JP2022090715A - Composition, film, organic photoelectric conversion element, and photo-detection element - Google Patents

Abstract

To provide a composition with which an organic photoelectric conversion element with less variation in characteristics can be produced.SOLUTION: A composition includes a p-type semiconductor material, an n-type semiconductor material, an insulation material and a solvent, in which the p-type semiconductor material includes a polymer comprising a constitutional unit represented by formula (I). (In formula (I), Ar1 and Ar2 each independently represent a trivalent aromatic heterocyclic group which may have a substituent. Z represents a group represented by formula (Z-1) to formula (Z-4). (In formula (Z-1) to (Z-4), R represents a hydrogen atom or the like, and two Rs in the formulas may be identical to or different from each other.))SELECTED DRAWING: Figure 1

Description

The present invention relates to compositions, films, organic photoelectric conversion elements, and photodetecting elements.

The photoelectric conversion element including an organic film is attracting attention as, for example, an extremely useful power generation device from the viewpoint of energy saving and reduction of carbon dioxide emissions, or as a photodetector of a highly sensitive optical sensor for near infrared rays.

As a composition for forming an active layer of an organic photoelectric conversion element, a composition containing a p-type semiconductor material, a fullerene compound which is an n-type semiconductor material, and a predetermined additive is known (Patent Document). 1). It is disclosed that it is effective to add a polymer other than a semiconductor material to the composition as a means for obtaining a composition having a viscous physical characteristic suitable for the coating film forming step of the active layer in the production of an organic electronic device.

Japanese Patent Publication No. 2018-525487

On the other hand, in the manufacture of an optical sensor including a photoelectric conversion element, a patterned electrode, an active layer, etc. are usually laminated on one substrate, and a plurality of photoelectric conversion elements are arranged on one substrate. A device with a similar structure is used. Here, the active layer is required to have a certain thickness in order to suppress a dark current that causes noise in the sensor performance, and to have a uniform film thickness so that the characteristics of each element do not vary. The spin coating method is often used as a method for easily producing an active layer having a uniform film thickness.
The inventors attempted to form an active layer by a spin coating method using a composition containing an additive with reference to Patent Document 1. As a result, a desired uniform and thick active layer was obtained, but the device contained many defective elements having an abnormally high dark current, and the dark current characteristics varied greatly among the elements contained in the device. It turned out.

Therefore, a composition capable of producing an organic photoelectric conversion element having a small variation in dark current characteristics; a film capable of being produced from the composition; an organic photoelectric conversion element containing the film; and a photodetection element including the organic photoelectric conversion element. Desired.

As a result of diligent studies to solve the above-mentioned problems, the present inventors can solve the above-mentioned problems by forming an active layer using a composition containing a specific p-type semiconductor material and an insulating material in combination. And completed the present invention. That is, the present invention provides the following.

（式（Ｉ）中、
Ａｒ^１及びＡｒ^２は、それぞれ独立して、置換基を有していてもよい３価の芳香族複素環基を表す。
Ｚは、下記式（Ｚ－１）～式（Ｚ－４）で表される基を表す。

（式（Ｚ－１）～（Ｚ－４）中、
Ｒは、
水素原子、
ハロゲン原子、
置換基を有していてもよいアルキル基、
置換基を有していてもよいシクロアルキル基、
置換基を有していてもよいアルケニル基、
置換基を有していてもよいシクロアルケニル基、
置換基を有していてもよいアルキニル基、
置換基を有していてもよいシクロアルキニル基、
置換基を有していてもよいアリール基、
置換基を有していてもよいアルキルオキシ基、
置換基を有していてもよいシクロアルキルオキシ基、
置換基を有していてもよいアリールオキシ基、
置換基を有していてもよいアルキルチオ基、
置換基を有していてもよいシクロアルキルチオ基、
置換基を有していてもよいアリールチオ基、
置換基を有していてもよい１価の複素環基、
置換基を有していてもよい置換アミノ基、
置換基を有していてもよいイミン残基、
置換基を有していてもよいアミド基、
置換基を有していてもよい酸イミド基、
置換基を有していてもよい置換オキシカルボニル基、
シアノ基、
ニトロ基、
－Ｃ（＝Ｏ）－Ｒ^ａで表される基、又は
－ＳＯ_２－Ｒ^ｂで表される基を表し、
Ｒ^ａ及びＲ^ｂは、それぞれ独立して、
水素原子、
置換基を有していてもよいアルキル基、
置換基を有していてもよいシクロアルキル基、
置換基を有していてもよいアリール基、
置換基を有していてもよいアルキルオキシ基、
置換基を有していてもよいシクロアルキルオキシ基、
置換基を有していてもよいアリールオキシ基、又は
置換基を有していてもよい１価の複素環基を表す。
式（Ｚ－１）～式（Ｚ－４）中、２つあるＲは同一であっても異なっていてもよい。））
［２］ 前記絶縁材料が、前記溶媒に２５℃で０．１重量％以上溶解する材料である、［１］に記載の組成物。
［３］ 前記絶縁材料が、下記式（ＩＩ）で表される構成単位を含む重合体を含む、［１］又は［２］に記載の組成物。

（式（ＩＩ）中、
Ｒ^ｉ１は、水素原子、ハロゲン原子、又は炭素原子数１～２０のアルキル基を表し、
Ｒ^ｉ２は、水素原子、ハロゲン原子、炭素原子数１～２０のアルキル基、下記式（ＩＩＩ－１）で表される基、式（ＩＩＩ－２）で表される基、又は式（ＩＩＩ－３）で表される基を表す。

（式（ＩＩＩ－１）中、
複数あるＲ^ｉ２ａは、それぞれ独立して、水素原子、ハロゲン原子、又は炭素原子数１～２０のアルキル基を表す。）

（式（ＩＩＩ－２）中、
Ｒ^ｉ２ｂは、水素原子又は炭素原子数１～２０のアルキル基を表す。）

（式（ＩＩＩ－３）中、
Ｒ^ｉ２ｃは、炭素原子数１～２０のアルキル基を表す。））
［４］ ｐ型半導体材料と、ｎ型半導体材料と、絶縁材料とを含み、
前記ｐ型半導体材料が、下記式（Ｉ）で表される構成単位を含む重合体を含む、膜。

（式（Ｉ）中、
Ａｒ^１及びＡｒ^２は、それぞれ独立して、置換基を有していてもよい３価の芳香族複素環基を表す。
Ｚは、下記式（Ｚ－１）～式（Ｚ－４）で表される基を表す。

（式（Ｚ－１）～（Ｚ－４）中、
Ｒは、
水素原子、
ハロゲン原子、
置換基を有していてもよいアルキル基、
置換基を有していてもよいシクロアルキル基、
置換基を有していてもよいアルケニル基、
置換基を有していてもよいシクロアルケニル基、
置換基を有していてもよいアルキニル基、
置換基を有していてもよいシクロアルキニル基、
置換基を有していてもよいアリール基、
置換基を有していてもよいアルキルオキシ基、
置換基を有していてもよいシクロアルキルオキシ基、
置換基を有していてもよいアリールオキシ基、
置換基を有していてもよいアルキルチオ基、
置換基を有していてもよいシクロアルキルチオ基、
置換基を有していてもよいアリールチオ基、
置換基を有していてもよい１価の複素環基、
置換基を有していてもよい置換アミノ基、
置換基を有していてもよいイミン残基、
置換基を有していてもよいアミド基、
置換基を有していてもよい酸イミド基、
置換基を有していてもよい置換オキシカルボニル基、
シアノ基、
ニトロ基、
－Ｃ（＝Ｏ）－Ｒ^ａで表される基、又は
－ＳＯ_２－Ｒ^ｂで表される基を表し、
Ｒ^ａ及びＲ^ｂは、それぞれ独立して、
水素原子、
置換基を有していてもよいアルキル基、
置換基を有していてもよいシクロアルキル基、
置換基を有していてもよいアリール基、
置換基を有していてもよいアルキルオキシ基、
置換基を有していてもよいシクロアルキルオキシ基、
置換基を有していてもよいアリールオキシ基、又は
置換基を有していてもよい１価の複素環基を表す。
式（Ｚ－１）～式（Ｚ－４）中、２つあるＲは同一であっても異なっていてもよい。））
［５］ 第一の電極と、［４］に記載の膜と、第二の電極とをこの順で含む、有機光電変換素子。
［６］ ［５］に記載の有機光電変換素子を含む、光検出素子。 [1] A composition containing a p-type semiconductor material, an n-type semiconductor material, an insulating material, and a solvent.
A composition in which the p-type semiconductor material contains a polymer containing a structural unit represented by the following formula (I).

(In formula (I),
Ar ¹ and Ar ² each independently represent a trivalent aromatic heterocyclic group which may have a substituent.
Z represents a group represented by the following formulas (Z-1) to (Z-4).

(In equations (Z-1) to (Z-4),
R is
Hydrogen atom,
Halogen atom,
Alkyl groups, which may have substituents,
Cycloalkyl groups, which may have substituents,
An alkenyl group which may have a substituent,
Cycloalkenyl groups, which may have substituents,
An alkynyl group, which may have a substituent,
A cycloalkynyl group which may have a substituent,
Aryl groups, which may have substituents,
Alkyloxy groups, which may have substituents,
Cycloalkyloxy groups, which may have substituents,
Aryloxy groups, which may have substituents,
Alkylthio groups, which may have substituents,
Cycloalkylthio groups, which may have substituents,
An arylthio group, which may have a substituent,
A monovalent heterocyclic group which may have a substituent,
Substituted amino groups, which may have substituents,
Imine residues, which may have substituents,
An amide group which may have a substituent,
An acidimide group, which may have a substituent,
Substituted oxycarbonyl group, which may have a substituent,
Cyano group,
Nitro group,
Represents a group represented by -C (= O) -R ^a or a group represented by -SO ₂ -R ^b .
R ^a and R ^b are independent of each other.
Hydrogen atom,
Alkyl groups, which may have substituents,
Cycloalkyl groups, which may have substituents,
Aryl groups, which may have substituents,
Alkyloxy groups, which may have substituents,
Cycloalkyloxy groups, which may have substituents,
Represents an aryloxy group which may have a substituent or a monovalent heterocyclic group which may have a substituent.
In the formulas (Z-1) to (Z-4), the two Rs may be the same or different. )))
[2] The composition according to [1], wherein the insulating material is a material that dissolves in the solvent at 25 ° C. in an amount of 0.1% by weight or more.
[3] The composition according to [1] or [2], wherein the insulating material contains a polymer containing a structural unit represented by the following formula (II).

(In formula (II),
R ⁱ¹ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms.
R ⁱ² is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a group represented by the following formula (III-1), a group represented by the formula (III-2), or a group represented by the formula (III-2). Represents the group represented by 3).

(In equation (III-1),
Each of the plurality of ^Ri2a independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms. )

(In equation (III-2),
R ^i2b represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. )

(In equation (III-3),
R ^i2c represents an alkyl group having 1 to 20 carbon atoms. )))
[4] A p-type semiconductor material, an n-type semiconductor material, and an insulating material are included.
A film in which the p-type semiconductor material contains a polymer containing a structural unit represented by the following formula (I).

(In formula (I),
Ar ¹ and Ar ² each independently represent a trivalent aromatic heterocyclic group which may have a substituent.
Z represents a group represented by the following formulas (Z-1) to (Z-4).

(In equations (Z-1) to (Z-4),
R is
Hydrogen atom,
Halogen atom,
Alkyl groups, which may have substituents,
Cycloalkyl groups, which may have substituents,
An alkenyl group which may have a substituent,
Cycloalkenyl groups, which may have substituents,
An alkynyl group, which may have a substituent,
A cycloalkynyl group which may have a substituent,
Aryl groups, which may have substituents,
Alkyloxy groups, which may have substituents,
Cycloalkyloxy groups, which may have substituents,
Aryloxy groups, which may have substituents,
Alkylthio groups, which may have substituents,
Cycloalkylthio groups, which may have substituents,
An arylthio group, which may have a substituent,
A monovalent heterocyclic group which may have a substituent,
Substituted amino groups, which may have substituents,
Imine residues, which may have substituents,
An amide group which may have a substituent,
An acidimide group, which may have a substituent,
Substituted oxycarbonyl group, which may have a substituent,
Cyano group,
Nitro group,
Represents a group represented by -C (= O) -R ^a or a group represented by -SO ₂ -R ^b .
R ^a and R ^b are independent of each other.
Hydrogen atom,
Alkyl groups, which may have substituents,
Cycloalkyl groups, which may have substituents,
Aryl groups, which may have substituents,
Alkyloxy groups, which may have substituents,
Cycloalkyloxy groups, which may have substituents,
Represents an aryloxy group which may have a substituent or a monovalent heterocyclic group which may have a substituent.
In the formulas (Z-1) to (Z-4), the two Rs may be the same or different. )))
[5] An organic photoelectric conversion element including the first electrode, the film according to [4], and the second electrode in this order.
[6] A photodetector including the organic photoelectric conversion element according to [5].

According to the present invention, a composition capable of producing an organic photoelectric conversion element having a small variation in dark current characteristics; a film capable of being produced from the composition; an organic photoelectric conversion element containing the film; including the organic photoelectric conversion element. A photodetector is provided.

FIG. 1 is a diagram schematically showing a configuration example of a photoelectric conversion element. FIG. 2 is a diagram schematically showing a configuration example of an image detection unit. FIG. 3 is a diagram schematically showing a configuration example of the fingerprint detection unit. FIG. 4 is a diagram schematically showing a configuration example of an image detection unit for an X-ray image pickup apparatus. FIG. 5 is a diagram schematically showing a configuration example of a vein detection unit for a vein authentication device. FIG. 6 is a diagram schematically showing a configuration example of an indirect type TOF type distance measuring device image detection unit.

[Explanation of common terms]
First, terms commonly used in the following description will be described.
The “polymer compound” means a polymer having a molecular weight distribution and having a polystyrene-equivalent number average molecular weight of 1 × 10 ³ or more and 1 × ¹⁰⁸ or less. The structural units contained in the polymer are 100 mol% in total.

The “constituent unit” means a unit of the structure of the polymer.

The "hydrogen atom" may be a light hydrogen atom or a deuterium atom.

Examples of "halogen atoms" include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

In the "may have substituents" embodiment, all hydrogen atoms constituting the compound or group are unsubstituted, and some or all of one or more hydrogen atoms are substituted with the substituents. Both aspects, if any, are included.

Examples of substituents include halogen atom, alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, cycloalkynyl group, alkyloxy group, cycloalkyloxy group, alkylthio group, cycloalkylthio group, aryl group, Examples thereof include an aryloxy group, an arylthio group, a monovalent heterocyclic group, a substituted amino group, an acyl group, an imine residue, an amide group, an acidimide group, a substituted oxycarbonyl group, a cyano group, an alkylsulfonyl group, and a nitro group. ..

The "alkyl group" may be linear or branched. The alkyl group may have a substituent. The number of carbon atoms of the alkyl group does not include the number of carbon atoms of the substituent, and is usually 1 to 50, preferably 1 to 30, and more preferably 1 to 20.

Examples of alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, 3-methylbutyl group, 2-ethylbutyl group, n. -Hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, 3-propylheptyl group, n-decyl group, 3,7-dimethyloctyl group, 3-heptyl dodecyl group, 2-ethyloctyl group, Alkyl groups having no substituents such as 2-hexyldecyl group, dodecyl group, n-tetradecyl group, hexadecyl tomb, octadecyl group and icosyl group, and the hydrogen atom in these groups are alkyloxy group, aryl group, etc. Examples thereof include a group substituted with a substituent such as a fluorine atom.

Specific examples of the alkyl having a substituent include a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group, a perfluorohexyl group, a perfluorooctyl group, a 3-phenylpropyl group and a 3- (4-methylphenyl) group. Examples thereof include a propyl group, a 3- (3,5-dihexylphenyl) propyl group and a 6-ethyloxyhexyl group.

The "cycloalkyl group" may be a monocyclic group or a polycyclic group. The cycloalkyl group may have a substituent. The number of carbon atoms of the cycloalkyl group does not include the number of carbon atoms of the substituent and is usually 3 to 30, preferably 3 to 20.

Examples of cycloalkyl groups include alkyl groups having no substituents such as cyclopentyl group, cyclohexyl group, cycloheptyl group and adamantyl group, and the hydrogen atom in these groups is an alkyl group, an alkyloxy group and an aryl group. , A group substituted with a substituent such as a fluorine atom.

Specific examples of the cycloalkyl group having a substituent include a methylcyclohexyl group and an ethylcyclohexyl group.

The "alkenyl group" may be linear or branched. The alkenyl group may have a substituent. The number of carbon atoms of the alkenyl group does not include the number of carbon atoms of the substituent and is usually 2 to 30, preferably 2 to 20.

Examples of alkenyl groups include vinyl group, 1-propenyl group, 2-propenyl group, 2-butenyl group, 3-butenyl group, 3-pentenyl group, 4-pentenyl group, 1-hexenyl group, 5-hexenyl group, Examples thereof include an alkenyl group having no substituent such as a 7-octenyl group, and a group in which a hydrogen atom in these groups is substituted with a substituent such as an alkyloxy group, an aryl group or a fluorine atom.

The "cycloalkenyl group" may be a monocyclic group or a polycyclic group. The cycloalkenyl group may have a substituent. The number of carbon atoms of the cycloalkenyl group does not include the number of carbon atoms of the substituent and is usually 3 to 30, preferably 3 to 20.

Examples of cycloalkenyl groups are cycloalkenyl groups having no substituents such as cyclohexenyl groups, and the hydrogen atom in these groups is a substituent such as an alkyl group, an alkyloxy group, an aryl group or a fluorine atom. Examples include substituted groups.

Examples of cycloalkenyl groups having a substituent include a methylcyclohexenyl group and an ethylcyclohexenyl group.

The "alkynyl group" may be linear or branched. The alkynyl group may have a substituent. The number of carbon atoms of the alkynyl group does not include the number of carbon atoms of the substituent and is usually 2 to 30, preferably 2 to 20.

Examples of alkynyl groups include ethynyl group, 1-propynyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, 3-pentynyl group, 4-pentynyl group, 1-hexynyl group, 5-hexynyl group and the like. Examples thereof include an alkynyl group having no substituent and a group in which the hydrogen atom in these groups is substituted with a substituent such as an alkyloxy group, an aryl group or a fluorine atom.

The "cycloalkynyl group" may be a monocyclic group or a polycyclic group. The cycloalkynyl group may have a substituent. The number of carbon atoms of the cycloalkynyl group does not include the number of carbon atoms of the substituent and is usually 4 to 30, preferably 4 to 20.

Examples of cycloalkynyl groups include cycloalkynyl groups that do not have substituents such as cyclohexynyl groups, and hydrogen atoms in these groups are substituted with substituents such as alkyl groups, alkyloxy groups, aryl groups, and fluorine atoms. The group that was made is mentioned.

Examples of the cycloalkynyl group having a substituent include a methylcyclohexynyl group and an ethylcyclohexynyl group.

The "alkyloxy group" may be linear or branched. The alkyloxy group may have a substituent. The number of carbon atoms of the alkyloxy group does not include the number of carbon atoms of the substituent and is usually 1 to 30, preferably 1 to 20.

Examples of alkyloxy groups include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, tert-butyloxy group, n-pentyloxy group, n-hexyloxy group, n-Heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group, 3,7-dimethyloctyloxy group, 3-heptyldodecyloxy group, lauryloxy group, etc. Examples thereof include an alkyloxy group having no substituent and a group in which the hydrogen atom in these groups is substituted with a substituent such as an alkyloxy group, an aryl group or a fluorine atom.

The cycloalkyl group contained in the "cycloalkyloxy group" may be a monocyclic group or a polycyclic group. The cycloalkyloxy group may have a substituent. The number of carbon atoms of the cycloalkyloxy group does not include the number of carbon atoms of the substituent and is usually 3 to 30, preferably 3 to 20.

Examples of the cycloalkyloxy group include a cycloalkyloxy group having no substituent such as a cyclopentyloxy group, a cyclohexyloxy group and a cycloheptyloxy group, and a hydrogen atom in these groups is a fluorine atom, an alkyl group and the like. Examples thereof include groups substituted with the substituents of.

The "alkylthio group" may be linear or branched. The alkylthio group may have a substituent. The number of carbon atoms of the alkylthio group does not include the number of carbon atoms of the substituent and is usually 1 to 30, preferably 1 to 20.

Examples of alkylthio groups that may have a substituent include a methylthio group, an ethylthio group, an n-propylthio group, an isopropylthio group, an n-butylthio group, an isobutylthio group, a tert-butylthio group, an n-pentylthio group, and the like. n-hexylthio group, n-heptylthio group, n-octylthio group, 2-ethylhexylthio group, n-nonylthio group, n-decylthio group, 3,7-dimethyloctylthio group, 3-heptyldodecylthio group, laurylthio group, And a trifluoromethylthio group.

The cycloalkyl group contained in the "cycloalkylthio group" may be a monocyclic group or a polycyclic group. The cycloalkylthio group may have a substituent. The number of carbon atoms of the cycloalkylthio group does not include the number of carbon atoms of the substituent and is usually 3 to 30, preferably 3 to 20.

An example of a cycloalkylthio group which may have a substituent is a cyclohexylthio group.

The "p-valent aromatic carbocyclic group" means the remaining atomic group obtained by removing p hydrogen atoms directly bonded to the carbon atoms constituting the ring from the aromatic hydrocarbons which may have a substituent. do. The p-valent aromatic carbocyclic group may further have a substituent.

"Aryl group" means a monovalent aromatic carbocyclic group. The aryl group may have a substituent. The number of carbon atoms of the aryl group does not include the number of carbon atoms of the substituent and is usually 6 to 60, preferably 6 to 48.

Examples of aryl groups include phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthrasenyl group, 2-anthrasenyl group, 9-anthrasenyl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, An aryl group having no substituent such as a 2-fluorenyl group, a 3-fluorenyl group, a 4-fluorenyl group, a 2-phenylphenyl group, a 3-phenylphenyl group, a 4-phenylphenyl group, and hydrogen in these groups. Examples thereof include a group in which an atom is substituted with a substituent such as an alkyl group, an alkyloxy group, an aryl group or a fluorine atom.

The "aryloxy group" may have a substituent. The number of carbon atoms of the aryloxy group does not include the number of carbon atoms of the substituent and is usually 6 to 60, preferably 6 to 48.

Examples of the aryloxy group include a substituent such as a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 1-anthrasenyloxy group, a 9-anthrasenyloxy group and a 1-pyrenyloxy group. Examples thereof include an aryloxy group that does not have an aryloxy group, and a group in which the hydrogen atom in these groups is substituted with a substituent such as an alkyl group, an alkyloxy group, or a fluorine atom.

The "arylthio group" may have a substituent. The number of carbon atoms of the arylthio group does not include the number of carbon atoms of the substituent and is usually 6 to 60, preferably 6 to 48.

Examples of arylthio groups that may have a substituent include a phenylthio group, a C1-C12 alkyloxyphenylthio group, a C1-C12 alkylphenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, and a pentafluorophenyl. The thio group is mentioned. "C1 to C12" indicates that the number of carbon atoms of the group described immediately after that is 1 to 12. Further, "Cm to Cn" indicates that the number of carbon atoms of the group described immediately after that is m to n. The same applies to the following.

The "p-valent heterocyclic group" (p represents an integer of 1 or more) is a hydrogen directly bonded to a carbon atom or a hetero atom constituting a ring from a heterocyclic compound which may have a substituent. It means the remaining atomic group excluding p hydrogen atoms among the atoms. The "p-valent heterocyclic group" includes a "p-valent aromatic heterocyclic group". The "p-valent aromatic heterocyclic group" is a p of hydrogen atoms directly bonded to a carbon atom or a hetero atom constituting a ring from an aromatic heterocyclic compound which may have a substituent. It means the remaining atomic group excluding one hydrogen atom.

Aromatic heterocyclic compounds include, in addition to compounds in which the heterocycle itself exhibits aromaticity, compounds in which the heterocycle itself has an aromatic ring condensed, even if the heterocycle itself does not exhibit aromaticity. To.

Among the aromatic heterocyclic compounds, specific examples of the compound in which the heterocycle itself exhibits aromaticity include oxadiazole, thiadiazole, thiazole, oxazole, thiophene, pyrrole, phosphole, furan, pyridine, pyrazine, pyrimidine, and triazine. , Pyridazine, quinoline, isoquinoline, carbazole, and dibenzophosphol.

Among aromatic heterocyclic compounds, specific examples of compounds in which the heterocycle itself does not exhibit aromaticity and the aromatic ring is fused to the heterocycle include phenoxazine, phenothiazine, dibenzoborol, and dibenzosyrol. And benzopyran.

The p-valent heterocyclic group may have a substituent. The number of carbon atoms of the p-valent heterocyclic group does not include the number of carbon atoms of the substituent and is usually 2 to 60, preferably 2 to 20.

Examples of monovalent heterocyclic groups include monovalent aromatic heterocyclic groups (eg, thienyl group, pyrrolyl group, frill group, pyridyl group, quinolyl group, isoquinolyl group, pyrimidinyl group, triazinyl group) and monovalent. Examples thereof include non-aromatic heterocyclic groups (eg, piperidyl group, piperazyl group) and groups in which the hydrogen atom in these groups is substituted with a substituent such as an alkyl group, an alkyloxy group or a fluorine atom.

"Substituted amino group" means an amino group having a substituent. As the substituent contained in the amino group, an alkyl group, an aryl group and a monovalent heterocyclic group are preferable. The number of carbon atoms of the substituted amino group is usually 2 to 30, not including the number of carbon atoms of the substituent.

Examples of substituted amino groups include dialkylamino groups (eg, dimethylamino group, diethylamino group), diarylamino groups (eg, diphenylamino group, bis (4-methylphenyl) amino group, bis (4-tert-butylphenyl). ) Amino group, bis (3,5-di-tert-butylphenyl) amino group).

The "acyl group" may have a substituent. The number of carbon atoms of the acyl group does not include the number of carbon atoms of the substituent and is usually 2 to 20, preferably 2 to 18. Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a benzoyl group, a trifluoroacetyl group, and a pentafluorobenzoyl group.

The "imine residue" means the remaining atomic group obtained by removing one hydrogen atom directly bonded to the carbon atom or the nitrogen atom constituting the carbon atom-nitrogen atom double bond from the imine compound. The "imine compound" means an organic compound having a carbon atom-nitrogen atom double bond in the molecule. Examples of imine compounds include compounds in which the hydrogen atom bonded to the carbon atom-nitrogen atom double bond in aldimine, ketimine, and aldimine is replaced with an alkyl group or the like.

The number of carbon atoms of the imine residue is usually 2 to 20, preferably 2 to 18. Examples of imine residues include groups represented by the following structural formulas.

The "amide group" means the remaining atomic group obtained by removing one hydrogen atom bonded to a nitrogen atom from the amide. The number of carbon atoms of the amide group is usually 1 to 20, preferably 1 to 18. Specific examples of the amide group include formamide group, acetamide group, propioamide group, butyroamide group, benzamide group, trifluoroacetamide group, pentafluorobenzamide group, diformamide group, diacetamide group, dipropioamide group, dibutyroamide group and dibenzamide group. , Ditrifluoroacetamide group, and dipentafluorobenzamide group.

The "acidimide group" means the remaining atomic group obtained by removing one hydrogen atom bonded to a nitrogen atom from the acidimide. The number of carbon atoms of the acidimide group is usually 4 to 20. Specific examples of the acidimide group include a group represented by the following structural formula.

The "substituted oxycarbonyl group" means a group represented by R'-O- (C = O)-. Here, R'represents an alkyl group, a cycloalkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group, which may have a substituent.

The number of carbon atoms of the substituted oxycarbonyl group is usually 2 to 60, preferably 2 to 48, not including the number of carbon atoms of the substituent.

Specific examples of the substituted oxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, an isobutoxycarbonyl group, a tert-butoxycarbonyl group, a pentyloxycarbonyl group, and a hexyloxycarbonyl group. Group, cyclohexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, 3,7-dimethyloctyloxycarbonyl group, dodecyloxycarbonyl group, tri Examples thereof include a fluoromethoxycarbonyl group, a pentafluoroethoxycarbonyl group, a perfluorobutoxycarbonyl group, a perfluorohexyloxycarbonyl group, a perfluorooctyloxycarbonyl group, a phenoxycarbonyl group, a naphthoxycarbonyl group, and a pyridyloxycarbonyl group.

The "alkylsulfonyl group" may be linear or branched. The alkylsulfonyl group may have a substituent. The number of carbon atoms of the alkylsulfonyl group is usually 1 to 30, not including the number of carbon atoms of the substituent. Specific examples of the alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, and a dodecylsulfonyl group.

The "*" attached to the chemical formula represents a bond.

The "π-conjugated system" means a system in which π electrons are delocalized to a plurality of bonds.

The term "(meth) acrylic" includes acrylics, methacrylics, and combinations thereof.

[1. Composition]
The composition according to one embodiment of the present invention contains a p-type semiconductor material, an n-type semiconductor material, an insulating material, and a solvent, and the p-type semiconductor material is a structural unit represented by the formula (I). Contains a polymer containing. By using such a composition, an organic photoelectric conversion element having a small variation in dark current characteristics can be manufactured.

Although the details of the mechanism for suppressing the variation in dark current characteristics in the composition of the present invention are unknown, the following mechanism can be considered, but the present invention is not limited. In the composition of the present invention, by including an insulating material that is not directly involved in the photoelectric conversion effect as an additive, the concentration and viscosity physical characteristics of the composition can be appropriately adjusted, and the thickness becomes uniform at the time of coating. A coating film can be manufactured. On the other hand, since the solid content concentration and viscosity of the composition are increased by adding the insulating material, it is considered that the aggregation of the p-type semiconductor material and the n-type semiconductor material is likely to proceed in the process of applying and drying the composition. Eh. In particular, many polymers used as p-type semiconductor materials have a planar and symmetric molecular structure in which π-conjugation is continuous from the viewpoint of light absorption and charge transportability. Therefore, it is considered that crystallization and crystal growth are likely to proceed in the process of coating and drying. It is presumed that the active layer containing a polymer, which is a p-type semiconductor material having such a molecular structure, contains large crystals of the p-type semiconductor material, and pinholes and local thinning occur from the crystals. Will be done.
On the other hand, the polymer containing the structural unit represented by the formula (I), which is a p-type semiconductor material, contained in the composition of the present invention has an asymmetric molecular structure. Therefore, in the coating and drying steps, it is considered that the polymer does not easily crystallize and exists as fine particles in the active layer. As a result, it is considered that defects such as minute pinholes and thinning due to large particles in the composition are unlikely to occur in the active layer obtained from the composition of the present invention, and the device obtained from the composition of the present invention. Is presumed to have excellent uniformity of dark current characteristics.

In the composition, the p-type semiconductor material and the n-type semiconductor material may be dissolved or dispersed. The p-type semiconductor material and the n-type semiconductor material are preferably at least partially dissolved, or more preferably completely dissolved.

[1.1. p-type semiconductor material]
The p-type semiconductor material according to the present embodiment includes a polymer containing a structural unit represented by the following formula (I). Hereinafter, the polymer containing the structural unit represented by the formula (I) is also referred to as a polymer (1). The p-type semiconductor material may contain only one kind of the polymer (1), or may contain two or more kinds of the polymer (1). Further, the polymer (1) may contain only one kind of the structural unit represented by the formula (I), or may contain two or more kinds.

In formula (I), Ar ¹ and Ar ² each independently represent a trivalent aromatic heterocyclic group which may have a substituent.
Z represents a group represented by the following formulas (Z-1) to (Z-4).

In the formulas (Z-1) to (Z-4), R is
Hydrogen atom,
Halogen atom,
Alkyl groups, which may have substituents,
Cycloalkyl groups, which may have substituents,
An alkenyl group which may have a substituent,
Cycloalkenyl groups, which may have substituents,
An alkynyl group, which may have a substituent,
A cycloalkynyl group which may have a substituent,
Aryl groups, which may have substituents,
Alkyloxy groups, which may have substituents,
Cycloalkyloxy groups, which may have substituents,
Aryloxy groups, which may have substituents,
Alkylthio groups, which may have substituents,
Cycloalkylthio groups, which may have substituents,
An arylthio group, which may have a substituent,
A monovalent heterocyclic group which may have a substituent,
Substituted amino groups, which may have substituents,
Imine residues, which may have substituents,
An amide group which may have a substituent,
An acidimide group, which may have a substituent,
Substituted oxycarbonyl group, which may have a substituent,
Cyano group,
Nitro group,
Represents a group represented by -C (= O) -R ^a or a group represented by -SO ₂ -R ^b .
R ^a and R ^b are independent of each other.
Hydrogen atom,
Alkyl groups, which may have substituents,
Cycloalkyl groups, which may have substituents,
Aryl groups, which may have substituents,
Alkyloxy groups, which may have substituents,
Cycloalkyloxy groups, which may have substituents,
Represents an aryloxy group which may have a substituent or a monovalent heterocyclic group which may have a substituent.
In the formulas (Z-1) to (Z-4), the two Rs may be the same or different.

Examples of aromatic heterocycles constituting a trivalent aromatic heterocyclic group represented by Ar ¹ or Ar ² include an oxadiazole ring, a thiadiazole ring, a thiazole ring, an oxazole ring, a thiophene ring, a pyrrole ring, and a phosphor. Ring, furan ring, pyridine ring, pyrazine ring, pyrimidine ring, triazine ring, pyridazine ring, quinoline ring, isoquinoline ring, carbazole ring, and dibenzophosphor ring, as well as phenoxazine ring, phenothiazine ring, dibenzobolol ring, dibenzo. Examples thereof include a silol ring and a benzopyran ring. These rings may have substituents.

Z is preferably a group represented by the formula (Z-1) or (Z-2).

R in the formulas (Z-1) to (Z-4) is preferably a hydrogen atom, an alkyl group, or an aryl group, more preferably a hydrogen atom or an alkyl group, and further preferably a hydrogen atom or a carbon. It is an alkyl group having 1 to 40 atoms, more preferably a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, and still more preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. These groups may have substituents. A plurality of R's may be the same as each other or may be different from each other.

In one embodiment, the structural unit represented by the formula (I) is preferably the structural unit represented by the following formula (I-1) or (I-2).

In formulas (I-1) and (I-2), X ¹ and X ² are independent sulfur atoms or oxygen atoms, and Z ¹ and Z ² are independent, respectively, = C ( R)-is a group or nitrogen atom represented by-, and R has the same definition as in the formulas (Z-1) to (Z-4). A plurality of R's may be the same as or different from each other.

As the structural unit represented by the formula (I-1), a structural unit in which X ¹ and X ² are sulfur atoms and Z ¹ and Z ² are groups represented by = C (R) − is preferable. R in the group represented by = C (R)-as Z ¹ and Z ² is preferably a hydrogen atom.
As the structural unit represented by the formula (I-2), a structural unit in which X ¹ and X ² are sulfur atoms and Z ¹ and Z ² are groups represented by = C (R)-is preferable. R in the group represented by = C (R)-as Z ¹ and Z ² is preferably a hydrogen atom.

Examples of the structural unit (I-1) include the structural units represented by the following formulas (I-1-1) to (I-1-14). In the following formulas (I-1-1) to (I-1-14), R has the same definition as in the formulas (Z-1) to (Z-4). A plurality of R's may be the same as or different from each other.
Above all, the structural unit represented by the formula (I-1-1) is preferable.

Examples of the structural unit (I-2) include the structural units represented by the following formulas (I-2-1) to (I-2-14). In the following formulas (I-2-1) to (I-2-14), R has the same definition as in the formulas (Z-1) to (Z-4). A plurality of R's may be the same as or different from each other.
Above all, the structural unit represented by the formula (I-2-1) is preferable.

The polymer (1) preferably contains, in addition to the structural unit represented by the formula (I), a structural unit represented by the formula (IV). The polymer (1) may contain only one type of structural unit represented by the formula (IV), or may contain two or more types.

-Ar ^3- (IV)

In formula (IV), Ar ³ represents a divalent aromatic heterocyclic group.

The number of carbon atoms of the divalent aromatic heterocyclic group represented by Ar ³ is usually 2 to 60, preferably 4 to 60, and more preferably 4 to 20. The divalent aromatic heterocyclic group represented by Ar ³ may have a substituent.
As the structural unit represented by the formula (IV), the structural unit represented by any of the following formulas (IV-1) to (IV-8) is preferable.

In formulas (IV- ¹ ) to (IV ^- 8), X1, X2, Z1, ^Z2 and R are the same as the definitions in formulas (I- ¹ ) and (I-2). When there are two Rs, the two Rs may be the same or different.
In formula (IV-6), the two Rs are preferably independently hydrogen atoms, alkyl groups, or halogen atoms, more preferably hydrogen atoms or halogen atoms at the same time, and even more preferably. At the same time, it is a halogen atom.

From the viewpoint of availability of the raw material compound, it is preferable that both X ¹ and X ² in the formulas (IV-1) to (IV-8) are sulfur atoms.

Specific examples of the divalent aromatic heterocyclic group represented by Ar ³ include groups represented by the following formulas (101) to (190) and groups in which these groups are substituted with substituents. .. As the substituent, a halogen atom and an alkyl group are preferable. Of these, the group represented by the formula (148) or the formula (190) is preferable.

In equations (101) to (190), R has the same meaning as described above. When there are a plurality of Rs, the plurality of Rs may be the same or different from each other.

The total amount of the structural unit represented by the formula (I) and the structural unit represented by the formula (IV) in the polymer (1) is 100 mol% based on the amount of all the structural units contained in the polymer (1). Then, it is preferably 20 mol% to 100 mol%, and since it can improve the charge transport property as a p-type semiconductor material, it is more preferably 40 mol% to 100 mol%, and further preferably 50 mol. % To 100 mol%. Here, when the polymer (1) does not contain the structural unit represented by the formula (IV), the total amount of the structural unit represented by the formula (I) and the structural unit represented by the formula (IV). Is the amount of the structural unit represented by the formula (I).

Preferably, the polymer (1) contains any of the following combinations of structural units.
-Combination of the structural unit represented by the formula (I-2) and the structural unit represented by the formula (IV-6) -The structural unit represented by the formula (I-2) and the table by the formula (IV-8). Combination of building blocks

More preferably, the polymer (1) contains any of the following combinations of structural units.
-Combination of the structural unit represented by the formula (I-2-1) and the structural unit represented by the formula (148) -The structural unit represented by the formula (I-2-1) and the table by the formula (190). Combination of building blocks

Specific examples of the polymer (1), which is a p-type semiconductor material in the present embodiment, include polymers represented by the following formulas (P-1) to (P-2).

The weight ratio of the polymer (1) in the p-type semiconductor material is preferably 20% by weight or more, more preferably 40% by weight or more, still more preferably 50% by weight or more, usually 100% by weight or less, and 100% by weight. May be%.

The composition of the present embodiment may optionally contain other compounds as the p-type semiconductor material in addition to the above-mentioned polymer (1).
Examples of other compounds that are p-type semiconductor materials include polyvinylcarbazole and its derivatives, polysilane and its derivatives, polysiloxane derivatives having an aromatic amine structure in the side chain or main chain, polyaniline and its derivatives, polythiophene and its derivatives. , Polypyrrole and its derivatives, polyphenylene vinylene and its derivatives, polythienylene vinylene and its derivatives, polyfluorene and its derivatives. The composition according to the present embodiment may optionally contain only one kind or a plurality of kinds of other compounds in addition to the polymer (1) as the p-type semiconductor material.

[1.2. n-type semiconductor material]
The composition according to this embodiment contains an n-type semiconductor material. The composition according to the present embodiment may contain only one kind of compound or may contain a plurality of kinds of compounds as the n-type semiconductor material. Various compounds are known as n-type semiconductor materials, and they can be used as the n-type semiconductor material according to the present embodiment.

Whether the semiconductor material contained in the composition functions as a p-type semiconductor material or an n-type semiconductor material can be relatively determined from the value of the HOMO energy level or the value of the LUMO energy of the selected compound. .. The relationship between the energy level values of HOMO and LUMO of the p-type semiconductor material and the energy level values of HOMO and LUMO of the n-type semiconductor material is such that the film produced from the composition has a desired function (for example, photoelectric conversion). It can be appropriately set within the range in which the function and the light detection function) are exhibited.

The n-type semiconductor material according to this embodiment may be a low molecular weight compound or a high molecular weight compound. Examples of n-type semiconductor materials ₍ electron-accepting compounds) include fullerene such as C60 fullerene and its derivatives, oxadiazole derivatives, anthracinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and Examples thereof include tetracyanoanthraquinodimethane and its derivatives, fluorenone derivatives, diphenyldicyanoethylene and its derivatives, diphenoquinone derivatives, 8-hydroxyquinolin and metal complexes of its derivatives, and phenanthrene derivatives such as basocproin.

In one embodiment, the composition may contain a fullerene or a fullerene derivative as an n-type semiconductor material.
Examples of fullerenes include C ₆₀ fullerenes, C ₇₀ fullerenes, C ₇₆ fullerenes, C ₇₈ fullerenes, and C ₈₄ fullerenes.

Examples of the fullerene derivative include compounds represented by the following formulas (F-1) to (F-4).

In equations (F-1) to (F-4),
^RX represents an alkyl group, an aryl group, a monovalent heterocyclic group, or a group having an ester structure. A plurality of ^RXs may be the same as or different from each other.
^RY represents an alkyl group or an aryl group. A plurality of ^RYs may be the same as or different from each other.

Examples of the monovalent heterocyclic group represented by RX include a thienyl group, a pyrrolyl group, a ^frill group, a pyridyl group, a quinolyl group, and an isoquinolyl group.

^Examples of the group having an ester structure represented by RX include a group represented by the formula (E-1).

(In the formula, u1 represents an integer of 1 to 6, ^u2 represents an integer of 0 to 6, and RZ represents an alkyl group, an aryl group or a monovalent heterocyclic group.)

Examples of _C60 fullerene derivatives include the following compounds. In the formula, R has the same meaning as described above.

Examples of the _C70 fullerene derivative include the following compounds.

Specific examples of the fullerene derivative include [6,6] -phenyl-C61 butyrate methyl ester (C60PCBM, [6,6] -Phenyl C61 butyric acid methyl ester), [6,6] -phenyl-C71 butyrate methyl ester (6,6] -phenyl-C71 butyrate methyl ester (6,6). C70PCBM, [6,6] -Phenyl C71 butyric acid methyl ester), [6,6] -phenyl-C85 butyrate methyl ester (C84PCBM, [6,6] -Phenyl C85 butyric acid methyl ester), and [6,6] ] -Thienyl-C61 butyrate methyl ester ([6,6] -Thienyl C61 butyric acid methyl ester).

The n-type semiconductor material according to the present embodiment may contain a compound that is neither fullerene nor a derivative of fullerene. Hereinafter, a compound that is neither fullerene nor a derivative of fullerene is also referred to as a non-fullerene compound.

In one embodiment, the n-type semiconductor material preferably contains a compound represented by the following formula (V).

A ¹ -B ¹⁰ -A ² (V)

In equation (V),
A ¹ and A ² each independently represent an electron-withdrawing group, and B ¹⁰ represents a group containing a π-conjugated system.

Examples of electron-withdrawing groups such as A ¹ and A ² are groups represented by -CH = C (-CN) ₂ and tables represented by the following formulas (a-1) to (a-9). The group to be done is mentioned.

In equations (a-1) to (a-7),
T represents a carbocycle which may have a substituent or a heterocycle which may have a substituent. The carbocycle and the heterocycle may be a monocyclic ring or a condensed ring. When these rings have a plurality of substituents, the plurality of substituents may be the same or different.

An example of a carbocycle that may have a substituent that is T is an aromatic carbocycle, preferably an aromatic carbocycle. Specific examples of the carbocycle which may have a substituent which is T include a benzene ring, a naphthalene ring, an anthracene ring, a tetracene ring, a pentacene ring, a pyrene ring, and a phenanthrene ring, and a benzene ring is preferable. It is a naphthalene ring and a phenanthrene ring, more preferably a benzene ring and a naphthalene ring, and further preferably a benzene ring. These rings may have substituents.

Examples of the heterocycle which may have a substituent which is T include an aromatic heterocycle, and an aromatic heterocycle is preferable. Specific examples of the heterocycle which may have a substituent which is T include a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, and a thiazole ring. And a thienothiophene ring, preferably a thiophene ring, a pyridine ring, a pyrazine ring, a thiazole ring, and a thienothiophene ring, and more preferably a thiophene ring. These rings may have substituents.

Examples of the substituent that the carbocycle or heterocycle which is T may have include a halogen atom, an alkyl group, an alkyloxy group, an aryl group, and a monovalent heterocyclic group, preferably a fluorine atom and /. Alternatively, it is an alkyl group having 1 to 6 carbon atoms.

X ⁴ , X ⁵ and X ⁶ independently represent an oxygen atom, a sulfur atom, an alkylidene group, or a group represented by = C (-CN) ₂ , preferably an oxygen atom, a sulfur atom, and the like. Or, it is a group represented by = C (-CN) ₂ .

X ⁷ is a hydrogen atom, a halogen atom, a cyano group, an alkyl group which may have a substituent, an alkyloxy group which may have a substituent, an aryl group which may have a substituent or a group. Represents a monovalent heterocyclic group.

R ^a1 , R ^a2 , R ^a3 , R ^a4 , and R ^a5 independently have a hydrogen atom, an alkyl group which may have a substituent, a halogen atom, and an alkyl which may have a substituent. Represents an oxy group, an aryl group which may have a substituent or a monovalent heterocyclic group, and preferably an alkyl group which may have a substituent or an aryl group which may have a substituent. Is.

In the formulas (a-8) and (a-9), ^Ra6 and ^Ra7 each independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, and a substituent. A cycloalkyl group which may have a substituent, an alkyloxy group which may have a substituent, a cycloalkyloxy group which may have a substituent, and a monovalent aromatic carbon which may have a substituent. It represents a monovalent aromatic heterocyclic group which may have a ring group or a substituent, and a plurality of Ra ⁶ and ^Ra 7 may be the same or different.

The following formulas (a-1-1) to (a-1-4), as well as formulas (a-6-1) and formulas (a-7) are used as the basis of the electron-withdrawing properties of A ¹ and A ² . The group represented by any one of -1) is preferable, and the group represented by the formula (a-1-1) is more preferable. Here, each of the plurality of ^{Ra 10} independently represents a hydrogen atom or a substituent, and preferably represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group which may have a substituent. R ^a3 , R ^a4 , and R ^a5 are independently synonymous with the above, and preferably each of them independently has an alkyl group or an aryl which may have a substituent. Represents a group.

As an example of a group containing a π-conjugated system of B ¹⁰ , the group represented by-(S ¹ ) _n1 -B ^11- (S ² ) _n2- in the compound represented by the formula (VI) described later is Can be mentioned.

In one embodiment, the n-type semiconductor material is preferably a compound represented by the following formula (VI).

A ^1- (S ¹ ) _n1 -B ^11- (S ² ) _n2 -A ² (VI)

In formula (VI), A ¹ and A ² each independently represent an electron-withdrawing group. The examples and preferred examples of A ¹ and A ² are the same as the examples described and preferred examples of A ¹ and A ² in the above formula (V).

S ¹ and S ² are independently a divalent carbocyclic group which may have a substituent and a divalent heterocyclic group which may have a substituent, -C (R ^s1 ). = Group represented by C (R ^s2 )-(where R ^s1 and R ^s2 each independently have a hydrogen atom or a substituent (preferably a hydrogen atom, a halogen atom, a substituent). Represents a monovalent heterocyclic group which may have an alkyl group which may have a substituent or a substituent), or a group represented by −C≡C−.

The divalent carbocyclic group which may have a substituent and the divalent heterocyclic group which may have a substituent represented by S ¹ and S ² may be a fused ring. .. When the divalent carbocyclic group or the divalent heterocyclic group has a plurality of substituents, the plurality of substituents may be the same or different.

In the formula (VI), n1 and n2 each independently represent an integer of 0 or more, preferably independently represent 0 or 1, and more preferably represent 0 or 1 at the same time.

Examples of divalent carbocyclic groups include divalent aromatic carbocyclic groups.
Examples of divalent heterocyclic groups include divalent aromatic heterocyclic groups.
When the divalent aromatic carbocyclic group or the divalent aromatic heterocyclic group is a fused ring, all of the rings constituting the fused ring may be a fused ring having aromaticity, and only a part thereof may be a fused ring. It may be a fused ring having aromaticity.

Examples of S ¹ and S ² include groups represented by any of the formulas (101) to (190) given as examples of the divalent aromatic heterocyclic group represented by Ar ³ already described. And groups in which the hydrogen atom in these groups is substituted with a substituent.

S ¹ and S ² preferably independently represent a group represented by the following formula (s-1) or (s-2).

In equations (s-1) and (s-2),
^X3 represents an oxygen atom or a sulfur atom.
R ^a10 is as defined above.

S ¹ and S ² are preferably independently represented by a group represented by the formula (142), the formula (148), or the formula (184), or the hydrogen atom in these groups is substituted with a substituent. A group, more preferably a group in which one hydrogen atom in the group represented by the above formula (142) or the formula (184) or the group represented by the formula (184) is substituted with an alkyloxy group. be.

B ¹¹ is a fused ring group having two or more structures selected from the group consisting of a carbocyclic structure and a heterocyclic structure, and is a fused ring group that does not contain an ortho-peri condensed structure, and has a substituent. Represents a fused ring group that may be present.

The fused ring group represented by B ¹¹ may contain a structure obtained by condensing two or more structures that are identical to each other.

When the condensed ring group represented by B ¹¹ has a plurality of substituents, the plurality of substituents may be the same or different.

Examples of the carbon ring structure that can form the fused ring group represented by B ¹¹ include a ring structure represented by the following formula (Cy1) or formula (Cy2).

Examples of the heterocyclic structure that can form the fused ring group represented by B ¹¹ include a ring structure represented by any of the following formulas (Cy3) to (Cy10).

In the formula (VI), B ¹¹ is preferably a fused ring group having two or more structures selected from the group consisting of the structures represented by the formulas (Cy1) to (Cy10), and is an ortho-peri. It is a condensed ring group that does not contain a condensed structure and may have a substituent. B ¹¹ may include a structure in which two or more of the same structures are condensed among the structures represented by the formulas (Cy1) to (Cy10).

B ¹¹ is more preferably a fused ring group having two or more structures selected from the group consisting of the structures represented by the formulas (Cy1) to (Cy6) and the formula (Cy8), and is an ortho-peri condensation. It is a condensed ring group that does not contain a structure and may have a substituent.

The substituent which the fused ring group of B ¹¹ may have may preferably have an alkyl group which may have a substituent, an aryl group which may have a substituent, and a substituent. It is an alkyloxy group which may have a substituent and a monovalent heterocyclic group which may have a substituent. The aryl group that the fused ring group represented by B ¹¹ may have may be substituted with, for example, an alkyl group.

As an example of the fused ring group of B11, the groups represented by the following formulas (b- ¹ ) to (b-14) and the hydrogen atom in these groups are substituents (preferably, substituents). An alkyl group which may have a substituent, an aryl group which may have a substituent, an alkyloxy group which may have a substituent, or a monovalent heterocyclic group which may have a substituent. ) Substituted groups.
The fused ring group of B ¹¹ is a group represented by the following formula (b-4), or an alkyl group in which the hydrogen atom in these groups is a substituent (preferably, an alkyl group which may have a substituent). A group substituted with an aryl group which may have a substituent, an alkyloxy group which may have a substituent, or a monovalent heterocyclic group which may have a substituent) is preferable. The group represented by the following formula (b-4) is more preferable.

In equations (b-1) to (b-14),
R ^a10 is as defined above.
In the formulas (b-1) to (b-14), each of the plurality of ^Ra10s may independently have an alkyl group or a substituent which may preferably have a substituent. It is an aryl group.

Examples of the compound represented by the formula (V) or the formula (VI) include a compound represented by the following formula.

In the above formula, R is as defined above, and X represents an alkyl group which may have a hydrogen atom, a halogen atom, a cyano group or a substituent.
In the above formula, R is preferably a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent or an alkyloxy group which may have a substituent. ..

Examples of the compound represented by the formula (V) or (VI) include the compound represented by the following formula N-1.

In one embodiment, the n-type semiconductor material is preferably a compound containing a perylenetetracarboxylic acid diimide structure. Examples of the compound containing a perylenetetracarboxylic acid diimide structure as a non-fullerene compound include a compound represented by the following formula.

In the formula, R is as defined above. A plurality of Rs may be the same as or different from each other.

In one embodiment, the n-type semiconductor material preferably contains a compound represented by the following formula (VII). The compound represented by the following formula (VII) is a non-fullerene compound containing a perylenetetracarboxylic acid diimide structure.

In the formula (VII), R ¹ has a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, and a substituent. A good alkyloxy group, a cycloalkyloxy group which may have a substituent, an aryl group which may have a substituent, or a monovalent aromatic heterocyclic group which may have a substituent. show. A plurality of R ^1s may be the same or different from each other.

Preferably, each of the plurality of R ^1s is an alkyl group which may independently have a substituent.

R ² is a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkyloxy group which may have a substituent, and a substituent. Represents a cycloalkyloxy group which may have a substituent, an aryl group which may have a substituent, or a monovalent aromatic heterocyclic group which may have a substituent. A plurality of R ^2s may be the same or different.

[1.3. Insulation material]
The composition of this embodiment contains an insulating material. Here, the insulating material means a material that is neither a conductor nor a semiconductor. Generally, the insulating material has an electrical resistivity of 1 × ¹⁰⁷ Ω · m or more at 20 ° C. Insulating materials are usually not involved in the photoelectric conversion process.

The insulating material is preferably an organic compound, more preferably an organic polymer. The insulating material may contain only one type of organic compound, or may contain a combination of two or more types.

Various organic compounds are known as insulating materials and can be used in the composition of the present embodiment.
Examples of organic polymers that are insulating materials include polyolefins (eg polyethylene, polypropylene, poly (1-butene), polyisobutylene), poly (aromatic vinyl) (eg polystyrene and its derivatives), poly (meth). Examples thereof include methyl acrylate, polyester, vinyl polycarboxylate, polyvinyl acetal, polycarbonate, polyurethane, polyarylate, polyamide, polyimide, cellulose and derivatives thereof, polysiloxane, rubber, and thermoplastic elastomer. The organic polymer that can be contained in the insulating material may be a homopolymer or a copolymer.

The insulating material preferably contains a polymer containing a structural unit represented by the following formula (II). Hereinafter, the polymer containing the structural unit represented by the formula (II) is also referred to as a polymer (2). The polymer (2) may contain only one type of the structural unit represented by the formula (II), or may contain a combination of two or more types.

In formula (II), R ⁱ¹ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms, and R ⁱ² is a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms, described below. It represents a group represented by the formula (III-1), a group represented by the formula (III-2), or a group represented by the formula (III-3).

In the formula (III-1), ^Ri2a represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms.
In the above formula (III-2), ^Ri2b represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
In the above formula (III-3), ^Ri2c represents an alkyl group having 1 to 20 carbon atoms.

R ⁱ¹ is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and further preferably a hydrogen atom.

R ^i2a is preferably a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms, and further preferably. Is a hydrogen atom.

R ^i2b is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and further preferably a methyl group.

R ^i2c is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and further preferably a methyl group.

R ⁱ² is preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a group represented by the formulas (III-1) to (III-3), and more preferably a hydrogen atom and carbon. An alkyl group having 1 to 10 atoms, or a group represented by the formulas (III-1) to (III-3), more preferably an alkyl group having 1 to 5 carbon atoms, or a formula (III-). 1) -A group represented by the formula (III-3).

In one embodiment, the polymer (2) has a structural unit in which R ⁱ² is an alkyl group having 1 to 20 carbon atoms in the formula (II) and R ⁱ² in the formula (II) is the formula (III-1). It is preferable to include one or more structural units selected from the group consisting of the structural units represented, and polystyrene or a styrene unit and a structural unit in which ^Ri2 is represented by the formula (III-1) in the formula (II). It is more preferable that the polymer contains the polymer.
In another embodiment, the polymer (2) preferably contains a structural unit in which ^Ri2 is represented by the formula (III-2) in the formula (II), and more preferably contains a methyl methacrylate unit.

The content of the polymer (2) in the insulating material is preferably 70% by weight or more, more preferably 80% by weight or more, further preferably 90% by weight or more, particularly preferably 95% by weight or more, and usually 100% by weight. % Or less, and may be 100% by weight. The insulating material may contain only one type of the polymer (2), or may contain a combination of two or more types.

The polymer (2) may contain any structural unit in addition to the structural unit represented by the formula (II). Examples of arbitrary building blocks include alkaziene units (eg, 1,3-butadiene units, isoprene units).

The polymer (2) can be produced by a conventionally known production method. Further, as the polymer (2), a commercially available product can also be used.

Preferably, the insulating material is a material that dissolves in an amount of 0.1% by weight or more at 25 ° C. with respect to the solvent used in the composition of the present invention.
More preferably, the insulating material is the polymer (2), which is a polymer that dissolves in an amount of 0.1% by weight or more at 25 ° C. with respect to the solvent used in the composition of the present invention.

The weight average molecular weight (Mw) of the organic polymer that can be contained in the insulating material is not particularly limited, but is preferably 1,000,000 or less, more preferably 500,000 or less, and further, from the viewpoint of solubility in a solvent. It is preferably 200,000 or less.

Specific examples of the insulating material according to the present embodiment are polystyrene-block-poly (ethylene-ran-butylene) -block-polystyrene (weight average molecular weight: 118,000 or less), polystyrene (weight average molecular weight: 35,000), polystyrene-block-. Polyisoprene-block-polystyrene (number average molecular weight 1900), and poly (methylmethacrylate) can be mentioned.

The content of the insulating material in the composition is, for example, 0.5% by weight or more or 0.1% by weight or more, and for example, 5% by weight or less or 1% by weight or less. Here, the total weight of the p-type semiconductor material, the n-type semiconductor material, the insulating material, and the solvent in the composition is 100% by weight.

It is preferable that at least a part of the insulating material is dissolved in the composition, and more preferably all of the insulating material is dissolved.

The weight ratio of the insulating material to the p-type semiconductor material (insulating material / p-type semiconductor material) in the composition is, for example, 1/10 or more or 1/5 or more, for example, 1/3 or less or 1/2 or less. ..

[1.4. solvent]
The composition according to this embodiment contains a solvent. The composition may contain only one type of solvent, or may contain a combination of two or more types.
The composition according to the present embodiment preferably contains the first solvent described below, and may optionally further contain a second solvent.

(First solvent)
The solvent may be selected in consideration of the solubility in the selected p-type semiconductor material and the n-type semiconductor material, and the characteristics (boiling point, etc.) corresponding to the drying conditions when forming the film.

The first solvent is preferably an aromatic hydrocarbon (hereinafter, simply referred to as an aromatic hydrocarbon) or an alkyl halide solvent which may have a substituent (for example, an alkyl group or a halogen atom). The first solvent is preferably selected in consideration of the solubility of the selected p-type semiconductor material and n-type semiconductor material.

Examples of the aromatic hydrocarbon as the first solvent include toluene, xylene (eg, o-xylene, m-xylene, p-xylene), trimethylbenzene (eg, mesitylene, 1,2,4-trimethylbenzene). )), Butylbenzene (eg n-butylbenzene, sec-butylbenzene, tert-butylbenzene), methylnaphthalene (eg 1-methylnaphthalene), tetralin, indan, chlorobenzene and dichlorobenzene (1,2-dichlorobenzene) ).

Examples of the alkyl halide solvent as the first solvent include chloroform.

The first solvent may be composed of only one kind of aromatic hydrocarbon or may be composed of two or more kinds of aromatic hydrocarbons. The first solvent is preferably composed of only one aromatic hydrocarbon.

The first solvent is preferably toluene, o-xylene, m-xylene, p-xylene, mesitylene, pseudocumene, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, methylnaphthalene, tetraline, indane, chlorobenzene, etc. Includes one or more selected from the group consisting of o-dichlorobenzene and chloroform.

(Second solvent)
The second solvent is preferably a solvent selected from the viewpoint of enhancing the solubility of the n-type semiconductor material. Examples of the second solvent include ketone solvents (eg, acetone, methyl ethyl ketone, cyclohexanone, acetophenone, propiophenone), ester solvents (eg, ethyl acetate, butyl acetate, phenyl acetate, ethyl cellsolve acetate, methyl benzoate, benzoic acid). Butylate, benzyl benzoate).

(Weight ratio of first solvent and second solvent)
When the composition contains the first solvent and the second solvent, the weight ratio of the first solvent to the second solvent (first solvent / second solvent) determines the solubility of the p-type semiconductor material and the n-type semiconductor material. From the viewpoint of improvement, it is preferably in the range of 85/15 to 99/1.

(Weight percentage of solvent in composition)
The total weight of the solvent contained in the composition is preferably 90% by weight or more from the viewpoint of further improving the solubility of the p-type semiconductor material and the n-type semiconductor material when the total weight of the composition is 100% by weight. , More preferably 92% by weight or more, still more preferably 95% by weight or more, and increase the concentration of the p-type semiconductor material and the n-type semiconductor material in the coating liquid to facilitate the formation of a layer having a certain thickness or more. From the viewpoint, it is preferably 99.9% by weight or less.

The composition may further contain any third solvent in addition to the first solvent and any second solvent described above. When the total weight of all the solvents contained in the coating liquid is 100% by weight, the content of any third solvent is preferably 5% by weight or less, more preferably 3% by weight or less, still more preferable. Is 1% by weight or less. As the arbitrary third solvent, a solvent having a boiling point higher than that of the second solvent is preferable.

[1.5. Any ingredient]
The composition according to the present embodiment may contain, in addition to the above-mentioned p-type semiconductor material, n-type semiconductor material, insulating material, and solvent, any component as long as the object and effect of the present invention are not impaired. good. Examples of optional components are UV absorbers, antioxidants, sensitizers to sensitize the ability to generate charge by absorbed light, and photostabilizers to increase stability from UV light. Can be mentioned.
The total content of the optional components in the composition is preferably 10% by weight or less, more preferably 5% by weight or less, and usually 0% by weight or more.

[1.6. Content ratio of p-type semiconductor material, n-type semiconductor material, and insulating material]
(Concentration of p-type semiconductor material and n-type semiconductor material in the composition)
The total concentration of the p-type semiconductor material and the n-type semiconductor material in the composition can be any suitable concentration depending on the required thickness of the active layer. The total concentration of the p-type semiconductor material and the n-type semiconductor material is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, preferably 10% by weight or less, and more preferably 5% by weight. % Or less, more preferably 0.01% by weight or more and 20% by weight or less, further preferably 0.01% by weight or more and 10% by weight or less, still more preferably 0.01% by weight or more and 5% by weight or less, particularly preferably. It is 0.1% by weight or more and 5% by weight or less.

(Weight ratio of p-type semiconductor material to n-type semiconductor material (p / n ratio))
The weight ratio of the p-type semiconductor material to the n-type semiconductor material (p-type semiconductor material / n-type semiconductor material) in the composition is preferably 1/9 or more, more preferably 1/5 or more, still more preferably 1/3. The above is preferably 9/1 or less, more preferably 5/1 or less, still more preferably 3/1 or less.

(Total content ratio of p-type semiconductor material, n-type semiconductor material, and insulating material)
The total content ratio of the p-type semiconductor material, the n-type semiconductor material, and the insulating material in the composition can be appropriately set according to, for example, the type of coating method, the viscosity of the component used, and the like. The total content of the p-type semiconductor material, the n-type semiconductor material, and the insulating material in the composition is not particularly limited as long as they can be dissolved in the composition, but is preferably 1% by weight or more, more preferably 2. By weight% or more, more preferably 3% by weight or more, preferably 20% by weight or less, more preferably 10% by weight or less, still more preferably 7% by weight or less.

[1.7. Method for producing composition]
The composition can be produced by a conventionally known method. For example, when the first solvent and the second solvent are used as the solvent, the first solvent and the second solvent are mixed to prepare a mixed solvent, and the p-type semiconductor material, the n-type semiconductor material, and the mixed solvent are used as the mixed solvent. Method of adding insulating material, p-type semiconductor material and insulating material are added to the first solvent, n-type semiconductor material is added to the second solvent, and then the first solvent and the second solvent to which each material is added are added. It can be manufactured by a mixing method or the like.

The solvent and the p-type semiconductor material, the n-type semiconductor material, and the insulating material may be heated to a temperature equal to or lower than the boiling point of the solvent and mixed.

After mixing the solvent with the p-type semiconductor material, the n-type semiconductor material, and the insulating material, the obtained mixture may be filtered using a filter, and the obtained filtrate may be used as a composition. As the filter, for example, a filter formed of a fluororesin such as polytetrafluoroethylene (PTFE) can be used.

[1.8. Use of composition]
The composition can be suitably used as an ink for forming a film containing a p-type semiconductor material, an n-type semiconductor material, and an insulating material by a coating method. In the present specification, "ink" means a liquid material used in a coating method, and is not limited to a colored liquid material. Further, the "coating method" includes a method of forming a film (layer) using a liquid material, for example, a slot die coating method, a slit coating method, a knife coating method, a spin coating method, a casting method, and a microgravure coating method. , Gravure coating method, Bar coating method, Roll coating method, Wire bar coating method, Dip coating method, Spray coating method, Screen printing method, Gravure printing method, Flexo printing method, Offset printing method, Inkjet coating method, Dispenser printing method, The nozzle coat method and the capillary coat method can be mentioned.

[2. film]
The film according to the embodiment of the present invention includes a polymer (1) as a p-type semiconductor material, an n-type semiconductor material, and an insulating material. Hereinafter, the film containing the polymer (1) as the p-type semiconductor material, the n-type semiconductor material, and the insulating material is also referred to as “film A”.
Examples of the polymer (1) as a p-type semiconductor material and preferred examples, examples of n-type semiconductor materials and preferred examples, and examples of insulating materials and preferred examples are described in Item [1. Composition] is the same as the example described.

The preferable range of the weight ratio (p-type semiconductor material / n-type semiconductor material) of the p-type semiconductor material to the n-type semiconductor material in the film according to the present embodiment may be the same as the preferable range of the weight ratio in the composition. can.

The preferable range of the weight ratio (insulating material / p-type semiconductor material) of the insulating material to the p-type semiconductor material in the film according to the present embodiment can be the same as the preferable range of the weight ratio in the composition.

The thickness of the film according to the present embodiment can be appropriately set according to the function of the target film. The thickness of the film according to the present embodiment is preferably 100 nm or more, more preferably 150 nm or more, further preferably 200 nm or more, preferably 10 μm or less, more preferably 5 μm or less, still more preferably 1 μm or less.

The film according to this embodiment can be produced by any method. For example, the film according to this embodiment can be produced by a method including the following steps.

Step (1): A step of applying the composition to a coating target to form a coating film.
Step (2): A step of drying the coating film.
The steps (1) and (2) are usually performed in this order.

(Step (1))
The composition is a composition containing a polymer (1) as a p-type semiconductor material, an n-type semiconductor material, an insulating material, and a solvent. As the composition, the preferred composition already exemplified can be used.

When the film according to the present embodiment functions as an active layer of a photoelectric conversion element, examples of objects to which the composition is applied include an electrode, an electron transport layer, and a hole transport layer.

Any coating method can be used as a method for applying the composition to the coating target. Examples of the method of applying the composition to the coating target in the step (1) include the above-exemplified coating method, and the spin coating method is preferable because it is easy to obtain a coating film having a uniform thickness.

(Step (2))
By drying the coating film, the solvent normally contained in the coating film is removed. Examples of methods for drying the coating film include a method of directly heating with a hot plate in an atmosphere of an inert gas such as nitrogen gas, a hot air drying method, an infrared heating drying method, a flash lamp annealing drying method, and a vacuum drying method. Drying methods such as the method and combinations thereof can be mentioned.
The drying conditions such as the drying temperature and the drying treatment time can be set to any suitable conditions in consideration of the boiling point of the solvent contained in the composition, the thickness of the coating film, and the like.

The method for producing a film according to the present embodiment may include any step in addition to the steps (1) and (2).

[3. Photoelectric conversion element]
[3.1. Configuration of photoelectric conversion element]
The photoelectric conversion element according to the embodiment of the present invention includes a first electrode, the film A, and a second electrode in this order. In a photoelectric conversion element, the film A can usually function as an active layer. When the photoelectric conversion element is irradiated with light, the first electrode is an electrode that causes a positive charge to flow out to an external circuit, and the second electrode is an electrode that allows a positive charge to flow in from the external circuit.
Hereinafter, the photoelectric conversion element of the present embodiment will be described with reference to the drawings.

FIG. 1 is a diagram schematically showing a configuration example of a photoelectric conversion element.

As shown in FIG. 1, the photoelectric conversion element 10 is provided on the support substrate 11. The photoelectric conversion element 10 is attached to a first electrode 12 provided in contact with the support substrate 11, a hole transport layer 13 provided in contact with the first electrode 12, and a hole transport layer 13. The active layer 14 provided in contact with the active layer 14, the electron transport layer 15 provided in contact with the active layer 14, and the second electrode 16 provided in contact with the electron transport layer 15 are provided. There is. In this configuration example, the sealing member 17 is further provided so as to be in contact with the second electrode 16.
Hereinafter, the constituent elements that can be included in the photoelectric conversion element of the present embodiment will be specifically described.

(substrate)
The photoelectric conversion element is usually formed on a substrate (support substrate). Further, it may be further sealed by a substrate (sealing substrate). Usually, one of a pair of electrodes consisting of a first electrode and a second electrode is formed on the substrate. The material of the substrate is not particularly limited as long as it is a material that does not chemically change when forming a layer containing an organic compound.

Examples of the material of the substrate include glass, plastic, polymer film, and silicon. When an opaque substrate is used, it is preferable that the electrode on the opposite side of the electrode provided on the opaque substrate side (in other words, the electrode on the side far from the opaque substrate) is a transparent or translucent electrode. ..

(electrode)
The photoelectric conversion element includes a first electrode and a second electrode, which are a pair of electrodes. It is preferable that at least one of the first electrode and the second electrode is a transparent or translucent electrode in order to allow light to enter.

Examples of the material of the transparent or translucent electrode include a conductive metal oxide film and a translucent metal thin film. Specifically, indium oxide, zinc oxide, tin oxide, and conductive materials such as indium tin oxide (ITO), indium zinc oxide (IZO), and NESA, which are composites thereof, gold, platinum, and silver. Copper is mentioned. As a transparent or translucent electrode material, ITO, IZO, and tin oxide are preferable. Further, as the electrode, a transparent conductive film using an organic compound such as polyaniline and its derivative, polythiophene and its derivative as a material may be used. The transparent or translucent electrode may be the first electrode or the second electrode.

If one of the pair of electrodes is transparent or translucent, the other electrode may be an electrode having low light transmission. Examples of materials for electrodes having low light transmission include metals and conductive polymers. Specific examples of materials for electrodes with low light transmission include lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, ittrium, indium, cerium, samarium, and europium. Metals such as rubidium and itterbium, and two or more alloys of these, or one or more of these metals, gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten and tin. Examples include alloys with one or more metals selected from the group consisting of, graphite, graphite interlayer compounds, polyaniline and its derivatives, polythiophene and its derivatives. Examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, and calcium-aluminum alloy.

(Active layer)
The photoelectric conversion element of this embodiment has the film A as an active layer. The active layer, which is the membrane A, according to the present embodiment has a bulk heterojunction type structure, and includes a polymer (1) as a p-type semiconductor material, an n-type semiconductor material, and an insulating material. Examples of the polymer (1) as a p-type semiconductor material and preferred examples, examples of n-type semiconductor materials and preferred examples, and examples of insulating materials and preferred examples are described in Item [1. Composition] is the same as the example described.

The preferable range of the weight ratio of the p-type semiconductor material to the n-type semiconductor material in the active layer (p-type semiconductor material / n-type semiconductor material) can be the same as the preferable range of the weight ratio in the composition.

The preferable range of the weight ratio of the insulating material to the p-type semiconductor material (insulating material / p-type semiconductor material) in the active layer can be the same as the preferable range of the weight ratio in the composition.

In the present embodiment, the thickness of the active layer is not particularly limited. The thickness of the active layer can be arbitrarily set in consideration of the balance between the suppression of the dark current and the extraction of the generated photocurrent. The thickness of the active layer is preferably 100 nm or more, more preferably 150 nm or more, still more preferably 200 nm or more, particularly from the viewpoint of further reducing the dark current. The thickness of the active layer is preferably 10 μm or less, more preferably 5 μm or less, and further preferably 1 μm or less.

(Middle layer)
As shown in FIG. 1, the photoelectric conversion element of the present embodiment has, for example, a charge transport layer (electron transport layer, hole transport layer, electron injection layer, etc.) as a component for improving characteristics such as photoelectric conversion efficiency. It is preferable to have an intermediate layer (buffer layer) such as a hole injection layer).

Examples of materials used for the intermediate layer include metals such as calcium, inorganic oxide semiconductors such as molybdenum oxide and zinc oxide, and PEDOT (poly (3,4-ethylenedioxythiophene)) and PSS (poly (poly (3,4-ethylenedioxythiophene)). 4-styrene sulfonate)) and a mixture (PEDOT: PSS) can be mentioned.

In one embodiment, as shown in FIG. 1, the photoelectric conversion element preferably includes a hole transport layer between the first electrode and the active layer. The hole transport layer has a function of transporting holes from the active layer to the electrode.
In another embodiment, the photoelectric conversion element may not include a hole transport layer.

The hole transport layer provided in contact with the first electrode may be particularly referred to as a hole injection layer. The hole transport layer (hole injection layer) provided in contact with the first electrode has a function of promoting the injection of holes into the first electrode. The hole transport layer (hole injection layer) may be in contact with the active layer.

The hole transport layer contains a hole transport material. Examples of hole transporting materials include polythiophene and its derivatives, aromatic amine compounds, polymer compounds containing building blocks with aromatic amine residues, CuSCN, CuI, NiO, tungsten oxide (WO ₃ ) and molybdenum oxide. (MoO ₃ ) can be mentioned.

The intermediate layer can be formed by any conventionally known suitable forming method. The intermediate layer can be formed by a coating method similar to the vacuum vapor deposition method or the active layer forming method.

In the photoelectric conversion element according to the present embodiment, the intermediate layer is a hole transport layer and an electron transport layer, and the substrate (support substrate), the first electrode, the hole transport layer, the active layer, the electron transport layer, and the second. It is preferable to have a structure in which the electrodes of the above are laminated so as to be in contact with each other in this order.

As shown in FIG. 1, the photoelectric conversion element of the present embodiment preferably includes an electron transport layer as an intermediate layer between the second electrode and the active layer. The electron transport layer has a function of transporting electrons from the active layer to the second electrode. The electron transport layer may be in contact with the second electrode. The electron transport layer may be in contact with the active layer.

The electron transport layer provided in contact with the second electrode may be particularly referred to as an electron injection layer. The electron transport layer (electron injection layer) provided in contact with the second electrode has a function of promoting the injection of electrons generated in the active layer into the second electrode.

The electron transport layer contains an electron transport material. Examples of the electron transporting material include polyalkyleneimine and its derivatives, polymer compounds containing a fluorene structure, metals such as calcium, and metal oxides.

Examples of polyalkyleneimines and derivatives thereof include alkyleneimines having 2 to 8 carbon atoms such as ethyleneimine, propyleneimine, butyleneimine, dimethylethyleneimine, pentyleneimine, hexyleneimine, heptyleneimine, and octyleneimine, especially the number of carbon atoms. Examples thereof include polymers obtained by polymerizing one or more of 2 to 4 alkyleneimines by a conventional method, and polymers obtained by reacting them with various compounds to chemically modify them. As the polyalkyleneimine and its derivative, polyethyleneimine (PEI) and ethoxylated polyethyleneimine (PEIE) are preferable.

Examples of polymer compounds containing a fluorene structure include poly [(9,9-bis (3'-(N, N-dimethylamino) propyl) -2,7-fluorene) -ortho-2,7- (9). , 9'-Dioctylfluorene)] (PFN) and PFN-P2.

Examples of metal oxides include zinc oxide, gallium-doped zinc oxide, aluminum-doped zinc oxide, titanium oxide and niobium oxide. As the metal oxide, a metal oxide containing zinc is preferable, and zinc oxide is particularly preferable.

Examples of other electron transporting materials include poly (4-vinylphenol) and perylene diimide.

(Sealing member)
It is preferable that the photoelectric conversion element of the present embodiment further includes a sealing member and is a sealed body sealed by such a sealing member.
Any suitable conventionally known member can be used as the sealing member. Examples of the sealing member include a combination of a glass substrate which is a substrate (sealing substrate) and a sealing material (adhesive) such as a UV curable resin.

The sealing member may be a sealing layer having a layer structure of one or more layers. Examples of the layer constituting the sealing layer include a gas barrier layer and a gas barrier film.

The sealing layer is preferably formed of a material having a property of blocking water (water vapor barrier property) or a property of blocking oxygen (oxygen barrier property). Examples of suitable materials for the sealing layer include polyethylene trifluoride, polyethylene trifluoride chloride (PCTFE), polyimide, polycarbonate, polyethylene terephthalate, alicyclic polyolefin, ethylene-vinyl alcohol copolymer and the like. Examples thereof include organic materials, silicon oxide, silicon nitride, aluminum oxide, and inorganic materials such as diamond-like carbon.

The sealing member is usually made of a material that can withstand the heat treatment that can be performed when the photoelectric conversion element is applied, for example, when it is incorporated into the device of the application example described later.

[3.2. Manufacturing method of photoelectric conversion element]
The photoelectric conversion element of the present embodiment can be manufactured by any method. The photoelectric conversion element of the present embodiment can be manufactured by combining a forming method suitable for the material selected for forming the constituent elements.

Hereinafter, as an embodiment of the present invention, a photoelectric conversion having a structure in which a substrate (supporting substrate), a first electrode, a hole transport layer, a film A as an active layer, an electron transport layer, and a second electrode are in contact with each other in this order. A method of manufacturing the element will be described.

(Process to prepare the board)
In this step, for example, a support substrate provided with the first electrode is prepared. Further, a substrate provided with a conductive thin film formed of the electrode material described above is obtained from the market, and if necessary, the conductive thin film is patterned to form the first electrode. A support substrate provided with the first electrode can be prepared.

In the method for manufacturing a photoelectric conversion element according to the present embodiment, the method for forming the first electrode when the first electrode is formed on the support substrate is not particularly limited. The first electrode has a structure in which the material already described should be formed of the first electrode by any conventionally known suitable method such as a vacuum deposition method, a sputtering method, an ion plating method, a plating method, and a coating method (a configuration in which the first electrode is formed. For example, it can be formed on a support substrate, an active layer, a hole transport layer).

(Process of forming hole transport layer)
The method for manufacturing a photoelectric conversion element may include a step of forming a hole transport layer (hole injection layer) provided between the active layer and the first electrode.

The method of forming the hole transport layer is not particularly limited. From the viewpoint of simplifying the step of forming the hole transport layer, it is preferable to form the hole transport layer by a conventionally known and arbitrary suitable coating method. The hole transport layer can be formed, for example, by a coating method using a coating liquid containing the material and solvent of the hole transport layer already described or a vacuum vapor deposition method.

(Process of forming active layer)
In the method for manufacturing a photoelectric conversion element of the present embodiment, a film A as an active layer is formed on the hole transport layer. The film A can be formed by any suitable conventionally known forming step. In the present embodiment, the membrane A as an active layer can be produced by a coating method using the above composition.

Membrane A as an active layer is [2. It can be formed by the same method as the method for producing a film described in [Membrane]. In the present embodiment, the above composition containing the polymer (1) as the p-type semiconductor material, the n-type semiconductor material, the insulating material, and the solvent is applied onto the hole transport layer to form a coating film. The film A as an active layer can be formed by a step including a step of drying the coating film.

(Process of forming electron transport layer)
The method for manufacturing a photoelectric conversion element of the present embodiment includes a step of forming an electron transport layer (electron injection layer) provided on the active layer.

The method of forming the electron transport layer is not particularly limited. From the viewpoint of simplifying the process of forming the electron transport layer, it is preferable to form the electron transport layer by a conventionally known arbitrary suitable vacuum vapor deposition method.

(Step of forming the second electrode)
The method for forming the second electrode is not particularly limited. For the second electrode, for example, the material of the above-exemplified electrode is formed on the electron transport layer by any conventionally known suitable method such as a coating method, a vacuum vapor deposition method, a sputtering method, an ion plating method, and a plating method. be able to. By the above steps, the photoelectric conversion element of the present embodiment is manufactured.

(Process of forming a sealed body)
In forming the encapsulant, in the present embodiment, a conventionally known arbitrary suitable encapsulant (adhesive) and substrate (encapsulating substrate) are used. Specifically, a sealing material such as a UV curable resin is applied onto the support substrate so as to surround the periphery of the manufactured photoelectric conversion element, and then the sealing material is used to bond them without gaps before selection. By encapsulating the photoelectric conversion element in the gap between the support substrate and the encapsulating substrate by using a method such as irradiation with UV light, which is suitable for the encapsulating material, a encapsulating body of the photoelectric conversion element can be obtained. can.

[3.3. Applications for photoelectric conversion elements]
Applications of the photoelectric conversion element of this embodiment include a photodetection element and a solar cell.
More specifically, in the photoelectric conversion element of the present embodiment, a light current is passed by irradiating light from the transparent or translucent electrode side in a state where a voltage (reverse bias voltage) is applied between the electrodes. It can be operated as a photodetection element (optical sensor). It can also be used as an image sensor by integrating a plurality of photodetecting elements. As described above, the photoelectric conversion element of the present embodiment can be particularly suitably used as a photodetection element.

Further, the photoelectric conversion element of the present embodiment can generate photovoltaic power between the electrodes by being irradiated with light, and can be operated as a solar cell. A solar cell module can also be obtained by integrating a plurality of photoelectric conversion elements.

(Application example of photoelectric conversion element)
The photoelectric conversion element according to the present embodiment is suitably applied as a photodetection element to a detection unit provided in various electronic devices such as a workstation, a personal computer, a personal digital assistant, an entrance / exit management system, a digital camera, and a medical device. can do.

The photoelectric conversion element of the present embodiment includes, for example, an image detection unit (for example, an image sensor such as an X-ray sensor) for a solid-state image pickup device such as an X-ray image pickup device and a CMOS image sensor, and a fingerprint, which are included in the above-exemplified electronic device. A detection unit (for example, a near-infrared sensor) of a biometric information authentication device that detects a predetermined feature of a part of a living body such as a detection unit, a face detection unit, a vein detection unit, and an iris detection unit, and an optical biosensor such as a pulse oximeter. It can be suitably applied to a detection unit or the like.

The photoelectric conversion element of the present embodiment can be suitably applied as an image detection unit for a solid-state imaging device, and further to a Time-of-flight (TOF) type distance measuring device (TOF type distance measuring device).

In the TOF type distance measuring device, the distance is measured by receiving the reflected light reflected by the light source from the light source by the photoelectric conversion element. Specifically, the flight time until the irradiation light emitted from the light source is reflected by the measurement target and returned as the reflected light is detected, and the distance to the measurement target is obtained. The TOF type includes a direct TOF method and an indirect TOF method. In the direct TOF method, the difference between the time when the light is emitted from the light source and the time when the reflected light is received by the photoelectric conversion element is directly measured, and in the indirect TOF method, the change in the charge accumulation amount depending on the flight time is converted into the time change. By measuring the distance. The distance measurement principle used in the indirect TOF method to obtain the flight time by accumulating charge is a continuous wave (especially sinusoidal) modulation method in which the flight time is obtained from the phase of the emitted light from the light source and the reflected light reflected by the measurement target. And the pulse modulation method.

Hereinafter, among the detection units to which the photoelectric conversion element according to the present embodiment can be suitably applied, an image detection unit for a solid-state image pickup device, an image detection unit for an X-ray image pickup device, and a biometric authentication device (for example, a fingerprint authentication device or a vein). A configuration example of a fingerprint detection unit and a vein detection unit for (authentication device, etc.) and an image detection unit of a TOF type ranging device (indirect TOF method) will be described with reference to the drawings.

(Image detector for solid-state image sensor)
FIG. 2 is a diagram schematically showing a configuration example of an image detection unit for a solid-state image sensor.

The image detection unit 1 comprises a CMOS transistor substrate 20, an interlayer insulating film 30 provided so as to cover the CMOS transistor substrate 20, and a photoelectric conversion according to an embodiment of the present invention provided on the interlayer insulating film 30. It is provided so as to penetrate the element 10 and the interlayer insulating film 30, and is provided so as to cover the interlayer wiring portion 32 that electrically connects the CMOS transistor substrate 20 and the photoelectric conversion element 10 and the photoelectric conversion element 10. The sealing layer 40 and the color filter 50 provided on the sealing layer 40 are provided.

The CMOS transistor substrate 20 is provided with a conventionally known arbitrary suitable configuration in a mode according to the design.

The CMOS transistor substrate 20 includes transistors, capacitors, and the like formed within the thickness of the substrate, and includes functional elements such as a CMOS transistor circuit (MOS transistor circuit) for realizing various functions.

Examples of the functional element include a floating diffusion, a reset transistor, an output transistor, and a selection transistor.

A signal readout circuit or the like is built in the CMOS transistor substrate 20 by such functional elements, wiring, and the like.

The interlayer insulating film 30 can be made of any conventionally known and suitable insulating material such as silicon oxide and an insulating resin. The interlayer wiring portion 32 can be made of, for example, any conventionally known suitable conductive material (wiring material) such as copper and tungsten. The interlayer wiring portion 32 may be, for example, an in-hole wiring formed at the same time as the formation of the wiring layer, or an embedded plug formed separately from the wiring layer.

The sealing layer 40 is made of any conventionally known suitable material, provided that the permeation of harmful substances such as oxygen and water that may functionally deteriorate the photoelectric conversion element 10 can be prevented or suppressed. Can be done. The sealing layer 40 can have the same configuration as the sealing member 17 described above.

As the color filter 50, for example, a primary color filter which is made of any suitable material known conventionally and which corresponds to the design of the image detection unit 1 can be used. Further, as the color filter 50, a complementary color filter that can be thinner than the primary color filter can also be used. Complementary color filters include, for example, three types (yellow, cyan, magenta), three types (yellow, cyan, transparent), three types (yellow, transparent, magenta), and three types (transparent, cyan, magenta). Color filters that combine types can be used. These can be arbitrarily arranged according to the design of the photoelectric conversion element 10 and the CMOS transistor substrate 20, provided that color image data can be generated.

The light received by the photoelectric conversion element 10 via the color filter 50 is converted into an electric signal according to the amount of light received by the photoelectric conversion element 10, and the light received signal outside the photoelectric conversion element 10 via the electrode, that is, an image pickup target. It is output as an electric signal corresponding to.

Next, the light receiving signal output from the photoelectric conversion element 10 is input to the CMOS transistor substrate 20 via the interlayer wiring unit 32, and is read out by the signal readout circuit built in the CMOS transistor substrate 20, which is not shown. Image information based on the imaging target is generated by signal processing by any suitable conventionally known functional unit.

(Fingerprint detector)
FIG. 3 is a diagram schematically showing a configuration example of a fingerprint detection unit integrally configured with a display device.

The display device 2 of the mobile information terminal includes a fingerprint detection unit 100 including the photoelectric conversion element 10 according to the embodiment of the present invention as a main component, and a display panel provided on the fingerprint detection unit 100 and displaying a predetermined image. It is equipped with a unit 200.

In this configuration example, the fingerprint detection unit 100 is provided in an area corresponding to the display area 200a of the display panel unit 200. In other words, the display panel unit 200 is integrally laminated above the fingerprint detection unit 100.

When fingerprint detection is performed only in a part of the display area 200a, the fingerprint detection unit 100 may be provided corresponding to only the part of the display area 200a.

The fingerprint detection unit 100 includes the photoelectric conversion element 10 according to the embodiment of the present invention as a functional unit that performs an essential function. The fingerprint detection unit 100 desired any suitable conventionally known member such as a protective film (projection film), a support substrate, a sealing substrate, a sealing member, a barrier film, a bandpass filter, and an infrared cut film (not shown). It can be provided in a manner corresponding to the design so that the characteristics can be obtained. For the fingerprint detection unit 100, the configuration of the image detection unit already described can also be adopted.

The photoelectric conversion element 10 may be included in the display region 200a in any manner. For example, a plurality of photoelectric conversion elements 10 may be arranged in a matrix.

As described above, the photoelectric conversion element 10 is provided on the support substrate 11, and the support substrate 11 is provided with electrodes (first electrode or second electrode) in a matrix, for example.

The light received by the photoelectric conversion element 10 is converted into an electric signal according to the amount of light received by the photoelectric conversion element 10, and the light received signal outside the photoelectric conversion element 10 via the electrode, that is, electricity corresponding to the captured fingerprint. It is output as a signal.

In this configuration example, the display panel unit 200 is configured as an organic electroluminescence display panel (organic EL display panel) including a touch sensor panel. The display panel unit 200 may be configured by, for example, instead of the organic EL display panel, a display panel having an arbitrary suitable conventionally known configuration such as a liquid crystal display panel including a light source such as a backlight.

The display panel unit 200 is provided on the fingerprint detection unit 100 already described. The display panel unit 200 includes an organic electroluminescence element (organic EL element) 220 as a functional unit that performs an essential function. The display panel unit 200 is further optionally suitable such as a substrate such as a conventionally known glass substrate (support substrate 210 or a sealing substrate 240), a sealing member, a barrier film, a polarizing plate such as a circular polarizing plate, and a touch sensor panel 230. Suitable conventionally known members may be provided in a manner corresponding to the desired characteristics.

In the configuration example described above, the organic EL element 220 is used as a light source for pixels in the display region 200a and also as a light source for fingerprint imaging in the fingerprint detection unit 100.

Here, the operation of the fingerprint detection unit 100 will be briefly described.
When performing fingerprint authentication, the fingerprint detection unit 100 detects a fingerprint using the light emitted from the organic EL element 220 of the display panel unit 200. Specifically, the light emitted from the organic EL element 220 passes through a component existing between the organic EL element 220 and the photoelectric conversion element 10 of the fingerprint detection unit 100, and is displayed within the display area 200a. It is reflected by the skin (finger surface) of the fingertips of the fingers placed so as to be in contact with the surface of the panel portion 200. At least a part of the light reflected by the finger surface passes through the components existing between them and is received by the photoelectric conversion element 10, and is converted into an electric signal according to the amount of light received by the photoelectric conversion element 10. Then, image information about the fingerprint on the finger surface is constructed from the converted electric signal.

The portable information terminal provided with the display device 2 performs fingerprint authentication by comparing the obtained image information with the fingerprint data for fingerprint authentication recorded in advance by an arbitrary suitable step known conventionally.

(Image detector for X-ray imager)
FIG. 4 is a diagram schematically showing a configuration example of an image detection unit for an X-ray image pickup apparatus.

The image detection unit 1 for the X-ray image pickup apparatus is provided on the CMOS transistor substrate 20, the interlayer insulating film 30 provided so as to cover the CMOS transistor substrate 20, and the interlayer insulating film 30 of the present invention. The photoelectric conversion element 10 according to the embodiment, the interlayer wiring portion 32 which is provided so as to penetrate the interlayer insulating film 30 and electrically connects the CMOS transistor substrate 20 and the photoelectric conversion element 10, and the photoelectric conversion element 10 A sealing layer 40 provided so as to cover the sealing layer 40, a reflecting layer 44 provided so as to cover the scintillator 42 and the scintillator 42 provided on the sealing layer 40, and a reflective layer 44 provided so as to cover the reflective layer 44. It is provided with a protective layer 46 that is provided.

The CMOS transistor substrate 20 is provided with a conventionally known arbitrary suitable configuration in a mode according to the design.

The CMOS transistor substrate 20 includes transistors, capacitors, and the like formed within the thickness of the substrate, and includes functional elements such as a CMOS transistor circuit (MOS transistor circuit) for realizing various functions.

Examples of the functional element include a floating diffusion, a reset transistor, an output transistor, and a selection transistor.

A signal readout circuit or the like is built in the CMOS transistor substrate 20 by such functional elements, wiring, and the like.

The interlayer insulating film 30 can be made of any conventionally known and suitable insulating material such as silicon oxide and an insulating resin. The interlayer wiring portion 32 can be made of, for example, any conventionally known suitable conductive material (wiring material) such as copper and tungsten. The interlayer wiring portion 32 may be, for example, an in-hole wiring formed at the same time as the formation of the wiring layer, or an embedded plug formed separately from the wiring layer.

The sealing layer 40 is made of any conventionally known suitable material, provided that the permeation of harmful substances such as oxygen and water that may functionally deteriorate the photoelectric conversion element 10 can be prevented or suppressed. Can be done. The sealing layer 40 can have the same configuration as the sealing member 17 described above.

The scintillator 42 can be made of any conventionally known suitable material corresponding to the design of the image detection unit 1 for the X-ray image pickup apparatus. Examples of suitable materials for the scintillator 42 are inorganic crystals of inorganic materials such as CsI (cesium iodide), NaI (sodium iodide), ZnS (zinc sulfide), GOS (gadrinium acid sulfide), and GSO (gadrinium silicate). , Organic crystals of organic materials such as anthracene, naphthalene, and stilben, organic liquids in which organic materials such as diphenyloxazole (PPO) and terphenyl (TP) are dissolved in organic solvents such as toluene, xylene, and dioxane, and xenone and helium. Gas, plastic, etc. can be used.

The above components correspond to the design of the photoelectric conversion element 10 and the CMOS transistor substrate 20 on the condition that the X-rays incident by the scintillator 42 can be converted into light having a wavelength centered on the visible region to generate image data. Any suitable arrangement can be made.

The reflective layer 44 reflects the light converted by the scintillator 42. The reflective layer 44 can reduce the loss of converted light and increase the detection sensitivity. Further, the reflective layer 44 can also block light directly incident from the outside.

The protective layer 46 can be made of any conventionally known suitable material, provided that the permeation of harmful substances such as oxygen and water that may functionally deteriorate the scintillator 42 can be prevented or suppressed.

Here, the operation of the image detection unit 1 for the X-ray image pickup apparatus having the above configuration will be briefly described.

When radiation energy such as X-rays or γ-rays is incident on the scintillator 42, the scintillator 42 absorbs the radiation energy and converts it into light (fluorescence) having a wavelength in the ultraviolet to infrared region centered on the visible region. Then, the light converted by the scintillator 42 is received by the photoelectric conversion element 10.

In this way, the light received by the photoelectric conversion element 10 via the scintillator 42 is converted into an electric signal according to the amount of light received by the photoelectric conversion element 10, and the light received signal is transmitted to the outside of the photoelectric conversion element 10 via the electrode. That is, it is output as an electric signal corresponding to the image pickup target. The radiation energy (X-ray) to be detected may be incident from either the scintillator 42 side or the photoelectric conversion element 10 side.

Next, the light receiving signal output from the photoelectric conversion element 10 is input to the CMOS transistor substrate 20 via the interlayer wiring unit 32, and is read out by the signal readout circuit built in the CMOS transistor substrate 20, which is not shown. Image information based on the imaging target is generated by signal processing by any suitable conventionally known functional unit.

(Vein detector)
FIG. 5 is a diagram schematically showing a configuration example of a vein detection unit for a vein authentication device.
The vein detection unit 300 for the finger vein recognition device includes a cover unit 306 that defines an insertion unit 310 into which a finger (eg, one or more fingertips, fingers and palm) to be measured at the time of measurement is inserted, and a cover. A support that supports the light source unit 304 that irradiates the measurement target with light, the photoelectric conversion element 10 that receives the light emitted from the light source unit 304 through the measurement target, and the photoelectric conversion element 10 provided in the unit 306. A glass substrate 302 that is arranged so as to face each other with the substrate 11 and the support substrate 11 and the photoelectric conversion element 10 interposed therebetween, separated from the cover portion 306 at a predetermined distance, and defines the insertion portion 306 together with the cover portion 306. It is composed of.

In this configuration example, the light source unit 304 shows a transmission type photographing method in which the light source unit 304 is integrally configured with the cover unit 306 so as to be separated from the photoelectric conversion element 10 with the measurement target interposed therebetween. The light source unit 304 does not necessarily have to be located on the cover unit 306 side.

On the condition that the light from the light source unit 304 can be efficiently irradiated to the measurement target, for example, a reflection type photographing method may be used in which the measurement target is irradiated from the photoelectric conversion element 10 side.

The vein detection unit 300 includes the photoelectric conversion element 10 according to the embodiment of the present invention as a functional unit that performs an essential function. The vein detection unit 300 is any suitable conventionally known member such as a protective film (projection film), a sealing member, a barrier film, a bandpass filter, a near-infrared transmission filter, a visible light cut film, and a finger rest guide (not shown). Can be provided in a manner corresponding to the design so as to obtain the desired characteristics. The configuration of the image detection unit 1 described above can also be adopted for the vein detection unit 300.

The photoelectric conversion element 10 may be included in any embodiment. For example, a plurality of photoelectric conversion elements 10 may be arranged in a matrix.

As described above, the photoelectric conversion element 10 is provided on the support substrate 11, and the support substrate 11 is provided with electrodes (first electrode or second electrode) in a matrix, for example.

The light received by the photoelectric conversion element 10 is converted into an electric signal according to the amount of light received by the photoelectric conversion element 10, and the light received signal outside the photoelectric conversion element 10 via the electrode, that is, the electricity corresponding to the imaged vein. It is output as a signal.

At the time of vein detection (during use), the measurement target may or may not be in contact with the glass substrate 302 on the photoelectric conversion element 10 side.

Here, the operation of the vein detection unit 300 will be briefly described.
At the time of vein detection, the vein detection unit 300 detects the vein pattern to be measured by using the light emitted from the light source unit 304. Specifically, the light radiated from the light source unit 304 passes through the measurement target and is converted into an electric signal according to the amount of light received by the photoelectric conversion element 10. Then, the image information of the vein pattern to be measured is constructed from the converted electrical signal.

In the vein recognition device, vein recognition is performed by comparing the obtained image information with the vein data for vein recognition recorded in advance by an arbitrary suitable step known conventionally.

(Image detector for TOF type distance measuring device)
FIG. 6 is a diagram schematically showing a configuration example of an indirect type TOF type distance measuring device image detection unit.

The image detection unit 400 for a TOF type distance measuring device is provided on the CMOS transistor substrate 20, the interlayer insulating film 30 provided so as to cover the CMOS transistor substrate 20, and the interlayer insulating film 30 of the present invention. It is provided so as to cover the photoelectric conversion element 10 according to the embodiment, two floating diffusion layers 402 arranged apart from each other so as to sandwich the photoelectric conversion element 10, and the photoelectric conversion element 10 and the floating diffusion layer 402. It includes an insulating layer 40 and two photogates 404 provided on the insulating layer 40 and arranged apart from each other.

A part of the insulating layer 40 is exposed from the gap between the two separated photo gates 404, and the remaining region is shielded by the light-shielding portion 406. The CMOS transistor substrate 20 and the floating diffusion layer 402 are electrically connected by an interlayer wiring portion 32 provided so as to penetrate the interlayer insulating film 30.

The interlayer insulating film 30 can be made of any conventionally known and suitable insulating material such as silicon oxide and an insulating resin. The interlayer wiring portion 32 can be made of, for example, any conventionally known suitable conductive material (wiring material) such as copper and tungsten. The interlayer wiring portion 32 may be, for example, an in-hole wiring formed at the same time as the formation of the wiring layer, or an embedded plug formed separately from the wiring layer.

In this configuration example, the insulating layer 40 can have any conventionally known and arbitrarily suitable configuration such as a field oxide film composed of silicon oxide.

The photogate 404 can be made of any conventionally known suitable material such as polysilicon.

The image detection unit 400 for a TOF type distance measuring device includes the photoelectric conversion element 10 according to the embodiment of the present invention as a functional unit that performs an essential function. The image detection unit 400 for a TOF type distance measuring device is any suitable conventional image detection unit 400 such as a protective film (projection film), a support substrate, a sealing substrate, a sealing member, a barrier film, a bandpass filter, and an infrared cut film (not shown). A known member may be provided in a manner corresponding to a design such that a desired characteristic can be obtained.

Here, the operation of the image detection unit 400 for a TOF type ranging device will be briefly described.

Light is emitted from the light source, the light from the light source is reflected from the measurement target, and the reflected light is received by the photoelectric conversion element 10. Two photogates 404 are provided between the photoelectric conversion element 10 and the floating diffusion layer 402, and by alternately applying pulses, the signal charges generated by the photoelectric conversion element 10 are transferred to the two floating diffusion layers 402. It is transferred to either, and the charge is accumulated in the floating diffusion layer 402. When the optical pulse arrives so as to spread evenly with respect to the timing of opening the two photo gates 404, the amount of electric charge accumulated in the two floating diffusion layers 402 becomes equal. When the optical pulse arrives at the other photogate 404 with a delay with respect to the timing at which the optical pulse arrives at one photogate 404, there is a difference in the amount of charge accumulated in the two floating diffusion layers 402.

The difference in the amount of charge stored in the floating diffusion layer 402 depends on the delay time of the optical pulse. Since the distance L to the measurement target has a relationship of L = (1/2) ctd using the round-trip time td of light and the speed of light c, the delay time is based on the difference in the amount of charge between the two floating diffusion layers 402. If it can be estimated, the distance to the measurement target can be obtained.

The amount of light received by the photoelectric conversion element 10 is converted into an electric signal as the difference between the amounts of electric charges stored in the two floating diffusion layers 402, and the received signal outside the photoelectric conversion element 10, that is, the electricity corresponding to the measurement target. It is output as a signal.

Next, the light receiving signal output from the floating diffusion layer 402 is input to the CMOS transistor substrate 20 via the interlayer wiring unit 32, and is read out by the signal readout circuit built in the CMOS transistor substrate 20, which is not shown. By signal processing by any suitable conventionally known functional unit, distance information based on the measurement target is generated.

[4. Photodetection]
As described above, the organic photoelectric conversion element of the present embodiment may have a photodetection function capable of converting the irradiated light into an electric signal according to the amount of received light and outputting it to an external circuit via an electrode.
Therefore, the photodetection element according to the embodiment of the present invention may have a photodetection function by including the organic photoelectric conversion element. The photodetection element of the present embodiment may be the organic photoelectric conversion element itself, or may include a functional element for voltage control or the like in addition to the organic photoelectric conversion element.

Hereinafter, examples will be shown in order to explain the present invention in more detail. The present invention is not limited to the examples described below. The following examples were carried out under normal temperature and pressure conditions unless otherwise specified. Further, "%" and "part" represent "% by weight" and "part by weight", respectively, unless otherwise specified.

<Material used>
The p-type semiconductor material (electron-donating compound), n-type semiconductor material (electron-accepting compound), and insulating material (compound not involved in the photoelectric conversion process) used in the following examples are as follows.

(P-type semiconductor material)
The following polymers P-1 to P-4, which are polymer compounds, were used as the p-type semiconductor material.

The polymer compound (polymer) P-1, which is a p-type semiconductor material, was synthesized and used with reference to the method described in International Publication No. 2013/051676.
The polymer compound (polymer) P-2, which is a p-type semiconductor material, was synthesized and used with reference to the method described in International Publication No. 2011/052709.
As the polymer compound (polymer) P-3, which is a p-type semiconductor material, PDTSTPD (trade name, manufactured by 1-material) was obtained from the market and used.
As the polymer compound (polymer) P-4, which is a p-type semiconductor material, PBDTTPD (trade name, manufactured by 1-material) was obtained from the market and used.

(N-type semiconductor material)
The following compounds N-1 to N-2 were used as the n-type semiconductor material.

For compound N-1, which is an n-type semiconductor material, Coi8DFIC (trade name, manufactured by 1-material) was obtained from the market and used.
For compound N-2, which is an n-type semiconductor material, E100 (trade name, manufactured by Frontier Carbon Co., Ltd.) was obtained from the market and used.

(Insulating material)
The following polymers Z-1 to Z-2 were used as the insulating material.

For the compound Z-1, which is an insulating material, Polystyrene-block-poly (ethylene-ran-butylene) -block-polystyrene (weight average molecular weight Mw 118000 or less, manufactured by Aldrich) was obtained from the market and used.
For compound Z-2, which is an insulating material, Polystyrene-block-polyisoprene-block-polystyrene (number average molecular weight Mn 1900, manufactured by Aldrich) was obtained from the market and used.

[Solubility of insulating material in solvent]
The solubility of the insulating material in the solvent was evaluated as follows.
Tetralin was used as the first solvent, butyl benzoate was used as the second solvent, and the weight ratio of the first solvent to the second solvent was 97: 3, and a mixed solvent was prepared.
To 99 parts by weight of the mixed solvent, 1 part by weight of the compound Z-1 or Z-2 as an insulating material was added, and the mixture was stirred at 60 ° C. for 1 hour. After cooling to 25 ° C., the mixture after stirring was visually observed to confirm whether or not the insulating material remained undissolved. When there was no undissolved residue of the insulating material, the solubility in the mixed solvent was regarded as "good".
The solubility in tetralin was also evaluated in the same manner as the evaluation of the solubility in the mixed solvent except that the mixed solvent was changed to the tetralin single solvent.
The evaluation results are shown in the table below. It was found that the insulating materials Z-1 to Z-2 are materials that are dissolved in the mixed solvent or tetralin at 25 ° C. in an amount of 0.1% by weight or more.

A composition as an ink was prepared using compound Z-1 or Z-2 as an insulating material.

[Preparation of ink (composition)]
[Preparation Example 1] Preparation of Ink I-1 Using tetralin as the first solvent and butyl benzoate as the second solvent, a mixed solvent was prepared with a weight ratio of 97: 3 between the first solvent and the second solvent.

In the obtained mixed solvent, the polymer compound (polymer) P-1 which is a p-type semiconductor material has a concentration of 1% by weight based on the total weight of the ink, and the compound N-1 which is an n-type semiconductor material. Was added so as to have a concentration of 1% by weight based on the total weight of the ink, and the insulating material compound Z-1 was added so as to have a concentration of 0.5% by weight based on the total weight of the ink. The mixture was stirred at 60 ° C. for 8 hours to obtain a mixed solution. The obtained mixed solution was filtered using a filter to obtain ink I-1.

[Preparation Example 2] Preparation of Ink I-2 ・ A tetralin solvent was used instead of the mixed solvent.
-Compound N-2, which is an n-type semiconductor material, was used instead of compound N-1, and compound N-2 was added to the tetralin solvent so as to have a concentration of 2% by weight based on the total weight of the ink.
-Compound Z-2, which is an insulating material, was used instead of Compound Z-1, and Compound Z-2 was added to the tetralin solvent so as to have a concentration of 1% by weight based on the total weight of the ink.
Ink I-2 was obtained by operating in the same manner as in Preparation Example 1 except for the above items.

[Preparation Example 3] Preparation of Ink I-3 ・ A tetralin solvent was used instead of the mixed solvent.
-A polymer compound (polymer) P-2, which is a p-type semiconductor material, was used instead of the polymer P-1.
-Compound N-2, which is an n-type semiconductor material, was used instead of compound N-1, and compound N-2 was added to the tetralin solvent so as to have a concentration of 2% by weight based on the total weight of the ink.
-Compound Z-2 was added to the tetralin solvent so as to have a concentration of 1% by weight based on the total weight of the ink.
Ink I-3 was obtained by operating in the same manner as in Preparation Example 1 except for the above items.

[Comparative Preparation Example 1] Preparation of Ink C-1 ・ A tetralin solvent was used instead of the mixed solvent.
-A polymer compound (polymer) P-3, which is a p-type semiconductor material, was used instead of the polymer P-1.
-Compound N-2, which is an n-type semiconductor material, was used instead of compound N-1, and compound N-2 was added to the tetralin solvent so as to have a concentration of 2% by weight based on the total weight of the ink.
-Compound Z-2 was added to the tetralin solvent so as to have a concentration of 1% by weight based on the total weight of the ink.
Ink C-1 was obtained by operating in the same manner as in Preparation Example 1 except for the above items.

[Comparative Preparation Example 2] Preparation of Ink C-2 ・ A tetralin solvent was used instead of the mixed solvent.
-A polymer compound (polymer) P-4, which is a p-type semiconductor material, was used instead of the polymer P-1.
-Compound N-2, which is an n-type semiconductor material, was used instead of compound N-1, and compound N-2 was added to the tetralin solvent so as to have a concentration of 2% by weight based on the total weight of the ink.
-Compound Z-2 was added to the tetralin solvent so as to have a concentration of 1% by weight based on the total weight of the ink.
Ink C-2 was obtained by operating in the same manner as in Preparation Example 1 except for the above items.

The formulation of each preparation example is shown in the table below.

<Manufacturing and evaluation of photoelectric conversion element>
[Example 1]
(1) Manufacture of photoelectric conversion element and its encapsulant The photoelectric conversion element and its encapsulant were manufactured as follows.

By the sputtering method, a glass substrate having a thickness of 50 nm and formed into a plurality of linear shapes (hereinafter referred to as stripes) in which a thin film of ITO (first electrode) is arranged so as to be separated from each other in parallel is prepared. The glass substrate was subjected to ozone UV treatment as a surface treatment.

Next, a coating film of Ink I-1 was formed on an ITO thin film by a spin coating method, and then heat-treated for 10 minutes using a hot plate heated to 100 ° C. under a nitrogen gas atmosphere to dry the active layer. 1 was formed. The thickness of the formed active layer was about 500 nm.

Next, in the resistance heating vapor deposition apparatus, a calcium (Ca) layer was formed on the formed active layer 1 with a thickness of about 5 nm to form an electron transport layer. A metal mask was used when forming the Ca layer so that the striped ITO thin film intersects with the Ca layer.

Next, a silver (Ag) layer was formed on the formed electron transport layer to a thickness of about 60 nm to form a second electrode. A metal mask was used when forming the Ag layer so that the striped ITO thin film intersects with the Ag layer. The unit of the portion where the thin film of ITO and the Ca layer and the Ag layer overlap when viewed from the thickness direction is a pixel, and 6 pixels are formed on one substrate. The effective area of the pixel is the area of the portion where the ITO thin film and the Ca layer and the Ag layer overlap each other when viewed from the thickness direction.

By the above steps, the photoelectric conversion element was manufactured on a glass substrate. The obtained structure was used as sample 1.

Next, a UV curable sealant as a sealing material was applied onto a glass substrate as a support substrate so as to surround the periphery of the manufactured photoelectric conversion element, and the glass substrate as a sealing substrate was bonded. .. Next, this was irradiated with UV light, and the photoelectric conversion element was sealed in the gap between the support substrate and the sealing substrate. As a result, a sealed body of the photoelectric conversion element was obtained. The planar shape of the photoelectric conversion element sealed in the gap between the support substrate and the sealing substrate when viewed from the thickness direction was a square of 2 mm × 2 mm.

(2) Evaluation of dark current of photoelectric conversion element In a dark state where no light was irradiated, a voltage of -8V to 2V was applied to the sealed body of the manufactured photoelectric conversion element for evaluation. The dark current was measured and evaluated using a source meter (KEITHLEY 2450 Source Meter, manufactured by Keithley Instruments). The current value at the time of applying a voltage of -8V measured by a known method was obtained as a dark current value, and the variation of the dark current of 6 pixels in one substrate was evaluated.

If the dark current values of the other 5 pixels are all within 10 times the lowest value of the dark current at a voltage of -8V among the 6 pixels in one substrate, the dark current will vary. The degree was evaluated as "Good". On the other hand, if the dark current value exceeds 10 times the lowest value among the other 5 pixels, the degree of variation in the dark current is evaluated as "bad".

Table 3 shows the evaluation results of the variation in dark current of Example 1.

[Example 2]
(1) Manufacture of photoelectric conversion element and its encapsulant The photoelectric conversion element and its encapsulant were manufactured as follows.

A glass substrate having an ITO thin film (second electrode) formed in stripes with a thickness of 50 nm was prepared by a sputtering method, and the glass substrate was subjected to ozone UV treatment as a surface treatment.

Next, a solution obtained by diluting an aqueous solution of polyethyleneimine ethoxylate (PEIE) (manufactured by Aldrich, trade name polyethyleneimine, 80% ethoxylated solution, weight average molecular weight 110,000) with ultrapure water 1000 times was applied for forming an electron transport layer. It was used as a liquid and was applied onto an ITO thin film of a glass substrate treated with ozone UV by a spin coating method to form a coating film.
The glass substrate on which the coating film was formed was heat-treated at 100 ° C. for 10 minutes using a hot plate to cure the formed coating film, whereby an electron transport layer was placed on the ITO thin film, which is the second electrode. Was formed.

Next, the ink (I-2) was formed into a coating film on an ITO thin film by a spin coating method, and then heat-treated for 10 minutes using a hot plate heated to 100 ° C. in a nitrogen gas atmosphere to dry it. , The active layer 2 was formed. The thickness of the formed active layer was about 500 nm.

Next, in the resistance heating vapor deposition apparatus, molybdenum oxide (MoO ₃ ) was vapor-deposited on the formed active layer 2 to a thickness of about 15 nm to form a hole transport layer which is a MoO ₃ layer. .. A metal mask was used when forming the MoO ₃ layer so that the striped ITO thin film intersects with the MoO ₃ layer.

Next, a silver (Ag) layer was formed on the formed hole transport layer to a thickness of about 60 nm to form a first electrode. A metal mask was used when forming the Ag layer so that the striped ITO thin film intersects with the Ag layer.

The unit of the portion where the ITO thin film and the MoO ₃ layer and the Ag layer overlap when viewed from the thickness direction is a pixel, and 6 pixels are formed on one substrate. The effective area of the pixel is the area of the portion where the ITO thin film, the MoO ₃ layer, and the Ag layer overlap each other when viewed from the thickness direction.

By the above steps, the photoelectric conversion element was manufactured on a glass substrate. The obtained structure was used as sample 2.

Next, a UV curable sealant as a sealing material was applied onto a glass substrate as a support substrate so as to surround the periphery of the manufactured photoelectric conversion element, and the glass substrate as a sealing substrate was bonded. .. Next, this was irradiated with UV light, and the photoelectric conversion element was sealed in the gap between the support substrate and the sealing substrate. As a result, a sealed body of the photoelectric conversion element was obtained. The planar shape of the photoelectric conversion element sealed in the gap between the support substrate and the sealing substrate when viewed from the thickness direction was a square of 2 mm × 2 mm.

(2) Evaluation of dark current of photoelectric conversion element The variation of dark current was evaluated for 6 pixels in one substrate by the same method as in Example 1.
The evaluation results are shown in Table 3.

[Example 3]
An ink (I-3) was used instead of the ink (I-2), and the rotation speed in the spin coating method was adjusted so that a film thickness of 500 nm could be obtained to obtain the active layer 3. Except for this, a sealed body of the photoelectric conversion element was manufactured in the same manner as in Example 2 described above, and the variation in dark current was evaluated. The evaluation results are shown in Table 3.

[Comparative Examples 1 and 2]
Using inks (C-1) and (C-2) instead of inks (I-2), the number of rotations in the spin coating method was adjusted so that a film thickness of 500 nm could be obtained. 5 were obtained respectively. Except for this, a sealed body of the photoelectric conversion element was manufactured in the same manner as in Example 2 described above, and the variation in dark current was evaluated. The evaluation results are shown in Table 3.

As is clear from Table 3, the compositions containing the polymer represented by the formula (I) as the p-type semiconductor material, the n-type semiconductor material, the insulating material, and the solvent (inks (I-1) to (I)). The elements (samples 1 to 3) according to Examples 1 to 3 in which the active layer was formed from -3)) have good evaluation results of variations in dark current.
On the other hand, in Comparative Examples 1 and 2 in which the active layer was formed from the composition (inks (C-1) to (C-2)) containing no polymer represented by the formula (I) as the p-type semiconductor material. Such elements (samples 4 to 5) had poor evaluation results of variations in dark current.
The inks (C-1) and (C-2) according to Comparative Examples 1 and 2 are the insulating material Z-2, similarly to the inks (I-2) and (I-3) according to Examples 2 and 3. including. However, in Comparative Examples 1 and 2, since the evaluation result of the variation in dark current is poor, some kind of mutual interaction between the polymer represented by the formula (I) as the p-type semiconductor material and the insulating material. It is inferred that the action is occurring. It is presumed that such an interaction affects the dissolution state of each component, the process of drying the active layer, and the like, which in turn affects the film thickness distribution of the active layer. However, the above inference does not limit the present invention.

1 Image detector 2 Display device 10 Photoelectric conversion element 11, 210 Support substrate 12 First electrode 13 Hole transport layer 14 Active layer 15 Electron transport layer 16 Second electrode 17 Sealing member 20 CMOS transistor substrate 30 Interlayer insulating film 32 Interlayer wiring part 40 Sealing layer 42 Scintillator 44 Reflecting layer 46 Protective layer 50 Color filter 100 Fingerprint detection part 200 Display panel part 200a Display area 220 Organic EL element 230 Touch sensor panel 240 Sealing board 300 Vein detection part 302 Glass board 304 Light source part 306 Cover part 310 Insertion part 400 Image detection part for TOF type ranging device 402 Floating diffusion layer 404 Photogate 406 Shading part

Claims (6)

A composition containing a p-type semiconductor material, an n-type semiconductor material, an insulating material, and a solvent.
A composition in which the p-type semiconductor material contains a polymer containing a structural unit represented by the following formula (I).

(In formula (I),
Ar ¹ and Ar ² each independently represent a trivalent aromatic heterocyclic group which may have a substituent.
Z represents a group represented by the following formulas (Z-1) to (Z-4).

(In equations (Z-1) to (Z-4),
R is
Hydrogen atom,
Halogen atom,
Alkyl groups, which may have substituents,
Cycloalkyl groups, which may have substituents,
An alkenyl group which may have a substituent,
Cycloalkenyl groups, which may have substituents,
An alkynyl group, which may have a substituent,
A cycloalkynyl group which may have a substituent,
Aryl groups, which may have substituents,
Alkyloxy groups, which may have substituents,
Cycloalkyloxy groups, which may have substituents,
Aryloxy groups, which may have substituents,
Alkylthio groups, which may have substituents,
Cycloalkylthio groups, which may have substituents,
An arylthio group, which may have a substituent,
A monovalent heterocyclic group which may have a substituent,
Substituted amino groups, which may have substituents,
Imine residues, which may have substituents,
An amide group which may have a substituent,
An acidimide group, which may have a substituent,
Substituted oxycarbonyl group, which may have a substituent,
Cyano group,
Nitro group,
Represents a group represented by -C (= O) -R ^a or a group represented by -SO ₂ -R ^b .
R ^a and R ^b are independent of each other.
Hydrogen atom,
Alkyl groups, which may have substituents,
Cycloalkyl groups, which may have substituents,
Aryl groups, which may have substituents,
Alkyloxy groups, which may have substituents,
Cycloalkyloxy groups, which may have substituents,
Represents an aryloxy group which may have a substituent or a monovalent heterocyclic group which may have a substituent.
In the formulas (Z-1) to (Z-4), the two Rs may be the same or different. ))) The composition according to claim 1, wherein the insulating material is a material that dissolves in the solvent at 25 ° C. in an amount of 0.1% by weight or more. The composition according to claim 1 or 2, wherein the insulating material contains a polymer containing a structural unit represented by the following formula (II).

(In formula (II),
R ⁱ¹ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms.
R ⁱ² is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a group represented by the following formula (III-1), a group represented by the formula (III-2), or a group represented by the formula (III-2). Represents the group represented by 3).

(In equation (III-1),
Each of the plurality of ^Ri2a independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms. )

(In equation (III-2),
R ^i2b represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. )

(In equation (III-3),
R ^i2c represents an alkyl group having 1 to 20 carbon atoms. ))) Including a p-type semiconductor material, an n-type semiconductor material, and an insulating material,
A film in which the p-type semiconductor material contains a polymer containing a structural unit represented by the following formula (I).

(In formula (I),
Ar ¹ and Ar ² each independently represent a trivalent aromatic heterocyclic group which may have a substituent.
Z represents a group represented by the following formulas (Z-1) to (Z-4).

(In equations (Z-1) to (Z-4),
R is
Hydrogen atom,
Halogen atom,
Alkyl groups, which may have substituents,
Cycloalkyl groups, which may have substituents,
An alkenyl group which may have a substituent,
Cycloalkenyl groups, which may have substituents,
An alkynyl group, which may have a substituent,
A cycloalkynyl group which may have a substituent,
Aryl groups, which may have substituents,
Alkyloxy groups, which may have substituents,
Cycloalkyloxy groups, which may have substituents,
Aryloxy groups, which may have substituents,
Alkylthio groups, which may have substituents,
Cycloalkylthio groups, which may have substituents,
An arylthio group, which may have a substituent,
A monovalent heterocyclic group which may have a substituent,
Substituted amino groups, which may have substituents,
Imine residues, which may have substituents,
An amide group which may have a substituent,
An acidimide group, which may have a substituent,
Substituted oxycarbonyl group, which may have a substituent,
Cyano group,
Nitro group,
Represents a group represented by -C (= O) -R ^a or a group represented by -SO ₂ -R ^b .
R ^a and R ^b are independent of each other.
Hydrogen atom,
Alkyl groups, which may have substituents,
Cycloalkyl groups, which may have substituents,
Aryl groups, which may have substituents,
Alkyloxy groups, which may have substituents,
Cycloalkyloxy groups, which may have substituents,
Represents an aryloxy group which may have a substituent or a monovalent heterocyclic group which may have a substituent.
In the formulas (Z-1) to (Z-4), the two Rs may be the same or different. ))) An organic photoelectric conversion element including the first electrode, the film according to claim 4, and the second electrode in this order. A photodetection element comprising the organic photoelectric conversion element according to claim 5.

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