WO2015092909A1

WO2015092909A1 - Polymeric compound, organic photoelectric conversion element, and method for producing said element

Info

Publication number: WO2015092909A1
Application number: PCT/JP2013/084162
Authority: WO
Inventors: 豪志武藤; 近藤　健; 正樹堀江; 書維張
Original assignee: リンテック株式会社
Priority date: 2013-12-19
Filing date: 2013-12-19
Publication date: 2015-06-25
Also published as: JPWO2015092909A1; JP6199992B2; TW201538558A; TWI647250B

Abstract

Provided are: a polymeric compound which constitutes a bulk-hetero junction photoelectric conversion layer; an organic photoelectric conversion element which has a high photoelectric conversion efficiency, is achromatic and transparent, includes the polymeric compound, and has a photoelectric conversion layer; and a method for producing the organic photoelectric conversion element. The organic photoelectric conversion element is a bulk-hetero junction organic photoelectric conversion element which is composed of a photoelectric conversion layer that includes a polymeric compound represented by general formula (1) or general formula (2) and a C[70] fullerene derivative, and the method is a method for producing the same.

Description

Polymer compound, organic photoelectric conversion element, and method for producing the element

The present invention relates to a novel polymer compound, an organic photoelectric conversion device having a photoelectric conversion layer containing the polymer compound, and a method for producing the device.

In recent years, development related to power generation using thermal energy and energy other than nuclear power has been attracting attention for reasons such as the suppression of global warming and the substitution of nuclear power generation. Is being promoted on a global scale.

Under such circumstances, organic thin-film solar cells are lighter, more flexible, easier to manufacture at relatively low temperatures, and can have a larger area than silicon-based solar cells. It is attracting attention as a next-generation solar cell. However, the power generation efficiency of solar cells using organic thin films remains low compared to silicon-based solar cells, not only for home-use power generation, but also for outdoor use (under sunlight) for portable information terminals. Even in practical use as a battery source or a battery source for in-vehicle low power consumption devices, improvement of power generation conversion efficiency is an important issue. In addition, in recent years, attention has been focused on see-through type organic thin-film solar cells that can be installed in windows and used for daylighting, which is a function of windows, as well as power generation and cooling costs. Also, normally, as shown in Patent Document 1, a see-through organic thin-film solar cell has a first transparent electrode, a bulk heterojunction photoelectric conversion layer, and a second transparent electrode laminated on a substrate. It has a structure. For this reason, as the external color of the organic thin film solar cell, basically, the transmitted color of the photoelectric conversion layer (thin film) is dominantly reflected. Generally, as a bulk heterojunction photoelectric conversion layer used in an organic thin film solar cell, a mixture of a conjugated polymer such as poly-3-hexylthiophene (P3HT) and a fullerene derivative such as PCBM is used.

JP 2012-69803 A

However, bulk heterojunction photoelectric conversion layers used in organic thin film solar cells basically have a low transmittance of about 30%, and most of them are colored (chromatic colors). Moreover, even if the transmittance of the photoelectric conversion layer is improved, it basically leads to a decrease in light absorption efficiency in the visible light region of sunlight, and there is a problem that the conversion efficiency cannot be maintained. Furthermore, when installed on a window glass of a car or the like, the visibility is poor, and it is not practically sufficient from the viewpoint of safety.

In view of the above problems, the present invention provides a polymer compound that constitutes a bulk heterojunction photoelectric conversion layer, and an organic photoelectric conversion layer having a photoelectric conversion layer containing the polymer compound that has high photoelectric conversion efficiency and is achromatic and transparent. It is an object to provide a conversion element and a method for producing the organic photoelectric conversion element.

The present inventors have found that the above problems can be solved by using a bulk hetero-type photoelectric conversion layer containing the following polymer compound and C [70] fullerene derivative, and completed the present invention.
That is, the present invention provides the following [1] to [18].
[1] A polymer compound represented by the following general formula (1) or general formula (2).

(In formula (1) or formula (2), X represents a divalent structural unit represented by any of the following formulas (3) to (7), and Ra represents a hydrogen atom, a halogen atom, carbon R ₁ , R ₂ , R ₃ , and R ₄ each independently represents a hydrogen atom, a halogen atom, a C 1-16 alkyl group or a substituted alkyl group. Or an alkoxy group having 1 to 12 carbon atoms, n represents the number of repeating units, and is 2 to 100.)

(In the formula (4), Rb represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 16 carbon atoms or a substituted alkyl group. In the formula (7), Rc represents a hydrogen atom, a halogen atom, 1 to carbon atoms. 16 represents an alkyl group or a substituted alkyl group, and in formula (3), m represents the number of repeating units and is 1 to 5.
[2] R ₁ to R ₄ in the general formula (1) are an alkyl group or substituted alkyl group having 1 to 16 carbon atoms, and X is represented by the formula (3) or the formula (4). The polymer compound according to the above [1], which is a divalent structural unit and represented by the general formula (1).
[3] R ₁ to R ₄ in the general formula (2) are alkyl groups or substituted alkyl groups having 1 to 16 carbon atoms, and X is represented by the formula (3) or the formula (6). The polymer compound according to the above [1], which is a divalent structural unit and represented by the general formula (2).
[4] R ₁ to R ₄ in the general formula (1) are a C 1-16 alkyl group or substituted alkyl group, and X is a divalent structural unit represented by the following formula (8) The polymer compound according to the above [1] or [2] represented by the general formula (1).

[5] R ₁ to R ₄ in the general formula (2) are alkyl groups or substituted alkyl groups having 1 to 16 carbon atoms, and X is a divalent structural unit represented by the formula (6) The polymer compound according to the above [1] or [3], which is represented by the general formula (2).

[6] An organic photoelectric conversion device having a bulk hetero photoelectric conversion layer, wherein the bulk hetero photoelectric conversion layer is a polymer compound represented by the following general formula (1) or general formula (2) and C [70] fullerene An organic photoelectric conversion element comprising a derivative.

(In the formula (4), Rb represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 16 carbon atoms or a substituted alkyl group. In the formula (7), Rc represents a hydrogen atom, a halogen atom, 1 to carbon atoms. 16 represents an alkyl group or a substituted alkyl group, and in formula (3), m represents the number of repeating units and is 1 to 5.
[7] R ₁ to R ₄ in the general formula (1) are alkyl groups or substituted alkyl groups having 1 to 16 carbon atoms, and X is represented by the formula (3) or the formula (4). The organic photoelectric conversion device according to the above [6], which is a divalent structural unit.
[8] R ₁ to R ₄ in the general formula (2) are an alkyl group or substituted alkyl group having 1 to 16 carbon atoms, and X is represented by the formula (3) or the formula (6). The organic photoelectric conversion device according to the above [6], which is a divalent structural unit.
[9] R ₁ to R ₄ in the general formula (1) are alkyl groups or substituted alkyl groups having 1 to 16 carbon atoms, and X is a divalent structural unit represented by the following formula (8) The organic photoelectric conversion element according to the above [6] or [7].

[10] R ₁ to R ₄ in the general formula (2) are alkyl groups or substituted alkyl groups having 1 to 16 carbon atoms, and X is a divalent structural unit represented by the formula (6) The organic photoelectric conversion device according to the above [6] or [8].
[11] The mass ratio of the polymer compound represented by the general formula (1) or the general formula (2) constituting the bulk hetero photoelectric conversion layer and the C [70] fullerene derivative is 1: 2 to 1: 5. The organic photoelectric conversion device according to any one of [6] to [10], which is 5.
[12] The organic photoelectric conversion device according to any one of [6] to [11] above, wherein the C [70] fullerene derivative is PC [70] BM.
[13] The bulk hetero photoelectric conversion layer includes at least one of an aliphatic thiol represented by the following general formula (I) and an iodine compound represented by the following general formula (II). ] The organic photoelectric conversion element in any one of.

(Wherein, R _M represents an alkylene group having 3 to 15 carbon atoms, R _N denotes an alkylene group having 3 to 15 carbon atoms.)
[14] The organic photoelectric conversion element according to the above [13], wherein the aliphatic thiol is octanedithiol and the iodine compound is diiodooctane.
[15] The organic photoelectric conversion element according to any one of the above [6] to [14], wherein the bulk hetero photoelectric conversion layer has a visible light region transmittance of 100 nm and 50% or more.
[16] The bulk hetero photoelectric conversion layer has a thickness of 100 nm, a C light source and a 2 ° field of view in a CIE (International Commission on Illumination) L ^* a ^* b ^* color system defined in JIS Z 8729-1994. The organic photoelectric conversion device according to any one of [6] to [15] above, wherein a saturation C ^* value measured under conditions is 10 or less.
[17] An organic thin-film solar cell comprising the organic photoelectric conversion element according to any one of [6] to [16].
[18] A method for producing an organic photoelectric conversion device according to any one of [6] to [17],
Forming an electrode serving as an anode on a transparent substrate;
Forming a bulk hetero photoelectric conversion layer comprising the polymer compound represented by the general formula (1) or the general formula (2) and the C [70] fullerene derivative;
Forming a cathode electrode;
The manufacturing method of the organic photoelectric conversion element containing this.

According to the present invention, an organic photoelectric compound having a bulk hetero-type photoelectric conversion layer comprising the novel polymer compound constituting the bulk hetero-type photoelectric conversion layer, and having a high photoelectric conversion efficiency, an achromatic and transparent polymer, and the polymer. A conversion element can be provided.

It is sectional drawing which shows an example of the organic photoelectric conversion element of this invention. Bulk hetero-type photoelectric conversion layer comprising PC [70] BM and (1-1) or (2-1) which is the polymer compound of the present invention, and bulk comprising P3HT and PC [70] BM The transmission spectrum of a terror-type photoelectric conversion layer is shown. 1 shows an example of a photograph of the appearance of the present invention and a conventional bulk hetero photoelectric conversion layer, wherein the photograph of (a) contains P3HT (3-hexylthiophene) and PC [60] BM. The photograph on the left of (b) is a photograph of the bulk hetero photoelectric conversion layer containing the polymer compound (1-1) of the present invention and PC [70] BM, and the photograph on the right is It is a photograph of the photoelectric converting layer which consists of P3HT and PC [70] BM.

[Polymer compound]
The polymer compound of the present invention is represented by the following general formula (1) or general formula (2).

In the formula (1) or the formula (2), n represents the number of repeating units and is 2 to 100. When n is less than 2, the π-electron conjugated system does not extend sufficiently, so that sufficient solar light absorption efficiency cannot be obtained, which is not preferable. On the other hand, when n exceeds 100, the solubility in a solvent is lowered, and film formation by a wet method as described later becomes difficult. Therefore, n is preferably 5 to 90, more preferably 10 to 50.
In addition, said n is a value calculated based on the weight average molecular weight of a polymer, and the said weight average molecular weight is a value measured by the method as described in an Example.

In Formula (1) or Formula (2), R ₁ , R ₂ , R ₃ , and R ₄ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 16 carbon atoms or a substituted alkyl group, 1 to 12 alkoxy groups are shown.
Examples of the alkyl group having 1 to 16 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group (isomer) ), Hexyl group (including isomer), heptyl group (including isomer), octyl group (including isomer), nonyl group (including isomer), decyl group (including isomer), undecyl Groups (including isomers) and dodecyl groups (including isomers).
As the substituted alkyl group having 1 to 16 carbon atoms, a hydrogen atom of the above alkyl group is a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, an oxygen atom, a silicon atom, a sulfur atom, a phosphorus atom, or the like. And an alkyl group substituted with.
The alkoxy group having 1 to 12 carbon atoms is the same as the above alkyl group.
Among these, from the viewpoint of improving solubility in a solvent, an alkyl group having 1 to 16 carbon atoms or a substituted alkyl group is preferable, and an alkyl group is more preferable. R ₁ to R ₄ are preferably the same. Further, among the alkyl groups, an alkyl group having 6 to 15 carbon atoms is preferable, and a 2-ethylhexyl group is more preferable.

In formula (2), Ra represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 16 carbon atoms or a substituted alkyl group. The alkyl group having 1 to 16 carbon atoms or the substituted alkyl group is the same as R ₁ , R ₂ , R ₃ , and R ₄ described above. Among these, from the viewpoint of improving solubility in a solvent, an alkyl group having 1 to 16 carbon atoms or a substituted alkyl group is preferable, and an alkyl group is more preferable. Among the alkyl groups, an alkyl group having 6 to 15 carbon atoms is preferable, and an n-hexyl group is more preferable.

In formula (1) or formula (2), X represents a divalent structural unit represented by any of the following (3) to (7).

M in the formula (3) represents the number of repeating units and is 1 to 5. Preferably, it is 1 to 3, more preferably 2. Rb in the formula (4) represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 16 carbon atoms or a substituted alkyl group. The alkyl group having 1 to 16 carbon atoms or the substituted alkyl group is the same as R ₁ , R ₂ , R ₃ , and R ₄ described above. Among these, an alkyl group having 1 to 16 carbon atoms or a substituted alkyl group is preferable, and from the viewpoint of improving solubility in a solvent, an alkyl group having 6 to 15 carbon atoms is preferable, and an alkyl group having 6 to 10 carbon atoms is preferable. Is more preferable.
Rc in the formula (7) represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 16 carbon atoms or a substituted alkyl group. The alkyl group having 1 to 16 carbon atoms or the substituted alkyl group is the same as R ₁ , R ₂ , R ₃ , and R ₄ described above. Among these, an alkyl group having 1 to 16 carbon atoms or a substituted alkyl group is preferable, and from the viewpoint of improving solubility in a solvent, an alkyl group having 6 to 15 carbon atoms is more preferable, and an alkyl group having 6 to 10 carbon atoms is preferable. Groups are more preferred.

In Formula (1), X is preferably a divalent structural unit represented by Formula (3) or (4), and more preferably X is represented by Formula (8) below. Unit of value.

In formula (2), X is preferably a divalent structural unit represented by formula (3) or (6), more preferably X is represented by formula (6). Unit of value.

[Method of synthesizing polymer compound]
The polymer compound of the present invention can be synthesized by a known method and is not particularly limited. However, the polymer compound represented by the general formula (1) can be synthesized, for example, according to the following synthesis scheme. . That is, it can be synthesized by a method in which a monomer constituting the polymer compound is polymerized by a coupling reaction in the presence of a metal catalyst.

Step 1 is a step of synthesizing an intermediate by halogenating a starting material. Examples of the reagent used at that time include N-bromosuccinimide and the like.

In step 2, an intermediate and a monomer having a divalent structural unit X represented by any of the above formulas (3) to (7) are polymerized by a coupling reaction in the presence of a metal complex catalyst. This is a step of synthesizing the polymer compound of the invention. The reaction used in that case is not particularly limited, and for example, a Suzuki coupling reaction, a Still coupling reaction, or the like can be used.

It does not restrict | limit especially as a metal complex, For example, reduction catalysts, such as a copper complex, a nickel complex, and a palladium complex, are mentioned. Among these, a nickel complex and a palladium complex are preferable.
Examples of the nickel complex include bis (1,5-cyclooctadiene) nickel, tetrakis (triphenylphosphine) nickel, dichloro (2,2′-bipyridine) nickel, and among these, the viewpoint of polymerization performance Therefore, bis (1,5-cyclooctadiene) nickel is preferable.
Examples of the palladium complex include tetrakis (triphenylphosphine) palladium, dichloro {1,3-bis (diphenylphosphine) propane} palladium, tris (dibenzylidene) dipalladium and the like. Among these, tris (dibenzylidene) dipalladium is preferable from the viewpoint of polymerization performance.
In addition, you may use these metal complexes individually or in combination of 2 or more types.

Step 2 is usually performed in air or under an inert atmosphere, and preferably performed under an inert atmosphere. Examples of the inert atmosphere include nitrogen gas or argon gas atmosphere.
The polymerization reaction is not particularly limited, but is preferably performed under heating and reflux. The heating temperature is usually room temperature to 180 ° C., preferably 80 to 150 ° C., more preferably 80 to 120 ° C. Although there is no restriction | limiting in particular as a pressure at the time of a polymerization reaction, Usually, it carries out at a normal pressure.
The polymerization time is usually 1 to 240 hours, preferably 20 to 120 hours, although it varies depending on the type of monomer and catalyst used, the temperature and pressure during polymerization, and the like.

The polymer compound represented by the general formula (2) is prepared by, for example, the monomer constituting the polymer compound in the presence of a metal catalyst in the same manner as the method for synthesizing the polymer compound represented by the general formula (1). It can be synthesized by a method of polymerization by a coupling reaction.

That is, a starting material is halogenated to synthesize an intermediate, and the intermediate and a monomer having a divalent structural unit X represented by any one of the above formulas (3) to (7) are synthesized in the presence of a metal catalyst. The polymer compound represented by the general formula (2) can be synthesized by polymerizing by a coupling reaction to synthesize the polymer compound of the present invention. The reaction used at that time is not particularly limited, and for example, a Suzuki coupling reaction, a Still coupling reaction, a direct arylation reaction, or the like can be used.

[Organic photoelectric conversion element]
The organic photoelectric conversion element of the present invention is an organic photoelectric conversion element having a bulk hetero photoelectric conversion layer, and the bulk hetero photoelectric conversion layer is a polymer compound represented by the following general formula (1) and C [70] fullerene. It is an organic photoelectric conversion element containing a derivative.

FIG. 1 shows an example of a cross-sectional view of the organic photoelectric conversion element of the present invention. In FIG. 1, an organic photoelectric conversion element 1 is an organic photoelectric conversion element having a bulk hetero photoelectric conversion layer 3 between a pair of an anode 2 and a cathode 4 stacked on a transparent substrate (not shown).

An organic photoelectric conversion element is an element that generates an electromotive force when irradiated with light energy. Generally, an element that converts light energy into electrical energy is provided with an electrode for taking out electric charges from the photoelectric conversion layer. It is a thing. Examples of the organic photoelectric conversion element include various organic semiconductor devices such as an organic thin film solar cell and a photodiode. Among these, in this invention, it is suitable for an organic thin film solar cell.

In the organic photoelectric conversion device of the present invention, the bulk hetero photoelectric conversion layer includes the polymer compound represented by the general formula (1) or the general formula (2) and a C [70] fullerene derivative.

In the present invention, C [70] fullerene derivative refers to a concept including a compound in which at least part of which is modified for C ₇₀ fullerene and C ₇₀ fullerene carbon atoms is 70. Examples of the C [70] fullerene derivative include phenyl C71 butyric acid methyl ester (PC [70] BM) indene C70 monoadduct (IC [70] MA) and indene C70 bisadduct (IC [70] BA). Among these, phenyl C71 butyric acid methyl ester (PC [70] BM) is more preferable because the obtained bulk hetero type light conversion layer tends to be achromatic.
In addition, the bulk hetero photoelectric conversion layer is, for example, C60, C76, C78, C82, C84, C90, C94 as an n-type semiconductor material other than the C [70] fullerene derivative as long as the effects of the present invention are not impaired. Unsubstituted fullerene compounds, and derivatives thereof, 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTCDA), 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) 3,4,9,10-perylenetetracarboxylic bisbenzimidazole (PTCBI), N, N′-dioctyl-3,4,9,10-naphthyltetracarboxydiimide (PTCDI-C8H), 2- (4- Biphenylyl) -5- (4-tert-butylphenyl) -1,3,4-o Oxazole derivatives such as oxadiazole (PBD), 2,5-di (1-naphthyl) -1,3,4-oxadiazole (BND), 3- (4-biphenylyl) -4-phenyl-5- (4- Triazole derivatives such as t-butylphenyl) -1,2,4-triazole (TAZ), phenanthroline derivatives, phosphine oxide derivatives, carbon nanotubes (CNT), and derivatives obtained by introducing cyano groups into poly-p-phenylene vinylene polymers (CN-PPV), etc. may be included.

In the present invention, the bulk hetero photoelectric conversion layer preferably contains at least one of an aliphatic thiol represented by the following general formula (I) and an iodine compound represented by the following general formula (II).

(Wherein, R _M represents an alkylene group having 3 to 15 carbon atoms, R _N denotes an alkylene group having 3 to 15 carbon atoms.)
By including the aliphatic thiol and iodine compound, the solubility of the polymer compound (1) is improved, and the layer separation of the polymer compound and the C [70] fullerene derivative is promoted, thereby improving the conversion efficiency.
The mass ratio of the aliphatic thiol represented by the general formula (I) and the iodine compound represented by the general formula (II) and the polymer compound is 10: 1 to 1: 1, preferably 5: 1: 1 to 1: 1.

Examples of the aliphatic thiol include octanedithiol and butanedithiol. Of these, octanedithiol is preferred. Examples of the iodine compound include diiodooctane and diiodobutane. Among these, diiodooctane is preferable.

In the present invention, the mass ratio of the polymer compound represented by the general formula (1) or the general formula (2) and the C [70] fullerene derivative is 1: 1 to 1:10, preferably 1: 2 to 1: 5. A mass ratio in this range is preferable because an achromatic and transparent bulk hetero photoelectric conversion layer can be obtained.
In the above, the polymer compound represented by the general formula (1) or the general formula (2) has an absorption spectrum peak in the near infrared region, while the C [70] fullerene derivative has an absorption spectrum around 500 nm. Although it has a peak, by mixing both, it is thought that the absorption spectrum in the visible light region of the mixture becomes flat and does not have a clear peak.

The transmittance in the visible light region (near 550 nm) of the bulk hetero photoelectric conversion layer is preferably 50% or more, more preferably 60% or more, and even more preferably 70% or more when the thickness is 100 nm. When the transmittance is in the above range, the photoelectric conversion layer is highly transparent, and when it is installed as a solar cell on a window glass of a car, a building, or a general house, sunlight can be sufficiently collected and high visibility is obtained. Therefore, it is preferable.

The bulk hetero photoelectric conversion layer has a thickness of 100 nm and is measured with a C light source and a 2 ° viewing condition in a CIE (International Commission on Illumination) L ^* a ^* b ^* color system defined in JIS Z 8729-1994. The saturation C ^* value is preferably 10 or less, and more preferably 4 or less. A chroma C ^* value of 10 or less is preferable because it is less colored and approaches an achromatic color.

The thickness of the bulk hetero photoelectric conversion layer of the present invention is preferably 30 to 300 nm, and more preferably 50 to 150 nm. If the thickness is within this range, the photoelectric conversion layer is preferable because it is highly transparent and has an achromatic color.

The anode 2 is preferably a transparent electrode. For example, tin-doped indium oxide (ITO), IrO ₂ , In ₂ O ₃ , SnO ₂ , indium oxide-zinc oxide (IZO), ZnO (Ga, Al doped), MoO Examples thereof include a transparent semiconductor electrode formed of a material such as ₃ . The thickness of the electrode is preferably 50 to 200 nm, more preferably 70 to 150 nm.

Examples of the cathode 4 include Ag, Al, Pt, Ir, Cr, ZnO, CNT, and alloys and composites thereof.

The transmittance in the visible light region (near 550 nm) of the transparent substrate is preferably 80% or more, more preferably 85% or more, and further preferably 90% or more. Examples of the transparent substrate include glass and plastic substrates. The thickness of the transparent substrate is usually about 0.1 to 10 mm, and is selected from the viewpoint of mechanical strength, thermal expansion coefficient, weight, and cost, but is not particularly limited.

In addition, the organic photoelectric conversion element of the present invention includes a hole transport layer such as poly (3,4) -ethylenedioxythiophene / polystyrene sulfonate (PEDOT-PSS) between the anode 2 and the bulk hetero photoelectric conversion layer. It is preferable to provide a hole blocking layer such as bathocuproine between the bulk hetero photoelectric conversion layer and the cathode 4.

[Organic thin film solar cells]
The organic photoelectric conversion element of the present invention can be used as an organic thin film solar cell. The organic thin film solar cell including the organic photoelectric conversion element of the present invention has high photoelectric conversion efficiency, the bulk hetero type photoelectric conversion layer has high transparency and an achromatic appearance, and the sheath type organic thin film solar cell Can be used as

[Method for producing organic photoelectric conversion element]
The method for producing an organic photoelectric conversion element of the present invention includes a step of forming an electrode serving as an anode on a transparent substrate,
A step of forming a bulk hetero photoelectric conversion layer containing the polymer compound represented by the general formula (1) or the general formula (2) and the C [70] fullerene derivative, and a step of forming an electrode serving as a cathode. It is a manufacturing method of the organic photoelectric conversion element containing.

(1-1 Anode formation process)
The anode forming step in the present invention is a step of forming an electrode serving as an anode on a transparent substrate. As a method for forming the electrode, a general electrode forming method can be used. For example, a dry method such as a sputtering method, a vacuum evaporation method, an ion plating method, or the like, and when forming ITO, a wet method such as a dip coating method or a spin coating method of a solution containing ITO fine particles can be used.

(1-2 Photoelectric conversion layer forming step)
The photoelectric conversion layer forming step is a step of forming the bulk hetero photoelectric conversion layer 3 including the polymer compound represented by the general formula (1) or the general formula (2) and a C [70] fullerene derivative. Specifically, on the anode formed in the anode forming step, a polymer compound and C [70] fullerene derivative are dissolved in a solvent, a mixed and dispersed solution is applied, the solvent is dried, and bulk hetero photoelectric conversion is performed. Form a layer. The solvent is not particularly limited, and chlorobenzene, orthodichlorobenzene, chloroform, dichloromethane, toluene, tetrahydrofuran and the like can be used as described above. A method for forming the bulk hetero photoelectric conversion layer is not particularly limited, but a general wet thin film forming method can be used. For example, formation methods such as a dip coating method, a spin coating method, a gravure coating method, and a roll coating method are exemplified.

(1-3 cathode formation process)
The cathode forming step is a step of forming an electrode serving as a cathode on the bulk hetero photoelectric conversion layer formed in 1-2. As a method for forming an electrode to be a cathode, a general electrode forming method can be used. For example, a sputtering method, a vacuum deposition method, an ion plating method, or the like can be used.

(1-4 Hole transport layer formation process)
In the method for producing a photoelectric conversion element of the present invention, a step of forming a hole transport layer may be provided between the anode and the bulk hetero photoelectric conversion layer.
As a method for forming the hole transport layer, a general thin film forming method can be used. For example, the film is formed by a vacuum deposition method, a sputtering method, an ion plating method, or the like. In addition, the film may be formed by a wet method such as a dip coating method, a spin coating method, or a roll coating method.

(1-5 Hole blocking layer forming step)
In the method for producing a photoelectric conversion element of the present invention, a step of forming a hole blocking layer may be further provided between the photoelectric conversion layer and the cathode.
As a method for forming the previous hole blocking layer, a general thin film forming method can be used. For example, the film is formed by a vacuum deposition method, a sputtering method, an ion plating method, or the like.
An organic photoelectric conversion element can be manufactured by implementing the process shown above.

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

The measuring method concerning the high molecular compound performed in the Example is shown below.
(A) Weight average molecular weight measurement of polymer GPC apparatus [manufactured by Tosoh Corporation, apparatus name “HLC-8228GPC”, column: product name “SHODEX GPC KF-804L + GPC KF-805L”, column temperature: 40 ° C., detector: Using a UV detector (254 nm), eluent: THF, column flow rate: 1.0 ml / min, in terms of polystyrene], the polymer obtained has a weight average molecular weight (Mw) in terms of standard polystyrene and polydispersity of the polymer. The degree (Mw / Mn) was measured. The number of repeating units n was calculated from this weight average molecular weight.
(B) ¹ H-NMR measurement An FT-NMR apparatus (manufactured by JEOL, apparatus name “JNM-A500”) was used.

Evaluation of the transmittance in the visible light region, the saturation C ^*, and the photoelectric conversion efficiency of the photoelectric conversion element of the photoelectric conversion layers prepared in Examples and Comparative Examples was performed by the following methods.
A bulk hetero photoelectric conversion layer is formed on a synthetic quartz substrate by spin coating using the mixed solution for forming the bulk hetero photoelectric conversion layer used in Examples 3 to 6 and Comparative Examples 1 to 5 so as to have a thickness of 100 nm. A sample for measurement of transmittance and saturation C ^* was formed. Using the obtained sample, light transmittance evaluation and saturation evaluation were performed by the following methods.
(C) Light transmittance evaluation The UV-Vis-NIR light transmission spectrum of the bulk hetero photoelectric conversion layer formed on the synthetic quartz substrate was measured with a spectrophotometer (manufactured by Shimadzu Corporation, model number: UV-3600).
(D) Evaluation of saturation Using a spectrophotometer (manufactured by Shimadzu Corporation, model number: UV-3600), L ^* a ^* b ^* color system L ^* value, a ^* value, b ^* value of the photoelectric conversion layer Was measured. Further, using the obtained a ^* value and b ^* value, the saturation C ^* was calculated from Equation (1). The smaller the saturation C ^* , the less the coloring tends to be (closer to an achromatic color).

The measurement was performed in a CIE (International Commission on Illumination) L ^* a ^* b ^* color system defined in JIS Z 8729-1994, using a C light source and under 2 ° viewing conditions.
The above is generally classified according to the CIE (International Lighting Commission) L ^* a ^* b ^* color space. The three components of this system are: L ^* (indicating brightness on a scale 0-100), a ^* (red / magenta-green axis; positive values are red / magenta, negative values are green And b ^* (yellow-blue axis; positive values are yellow and negative values are blue).

(E) Photoelectric conversion efficiency evaluation A solar simulator (manufactured by Wacom Denso Co., model number: WXS-50S-1.5) and voltage-current generator (manufactured by ADC, R6243) while irradiating light of a uniform 100W tungsten lamp ) Were used to measure the short circuit current density (J _SC ) and the open circuit voltage (Voc). The obtained data was processed with solar cell characteristic measurement software (manufactured by System House Sunrise, product name: W32-R6244SOL-C) to calculate photoelectric conversion efficiency (PCE).

[Synthesis Example 1: Synthesis of oligomer (1a)]
4,4-bis (2-ethylhexyl) -4H-cyclopenta [2,1-b; 3,4-b ′] dithiophene 2.80 g (6.97 mmol), 4,7-dibromo-2,1,3- Benzothiadiazole 0.340 g (1.16 mmol), potassium carbonate 2.40 g (0.017 mol), Pd (OAc) ₂ 0.081 g (0.363 mmol) and vibalic acid 0.212 g (2.08 mmol) In a Schlenk tube, 100 mL of DMF was used for dissolution. The resulting solution was purged with nitrogen for 5 minutes, and the reaction mixture was stirred at 80 ° C. for 2 hours, and then directly dried under vacuum to distill off DMF from the organic layer. The reaction residue was purified by silica gel chromatography using hexane as an eluent. After concentration in vacuo, the residue was dissolved in 10 mL of chloroform, and the molecular weight was determined by SEC (size exclusion chromatography) (flow rate: 14 mL / min). Distribution was measured. By the above operation, the compound (1a) represented by the following formula was obtained as 0.485 g of a dark purple solid (yield 45%).
¹ H-NMR (500 MHz, CDCl ₃ ): δ 8.08, 8.06, 8.05 (s, 2H, 3-CPDT, peak ratio (racemic 2-ethylhexyl group) 1: 2: 1), 83 (s, 2H, BT), 7.21, 7.20 (d, 2H, J = 5.0 Hz, 6-CPDT), 6.99 (m, 2H, 5-CPDT), 1.98 ( _{m, 8H, CH 2),} 1.27 (m, 4H, CH), 1.03-0.84 (m, 32H, CH 2), 0.76 (t, J = 10.0 Hz, 12H, CH _3).
¹³ C NMR (125 MHz, CDCl ₃ ): δ 158.6, 158.3, 152.6, 139.1, 138.7, 137.0, 126.1 (CH), 125.3 (CH), 124.2 (CH), 122.6 (CH), 53.7 (4-CPDT), 43.3 (CH ₂ ), 35.2 (CH), 34.2, 28.7, 27.4 22.8 (CH ₂ ), 14.1, 10.7 (CH ₃ ).
FABMS: m / z = 937 [M] +.

[Synthesis Example 2: Synthesis of oligomer (1b)]
Oligomer (1a), 0.410 g (0.438 mmol), was dissolved in 4.0 mL of THF, and 0.172 g (0.966 mmol) of N-bromosuccinimide was dissolved in 5.0 mL of THF. Dropped into the solution. The resulting solution was stirred for 1 hour. The THF was distilled off under vacuum and the product was dissolved in hexane and purified by silica gel chromatography using hexane as the eluent. Furthermore, molecular weight distribution was measured by SEC using chloroform as an eluent. By the above operation, a compound (1b) represented by the following formula was obtained as 0.347 g of dark purple oil (yield 72%).
¹ H-NMR (500 MHz, CDCl ₃ ): δ 8.03, 8.01, 7.9 (s, 2H, 3-CPDT, peak ratio (racemic 2-ethylhexyl group) 1: 2: 1), 79 (s, 2H, BT), 6.98, 6.97, 6.96 (s, 2H, 5-CPDT, peak ratio (racemic 2-ethylhexyl group) 1: 2: 1), 1.991-1 .83 (m, 8H, CH ₂ ), 1.24 (m, 4H, CH), 1.03-0.59 (m, 32H, CH ₂ , CH3).
¹³ C NMR (125 MHz, CDCl ₃ ): δ 157.8, 157.0, 152.5, 139.5, 138.1, 137.3, 126.0, 125.4 (CH), 124.2 (CH), 122.5 (CH), 54.6 (4-CPDT), 43.1 (CH ₂ ), 35.2 (CH), 34.1, 28.5, 27.4, 22.8 _{(CH 2), 14.0, 10.7} (CH 3).
FABMS: m / z = 1095 [M] +.

[Synthesis Example 3: Synthesis of oligomer (2a)]
4,4-bis (2-ethylhexyl) -4H-cyclopenta [2,1-b; 3,4-b ′] dithiophene 1.63 g (4.06 mmol), 1,3-dibromo-5-hexyl-5H— Thienopyrrole-4,6-dione 0.200 g (0.508 mmol), potassium carbonate 0.352 g (1.27 mmol), Pd (OAc) ₂ 56 mg (0.25 mmol) and vivaric acid 76 mg (75 mmol) were added to 250 mL of Schlenk. In a tube, 45 mL of DMF was used for dissolution, and the resulting solution was purged with nitrogen for 5 minutes. The reaction mixture was stirred at 80 ° C. for 2 hours and then directly dried under vacuum in order to distill off DMF from the organic layer. The reaction residue was purified by silica gel chromatography using hexane and dichloromethane as eluents, concentrated in vacuo, dissolved in 10 mL chloroform, and SEC (size exclusion chromatography) (flow rate 14 mL / min). The molecular weight distribution was measured. By the above operation, a compound (2a) represented by the following formula was obtained as 228 mg of an orange-yellow oil (43% yield).
¹ H-NMR (500 MHz, CDCl ₃ ): δ 7.95, 7.91, 7.88 (s, 2H, 3-CPDT (cyclopenta [2,1-b; 3,4-b ′] dithiophene), peak Ratio (racemic 2-ethylhexyl group) 1: 2: 1), 7.25 (d, J = 5.0 Hz, 2H, 6-CPDT), 6.97 (m, 2H, 5-CPDT), 69 (t, 2H, J = 10.0 Hz, α proton of TPD (5H-thienopyrrole-4,6-dione)), 2.17? 0.61 (m, 49H, CH, CH ₂ , CH ₃ ) .
FABMS: m / z = 1038 [M] +.

[Synthesis Example 4: Synthesis of oligomer (2b)]
Oligomer (2a), 0.428 g (0.412 mmol) was dissolved in 10 mL of THF, 0.161 g (0.906 mmol) of N-bromosuccinimide was further dissolved in 10 mL of THF, and the oligomer (2a) was dissolved in THF under 0 ° C. It was dripped in. The resulting solution was stirred for 1 hour. The THF was then distilled off under vacuum and the product was dissolved in dichloromethane and purified by silica gel chromatography using hexane and dichloromethane as eluents. Furthermore, molecular weight distribution was measured by SEC using chloroform as an eluent. By the above operation, a compound (2b) represented by the following formula was obtained as 0.416 g of a pale yellow oil (yield 84%).
¹ H-NMR (500 MHz, CDCl ₃ ): δ 7.89, 7.86, 7.82 (s, 2H, 3-CPDT, peak ratio (racemic 2-ethylhexyl group) 1: 2: 1), 6. 98, 6.97, 6.96 (s, 2H, 5-CPDT, peak ratio (racemic 2-ethylhexyl group) 1: 2: 1), 3.66 (t, 2H, J = 7.5 Hz, TPD Α proton), 1.94 to 0.58 (m, 49H, CH, CH ₂ , CH ₃ ).
¹³ C NMR (125 MHz, CDCl ₃ ): δ 162.7, 158.3, 157.8, 140.5, 136.4, 132.2, 127.3, 125.4 (5-CPDT), 124 .4 (3-CPDT), 113.1, 54.7 (4-cyclopentadithiophene), 43.0, 38.6 (CH ₂ ), 35.2 (CH), 34.1, 31.4 , 28.6, 28.4, 27.4, 26.6, 22.8, 22.5 (CH ₂ ), 14.1, 14.0, and 10.7 (CH ₃ ).
FABMS: m / z = 1196 [M] +.

[Example 1: Synthesis of polymer compound (1-1)] Oligomer (1b), 130 mg (0.119 mmol), and 5,5′-bis (trimethylstannyl) -2,2′-bithiophene 58 mg (0. 119 mmol) was dissolved in 10 mL Schlenk tube using 1.8 mL anhydrous p-xylene and 0.6 mL anhydrous p-DMF. The solution was purged with argon gas for 30 minutes, and 6.9 mg (0.006 mmol) of tetrakis (triphenylphosphine) palladium (0) was added. The reaction mixture was stirred at 120 ° C. for 1 day and poured into 150 mL of methanol containing 8 mL of 37% hydrochloric acid. The precipitate was washed with ethanol and methyl ethyl ketone by Soxhlet extraction for 1 day and extracted into chloroform. The polymer chloroform solution was filtered through a silica gel column and precipitated into methanol. The precipitate was collected by a centrifuge (6000 rpm, 1 minute) and dried under vacuum to obtain a polymer compound (1-1) represented by the following formula as 0.110 g of a dark blue powder (yield 84). %).
¹ H-NMR (500 MHz, CDCl ₃ ): δ 8.05 (br, 2H, 3-CPDT), 7.81 (br, 2H, phenyl), 7.07 (br, 6H, 5-CPDT & bithiophene) , 1.97 (br, 8H, CH 2), 1.10? 0.60 (m, 30H, CH, CH 2, CH 3). GPC (THF, polystyrene standard solution): Mn = 27,600, Mw / Mn = 1.88.

[Example 2: Synthesis of polymer compound (2-1)]
Oligomer (2b), 98 mg (0.082 mmol), 2,1,3-benzothiadiazole-4,7-bis (boronic acid pinacol ester) 33 mg (0.086 mmol) Aqueous potassium carbonate 0.5 mL (2M), Aliquat 336 1 catalyst (catalyst) was dissolved in 1.6 mL of xylene in a 25 mL Schlenk tube. The solution was purged with argon gas for 30 minutes, and 4.74 mg (0.004 mmol) of tetrakis (triphenylphosphine) palladium (0) was added. The reaction was carried out by stirring at 90 ° C. for 1 day, 4-bromoanisole (0.2 eq) and benzeneboronic acid 2,2-dimethyltrimethylene ester (0.1 eq) were added, and the mixture was further stirred for 8 hours. did. Thereafter, the obtained mixture was poured into 150 mL of methanol containing 8 mL of 37% hydrochloric acid.
The precipitate was washed with ethanol and methyl ethyl ketone by Soxhlet extraction for 1 day and extracted into chloroform. The polymer chloroform solution was filtered through a silica gel column and precipitated into methanol. The precipitate was collected with a centrifuge (6000 rpm, 1 minute) and vacuum-dried to obtain a polymer compound (2-1) represented by the following formula as 0.067 g of a dark blue powder (yield 70). %).
¹ H NMR (500 MHz, CDCl ₃ ): δ 8.11 (br, 2H, thienyl), 7.97 (br, 2H, thienyl), 7.87 (br, 2H, phenyl), 3.70 (br _{, 2H, CH 2), 2.02-0.50} (br, 79H, CH, CH 2, CH 3). GPC (THF, polystyrene standard solution): Mn = 14,100, Mw / Mn = 2.04.

[Example 3]
2.3 mg of the polymer compound (1-1) as the p-type semiconductor, 6.6 mg of PC [70] BM (manufactured by Frontier Carbon Corporation, trade name “Nanom Spectra E110”) as the n-type semiconductor material, and 1,8 -6.6 mg of octanedithiol (manufactured by Tokyo Chemical Industry Co., Ltd.) was weighed, 0.66 mL of dehydrated chlorobenzene (manufactured by Sigma Aldrich, dehydrated product) was added under a nitrogen atmosphere, and the mixture was stirred under a nitrogen atmosphere for 24 hours. Next, the mixture was filtered through a syringe filter having a pore diameter of 0.45 μm to prepare a mixed solution for forming a photoelectric conversion layer (the mass ratio of the polymer compound (1-1): PC [70] BM was 1: 2.9). .
Next, a glass substrate with an ITO film cleaned by cleaning and UV-ozone treatment (a glass substrate with a transparent conductive film in which a tin-doped indium oxide film is formed on the glass substrate, surface resistivity: 14 (Ω / □)) In this way, PEDOT-PSS (manufactured by Clevios) is formed into a 20 nm film as a hole transport layer by the method described in the literature (Brabec, CJ et al., Advanced Materials, 2009, Vol. 21, page 1). And it formed so that the thickness of a photoelectric converting layer might be set to 100 nm by the spin coat method using the said mixed solution on the obtained positive hole transport layer. The surface of the obtained photoelectric conversion layer was a uniform and cloudless film.
Furthermore, 10 nm of calcium (manufactured by Kanto Chemical Co., Inc.) and 100 nm of aluminum (manufactured by High Purity Chemical Laboratories Co., Ltd.) on this photoelectric conversion layer (degree of vacuum: 8.2 × 10 ⁻⁵ Pa, film formation rate: 0.15 nm / s), the organic photoelectric conversion element 1 was produced by stacking in this order.
Using the obtained organic photoelectric conversion element 1, (e) photoelectric conversion efficiency evaluation mentioned above was performed and the photoelectric conversion efficiency (PCE) was computed. The results are shown in Table 1.

Further, (c) the light transmittance evaluation described above was performed, and the UV-Vis-NIR light transmission spectrum was measured. The results are shown in FIG. Table 1 shows the evaluation results of the visible light transmittance (550 nm) of the photoelectric conversion layer and the above-described evaluation of (d) saturation. In addition, the appearance of the photoelectric conversion layer is shown on the left side of FIG.

[Example 4]
Organic photoelectric conversion element 2 was produced in the same manner as in Example 3, except that polymer compound (2-1) was used instead of polymer compound (1-1) as the p-type semiconductor. Using the obtained organic photoelectric conversion element 2, (e) photoelectric conversion efficiency evaluation mentioned above was performed and the photoelectric conversion efficiency (PCE) was computed. The results are shown in Table 1.

Further, (c) the light transmittance evaluation described above was performed, and the UV-Vis-NIR light transmission spectrum was measured. The results are shown in FIG. Table 1 shows the evaluation results of the visible light transmittance (550 nm) of the photoelectric conversion layer and the above-described evaluation of (d) saturation.

[Example 5]
In Example 3, except that 1,8-diiodooctane (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 1,8-octanedithiol (manufactured by Tokyo Chemical Industry Co., Ltd.), the organic photoelectric conversion element 3 was prepared in the same manner as in Example 3. Produced. Using the obtained organic photoelectric conversion element 3, (e) photoelectric conversion efficiency evaluation mentioned above was performed and the photoelectric conversion efficiency (PCE) was computed. The results are shown in Table 1.

Further, (c) the light transmittance evaluation described above was performed, and the UV-Vis-NIR light transmission spectrum was measured. Table 1 shows the evaluation results of the visible light transmittance (550 nm) of the photoelectric conversion layer and the above-described (d) saturation.

[Example 6]
In Example 4, except that 1,8-diiodooctane (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 1,8-octanedithiol (manufactured by Tokyo Chemical Industry Co., Ltd.), the organic photoelectric conversion element 4 was prepared in the same manner as in Example 4. Produced. Using the obtained organic photoelectric conversion element 4, (e) photoelectric conversion efficiency evaluation mentioned above was performed and the photoelectric conversion efficiency (PCE) was computed. The results are shown in Table 1.

[Example 7]
In Example 3, an organic photoelectric conversion element 5 was produced in the same manner as in Example 3 except that the mass ratio of the polymer compound (1-1) to PC [70] BM was 1: 4. Using the obtained organic photoelectric conversion element 5, (e) photoelectric conversion efficiency evaluation mentioned above was performed and the photoelectric conversion efficiency (PCE) was computed. The results are shown in Table 1.

[Example 8]
In Example 4, the organic photoelectric conversion element 6 was produced in the same manner as in Example 4 except that the mass ratio of the polymer compound (2-1) and PC [70] BM was 1: 4. Using the obtained organic photoelectric conversion element 6, (e) photoelectric conversion efficiency evaluation mentioned above was performed and the photoelectric conversion efficiency (PCE) was computed. The results are shown in Table 1.

[Comparative Example 1]
An organic photoelectric conversion element 7 was produced in the same manner as in Example 3 except that PC [60] BM (trade name “Nanom Spectra E100H” manufactured by Frontier Carbon Co., Ltd.) was used as the n-type semiconductor material. Using the obtained organic photoelectric conversion element 7, (e) photoelectric conversion efficiency evaluation mentioned above was performed and the photoelectric conversion efficiency (PCE) was computed. The results are shown in Table 1.

[Comparative Example 2]
An organic photoelectric conversion element 8 was produced in the same manner as in Example 4 except that PC [60] BM (trade name “Nanom Spectra E100H” manufactured by Frontier Carbon Co., Ltd.) was used as the n-type semiconductor material. Using the obtained organic photoelectric conversion element 8, (e) photoelectric conversion efficiency evaluation mentioned above was performed and the photoelectric conversion efficiency (PCE) was computed. The results are shown in Table 1.

In addition, (c) the light transmittance evaluation described above was performed, and the UV-Vis-NIR light transmission spectrum was measured. Table 1 shows the evaluation results of the visible light transmittance (550 nm) of the photoelectric conversion layer and the above-described (d) saturation.

[Comparative Example 3]
An organic photoelectric conversion element 9 was produced in the same manner as in Example 3 except that 3-hexylthiophene (P3HT) was used instead of the polymer compound (1-1) as the p-type semiconductor. Using the obtained organic photoelectric conversion element 9, (e) photoelectric conversion efficiency evaluation mentioned above was performed and the photoelectric conversion efficiency (PCE) was computed. The results are shown in Table 1.

[Comparative Example 4]
An organic photoelectric conversion element 10 was produced in the same manner as in Comparative Example 1 except that P3HT was used instead of the polymer compound (1-1) as the p-type semiconductor. Using the obtained organic photoelectric conversion element 10, (e) photoelectric conversion efficiency evaluation mentioned above was performed and the photoelectric conversion efficiency (PCE) was computed. The results are shown in Table 1.

[Comparative Example 5]
In place of the polymer compound (1-1) as a p-type semiconductor, the polymer compound (1-1) contains a polymer compound (polymer of the oligomer (1a)) that does not contain X which is a divalent structural unit; An organic photoelectric conversion device 11 was produced in the same manner as in Example 3 except that. Using the obtained organic photoelectric conversion element 11, (e) photoelectric conversion efficiency evaluation mentioned above was performed and the photoelectric conversion efficiency (PCE) was computed. The results are shown in Table 1.

In the organic photoelectric conversion elements of the present invention used in Examples 3 to 8, the conversion efficiency is higher and the transparency is higher than that of the comparative example, and the value of chroma C ^* is small, which is close to an achromatic color. I understood that.

The organic photoelectric conversion device of the present invention is installed in a window of a car, a building, a general house, etc. It is possible to use.

1: Organic photoelectric conversion element 2: Anode 3: Bulk hetero photoelectric conversion layer 4: Cathode

Claims

The high molecular compound represented by the following general formula (1) or general formula (2).

(In formula (1) or formula (2), X represents a divalent structural unit represented by any of the following formulas (3) to (7), and Ra represents a hydrogen atom, a halogen atom, carbon R 1 , R 2 , R 3 , and R 4 each independently represents a hydrogen atom, a halogen atom, a C 1-16 alkyl group or a substituted alkyl group. Or an alkoxy group having 1 to 12 carbon atoms, n represents the number of repeating units, and is 2 to 100.)

(In the formula (4), Rb represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 16 carbon atoms or a substituted alkyl group. In the formula (7), Rc represents a hydrogen atom, a halogen atom, 1 to carbon atoms. 16 represents an alkyl group or a substituted alkyl group, and in formula (3), m represents the number of repeating units and is 1 to 5.
R 1 to R 4 in the general formula (1) are an alkyl group or substituted alkyl group having 1 to 16 carbon atoms, and X is a divalent group represented by the formula (3) or the formula (4). The high molecular compound of Claim 1 represented by General formula (1) which is a structural unit.
R 1 to R 4 in the general formula (2) are alkyl groups or substituted alkyl groups having 1 to 16 carbon atoms, and X is a divalent group represented by the formula (3) or the formula (6). The high molecular compound of Claim 1 represented by General formula (2) which is a structural unit.
R 1 to R 4 in the general formula (1) are alkyl groups or substituted alkyl groups having 1 to 16 carbon atoms, and X is a divalent structural unit represented by the following formula (8). The high molecular compound of Claim 1 or 2 represented by General formula (1).
R 1 to R 4 in the general formula (2) are an alkyl group having 1 to 16 carbon atoms or a substituted alkyl group, and X is a divalent structural unit represented by the formula (6). The high molecular compound of Claim 1 or 3 represented by General formula (2).
An organic photoelectric conversion element having a bulk hetero photoelectric conversion layer, wherein the bulk hetero photoelectric conversion layer comprises a polymer compound represented by the following general formula (1) or general formula (2) and a C [70] fullerene derivative: Including an organic photoelectric conversion element.

(In formula (1) or formula (2), X represents a divalent structural unit represented by any of the following formulas (3) to (7), and Ra represents a hydrogen atom, a halogen atom, carbon R 1 , R 2 , R 3 , and R 4 each independently represents a hydrogen atom, a halogen atom, a C 1-16 alkyl group or a substituted alkyl group. Or an alkoxy group having 1 to 12 carbon atoms, n represents the number of repeating units, and is 2 to 100.)

(In the formula (4), Rb represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 16 carbon atoms or a substituted alkyl group. In the formula (7), Rc represents a hydrogen atom, a halogen atom, 1 to carbon atoms. 16 represents an alkyl group or a substituted alkyl group, and in formula (3), m represents the number of repeating units and is 1 to 5.
R 1 to R 4 in the general formula (1) are an alkyl group or substituted alkyl group having 1 to 16 carbon atoms, and X is a divalent group represented by the formula (3) or the formula (4). The organic photoelectric conversion element according to claim 6, which is a structural unit.
R 1 to R 4 in the general formula (2) are alkyl groups or substituted alkyl groups having 1 to 16 carbon atoms, and X is a divalent group represented by the formula (3) or the formula (6). The organic photoelectric conversion element according to claim 6, which is a structural unit.
R 1 to R 4 in the general formula (1) are alkyl groups or substituted alkyl groups having 1 to 16 carbon atoms, and X is a divalent structural unit represented by the following formula (8). The organic photoelectric conversion element according to claim 6 or 7.
R 1 to R 4 in the general formula (2) are an alkyl group having 1 to 16 carbon atoms or a substituted alkyl group, and X is a divalent structural unit represented by the formula (6). The organic photoelectric conversion element of Claim 6 or 8.
The mass ratio of the polymer compound represented by the general formula (1) or the general formula (2) constituting the bulk hetero photoelectric conversion layer and the C [70] fullerene derivative is 1: 2 to 1: 5. The organic photoelectric conversion device according to any one of claims 6 to 10.
The organic photoelectric conversion device according to any one of claims 6 to 11, wherein the C [70] fullerene derivative is PC [70] BM.
The bulk hetero photoelectric conversion layer includes at least one of an aliphatic thiol represented by the following general formula (I) and an iodine compound represented by the following general formula (II). Organic photoelectric conversion element.

(Wherein, R M represents an alkylene group having 3 to 15 carbon atoms, R N denotes an alkylene group having 3 to 15 carbon atoms.)
The organic photoelectric conversion device according to claim 13, wherein the aliphatic thiol is octanedithiol and the iodine compound is diiodooctane.
The organic photoelectric conversion device according to any one of claims 6 to 14, wherein the bulk hetero photoelectric conversion layer has a visible light region transmittance of 50% or more at a thickness of 100 nm.
The bulk hetero photoelectric conversion layer has a thickness of 100 nm and is measured with a C light source and a 2 ° viewing condition in a CIE (International Commission on Illumination) L * a * b * color system defined in JIS Z 8729-1994. The organic photoelectric conversion device according to any one of claims 6 to 15, which has a saturation C * value of 10 or less.
An organic thin-film solar cell comprising the organic photoelectric conversion element according to any one of claims 6 to 16.
A method for producing an organic photoelectric conversion element according to any one of claims 6 to 17,
Forming an electrode serving as an anode on a transparent substrate;
Forming a bulk hetero photoelectric conversion layer comprising the polymer compound represented by the general formula (1) or the general formula (2) and the C [70] fullerene derivative;
Forming a cathode electrode;
The manufacturing method of the organic photoelectric conversion element containing this.