elements extracted at random).
[Humidity durability retention rate (%)] = (Power generation efficiency after humidity durability test) / (Power generation efficiency before durability test) × 100
These results are summarized in Table 1 below.

As described above, the solar cell using the polymer having the specific structural unit of the present invention as a P-type semiconductor exhibits high performance with respect to photoelectric conversion, suppresses coating unevenness at the time of device manufacture, and has excellent thermal durability. Performance and humidity durability.
Test No. Reference numerals 201, 301, 602, and 701 are reference examples.

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 (15)

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

X ¹ : selected from C (R ² ) ₂ , N (R ³ ), O, S, Si (R ³ ) ₂ .
X ^{2 is selected from} C (R ² ) ₂ , N (R ³ ), O, Si (R ³ ) ₂ .
X ³ is selected from C (R ² ) ₂ and S.
X ⁴ is selected from N (R ³ ), O, S, Si (R ³ ) ₂ . However, when X ³ is S, X ⁴ is selected from O, Si (R ³ ) ₂ .
R ¹ and R ^{2 represent a} hydrogen atom, a halogen atom , an alkyl group, a cycloalkyl group, an aryl group, or an aromatic heterocyclic group.
R ^{3 represents a} hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aromatic heterocyclic group.

In the formula (2a) and the formula (2f),
X ^{21 is selected from} C (R ² ) ₂ , N (R ³ ), O, S, Si (R ³ ) ₂ .
X ²² : selected from C (R ² ) ₂ , N (R ³ ), O, S, Si (R ³ ) ₂ .
In the formula (2b) and the formula (2d),
X ²¹ is selected from C (R ² ) ₂ , N (R ³ ), O, and S.
X ²² : selected from C (R ² ) ₂ , N (R ³ ), O, S, Si (R ³ ) ₂ .
In the formula (2c),
X ²² : selected from C (R ² ) ₂ , N (R ³ ), O, S, Si (R ³ ) ₂ .
X ²³ is selected from N (R ³ ), O, and S.
In the formula (2e),
X ²¹ is selected from C (R ² ) ₂ and Si (R ³ ) ₂ .
X ²² is selected from C (R ² ) ₂ and Si (R ³ ) ₂ .
R ¹ , R ² and R ³ have the same meanings as in formula (1a).
* Is a bond incorporated in the main chain.
However, if the above formula (2a) is represented by the following formula (c-1), ^{X 8 _{is, C (R 2) 2,}} O, N (R 3), is selected from _{^{Si (R 3) 2, X}} 9 is , C (R ² ) ₂ , O, N (R ³ ), S, Si (R ³ ) ₂ . The structural unit represented by the formula (2c) excludes the structural unit represented by the formula (c-2). R ⁴ represents a hydrogen atom, a halogen atom , an alkyl group, a cycloalkyl group, an aryl group, or an aromatic heterocyclic group. R ¹ and R ² have the same meaning as in the formula (1a).

  The organic thin-film solar cell according to claim 1, wherein the polymer has a structural unit represented by the formula (1a) or (1b). X ^{2 in} formula (1a) is C (R ² ) ₂ , N (R ³ ), or Si (R ³ ) ₂ , and X ^{4 in} formula (1b) is N (R ³ ), O, or Si ^(R _{3) 2,} provided that when ^{X 3} is S, O or Si ^(R _{3) 2} in an organic thin-film solar cells according to claim 1.   The organic thin-film solar cell according to any one of claims 1 to 3, wherein the polymer has structural units represented by the following formulas (II-1) to (II-23).

(Where Xa is C (Ra) ₂ , C = C (Ra) ₂ , Si (Ra) ₂ , S, Se, S = O, SO ₂ , C═O, NH or NRb. Xb represents NH, O or S. Xc represents CRa or N. Ra represents a hydrogen atom or a substituent. Rb represents a hydrogen atom or a substituent. When a plurality of Ra or Rb are substituents, they may be connected to each other or condensed to form a ring. )   The organic thin-film solar cell according to any one of claims 1 to 4, wherein the photoelectric conversion layer contains an n-type organic semiconductor compound.   The organic thin film solar cell according to claim 5, wherein the n-type organic semiconductor compound is fullerene or a derivative thereof.   The fullerene or a derivative thereof is 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 The organic thin film solar cell according to claim 6, which is a butyric acid ester.   The organic thin-film solar cell of any one of Claims 1-7 which has a hole transport layer between said 1st electrode and said photoelectric conversion layer.   The organic thin-film solar cell according to any one of claims 1 to 8, further comprising an electron transport layer between the second electrode and the photoelectric conversion layer.   The organic thin-film solar cell according to any one of claims 1 to 9, wherein the first electrode is a transparent electrode.   The organic thin-film solar cell according to any one of claims 1 to 10, wherein the second electrode is a metal electrode.   The composition which contained the polymer which has a structural unit represented by either of following formula (1a), Formula (1b), and Formula (2a)-(2f) in the organic solvent.

  X ¹ : C (R ² ) ₂ , N (R ³ ), O, S, Si (R ³ ) ₂ Chosen from.
  X ² : C (R ² ) ₂ , N (R ³ ), O, Si (R ³ ) ₂ Chosen from.
  X ³ : C (R ² ) ₂ , S.
  X ⁴ : N (R ³ ), O, S, Si (R ³ ) ₂ Chosen from. However, X ³ X is S ⁴ Is O, Si (R ³ ) ₂ Chosen from.
  R ¹ , R ² : Represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aromatic heterocyclic group.
  R ³ : Represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aromatic heterocyclic group.

  In the formula (2a) and the formula (2f),
  X ²¹ : C (R ² ) ₂ , N (R ³ ), O, S, Si (R ³ ) ₂ Chosen from.
  X ²² : C (R ² ) ₂ , N (R ³ ), O, S, Si (R ³ ) ₂ Chosen from.
  In the formula (2b) and the formula (2d),
  X ²¹ : C (R ² ) ₂ , N (R ³ ), O, S.
  X ²² : C (R ² ) ₂ , N (R ³ ), O, S, Si (R ³ ) ₂ Chosen from.
  In the formula (2c),
  X ²² : C (R ² ) ₂ , N (R ³ ), O, S, Si (R ³ ) ₂ Chosen from.
  X ²³ : N (R ³ ), O, S.
  In the formula (2e),
  X ²¹ : C (R ² ) ₂ , Si (R ³ ) ₂ Chosen from.
  X ²² : C (R ² ) ₂ , Si (R ³ ) ₂ Chosen from.
  R ¹ , R ² , R ³ Is synonymous with the formula (1a).
  * Is a bond incorporated in the main chain.
  However, when the formula (2a) is the following formula (c-1), X ⁸ Is C (R ² ) ₂ , O, N (R ³ ), Si (R ³ ) ₂ Selected from X ⁹ Is C (R ² ) ₂ , O, N (R ³ ), S, Si (R ³ ) ₂ Chosen from. The structural unit represented by the formula (2c) excludes the structural unit represented by the formula (c-2). R ⁴ Represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aromatic heterocyclic group. R ¹ , R ² Is synonymous with the formula (1a).

  The composition according to claim 12, which is used for an organic semiconductor material.   A method for producing a semiconductor film having photoelectric conversion ability, which is formed by coating using the composition according to claim 13. A monomer comprising a compound represented by any one of the following formula (1a ′), formula (1b ′), and formulas (2a ′) to (2f ′) .

X ¹ : selected from C (R ² ) ₂ , N (R ³ ), O, S, Si (R ³ ) ₂ .
X ^{2 is selected from} C (R ² ) ₂ , N (R ³ ), O, Si (R ³ ) ₂ .
X ³ is selected from C (R ² ) ₂ and S.
X ⁴ is selected from N (R ³ ), O, S, Si (R ³ ) ₂ . However, when X ³ is S, X ⁴ is selected from O, Si (R ³ ) ₂ .
R ¹ and R ^{2 represent a} hydrogen atom, a halogen atom , an alkyl group, a cycloalkyl group, an aryl group, or an aromatic heterocyclic group.
R ^{3 represents a} hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aromatic heterocyclic group.

In the formula (2a ′) and the formula (2f ′),
X ^{21 is selected from} C (R ² ) ₂ , N (R ³ ), O, S, Si (R ³ ) ₂ .
X ²² : selected from C (R ² ) ₂ , N (R ³ ), O, S, Si (R ³ ) ₂ .
In the formula (2b ′) and the formula (2d ′),
X ²¹ is selected from C (R ² ) ₂ , N (R ³ ), O, and S.
X ²² : selected from C (R ² ) ₂ , N (R ³ ), O, S, Si (R ³ ) ₂ .
In the formula (2c ′),
X ²² : selected from C (R ² ) ₂ , N (R ³ ), O, S, Si (R ³ ) ₂ .
X ²³ is selected from N (R ³ ), O, and S.
In the formula (2e ′),
X ²¹ is selected from C (R ² ) ₂ and Si (R ³ ) ₂ .
X ²² is selected from C (R ² ) ₂ and Si (R ³ ) ₂ .
R ¹ , R ² , and R ³ have the same meaning as in formula (1a).
* Is a bond incorporated in the main chain.
However, in the aforesaid formula (2a ') is the following formula ^{(c-1'), X} 8 _{^{is, C (R 2) 2,}} O, N (R 3), is selected from Si ^(R _{3) 2,} X ⁹ is selected from C (R ² ) ₂ , O, N (R ³ ), S, Si (R ³ ) ₂ . The structural unit represented by the formula (2c ′) excludes the structural unit represented by the formula (c-2 ′ ). R ⁴ represents a hydrogen atom, a halogen atom , an alkyl group, a cycloalkyl group, an aryl group, or an aromatic heterocyclic group. R ¹ and R ² have the same meaning as in the formula (1a).

[In the above formula, Ya and Yb represent a halogen atom, a trifluoromethanesulfonyloxy group, a trialkyltin group, a boric acid ester group, or a boric acid group. ]

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