JP2011124361A - Organic photoelectric conversion element, solar battery and optical sensor array - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic photoelectric conversion element having high photoelectric conversion efficiency and high durability; and to provide a solar battery and an optical sensor array each having the element. <P>SOLUTION: The organic photoelectric conversion element has a layer containing a fullerene derivative represented by formula (1) and a p-type semiconductor material between a cathode and an anode. In the formula (1), a dotted line denotes an atomic group forming a cross-linking structure and R denotes a substituted group. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an organic photoelectric conversion element, a solar cell, and an optical sensor array, and more particularly to a bulk heterojunction type organic photoelectric conversion element, a solar cell using the organic photoelectric conversion element, and an optical array sensor.

  Due to the recent rise in fossil energy, there is a demand for a system that can generate power directly from natural energy. Solar cells using single-crystal / polycrystalline / amorphous Si, compound-based solar cells such as GaAs and CIGS, or Dye-sensitized photoelectric conversion elements (Gretzel cells) have been proposed and put into practical use.

  However, the cost of generating electricity with these solar cells is still higher than the price of electricity generated and transmitted using fossil fuels, which has hindered widespread use. In addition, since heavy glass must be used for the substrate, reinforcement work is required at the time of installation, which is one of the causes that increase the power generation cost.

  In such a situation, as a solar cell that can achieve a power generation cost lower than that of fossil fuel, an electron donor layer (p-type semiconductor layer) and an electron acceptor layer (n-type) are provided between the anode and the cathode. There has been proposed a bulk heterojunction photoelectric conversion element sandwiching a bulk heterojunction layer mixed with a semiconductor layer (for example, see Non-Patent Document 1).

  Since these bulk heterojunction photoelectric conversion elements are formed by a coating process except for the anode and cathode, it is expected that they can be manufactured at high speed and at low cost, and the above-mentioned problem of power generation cost can be solved. There is sex. Furthermore, unlike the above Si-based solar cells, compound semiconductor-based solar cells, dye-sensitized solar cells, etc., there is no process at a temperature higher than 160 ° C., so it is expected that it can be formed on a cheap and lightweight plastic substrate. Is done.

  In addition to the initial manufacturing cost, the power generation cost must be calculated including the power generation efficiency and the durability of the element. In Non-Patent Document 1, in order to efficiently absorb the solar spectrum, a long wavelength is used. By using an organic polymer capable of absorbing up to 5%, conversion efficiency exceeding 5% has been achieved.

  In such an environment, Non-Patent Document 2 reports that Voc is improved by using a bifunctional fullerene derivative as an n-type semiconductor. This is considered to be because the bifunctional fullerene derivative has a shallow LUMO level compared to the monofunctional fullerene derivative. However, in the said nonpatent literature 2, purification operation is performed in order to remove the produced | generated isomer. The operation is complicated, and in order to achieve low power generation cost, high-speed and low-cost manufacturing is possible, and higher power generation efficiency and element durability are required.

JP 2000-344664 A

A. Heeger, Nature Mat. vol. 6 (2007), p497 Adv. Mater. , Vol. 20 (2008), p2116 Acc. Chem. Res. 1999, 32, p537-545.

  The present invention has been made in view of the above problems, and an object thereof is to provide an organic photoelectric conversion element having high photoelectric conversion efficiency and durability, a solar cell having the same, and an optical sensor array. is there.

  In order to solve such a problem, the present inventors have taken an approach of introducing a cross-linked bifunctional group into a fullerene skeleton. As a result, the addition position to fullerene was limited by crosslinking two functional groups, and the number of isomers was successfully reduced.

  Surprisingly, when a solar battery cell was produced using the fullerene derivative compound of the present invention, higher conversion efficiency was obtained and higher durability was obtained as compared with the fullerene derivative described in Non-Patent Document 2. Since the functional groups are linked by a cross-linked structure, and the fullerene derivative can be regularly arranged in the mixed layer with the conductive polymer, it can be seen in monofunctional fullerenes and non-crosslinkable bifunctional fullerenes. It is speculated that this was due to the behavior that was not achieved.

  The idea of crosslinking the bifunctionalized fullerene derivative is described in Patent Document 1 and Non-Patent Document 3, but the application is limited to the notation of an electric device and an optical device, specifically to solar cells. There is no description about the use, and there is no suggestion or description about the control of Voc and the control of p / n domain formation, which are problems specific to the organic photoelectric conversion element.

  The above object of the present invention is achieved by the following configurations.

  1. An organic photoelectric conversion element comprising a layer containing a fullerene derivative represented by the general formula (1) and a p-type semiconductor material between a cathode and an anode.

(In the formula, the dotted line portion represents an atomic group forming a crosslinked structure. R represents a substituent)
2. 2. The organic photoelectric conversion element as described in 1 above, wherein the fullerene derivative represented by the general formula (1) is composed of fullerene C60.

3. 3. The organic photoelectric conversion device as described in 1 or 2 above, wherein R of the fullerene derivative represented by the general formula (1) is a structure represented by Ar.
(Here Ar represents a substituted or unsubstituted aromatic ring structure.)
4). 4. The organic photoelectric conversion device according to any one of 1 to 3, wherein the fullerene derivative represented by the general formula (1) has a cross-linked structure portion of 2 atoms or more and 15 atoms or less.

  5. 5. The organic photoelectric conversion device as described in 3 or 4 above, wherein the structure represented by Ar is a substituted or unsubstituted 6-membered ring structure.

  6). 6. The organic photoelectric conversion element as described in 5 above, wherein the structure represented by Ar is substituted with an electron donating group.

  7. 6. The organic photoelectric conversion device as described in 5 above, wherein the structure represented by Ar is substituted with an alkoxy group.

  8). 8. The organic photoelectric conversion device as described in 7 above, wherein the meta position of the structure represented by Ar is substituted with an alkoxy group.

  9. 9. The organic photoelectric conversion element as described in any one of 1 to 8 above, wherein the p-type semiconductor material is a conjugated polymer.

  10. The organic photoelectric conversion element has a bulk heterojunction layer made of an n-type semiconductor material and a p-type semiconductor material, and the fullerene derivative represented by the general formula (1) is contained in the bulk heterojunction layer. 10. The organic photoelectric conversion element according to any one of 1 to 9, which is characterized by the following.

  11. The organic photoelectric conversion element has a bulk heterojunction layer made of an n-type semiconductor material and a p-type semiconductor material, the fullerene derivative represented by the general formula (1) is contained in the bulk heterojunction layer, and the bulk 11. The organic photoelectric conversion device according to any one of 1 to 10, wherein the telojunction layer is formed by a solution process.

  12 It consists of the organic photoelectric conversion element of any one of said 1-11, The solar cell characterized by the above-mentioned.

  13. The organic photoelectric conversion element of any one of said 1-11 is arrange | positioned at array form, The optical sensor array characterized by the above-mentioned.

  According to the present invention, an organic photoelectric conversion element having high photoelectric conversion efficiency and durability, a solar cell including the organic photoelectric conversion element, and an optical sensor array can be provided.

It is sectional drawing which shows the solar cell which consists of a bulk hetero junction type organic photoelectric conversion element. It is sectional drawing which shows the solar cell which consists of an organic photoelectric conversion element provided with a tandem-type bulk heterojunction layer. It is sectional drawing which shows the solar cell which consists of an organic photoelectric conversion element provided with a tandem-type bulk heterojunction layer. It is a figure which shows the structure of an optical sensor array.

  DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments for carrying out the present invention will be described in detail, but the present invention is not limited thereto.

[N-type semiconductor materials]
In general, as an n-type semiconductor material that is an electron acceptor, for example, fullerene, octaazaporphyrin, and the like, a perfluoro body in which a hydrogen atom of a p-type semiconductor is substituted with a fluorine atom (perfluoropentacene, perfluorophthalocyanine, etc.), Examples thereof include aromatic carboxylic acid anhydrides such as naphthalenetetracarboxylic acid anhydride, naphthalenetetracarboxylic acid diimide, perylenetetracarboxylic acid anhydride, and perylenetetracarboxylic acid diimide, and polymer compounds containing an imidized product thereof as a skeleton. .

  However, among them, fullerene derivatives that can perform charge separation efficiently with various p-type semiconductor materials at high speed (˜50 fs) are preferable.

  Fullerene derivatives include fullerene C60, fullerene C70, fullerene C76, fullerene C78, fullerene C84, fullerene C240, fullerene C540, mixed fullerene, fullerene nanotubes, multi-walled nanotubes, single-walled nanotubes, nanohorns (conical), and the like. Partially by hydrogen atom, halogen atom, substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, cycloalkyl group, silyl group, ether group, thioether group, amino group, silyl group, etc. Examples thereof include substituted fullerene derivatives.

  Among them, [6,6] -phenyl C61-butyric acid methyl ester (abbreviation PCBM), [6,6] -phenyl C61-butyric acid-nbutyl ester (PCBnB), [6,6] -phenyl C61-buty Rick acid-isobutyl ester (PCBiB), [6,6] -phenyl C61-butyric acid-n hexyl ester (PCBH), Adv. Mater. , Vol. 20 (2008), p2116, etc., aminated fullerenes such as JP-A 2006-199674, metallocene fullerenes such as JP-A 2008-130889, and cyclics such as US Pat. No. 7,329,709. Fullerene derivatives having a substituent and having improved solubility, such as fullerene having an ether group, are known.

  As a result of intensive studies on a p-type semiconductor material and a fullerene derivative capable of separating charges more quickly and more efficiently, the organic photoelectric conversion element has a fullerene derivative represented by the following general formula (1), It has been found that the object can be achieved by using a fullerene derivative in which two functional groups substituted with fullerene are crosslinked.

  Such fullerene derivatives have a limited number of functional group introduction positions, and the number of isomers to be generated is significantly less than that of uncrosslinked fullerene derivatives. Therefore, it is possible to achieve both the shallow LUMO level and the orientation. As a result, the orientation within the bulk heterojunction layer is excellent, and high Jsc can be provided while maintaining Voc, and thus high conversion efficiency can be provided.

  [Fullerene derivative represented by general formula (1)]

  In the general formula (1), R represents an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, etc.), cycloalkyl group (for example, cyclohexyl group, cyclopentyl group, etc.) ), Alkenyl group, cycloalkenyl group, alkynyl group (for example, propargyl group), glycidyl group, acrylate group, methacrylate group, aromatic group (for example, phenyl group, naphthyl group, anthracenyl group, etc.), heterocyclic group (for example, , Pyridyl group, thiazolyl group, oxazolyl group, imidazolyl group, furyl group, pyrrolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, selenazolyl group, triphoranyl group, piperidinyl group, pyrazolyl group, tetrazolyl group, etc.), alkoxy group (for example, Methoxy group, ethoxy group, Propyloxy group, pentyloxy group, cyclopentyloxy group, hexyloxy group, cyclohexyloxy group, etc.), aryloxy group (eg, phenoxy group, etc.), alkoxycarbonyl group (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxy) Carbonyl group etc.), aryloxycarbonyl group (eg phenyloxycarbonyl group etc.), sulfonamide group (eg methanesulfonamide group, ethanesulfonamide group, butanesulfonamide group, hexanesulfonamide group, cyclohexanesulfonamide group, Benzenesulfonamido group, etc.), sulfamoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group) Group, cyclohexylaminosulfonyl group, phenylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), urethane group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, phenylureido group, 2-pyridylureido group) Etc.), acyl groups (eg acetyl group, propionyl group, butanoyl group, hexanoyl group, cyclohexanoyl group, benzoyl group, pyridinoyl group etc.), carbamoyl groups (eg aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl) Group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, phenylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), acylamino group (for example, acetyl) Sulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, phenylsulfonyl group, 2-pyridylsulfonyl group), amino group (for example, methylamino group, benzoylamino group, methylureido group, etc.) Amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, anilino group, 2-pyridylamino group, etc.), halogen atom (for example, chlorine atom, bromine atom, iodine atom etc.), cyano group, nitro group Group, sulfo group, carboxyl group, hydroxyl group, phosphono group (for example, phosphonoethyl group, phosphonopropyl group, phosphonooxyethyl group) and the like. Further, these groups may be further substituted with these groups.

  In addition, as described in claim 2, the fullerene derivative represented by the general formula (1) is preferably composed of fullerene C60 in order to enhance the effect of the present invention.

  In addition, Ar described in claim 3 represents a substituted or unsubstituted aromatic ring structure. Ar includes, for example, phenyl, indenyl, azulenyl, naphthyl, biphenyl, terphenylyl or quadphenylyl, as-indacenyl, s-indacenyl, acenaphthylenyl, phenanthryl, fluoranthenyl, triphenylenyl, chrysenyl, naphthacene, picenyl, perylenyl, pentaphenyl , Hexacenyl, pyrenyl, anthracenyl, thienyl, benzo [b] thienyl, dibenzo [b, d] thienyl, thiantenyl, furyl, furfuryl, 2H-pyranyl, benzofuranyl, isobenzofuranyl, 2H-chromenyl, xanthenyl, dibenzofuranyl, Phenoxythienyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, bipyridyl, triazinyl, pyrimidinyl, pyrazinyl, 1H-pyrrolidinyl, iso Ndolyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, 3H-indolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinnolinyl, indazolyl, purinyl, quinolidinyl, quinolyl, isoquinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinoxalinyl, quinoxalinyl Examples include carbazolyl, carbolinyl, benzotriazolyl, benzoxazolyl, phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl, or phenoxazinyl.

  The dotted line portion represents a substituted or unsubstituted atomic group having a terminal bonded to the apex of the three-membered ring and having a bridge structure. The atoms contained in the atomic group are not particularly limited.

  In the general formula (1), when the R moiety is substituted with an aromatic ring structure, the crystallinity of the compound is improved and the p / n domain forming ability is excellent. The crystallinity is better when substituted with a 6-membered ring than when substituted with a 5-membered ring.

  If the cross-linked portion is too short, the addition reaction of the second functional group to fullerene does not proceed due to steric hindrance between substituents. Therefore, the atomic group constituting the cross-linked portion is preferably 2 atoms or more. On the other hand, when the length is too long, the degree of freedom of the functional group introduction position increases, and it becomes difficult to limit the introduction position. Therefore, the atomic group in the dotted line portion preferably has 15 atoms or less.

  In the general formula (1), when the R moiety is substituted with a 6-membered ring structure, if the 6-membered ring is further substituted with an electron donating group, the LUMO of the fullerene derivative becomes shallow, and Voc as an organic photoelectric conversion device Will improve. Furthermore, this substituent is highly effective when it is substituted at the meta position.

  Specific examples of the fullerene derivative represented by the general formula (1) according to the present invention include the following compounds. However, it is not limited to these.

  These compounds are described in organic letter 2007 Vol. 9 No. 4 Synthesis is possible with reference to p551.

  The n-type semiconductor material of the present invention can be used by mixing a known n-type semiconductor material for the purpose of controlling crystallization, controlling the phase separation structure, controlling the morphology, and the like. Known n-type semiconductor materials include, for example, fullerene, octaazaporphyrin and the like, p-type semiconductor perfluoro compounds (perfluoropentacene, perfluorophthalocyanine, etc.), naphthalene tetracarboxylic anhydride, naphthalene tetracarboxylic acid diimide, perylene. Examples thereof include aromatic carboxylic acid anhydrides such as tetracarboxylic acid anhydride and perylenetetracarboxylic acid diimide, and polymer compounds containing the imidized product thereof as a skeleton.

[P-type semiconductor materials]
Examples of the p-type semiconductor material used in the bulk heterojunction layer of the present invention include various condensed polycyclic aromatic low-molecular compounds and conjugated polymers. In combination with the fullerene derivative of the present invention, conjugated polymers Is preferably used.

  Examples of the condensed polycyclic aromatic low molecular weight compound include anthracene, tetracene, pentacene, hexacene, heptacene, chrysene, picene, fluorene, pyrene, peropyrene, perylene, terylene, quaterylene, coronene, ovalene, circumanthanthene, bisanthene, zeslene. , Compounds such as heptazesulene, pyranthrene, violanthene, isoviolanthene, cacobiphenyl, anthradithiophene, porphyrin, copper phthalocyanine, tetrathiafulvalene (TTF) -tetracyanoquinodimethane (TCNQ) complex, bisethylenetetrathiafulvalene ( BEDTTTTF) -perchloric acid complexes, and derivatives and precursors thereof.

  Examples of the derivative having the above-mentioned condensed polycycle include WO 03/16599 pamphlet, WO 03/28125 pamphlet, US Pat. No. 6,690,029, JP 2004-107216 A. A pentacene derivative having a substituent described in JP-A No. 2003-136964, a pentacene precursor described in US Patent Application Publication No. 2003/136964, and the like; Amer. Chem. Soc. , Vol127. No. 14.4986, J. MoI. Amer. Chem. Soc. , Vol. 123, p9482; Amer. Chem. Soc. , Vol. 130 (2008), no. 9, acene-based compounds substituted with a trialkylsilylethynyl group described in 2706 and the like.

  As the conjugated polymer, for example, a polythiophene such as poly-3-hexylthiophene (P3HT) and an oligomer thereof, or a technical group described in Technical Digest of the International PVSEC-17, Fukuoka, Japan, 2007, P1225. Polythiophene, Nature Material, (2006) vol. 5, p328, polythiophene-thienothiophene copolymer, polythiophene-diketopyrrolopyrrole copolymer described in International Publication No. 2008/000664 pamphlet, Adv. Mater, 2007, p4160, polythiophene-thiazolothiazole copolymer, Nature Mat. vol. 6 (2007), p497 described in PCPDTBT, etc., polypyrrole and its oligomer, polyaniline, polyphenylene and its oligomer, polyphenylene vinylene and its oligomer, polythienylene vinylene and its oligomer, polyacetylene, polydiacetylene, Examples thereof include polymer materials such as σ-conjugated polymers such as polysilane and polygermane.

  In addition, oligomer materials instead of polymer materials include thiophene hexamer α-seccithiophene, α, ω-dihexyl-α-sexualthiophene, α, ω-dihexyl-α-kinkethiophene, α, ω-bis ( Oligomers such as 3-butoxypropyl) -α-sexithiophene can be preferably used.

  Among these compounds, compounds that have high solubility in organic solvents to the extent that solution processing is possible, can form a crystalline thin film after drying, and can achieve high mobility are preferable. More preferably, it is a compound (a compound capable of forming an appropriate phase separation structure) having appropriate compatibility with the fullerene derivative which is the n-type organic semiconductor material of the present invention.

  On the other hand, in order to obtain a thicker film, a thick film can be easily obtained if it can be further coated on a layer that has been coated once. When a layer is used by lamination by a solution process, there is a problem that the layer cannot be laminated because the underlying layer is dissolved. Therefore, a material that can be insolubilized after application by a solution process is preferable.

  Examples of such materials include materials that can be insolubilized by polymerizing the coating film after coating, such as polythiophene having a polymerizable group described in Technical Digest of the International PVSEC-17, Fukuoka, Japan, 2007, P1225. Or a material in which soluble substituents react and become insoluble (pigmented) by applying energy such as heat, as described in US Patent Application Publication No. 2003/136964, and Japanese Patent Application Laid-Open No. 2008-16834 Etc.

  Among these, materials that can be pigmented after coating with high mobility after insolubilization are preferable, and among them, porphyrin compounds described in JP-A-2008-16834 are preferably used. This porphyrin-based compound (BP-1 precursor) has four sterically bulky bicyclo groups at the molecular end at the time of coating. However, when energy such as heat is applied, the reverse Diels-Alder reaction is performed. Then, the bicyclo group part reacts to release 4 molecules of ethylene gas, which is converted into a benzoporphyrin derivative (BP-1) insoluble in the solvent.

  Examples of such a material that can be converted into an insoluble pigment after coating include compounds described in paragraph numbers 0044 and 0045 of JP-A-2008-16834.

  Such porphyrin-based compounds are disclosed in JP 2008-16834 A, Chem. Commun. 1998, p1661 etc. can be synthesized with reference.

[Configuration of organic photoelectric conversion element and solar cell]
Although the structure of the organic photoelectric conversion element and solar cell of this invention is demonstrated using figures, this invention is not limited to this.

  FIG. 1 is a cross-sectional view showing an example of a solar cell composed of a bulk heterojunction organic photoelectric conversion element. In FIG. 1, a bulk heterojunction organic photoelectric conversion element 10 has an anode 12, a hole transport layer 17, a bulk heterojunction layer photoelectric conversion section 14, an electron transport layer 18, and a cathode 13 in this order on one surface of a substrate 11. Are stacked.

  The substrate 11 is a member that holds the anode 12, the photoelectric conversion unit 14, and the cathode 13 that are sequentially stacked. In the present embodiment, since light that is photoelectrically converted enters from the substrate 11 side, the substrate 11 can transmit the light that is photoelectrically converted, that is, with respect to the wavelength of the light to be photoelectrically converted. It is a transparent member. As the substrate 11, for example, a glass substrate or a resin substrate is used. The substrate 11 is not essential. For example, the bulk heterojunction type organic photoelectric conversion element 10 may be configured by forming the anode 12 and the cathode 13 on both surfaces of the photoelectric conversion unit 14.

  The photoelectric conversion unit 14 is a layer that converts light energy into electric energy, and includes a bulk heterojunction layer in which a p-type semiconductor material and an n-type semiconductor material are uniformly mixed. The p-type semiconductor material functions relatively as an electron donor (donor), and the n-type semiconductor material functions relatively as an electron acceptor (acceptor). Here, the electron donor and the electron acceptor are “an electron donor in which, when light is absorbed, electrons move from the electron donor to the electron acceptor to form a hole-electron pair (charge separation state)”. And an electron acceptor ”, which does not simply donate or accept electrons like an electrode, but donates or accepts electrons by a photoreaction.

  In FIG. 1, light incident from the anode 12 through the substrate 11 is absorbed by the electron acceptor or electron donor in the bulk heterojunction layer of the photoelectric conversion unit 14, and electrons move from the electron donor to the electron acceptor. A hole-electron pair (charge separation state) is formed. The generated electric charge is caused by an internal electric field, for example, when the work function of the anode 12 and the cathode 13 is different, the electrons pass between the electron acceptors and the holes are electron donors due to the potential difference between the anode 12 and the cathode 13. The photocurrent is detected by passing through different electrodes to different electrodes. For example, when the work function of the anode 12 is larger than that of the cathode 13, electrons are transported to the anode 12 and holes are transported to the cathode 13. If the work function is reversed, electrons and holes are transported in the opposite direction. In addition, the transport direction of electrons and holes can be controlled by applying a potential between the anode 12 and the cathode 13.

  Although not shown in FIG. 1, other layers such as a hole blocking layer, an electron blocking layer, an electron injection layer, a hole injection layer, or a smoothing layer may be included.

  As a more preferable configuration, the photoelectric conversion unit 14 has a so-called p-i-n three-layer configuration (FIG. 2). A normal bulk heterojunction layer is a 14i layer composed of a mixture of a p-type semiconductor material and an n-type semiconductor layer, but a 14p layer composed of a single p-type semiconductor material and a 14n layer composed of a single n-type semiconductor material. By sandwiching, the rectification of holes and electrons becomes higher, loss due to recombination of charge-separated holes and electrons is reduced, and higher photoelectric conversion efficiency can be obtained.

  Furthermore, it is good also as a tandem-type structure which laminated | stacked such a photoelectric conversion element for the purpose of the improvement of sunlight utilization factor (photoelectric conversion efficiency). FIG. 3 is a cross-sectional view showing a solar cell composed of an organic photoelectric conversion element including a tandem bulk heterojunction layer. In the case of the tandem configuration, the anode 12 and the first photoelectric conversion unit 14 ′ are sequentially stacked on the substrate 11, the charge recombination layer 15 is stacked, the second photoelectric conversion unit 16, and then the cathode 13 are stacked. By stacking, a tandem structure can be obtained. The second photoelectric conversion unit 16 may be a layer that absorbs the same spectrum as the absorption spectrum of the first photoelectric conversion unit 14 'or may be a layer that absorbs a different spectrum, but is preferably a layer that absorbs a different spectrum. is there. Further, the first photoelectric conversion unit 14 ′ and the second photoelectric conversion unit 16 may both have the above-described three-layer configuration of pin.

[Method of forming bulk heterojunction layer]
Examples of a method for forming a bulk heterojunction layer in which an electron acceptor and an electron donor are mixed include a vapor deposition method and a coating method (including a casting method and a spin coating method). Among these, the coating method is preferable in order to increase the area of the interface where charges and electrons are separated from each other as described above and to produce a device having high photoelectric conversion efficiency. The coating method is also excellent in production speed.

  After coating, it is preferable to perform heating in order to cause removal of residual solvent, moisture and gas, and improvement of mobility and absorption longwave due to crystallization of the semiconductor material. When annealing is performed at a predetermined temperature during the manufacturing process, a part of the particles is microscopically aggregated or crystallized, and the bulk heterojunction layer can have an appropriate phase separation structure. As a result, the carrier mobility of the bulk heterojunction layer is improved and high efficiency can be obtained.

  The photoelectric conversion part (bulk heterojunction layer) 14 may be composed of a single layer in which the electron acceptor and the electron donor are uniformly mixed, but a plurality of the mixture ratios of the electron acceptor and the electron donor are changed. It may consist of layers. In this case, it can be formed by using a material that can be insolubilized after coating as described above.

[Hole Transport Layer / Electron Blocking Layer]
In the organic photoelectric conversion element 10 of the present invention, the charge generated in the bulk heterojunction layer can be taken out more efficiently between the bulk heterojunction layer and the anode. It is preferable to have.

  As a material constituting the hole transport layer 17, PEDOT such as trade name BaytronP, polyaniline and a doped material thereof, a cyan compound described in International Publication No. 2006/019270, etc. may be used. it can. Note that electrons generated in the bulk heterojunction layer do not flow to the anode side in the hole transport layer having a LUMO level shallower than the LUMO level of the n-type semiconductor material used for the bulk heterojunction layer. An electronic block function having a rectifying effect is provided. Such a hole transport layer is also called an electron block layer, and it is preferable to use a hole transport layer having such a function. As such a material, a triarylamine compound described in JP-A-5-271166 or a metal oxide such as molybdenum oxide, nickel oxide, or tungsten oxide can be used. Moreover, the layer which consists of a p-type semiconductor material single-piece | unit used for the bulk heterojunction layer can also be used. As a means for forming the hole transport layer, either a vacuum vapor deposition method or a solution coating method may be used, but a solution coating method is preferable. Forming the coating film in the lower layer before forming the bulk heterojunction layer is preferable because it has the effect of leveling the coating surface and reduces the influence of leakage and the like.

[Electron transport layer / hole blocking layer]
In the organic photoelectric conversion element 10 of the present invention, the charge generated in the bulk heterojunction layer can be taken out more efficiently between the bulk heterojunction layer 14 and the cathode 13. 18 is preferably formed.

  The electron transport layer 18 may be octaazaporphyrin or a p-type semiconductor perfluoro compound (perfluoropentacene, perfluorophthalocyanine, etc.). Similarly, a p-type semiconductor used for a bulk heterojunction layer. The electron transport layer having a HOMO level deeper than the HOMO level of the material is provided with a hole blocking function having a rectifying effect that prevents holes generated in the bulk heterojunction layer from flowing to the cathode side. The Such an electron transport layer is also called a hole blocking layer, and it is preferable to use an electron transport layer having such a function. Examples of such materials include phenanthrene compounds such as bathocuproine, n-type semiconductor materials such as naphthalenetetracarboxylic acid anhydride, naphthalenetetracarboxylic acid diimide, perylenetetracarboxylic acid anhydride, perylenetetracarboxylic acid diimide, and titanium oxide. N-type inorganic oxides such as zinc oxide and gallium oxide, and alkali metal compounds such as lithium fluoride, sodium fluoride, and cesium fluoride can be used. A layer made of a single n-type semiconductor material used for the bulk heterojunction layer can also be used. The means for forming these layers may be either a vacuum deposition method or a solution coating method, but is preferably a solution coating method.

[Other layers]
For the purpose of improving energy conversion efficiency and improving the lifetime of the element, a structure having various intermediate layers in the element may be employed. Examples of the intermediate layer include a hole block layer, an electron block layer, a hole injection layer, an electron injection layer, an exciton block layer, a UV absorption layer, a light reflection layer, and a wavelength conversion layer.

〔anode〕
In the present invention, the anode means an electrode for extracting holes. For example, when used as an anode, it is preferably an electrode that transmits light of 380 to 800 nm. As the material, for example, transparent conductive metal oxides such as indium tin oxide (ITO), SnO ₂ and ZnO, metal thin films such as gold, silver and platinum, metal nanowires and carbon nanotubes can be used.

  Also selected from the group consisting of derivatives of polypyrrole, polyaniline, polythiophene, polythienylene vinylene, polyazulene, polyisothianaphthene, polycarbazole, polyacetylene, polyphenylene, polyphenylene vinylene, polyacene, polyphenylacetylene, polydiacetylene and polynaphthalene. Conductive polymers can also be used. Further, a plurality of these conductive compounds can be combined to form an anode.

〔cathode〕
In the present invention, the cathode means an electrode for taking out electrons. For example, when used as a cathode, the conductive material may be a single layer, but in addition to a conductive material, a resin that holds these may be used in combination. As a conductive material for the cathode, a material having a work function (4 eV or less) metal, alloy, electrically conductive compound, and a mixture thereof as an electrode material is used. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like. Among these, from the viewpoint of electron extraction performance and durability against oxidation, etc., a mixture of these metals and a second metal which is a stable metal having a larger work function value than this, for example, a magnesium / silver mixture, magnesium / Aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred. The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The film thickness is usually selected in the range of 10 nm to 5 μm, preferably 50 to 200 nm.

  If a metal material is used as the conductive material of the cathode, the light coming to the cathode side is reflected and reflected to the first electrode side, and this light can be reused and absorbed again by the photoelectric conversion layer, further improving the photoelectric conversion efficiency. It is preferable.

  Further, the cathode 13 may be a metal (for example, gold, silver, copper, platinum, rhodium, ruthenium, aluminum, magnesium, indium, etc.), a nanoparticle made of carbon, a nanowire, or a nanostructure. A dispersion is preferable because a transparent and highly conductive cathode can be formed by a coating method.

  When the cathode side is made light transmissive, for example, a conductive material suitable for the cathode, such as aluminum and aluminum alloy, silver and silver compound, is formed with a thin film thickness of about 1 to 20 nm, and By providing a film of the conductive light-transmitting material mentioned in the description, a light-transmitting cathode can be obtained.

[Intermediate electrode]
In addition, the intermediate electrode material required in the case of the tandem configuration as shown in FIG. 3 is preferably a layer using a compound having both transparency and conductivity, and the material (ITO as used in the anode). , Transparent metal oxides such as AZO, FTO and titanium oxide, very thin metal layers such as Ag, Al and Au, or layers containing nanoparticles / nanowires, conductive polymer materials such as PEDOT: PSS, polyaniline, etc. ) Can be used.

  In addition, in the hole transport layer and the electron transport layer described above, there is also a combination that works as an intermediate electrode (charge recombination layer) by appropriately combining and laminating, and with such a configuration, the process of forming one layer This is preferable because it can be omitted.

〔substrate〕
When light that is photoelectrically converted enters from the substrate side, the substrate is preferably a member that can transmit the light that is photoelectrically converted, that is, a member that is transparent to the wavelength of the light to be photoelectrically converted. As the substrate, for example, a glass substrate, a resin substrate and the like are preferably mentioned, but it is desirable to use a transparent resin film from the viewpoint of light weight and flexibility. There is no restriction | limiting in particular in the transparent resin film which can be preferably used as a transparent substrate by this invention, The material, a shape, a structure, thickness, etc. can be suitably selected from well-known things. For example, polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) modified polyester, polyethylene (PE) resin film, polypropylene (PP) resin film, polystyrene resin film, polyolefin resins such as cyclic olefin resin Film, vinyl resin film such as polyvinyl chloride, polyvinylidene chloride, polyether ether ketone (PEEK) resin film, polysulfone (PSF) resin film, polyether sulfone (PES) resin film, polycarbonate (PC) resin film, A polyamide resin film, a polyimide resin film, an acrylic resin film, a triacetyl cellulose (TAC) resin film, and the like can be given. If the resin film transmittance of 80% or more at ~800nm), can be preferably applied to a transparent resin film according to the present invention. Among these, from the viewpoint of transparency, heat resistance, ease of handling, strength and cost, it is preferably a biaxially stretched polyethylene terephthalate film, a biaxially stretched polyethylene naphthalate film, a polyethersulfone film, or a polycarbonate film, and biaxially stretched. More preferred are polyethylene terephthalate films and biaxially stretched polyethylene naphthalate films.

  The transparent substrate used in the present invention can be subjected to a surface treatment or an easy adhesion layer in order to ensure the wettability and adhesiveness of the coating solution. A conventionally well-known technique can be used about a surface treatment or an easily bonding layer. For example, the surface treatment includes surface activation treatment such as corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, and laser treatment. Examples of the easy adhesion layer include polyester, polyamide, polyurethane, vinyl copolymer, butadiene copolymer, acrylic copolymer, vinylidene copolymer, and epoxy copolymer.

  In order to suppress permeation of oxygen and water vapor, a barrier coat layer may be formed in advance on the transparent substrate.

(Optical function layer)
The organic photoelectric conversion element of the present invention may have various optical functional layers for the purpose of more efficient reception of sunlight. As the optical functional layer, for example, a light condensing layer such as an antireflection film or a microlens array, or a light diffusion layer that can scatter light reflected by the cathode and enter the power generation layer again may be provided. .

  Various known antireflection layers can be provided as the antireflection layer. For example, when the transparent resin film is a biaxially stretched polyethylene terephthalate film, the refractive index of the easy adhesion layer adjacent to the film is 1.57. It is more preferable to set it to ˜1.63 because the interface reflection between the film substrate and the easy adhesion layer can be reduced and the transmittance can be improved. The method for adjusting the refractive index can be carried out by appropriately adjusting the ratio of the oxide sol having a relatively high refractive index such as tin oxide sol or cerium oxide sol and the binder resin. The easy adhesion layer may be a single layer, but may be composed of two or more layers in order to improve adhesion.

  As the condensing layer, for example, it is processed so as to provide a structure on the microlens array on the sunlight receiving side of the support substrate, or the amount of light received from a specific direction is increased by combining with a so-called condensing sheet. Conversely, the incident angle dependency of sunlight can be reduced.

  As an example of the microlens array, quadrangular pyramids having a side of 30 μm and an apex angle of 90 degrees are two-dimensionally arranged on the light extraction side of the substrate. One side is preferably 10 to 100 μm. If it becomes smaller than this, the effect of diffraction will generate | occur | produce and color, and if too large, thickness will become thick and is not preferable.

  Examples of the light scattering layer include various antiglare layers, layers in which nanoparticles or nanowires such as metals or various inorganic oxides are dispersed in a colorless and transparent polymer, and the like.

[Method of forming a bulk heterojunction layer in which an electron acceptor and an electron donor are mixed]
Examples of a method for forming a bulk heterojunction layer in which an electron acceptor and an electron donor are mixed include a vapor deposition method and a coating method (including a casting method and a spin coating method). Among these, in order to increase the area of the interface where charges and electrons are separated from each other as described above and to produce a device having high photoelectric conversion efficiency, a coating method by a solution process is preferable. The coating method is also excellent in production speed.

  Although there is no restriction | limiting in the coating method used in this case, For example, a spin coat method, the casting method from a solution, a dip coat method, a blade coat method, a wire bar coat method, a gravure coat method, a spray coat method etc. are mentioned. Furthermore, patterning can also be performed by a printing method such as an ink jet method, a screen printing method, a relief printing method, an intaglio printing method, an offset printing method, or a flexographic printing method.

  After coating, it is preferable to perform heating in order to cause removal of residual solvent, moisture and gas, and improvement of mobility and absorption longwave due to crystallization of the semiconductor material. When annealing is performed at a predetermined temperature during the manufacturing process, a part of the particles is microscopically aggregated or crystallized, and the bulk heterojunction layer can have an appropriate phase separation structure. As a result, the carrier mobility of the bulk heterojunction layer is improved and high efficiency can be obtained.

  The photoelectric conversion part (bulk heterojunction layer) 14 may be composed of a single layer in which the electron acceptor and the electron donor are uniformly mixed, but a plurality of the mixture ratios of the electron acceptor and the electron donor are changed. It may consist of layers. In this case, it can be formed by using a material that can be insolubilized after coating as described above.

[Patterning]
There are no particular limitations on the method and process for patterning the electrode, bulk heterojunction layer, hole transport layer, electron transport layer, etc. according to the present invention, and any known method can be applied as appropriate.

  If it is a soluble material such as a bulk heterojunction layer and a transport layer, only unnecessary portions may be wiped after the entire surface application such as die coating and dip coating, or directly at the time of application using a method such as ink jet method or screen printing. Patterning may be performed.

  In the case of an insoluble material such as an electrode material, the electrode can be patterned by a known method such as mask evaporation at the time of vacuum deposition or etching or lift-off. Alternatively, the pattern may be formed by transferring a pattern formed on another substrate.

[Sealing]
Moreover, since the produced organic photoelectric conversion element 10 is not deteriorated by oxygen, moisture, or the like in the environment, it is preferable to seal not only the organic photoelectric conversion element but also an organic electroluminescence element by a known method. For example, a method of sealing a cap made of aluminum or glass by bonding with an adhesive, a plastic film on which a gas barrier layer such as aluminum, silicon oxide, or aluminum oxide is formed and an organic photoelectric conversion element 10 are pasted with an adhesive. Method, spin coating of organic polymer material (polyvinyl alcohol, etc.) with high gas barrier property, inorganic thin film (silicon oxide, aluminum oxide, etc.) or organic film (parylene etc.) with high gas barrier property are deposited under vacuum Examples thereof include a method and a method of laminating these in a composite manner.

[Optical sensor array]
Next, an optical sensor array to which the bulk heterojunction type organic photoelectric conversion element 10 described above is applied will be described in detail. The optical sensor array is produced by arranging the photoelectric conversion elements in a fine pixel form by utilizing the fact that the bulk heterojunction type organic photoelectric conversion elements generate a current upon receiving light, and projected onto the optical sensor array. A sensor having an effect of converting an image into an electrical signal.

  FIG. 4 is a diagram showing the configuration of the photosensor array. 4A is a top view, and FIG. 4B is a cross-sectional view taken along the line A-A ′ of FIG.

  In FIG. 4, an optical sensor array 20 is paired with an anode 22 as a lower electrode, a photoelectric conversion unit 24 for converting light energy into electrical energy, and an anode 22 on a substrate 21 as a holding member. The cathode 23 is sequentially laminated. The photoelectric conversion unit 24 includes two layers, a photoelectric conversion layer 24b having a bulk heterojunction layer in which a p-type semiconductor material and an n-type semiconductor material are uniformly mixed, and a buffer layer 24a. In the example shown in FIG. 4, six bulk heterojunction type organic photoelectric conversion elements are formed.

  The substrate 21, the anode 22, the photoelectric conversion layer 24b, and the cathode 23 have the same configuration and role as the anode 12, the photoelectric conversion unit 14, and the cathode 13 in the bulk heterojunction photoelectric conversion element 10 described above.

  For example, glass is used for the substrate 21, ITO is used for the anode 22, and aluminum is used for the cathode 23, for example. For example, the P3HT is used as the p-type semiconductor material of the photoelectric conversion layer 24b, and the compound 115 of the present invention is used as the n-type semiconductor material, for example. The buffer layer 24a is made of PEDOT (poly-3,4-ethylenedioxythiophene) -PSS (polystyrene sulfonic acid) conductive polymer (trade name BaytronP, manufactured by Stark Vitec). Such an optical sensor array 20 was manufactured as follows.

  An ITO film was formed on the glass substrate by sputtering and processed into a predetermined pattern shape by photolithography. The thickness of the glass substrate was 0.7 mm, the thickness of the ITO film was 200 nm, and the measurement area (light receiving area) of the ITO film after photolithography was 0.5 mm × 0.5 mm. Next, a PEDOT-PSS film was formed on the glass substrate 21 by spin coating (conditions: rotational speed = 1000 rpm, filter diameter = 1.2 μm). Thereafter, the substrate was heated in an oven at 140 ° C. for 10 minutes and dried. The thickness of the PEDOT-PSS film after drying was 30 nm.

  Next, a 1: 1 mixed film of P3HT: Compound 115 of the present invention was formed on the PEDOT-PSS film by a spin coating method (conditions: rotational speed = 3300 rpm, filter diameter = 0.8 μm). In this spin coating, P3HT and the compound 115 of the present invention were mixed in a chlorobenzene solvent at a ratio of 1: 1, and a mixture obtained by stirring (5 minutes) was used. After forming a mixed film of P3HT and the compound 115 of the present invention, annealing was performed by heating in an oven at 130 ° C. for 30 minutes in a nitrogen gas atmosphere. The thickness of the coating film after the annealing treatment was 70 nm.

  Thereafter, using a metal mask having a predetermined pattern opening, an aluminum layer as an upper electrode was formed on the coating film by a vapor deposition method (thickness = 10 nm). Thereafter, 1 μm of PVA (polyvinyl alcohol) was formed by spin coating and baked at 150 ° C. to prepare a passivation layer (not shown). The optical sensor array 20 was produced as described above.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Example (Production of Comparative Organic Photoelectric Conversion Element 1)
An indium tin oxide (ITO) transparent conductive film deposited on a glass substrate with a thickness of 110 nm (sheet resistance 13Ω / □) is patterned to a width of 2 mm using a normal photolithography technique and hydrochloric acid etching, and the anode (Anode) was formed.

  The patterned anode was cleaned in the order of ultrasonic cleaning with a surfactant and ultrapure water, followed by ultrasonic cleaning with ultrapure water, dried with nitrogen blow, and finally subjected to ultraviolet ozone cleaning.

  On this transparent substrate, Baytron P4083 (manufactured by Starck Vitec), which is a conductive polymer, was spin-coated to a thickness of 30 nm, and then heated and dried at 140 ° C. in the atmosphere for 10 minutes.

  After this, the substrate was brought into the glove box and worked under a nitrogen atmosphere. First, the substrate was heat-treated at 140 ° C. for 3 minutes in a nitrogen atmosphere. A solution was prepared by dissolving 1.5 mass% of plexcore OS2100 (P3HT) manufactured by Plextronics as a p-type semiconductor material and 1.5 mass% of E100 (PCBM) manufactured by Frontier Carbon as an n-type semiconductor material in chlorobenzene. While being filtered through a 0.45 μm filter, spin coating was performed at 500 rpm for 60 seconds, then at 2200 rpm for 1 second, and left at room temperature for 30 minutes.

  Next, a solution in which batocuproine (BCP) manufactured by Aldrich was mixed with 2,2,3,3-tetrafluoro-1-propanol at a ratio of 0.5 mass% was spin-coated at 1500 rpm, and a hole block having a thickness of 10 nm was formed. A layer was formed.

Next, the substrate on which the series of organic layers was formed was placed in a vacuum deposition apparatus without being exposed to the atmosphere. The element was set so that the shadow mask with a width of 2 mm was orthogonal to the transparent electrode, and the inside of the vacuum deposition apparatus was depressurized to 10 ⁻³ Pa or less, and then 100 nm of Al was deposited. Finally, the heating for 30 minutes was performed at 120 degreeC, and the comparative organic photoelectric conversion element 1 was obtained. The deposition rate was 2 nm / second, and the size was 2 mm square.

  The obtained organic photoelectric conversion element 1 was taken out into the atmosphere after sealing using an aluminum cap and a UV curable resin (manufactured by Nagase ChemteX Corporation, UV RESIN XNR5570-B1) in a nitrogen atmosphere.

(Preparation of organic photoelectric conversion elements 2 to 16)
In producing the comparative organic photoelectric conversion element 1, organic photoelectric conversion elements 2 to 16 were produced in the same manner except that the n-type semiconductor material shown in Table 1 was used instead of PCBM.

  The comparative compound was synthesized with reference to Example 2 of Patent Document 1.

(Preparation of organic photoelectric conversion element 17)
In the production of the comparative organic photoelectric conversion element 1, α-secsithiophene was used instead of Plexcore OS2100 manufactured by Plextronics, and the exemplified compound 202 according to the present invention was used as an n-type semiconductor material instead of PCBM. In the same manner, an organic photoelectric conversion element 17 was produced.

(Evaluation of organic photoelectric conversion element)
The produced organic photoelectric conversion element was sealed with an aluminum cap and a UV curable resin (manufactured by Nagase ChemteX Corp., UV RESIN XNR5570-B1) in a nitrogen atmosphere, and then taken out into the atmosphere, and light from a solar simulator. Was irradiated at an irradiation intensity of 100 mW / cm ² (AM1.5G), voltage-current characteristics were measured, and conversion efficiency was measured.

Furthermore, the conversion efficiency at this time was set to 100, the conversion efficiency after continuing irradiation for 1000 h with the irradiation intensity of 100 mW / cm < ² >, connecting resistance between an anode and a cathode was evaluated, and the conversion efficiency fall was computed.

  The evaluation results are shown in Table 1.

  As is clear from Table 1, it can be seen that the organic photoelectric conversion element of the present invention has high conversion efficiency and durability.

DESCRIPTION OF SYMBOLS 10 Bulk heterojunction type organic photoelectric conversion element 11 Substrate 12 Anode 13 Cathode 14 Photoelectric conversion part (bulk heterojunction layer)
14p p layer 14i i layer 14n n layer 14 'first photoelectric conversion part 15 charge recombination layer 16 second photoelectric conversion part 17 hole transport layer 18 electron transport layer 20 photosensor array 21 substrate 22 anode 23 cathode 24 photoelectric Conversion unit 24a Buffer layer 24b Photoelectric conversion layer 25 Measurement unit (light receiving unit: light receiving area 5 mm)
26 Incident light

Claims (13)

An organic photoelectric conversion element comprising a layer containing a fullerene derivative represented by the general formula (1) and a p-type semiconductor material between a cathode and an anode.

(In the formula, the dotted line portion represents an atomic group forming a crosslinked structure. R represents a substituent)   The organic photoelectric conversion device according to claim 1, wherein the fullerene derivative represented by the general formula (1) is composed of fullerene C60. The organic photoelectric conversion device according to claim 1, wherein R of the fullerene derivative represented by the general formula (1) has a structure represented by Ar.
(Here Ar represents a substituted or unsubstituted aromatic ring structure.)   The organic photoelectric conversion device according to any one of claims 1 to 3, wherein the fullerene derivative represented by the general formula (1) has a cross-linked structure portion of 2 atoms or more and 15 atoms or less.   The organic photoelectric conversion device according to claim 3 or 4, wherein the structure represented by Ar is a substituted or unsubstituted six-membered ring structure.   The organic photoelectric conversion device according to claim 5, wherein the structure represented by Ar is substituted with an electron donating group.   The organic photoelectric conversion device according to claim 5, wherein the structure represented by Ar is substituted with an alkoxy group.   The organic photoelectric conversion element according to claim 7, wherein the meta position of the structure represented by Ar is substituted with an alkoxy group.   The organic photoelectric conversion element according to claim 1, wherein the p-type semiconductor material is a conjugated polymer.   The organic photoelectric conversion element has a bulk heterojunction layer made of an n-type semiconductor material and a p-type semiconductor material, and the fullerene derivative represented by the general formula (1) is contained in the bulk heterojunction layer. The organic photoelectric conversion device according to any one of claims 1 to 9, wherein   The organic photoelectric conversion element has a bulk heterojunction layer made of an n-type semiconductor material and a p-type semiconductor material, the fullerene derivative represented by the general formula (1) is contained in the bulk heterojunction layer, and the bulk The organic photoelectric conversion element according to claim 1, wherein the telojunction layer is formed by a solution process.   It consists of the organic photoelectric conversion element of any one of Claims 1-11, The solar cell characterized by the above-mentioned.   The organic photoelectric conversion element of any one of Claims 1-11 is arrange | positioned at array form, The optical sensor array characterized by the above-mentioned.

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