JP2012023324A - Composition containing polymer compound having fullerene structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition capable of producing an organic photoelectric conversion element having a sufficiently high open end voltage (Voc).SOLUTION: The composition contains a polymer compound and an electron donative compound which can be synthesized by reacting polymer compound containing a chloromethylphenyl ethylene group as a repeating unit and fullerene. The electron donative compound is preferably a polymer compound having one kind or more of groups selected from a group made of a thiophenediyl group and a fluorenediyl group.

Description

  The present invention relates to a composition containing a polymer compound having a fullerene structure and an organic photoelectric conversion device using the same.

  Organic semiconductor materials having charge (electron, hole) transport properties are being studied for application to organic photoelectric conversion elements (organic solar cells, optical sensors, etc.). For example, organic semiconductors using compositions containing fullerene derivatives are used. Solar cells are being considered. For example, it contains [6,6] -phenyl C61-butyric acid methyl ester (hereinafter sometimes referred to as [60] -PCBM) which is a fullerene derivative and poly (3-hexylthiophene) which is an electron donating compound. A composition is known (see Non-Patent Document 1).

Advanced Functional Materials, 2003, Vol. 13, p. 85

  However, an organic photoelectric conversion element having an organic layer composed of [60] -PCBM and an electron donating compound has a problem that the open-circuit voltage (Voc) is not always sufficient.

  Then, an object of this invention is to provide the composition which can produce the organic photoelectric conversion element whose open-circuit voltage (Voc) is high enough.

（１）
（式中、Ａ環は、炭素数６０以上のフラーレン骨格を表す。ｐは、０〜１０の整数を表す。） That is, the present invention first provides a composition comprising a polymer compound having a repeating unit represented by the formula (1) and an electron donating compound.

(1)
(In the formula, ring A represents a fullerene skeleton having 60 or more carbon atoms. P represents an integer of 0 to 10.)

  The present invention secondly provides the composition, wherein the electron donating compound is a polymer compound having one or more groups selected from the group consisting of a thiophenediyl group and a fluorenediyl group.

  Thirdly, the present invention provides an organic photoelectric conversion element having a pair of electrodes and an organic layer containing the composition provided between the electrodes.

  An organic photoelectric conversion element having an organic layer containing the composition of the present invention has a high open-circuit voltage (Voc), and is therefore suitable for an organic thin film solar cell or an organic photosensor, and the present invention is extremely useful. is there.

  Hereinafter, the present invention will be described in detail.

<Composition>
The composition of this invention contains the high molecular compound which has a repeating unit represented by Formula (1), and an electron-donating compound.

  In formula (1), the A ring represents a fullerene skeleton having 60 or more carbon atoms. Specifically, a fullerene skeleton having 60 carbon atoms, a fullerene skeleton having 70 carbon atoms, and a fullerene skeleton having 84 carbon atoms can be given. Part of the fullerene skeleton having 60 or more carbon atoms may be modified. p represents an integer of 0 to 10.

  The polymer compound having a repeating unit represented by the formula (1) of the present invention includes, for example, a polymer compound containing a chloromethylphenylethylene group as a repeating unit and fullerene, Journal of Applied Polymer Science (Journal of Applied Polymer Science). Science), 2010, 116, p. It can synthesize | combine by making it react by the method shown by 433-440.

The fullerene used in the reaction is preferably C ₆₀ fullerene or C ₇₀ fullerene from the viewpoint of easy availability of raw materials.

  The high molecular compound which has a repeating unit represented by Formula (1) may contain repeating units other than the repeating unit represented by Formula (1). Examples of the repeating unit include a repeating unit derived from a compound having an ethylene structure. Examples of the compound having an ethylene structure include ethylene, butylene, styrene, acrylonitrile, acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester, and maleic anhydride.

  The electron donating compound is preferably a polymer compound from the viewpoint of coatability. Examples of the polymer compound include polyvinyl carbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having an aromatic amine in the side chain or main chain, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyphenylene Examples include vinylene and its derivatives, polythienylene vinylene and its derivatives, and polyfluorene and its derivatives.

（１０） （１１）
[式中、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴及びＲ¹⁵は、同一又は相異なり、水素原子、アルキル基、アルコキシ基又はアリール基を表す。] The electron donating compound used in the organic photoelectric conversion element is preferably a polymer compound having one or more groups selected from the group consisting of a thiophenediyl group and a fluorenediyl group from the viewpoint of photoelectric conversion efficiency. Especially, it is preferable that it is a high molecular compound which has 1 or more types of repeating units chosen from the group which consists of the repeating unit represented by Formula (10), and the repeating unit represented by Formula (11), Formula (10) It is more preferable that the polymer compound has a repeating unit represented by:

(10) (11)
[Wherein, R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are the same or different and are a hydrogen atom, an alkyl group, an alkoxy group or an aryl group. Represents a group. ]

The alkyl group represented by R ^{6 to} R ¹⁵ usually has 1 to 20 carbon atoms, may be linear or branched, and may be a cycloalkyl group. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, tert-butyl group, sec-butyl group, 3-methylbutyl group, n -Pentyl group, n-hexyl group, 2-ethylhexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-lauryl group can be mentioned. The hydrogen atom in the alkyl group may be substituted with a halogen atom, and specific examples include a monohalomethyl group, a dihalomethyl group, a trihalomethyl group, a pentahaloethyl group, and the like. Of the halogen atoms, it is preferably substituted with a fluorine atom. Specific examples of the alkyl group in which a hydrogen atom is substituted with a fluorine atom include a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group, a perfluorohexyl group, and a perfluorooctyl group.

The alkoxy group represented by R ^{6 to} R ¹⁵ usually has 1 to 20 carbon atoms, may be linear or branched, and may be a cycloalkyloxy group. Specific examples of the alkoxy group include methoxy group, ethoxy group, n-propyloxy group, i-propyloxy group, n-butoxy group, i-butoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy. Group, n-hexyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group, 3,7-dimethyloctyloxy group, n -Lauryloxy group is mentioned. A hydrogen atom in the alkoxy group may be substituted with a halogen atom. Of the halogen atoms, it is preferably substituted with a fluorine atom. Specific examples of the alkoxy group in which a hydrogen atom is substituted with a fluorine atom include a trifluoromethoxy group, a pentafluoroethoxy group, a perfluorobutoxy group, a perfluorohexyloxy group, and a perfluorooctyloxy group.

The aryl group represented by R ^{6 to} R ¹⁵ usually has 6 to 60 carbon atoms and may have a substituent. Examples of the substituent that the aryl group has include a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, a linear or branched chain having 1 to 20 carbon atoms. Or an alkoxy group containing a cycloalkyl group having 1 to 20 carbon atoms in its structure. Specific examples of the aryl group include a phenyl group, a C _{1 to} C ₁₂ alkoxyphenyl group (C _{1 to} C ₁₂ represents ₁ to ₁₂ carbon atoms, and the same applies to the following), C ₁ to C. Examples thereof include a ₁₂ alkylphenyl group, a 1-naphthyl group, and a 2-naphthyl group, preferably an aryl group having 6 to 20 carbon atoms, and more preferably a C _{1 to} C ₁₂ alkoxyphenyl group and a C _{1 to} C ₁₂ alkylphenyl group. A hydrogen atom in the aryl group may be substituted with a halogen atom. Of the halogen atoms, it is preferably substituted with a fluorine atom.

In formula (10), from the viewpoint of photoelectric conversion efficiency, at least one of R ⁶ and R ⁷ is preferably an alkyl group having 1 to 20 carbon atoms, and preferably an alkyl group having 4 to 8 carbon atoms. More preferred.

In formula (11), R ^{10 to} R ¹⁵ are preferably hydrogen atoms from the viewpoint of ease of monomer synthesis. From the viewpoint of photoelectric conversion efficiency, R ⁸ and R ⁹ are preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and an alkyl group having 5 to 8 carbon atoms or a carbon number. More preferably, it is a 6-15 aryl group.

  The polymer compound having a repeating unit represented by the formula (1) contained in the composition of the present invention is preferably 10 to 1000 parts by weight, and 50 to 500 parts per 100 parts by weight of the electron donating compound. More preferred are parts by weight.

<Organic photoelectric conversion element>
The organic photoelectric conversion device of the present invention has an organic layer containing a composition comprising a pair of electrodes, a polymer compound having a repeating unit represented by the formula (1) between the electrodes, and an electron donating compound. . Of the pair of electrodes, at least one of the electrodes is preferably transparent or translucent.

  Next, the operation mechanism of the organic photoelectric conversion element will be described. Light energy incident from a transparent or translucent electrode is absorbed by the electron-accepting compound and / or the electron-donating compound to generate excitons in which electrons and holes are combined. When the generated excitons move and reach the heterojunction interface where the electron-accepting compound and the electron-donating compound are adjacent to each other, electrons and holes are separated due to the difference in HOMO energy and LUMO energy at the interface. Electric charges (electrons and holes) that can move are generated. The generated charges can be taken out as electric energy (current) by moving to the electrodes.

  In the organic photoelectric conversion device of the present invention, an additional layer is provided between the electrode and an organic layer containing a composition containing a polymer compound having a repeating unit represented by formula (1) and an electron donating compound. May be provided. Examples of the additional layer include a charge transport layer that transports holes or electrons.

  An organic layer containing a composition containing a polymer compound having a repeating unit represented by formula (1) and an electron donating compound used in the organic photoelectric conversion device of the present invention is an organic thin film containing the composition. It is preferable that it is formed from. The thickness of the organic thin film is usually 1 nm to 100 μm, preferably 2 nm to 1000 nm, more preferably 5 nm to 500 nm, and further preferably 20 nm to 200 nm.

  The organic photoelectric conversion element of the present invention is usually formed on a substrate. The substrate may be any substrate that does not chemically change when the electrodes are formed and the organic layer is formed. Examples of the material for the substrate include glass, plastic, polymer film, and silicon. In the case of an opaque substrate, the opposite electrode (that is, the electrode far from the substrate) is preferably transparent or translucent.

  Examples of the material for the transparent or translucent electrode include a conductive metal oxide film and a translucent metal thin film. Specifically, a film formed using a conductive material made of indium oxide, zinc oxide, tin oxide, and indium tin oxide (ITO), indium zinc oxide, etc., which is a composite thereof, NESA Gold, platinum, silver, copper and the like are used, and ITO, indium / zinc / oxide, and tin oxide are preferable. Examples of the method for producing the electrode include a vacuum deposition method, a sputtering method, an ion plating method, a plating method, and the like. Moreover, you may use organic transparent conductive films, such as polyaniline and its derivative (s), polythiophene, and its derivative (s) as an electrode material.

  As the electrode material, one of the pair of electrodes is preferably a material having a small work function. An electrode including a material having a low work function may be transparent or translucent. Examples of the material include metals such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, And alloys of two or more of them, or one or more of them and one or more of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin, graphite or graphite Intercalation compounds are used. 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.

  The additional layer that may be provided between the electrode and the organic layer used in the present invention may be a buffer layer. Materials used as the buffer layer include alkali metals such as lithium fluoride, alkaline earth Examples thereof include metal halides and oxides such as titanium oxide. When an inorganic semiconductor is used, it can be used in the form of fine particles.

<Method for producing organic thin film>
The method for producing the organic thin film is not particularly limited, and examples thereof include a method by film formation from a solution containing the composition of the present invention and a solvent. Specifically, an organic thin film can be produced by applying the solution on one electrode.

  The solvent used for film formation from a solution is not particularly limited as long as it dissolves a polymer compound having a repeating unit represented by the formula (1). Examples of the solvent include hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decalin, bicyclohexyl, n-butylbenzene, sec-butylbezen, tert-butylbenzene, carbon tetrachloride, chloroform, dichloromethane, dichloroethane, Halogenated saturated hydrocarbon solvents such as chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane and bromocyclohexane, halogenated unsaturated hydrocarbon solvents such as chlorobenzene, dichlorobenzene and trichlorobenzene, tetrahydrofuran And ether solvents such as tetrahydropyran. The polymer compound having a repeating unit represented by the formula (1) can be usually dissolved in the solvent in an amount of 0.1% by weight or more.

  For film formation from solution, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen printing method, flexographic method Coating methods such as a printing method, an offset printing method, an ink jet printing method, a dispenser printing method, a nozzle coating method, a capillary coating method can be used, and a spin coating method, a flexographic printing method, an ink jet printing method, and a dispenser printing method are preferable.

  By irradiating light such as sunlight from a transparent or translucent electrode, the organic photoelectric conversion element generates a photovoltaic force between the electrodes and can be operated as an organic thin film solar cell. It can also be used as an organic thin film solar cell module by integrating a plurality of organic thin film solar cells.

  In addition, by applying light from a transparent or translucent electrode in a state where a voltage is applied between the electrodes, a photocurrent flows and it can be operated as an organic photosensor. It can also be used as an organic image sensor by integrating a plurality of organic photosensors.

  Examples will be shown below for illustrating the present invention in more detail, but the present invention is not limited to these examples.

(Measurement method of molecular weight)
In the following Examples, the molecular weight of the conjugated polymer compound was determined by GPC Laboratories GPC (PL-GPC2000). The conjugated polymer compound was dissolved in o-dichlorobenzene to a concentration of about 1% by weight. As the mobile phase of GPC, o-dichlorobenzene was used and allowed to flow at a measurement temperature of 140 ° C. at a flow rate of 1 mL / min. As the column, three PLGEL 10 μm MIXED-B (manufactured by PL Laboratory) were connected in series.

(Ａ) （Ｂ）

窒素雰囲気下、ジムロートコンデンサーを装着した１００ｍＬの３口フラスコに、銅粉を３９ｍｇ（０．６１ｍｍｏｌ）、臭化銅（Ｉ）を８．６ｍｇ（０．０６ｍｍｏｌ）、ビピリジルを９０ｍｇ（０．５８ｍｍｏｌ）入れた。次いで、真空ポンプにてフラスコ内を脱気し、その後、フラスコ内に窒素ガスを導入して常圧に戻す操作を行った。脱気及び常圧に戻す操作を５回繰り返し、フラスコ中の気体を窒素で十分に置換した。トルエン５０ｍＬに、Ｃ_６０フラーレンを３９ｍｇ（０．０５ｍｍｏｌ）、式（Ａ）で表されるスチレン−クロロメチルスチレン共重合体（製品番号６５９１７７、式（Ａ）中のｎ：ｍは１：１、シグマアルドリッチ社製）を３００ｍｇ加え、窒素バブリングをしながらよく攪拌した溶液を、シリンジでフラスコ内に加え、反応液を１００℃で２４時間加熱した。その後、反応液をメタノール１００ｍＬ中に注ぎ、沈殿物をろ取した後、沈殿物をイオン交換水１００ｍＬ、６Ｎの塩酸１００ｍＬ、二硫化炭素１００ｍＬでリパルプ洗浄し、得られた固体を１０ｍｍＨｇ、５０℃の条件で２時間減圧乾燥し、式（Ｂ）で表される高分子化合物１を２０８ｍｇ得た。 Synthesis example 1
(Synthesis of polymer compound 1)

(A) (B)

Under a nitrogen atmosphere, in a 100 mL three-necked flask equipped with a Dimroth condenser, 39 mg (0.61 mmol) of copper powder, 8.6 mg (0.06 mmol) of copper (I) bromide, and 90 mg (0.58 mmol) of bipyridyl I put it in. Next, the inside of the flask was evacuated with a vacuum pump, and then an operation of introducing nitrogen gas into the flask to return to normal pressure was performed. Degassing and returning to normal pressure were repeated 5 times, and the gas in the flask was sufficiently replaced with nitrogen. In 50 mL of toluene, 39 mg (0.05 mmol) of C ₆₀ fullerene, a styrene-chloromethylstyrene copolymer represented by formula (A) (product number 659177, n: m in formula (A) is 1: 1, Sigma Aldrich Co.) was added in an amount of 300 mg, and the solution well stirred while nitrogen bubbling was added to the flask with a syringe, and the reaction solution was heated at 100 ° C. for 24 hours. Thereafter, the reaction solution was poured into 100 mL of methanol, and the precipitate was collected by filtration. Then, the precipitate was repulped with 100 mL of ion exchange water, 100 mL of 6N hydrochloric acid, and 100 mL of carbon disulfide, and the resulting solid was 10 mmHg, 50 ° C. This was dried under reduced pressure for 2 hours to obtain 208 mg of the polymer compound 1 represented by the formula (B).

フラスコ内の気体をアルゴンで置換した２Ｌ四つ口フラスコに、化合物（Ｃ）を７．９２８ｇ（１６．７２ｍｍｏｌ）、化合物（Ｄ）を１３．００ｇ（１７．６０ｍｍｏｌ）、メチルトリオクチルアンモニウムクロライド（商品名：aliquat336（登録商標）、Aldrich製、CH₃N[(CH₂)₇CH₃]₃Cl、density 0.884g/ml，25℃）を４．９７９ｇ、及びトルエンを４０５ｍｌ入れ、撹拌しながら反応系内を３０分間アルゴンバブリングした。フラスコ内にジクロロビス（トリフェニルホスフィン）パラジウム（ＩＩ）を０．０２ｇ加え、１０５℃に昇温し、撹拌しながら２ｍｏｌ／Ｌの炭酸ナトリウム水溶液４２．２ｍｌを滴下した。滴下終了後５時間反応させ、反応液にフェニルボロン酸２．６ｇとトルエン１．８ｍｌとを加え、１０５℃で１６時間撹拌した。その後、反応液にトルエン７００ｍｌ及び７．５％ジエチルジチオカルバミン酸ナトリウム三水和物水溶液２００ｍｌを加え、８５℃で３時間撹拌した。反応液の水層を除去後、有機層を６０℃のイオン交換水３００ｍｌで２回、６０℃の３％酢酸３００ｍｌで１回、さらに６０℃のイオン交換水３００ｍｌで３回洗浄した。有機層をセライト、アルミナ及びシリカを充填したカラムに通し、ろ液を回収した。その後、熱トルエン８００ｍｌでカラムを洗浄し、洗浄後のトルエン溶液をろ液に加えた。得られた溶液を７００ｍｌまで濃縮した後、濃縮した溶液を２Ｌのメタノールに加え、重合体を再沈殿させた。重合体をろ過して回収し、５００ｍｌのメタノール、５００ｍｌのアセトン、５００ｍｌのメタノールで重合体を洗浄した。重合体を５０℃で一晩真空乾燥することにより、下記式：

で表されるペンタチエニル−フルオレンコポリマー（以下、「共役高分子化合物１」という）を１２．２１ｇ得た。共役高分子化合物１のポリスチレン換算の数平均分子量は５．４×１０⁴、ポリスチレン換算の重量平均分子量は１．１×１０⁵であった。 Synthesis example 2
(Synthesis of Conjugated Polymer Compound 1)

In a 2 L four-necked flask in which the gas in the flask was replaced with argon, 7.928 g (16.72 mmol) of compound (C), 13.00 g (17.60 mmol) of compound (D), methyltrioctylammonium chloride ( Product name: aliquat336 (registered trademark), manufactured by Aldrich, 4.979 g of CH ₃ N [(CH ₂ ) ₇ CH ₃ ] ₃ Cl, density 0.884 g / ml, 25 ° C.) and 405 ml of toluene are added and stirred. The reaction system was bubbled with argon for 30 minutes. 0.02 g of dichlorobis (triphenylphosphine) palladium (II) was added to the flask, the temperature was raised to 105 ° C., and 42.2 ml of a 2 mol / L sodium carbonate aqueous solution was added dropwise with stirring. After completion of the dropwise addition, the reaction was allowed to proceed for 5 hours, and 2.6 g of phenylboronic acid and 1.8 ml of toluene were added to the reaction solution, followed by stirring at 105 ° C. for 16 hours. Thereafter, 700 ml of toluene and 200 ml of 7.5% sodium diethyldithiocarbamate trihydrate aqueous solution were added to the reaction solution, followed by stirring at 85 ° C. for 3 hours. After removing the aqueous layer from the reaction solution, the organic layer was washed twice with 300 ml of ion exchanged water at 60 ° C., once with 300 ml of 3% acetic acid at 60 ° C., and further three times with 300 ml of ion exchanged water at 60 ° C. The organic layer was passed through a column packed with celite, alumina and silica, and the filtrate was recovered. Thereafter, the column was washed with 800 ml of hot toluene, and the washed toluene solution was added to the filtrate. After the obtained solution was concentrated to 700 ml, the concentrated solution was added to 2 L of methanol to reprecipitate the polymer. The polymer was recovered by filtration, and the polymer was washed with 500 ml of methanol, 500 ml of acetone, and 500 ml of methanol. By vacuum drying the polymer at 50 ° C. overnight, the following formula:

12.21 g of a pentathienyl-fluorene copolymer represented by the following (hereinafter referred to as “conjugated polymer compound 1”) was obtained. The conjugated polymer compound 1 had a polystyrene-equivalent number average molecular weight of 5.4 × 10 ⁴ and a polystyrene-equivalent weight average molecular weight of 1.1 × 10 ⁵ .

Example 1
(Production and evaluation of organic thin-film solar cells)
The conjugated polymer compound 1 was dissolved in o-dichlorobenzene at a concentration of 0.5% (weight%) as an electron donating compound. Thereafter, the polymer compound 1 as an electron-accepting compound was mixed in the solution so as to have an equal weight with respect to the weight of the electron-donating compound. Then, it filtered with the Teflon (trademark) filter with the hole diameter of 5.0 micrometers, and produced the application | coating solution.

A glass substrate provided with an ITO film with a thickness of 150 nm by a sputtering method was subjected to surface treatment by ozone UV treatment. Next, the coating solution was applied onto the ITO film by spin coating to obtain an active layer of an organic thin film solar cell. The thickness of the active layer was about 100 nm. Thereafter, heating was performed in a vacuum at 90 ° C. for 60 minutes. Then, lithium fluoride was vapor-deposited with a thickness of 4 nm by a vacuum vapor deposition machine, and then Al was vapor-deposited with a thickness of 100 nm. The degree of vacuum at the time of vapor deposition was 1 to 9 × 10 ⁻³ Pa in all cases. Moreover, the shape of the obtained organic thin film solar cell was a square of 2 mm × 2 mm. The open-circuit voltage (Voc) of the obtained organic thin-film solar cell was irradiated with constant light using a solar simulator (trade name OTENTO-SUNII: AM1.5G filter, irradiance 100 mW / cm ² , manufactured by Spectrometer Co., Ltd.). The current and voltage generated were measured and determined. The results are shown in Table 1.

Comparative Example 1
(Production and evaluation of organic thin-film solar cells)
The conjugated polymer compound 1 was dissolved in o-dichlorobenzene at a concentration of 0.5% (weight%) as an electron donating compound. Then, [6,6] -phenyl C61-butyric acid methyl ester ([60] -PCBM) (Phenyl C61-butyric acid methyl ester, manufactured by Frontier Carbon Corporation, trade name E100, lot number: 8A0125A) as an electron-accepting compound. The solution was mixed so as to be 0.75 times the weight of the electron donating compound. Further, a styrene-chloromethylstyrene copolymer represented by the formula (A) (product number 659177, n: m in the formula (A) is 1: 1, manufactured by Sigma-Aldrich) is used as the weight of the electron donating compound. The solution was mixed so that the weight was 0.25 times. Then, it filtered with the Teflon (trademark) filter with the hole diameter of 5.0 micrometers, and produced the application | coating solution.

  Except having used this coating solution, operation similar to Example 1 was performed, the organic thin film solar cell was produced, and the open circuit voltage was measured. The results are shown in Table 1.

Comparative Example 2
(Production and evaluation of organic thin-film solar cells)
As an electron-accepting compound, instead of the polymer compound 1, [6,6] -phenyl C61-butyric acid methyl ester ([60] -PCBM) (Phenyl C61-butyric acid methyl ester, manufactured by Frontier Carbon Corporation, trade name E100, Except having used lot number: 8A0125A), operation similar to Example 1 was performed, the organic thin-film solar cell was produced, and the open end voltage was measured. The results are shown in Table 1.

Claims (3)

A composition comprising a polymer compound having a repeating unit represented by formula (1) and an electron donating compound.

(1)
(In the formula, ring A represents a fullerene skeleton having 60 or more carbon atoms. P represents an integer of 0 to 10.)   The composition according to claim 1, wherein the electron donating compound is a polymer compound having one or more groups selected from the group consisting of a thiophenediyl group and a fluorenediyl group.   The organic photoelectric conversion element which has a pair of electrode and the organic layer containing the composition of Claim 1 or 2 provided between this electrode.