WO2013176180A1 - Élément de puissance photovoltaïque et procédé de fabrication d'un élément de puissance photovoltaïque - Google Patents

Élément de puissance photovoltaïque et procédé de fabrication d'un élément de puissance photovoltaïque Download PDF

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WO2013176180A1
WO2013176180A1 PCT/JP2013/064220 JP2013064220W WO2013176180A1 WO 2013176180 A1 WO2013176180 A1 WO 2013176180A1 JP 2013064220 W JP2013064220 W JP 2013064220W WO 2013176180 A1 WO2013176180 A1 WO 2013176180A1
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photoelectric conversion
conversion layer
electron
organic semiconductor
solvent
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Japanese (ja)
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山本　修平
悟 下村
北澤　大輔
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東レ株式会社
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/151—Copolymers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
    • H10K85/211—Fullerenes, e.g. C60
    • H10K85/215—Fullerenes, e.g. C60 comprising substituents, e.g. PCBM
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a photovoltaic device and a method for manufacturing a photovoltaic device.
  • Solar cells are attracting attention as an effective solution to energy problems that are becoming increasingly serious as environmentally friendly electrical energy sources.
  • inorganic materials such as single crystal silicon, polycrystalline silicon, amorphous silicon, and compound semiconductors are used as semiconductor materials for photovoltaic elements of solar cells.
  • solar cells manufactured using inorganic semiconductors are still expensive, they have not been widely used in general households.
  • the high cost factor is mainly in the process of forming the semiconductor thin film under vacuum and high temperature. Therefore, organic semiconductor cells using organic semiconductors such as conjugated polymers and organic crystals and organic dyes are being studied as semiconductor materials that are expected to simplify the manufacturing process.
  • a semiconductor material can be manufactured by a coating method, so that the manufacturing process can be simplified.
  • an organic solar cell using a conjugated polymer or the like has not yet been put into practical use because it has a lower photoelectric conversion efficiency than a solar cell using a conventional inorganic semiconductor.
  • a technique for realizing higher photoelectric conversion efficiency is required.
  • the domain size can be changed by the electrostatic coating method according to the time for injecting the p-type material and the n-type material, the strength of applied voltage at the time of injection, the mixing ratio of the p-type material and the n-type material, and the like.
  • the photoelectric conversion efficiency of the organic solar cell manufactured by the method is improved.
  • C 60 fullerene compound is an electron-accepting organic semiconductor on the polythiophene film is an electron-donating organic semiconductor
  • a method of applying a second organic semiconductor solution on the first organic semiconductor layer is disclosed, such as a method of applying a dichloromethane solution (see, for example, Non-Patent Document 1 and Patent Document 2). According to this method, although the concentration difference polythiophene and C 60 fullerene compound in the photoelectric conversion layer can be applied, an example of using the C 70 fullerene compound as an electron-accepting organic semiconductor is not disclosed.
  • an organic thin-film solar cell having at least two organic semiconductor layers or a method for producing the same, and by blending a polymer material in a coating liquid for forming the lower layer of the organic semiconductor layer, the upper layer of the lower layer component
  • a technique for improving photoelectric conversion efficiency by preventing elution of the liquid or by forming irregularities at the interface between the organic semiconductor layers has been disclosed (see, for example, Patent Documents 3 and 4).
  • such techniques are not intended to electron-donating organic semiconductor and an electron-accepting organic semiconductor photoelectric conversion layer to impart density difference, an example of using the C 70 fullerene compound as an electron-accepting organic semiconductor also been disclosed Absent.
  • JP 2012-4299 A Special table 2009-514184 gazette JP 2006-310727 A JP 2007-73717 A JP 2011-124467 A JP 2007-273939 A
  • the present inventors have, for the purpose of photoelectric conversion efficiency of the photovoltaic element, the method disclosed in Non-Patent Document 1, similarly using a C 70 fullerene compounds having excellent light absorption characteristics than the C 60 fullerene compound was evaluated, would occur aggregate size of about a few micrometers of C 70 fullerene, photoelectric conversion efficiency was found to decrease. The decrease in photoelectric conversion efficiency is presumed to be because the generated aggregates inhibit charge separation and charge transport.
  • the present invention was made in view of the above, the photoelectric conversion layer C 70 fullerene compounds having excellent light absorption characteristics are present with a density difference, the photovoltaic element and has excellent photoelectric conversion characteristics
  • An object of the present invention is to provide a method for manufacturing a photovoltaic device.
  • the present inventors have found that aggregation of C 70 fullerene compounds, thought to be due to solubility lack of C 70 fullerene compound solvent. Therefore, simply by applying onto the electron-donating organic semiconductor film by using a solvent of high solubility in C 70 fullerene compound attempts to stack the electron-accepting organic semiconductor layer, the solvent used in the electron-donating organic semiconductor As the solubility increases, a new problem arises that the electron-donating organic semiconductor is dissolved. Also, during coating is dissolved in the electron-donating organic semiconductor, and even C 70 solvent system is no problem that aggregation of the fullerene, the problem that C 70 fullerene compounds by increasing the C 70 fullerene concentration during drying aggregate I also noticed that there was a case.
  • the present inventors have further conducted intensive studies, as a solvent of the electron-accepting organic semiconductor solution containing a C 70 fullerene compounds, the solubility of the electron-donating organic semiconductor material is less than 5 g / L, of C 70 fullerene compound Using a solvent containing at least a first solvent having a solubility of 5 g / L or more and a second solvent having a solubility of C 70 fullerene compound of 20 g / L or more and a boiling point 30 ° C.
  • the present invention provides a photoelectric conversion layer having an electron-accepting organic semiconductor containing an electron-donating organic semiconductor and C 70 fullerene compounds, a photovoltaic element was sandwiched between the anode and the cathode, the C 70 fullerene compound It is a photovoltaic device that exists with a high density difference from the cathode side to the anode side.
  • a photovoltaic device having excellent photoelectric conversion efficiency can be provided.
  • the average slope of the C 70 fullerene compound is a diagram showing an example of a film thickness direction distribution pattern for 1% / nm.
  • FIG. 2 is a cross-sectional view showing one embodiment of the photovoltaic element of the present invention.
  • FIG. 3 is a photograph of the surface of the photoelectric conversion layer of the photovoltaic element of Example 1 taken with a laser microscope.
  • FIG. 4 is a photograph of the surface of the photoelectric conversion layer of the photovoltaic element of Comparative Example 2 imaged with a laser microscope.
  • the photovoltaic element of the present invention is a photovoltaic element of the photoelectric conversion layer, was sandwiched between an anode and a cathode with an electron-accepting organic semiconductor and an electron-donating organic semiconductor comprising a C 70 fullerene compounds, C 70 fullerene
  • This is a photovoltaic device in which the compound exists with a high concentration difference from the anode side to the cathode side.
  • the C 70 fullerene compound has a high density difference from the cathode side to the anode side in the photoelectric conversion element. At least the density difference among the following three types (density difference A, density difference B, density difference C). Satisfying C. Furthermore, it is preferable to satisfy the density difference A and the density difference B in addition to the density difference C.
  • Satisfying the concentration difference A means that from the depth d 1 indicating the maximum abundance M 1 of the C 70 fullerene compound from the cathode / photoelectric conversion layer interface to half the depth of the photoelectric conversion layer, the anode / photoelectric conversion layer interface
  • d 1 -d 2 ) is 1% / nm or more.
  • the depth closer to the cathode is selected.
  • the depth of the minimum abundance M 2 of the C 70 fullerene compound is two or more, the depth closer to the anode is selected.
  • the average slope of the abundance of C 70 fullerene compounds exemplified some thickness direction distribution pattern of C 70 fullerene compound in the case of 1% / nm in FIG.
  • the present invention is not particularly limited to this.
  • Satisfying the density difference B means that the maximum abundance M 1 of the C 70 fullerene compound from the cathode / photoelectric conversion layer interface to 1/2 the depth of the photoelectric conversion layer and 1 of the photoelectric conversion layer from the anode / photoelectric conversion layer interface. It means that the difference (M 1 -M 2 ) from the minimum abundance M 2 of the C 70 fullerene compound up to a depth of / 2 is 60% or more. Also in the density difference B, the definitions of M 1 and M 2 are the same as the density difference A.
  • Satisfying the density difference C means that the average value M 1a of the abundance of C 70 fullerene compound from the cathode / photoelectric conversion layer interface to 1/2 the depth of the photoelectric conversion layer, and from the anode / photoelectric conversion layer interface to the photoelectric conversion layer
  • the difference (M 1a -M 2a ) with respect to the average value M 2a of the C 70 fullerene compound existing up to 1 ⁇ 2 of the depth is 20% or more.
  • Mean value M 1a and the average value M 2a abundance of C 70 fullerene compounds by the measurement method to be described later, from the cathode / the photoelectric conversion layer interface in the half of the depth of the photoelectric conversion layer, the C 70 fullerene compound
  • the value at which the abundance is maximum is 100%, it is an average value of relative values with respect to the maximum value (100%).
  • Concentration differences A, B, and C can be determined by, for example, using the method described in Applied Surface Science 2004, 231-232, pages 353-356 and the photoelectric conversion layer. Can be measured by time-of-flight secondary ion mass spectrometry (TOF-SIMS).
  • TOF-SIMS time-of-flight secondary ion mass spectrometry
  • a sample including a photoelectric conversion layer and an electrode is cut obliquely over several ⁇ m or more to expose the inside of the photoelectric conversion layer.
  • TOF-SIMS analysis is performed on the exposed portion of the oblique cut surface corresponding to the photoelectric conversion layer.
  • Other methods include a method of performing TOF-SIMS analysis while gradually exposing the inside by sputtering.
  • the distribution in the film thickness direction of each constituent of the photoelectric conversion layer can be examined.
  • the distribution of this film thickness direction to know the distribution of the C 70 fullerene compounds, focusing on the secondary ion derived from the C 70 fullerene compounds, it may be plotted against film thickness corresponding to the signal intensity.
  • the secondary ion derived from the C 70 fullerene compounds used depending on the kind of C 70 fullerene compounds, e.g., C 70 positive ions (C70 +, mass number 840) is better.
  • the signal intensity distribution in the film thickness direction of the C 70 plus ion component obtained by TOF-SIMS (it is better to smooth the distribution by taking an average of 10 points in the film thickness direction) from the cathode / photoelectric conversion layer interface.
  • the maximum intensity of the C 70 plus ion component up to 1/2 the depth of the photoelectric conversion layer as the maximum abundance M 1 (100%)
  • the abundance distribution in the depth direction in the photoelectric conversion layer is relatively Can be obtained.
  • the density difference can be calculated from the relative abundance distribution in the depth direction.
  • the electron-donating organic semiconductor material has a higher density difference to the cathode side from the anode side, it can be defined as in the case of the C 70 fullerene compounds. That is, the fact that the electron-donating organic semiconductor has a high concentration difference from the anode side to the cathode side means that at least the concentration difference F is satisfied among the following three types (concentration difference D, concentration difference E, concentration difference F). . Further, in addition to the density difference F, it is preferable to satisfy the density difference D and the density difference E.
  • the cathode / photoelectric conversion layer has a depth d 3 indicating the maximum abundance M 3 of the electron-donating organic semiconductor from the anode / photoelectric conversion layer interface to a depth of 1 ⁇ 2 of the photoelectric conversion layer.
  • Average slope of the abundance of the electron-donating organic semiconductor from the interface to a depth indicating the minimum abundance M 4 of the electron-donating organic semiconductor from the depth of 1/2 of the photoelectric conversion layer (M 3 -M 4 ) / ( d 3 -d 4 ) is 1% / nm or more.
  • the maximum abundance M 3 and the minimum abundance M 4 of the electron-donating organic semiconductor material are measured at a depth of 1 ⁇ 2 of the photoelectric conversion layer from the anode / photoelectric conversion layer interface by the measurement method described later.
  • the value at which the abundance of the semiconductor material is maximized is 100% (M 3 )
  • the abundance of the electron-donating organic semiconductor material is at a depth of 1 ⁇ 2 of the photoelectric conversion layer from the cathode / photoelectric conversion layer interface.
  • a relative value (M 4 ) with respect to M 3 was used.
  • Satisfying the concentration difference E means that the maximum abundance M 3 of the electron-donating organic semiconductor material from the anode / photoelectric conversion layer interface to 1/2 the depth of the photoelectric conversion layer and from the cathode / photoelectric conversion layer interface to the photoelectric conversion layer
  • the difference (M 3 ⁇ M 4 ) from the minimum abundance M 4 of the electron-donating organic semiconductor material up to a depth of 1 ⁇ 2 is 60% or more.
  • the definitions of M 3 and M 4 are the same as the density difference D.
  • Satisfying the concentration difference F means that the average value M 3a of the abundance of the electron-donating organic semiconductor material from the anode / photoelectric conversion layer interface to 1/2 the depth of the photoelectric conversion layer and the photoelectric from the cathode / photoelectric conversion layer interface. It means that the difference (M 3a -M 4a ) from the average value M 4a of the amount of the electron-donating organic semiconductor material up to half the depth of the conversion layer is 20% or more.
  • the average value M 3a and the average value M 4a of the abundance of the electron-donating organic semiconductor material are determined according to the measurement method described later, etc. When the value at which the abundance of the organic semiconductor material is maximum is 100%, it is an average value of relative values with respect to the maximum value (100%).
  • a signal derived from the electron-donating organic semiconductor material may be examined in the same method as the method for analyzing the electron-accepting organic semiconductor material.
  • a solution containing an electron donating organic semiconductor material is applied to the anode surface to produce an electron donating organic semiconductor layer, and a C 70 fullerene compound is formed on the electron donating organic semiconductor layer.
  • an electron-accepting organic semiconductor solution containing a C 70 fullerene compound By applying an electron-accepting organic semiconductor solution containing a C 70 fullerene compound, a photoelectric conversion layer in which a C 70 fullerene compound exists with a high concentration difference from the cathode side to the anode side is produced.
  • the surface roughness Ra of the photoelectric conversion layer produced by applying the organic semiconductor solution is preferably 0 nm to 5 nm.
  • the surface roughness Ra (arithmetic average roughness) of the photoelectric conversion layer is a value (JISB0601) obtained by measuring an arbitrary place (5 ⁇ m ⁇ 5 ⁇ m) on the surface of the photoelectric conversion layer with an atomic force microscope.
  • the line roughness Rq of the photoelectric conversion layer is preferably 0 nm to 6 nm. If the linear roughness Rq of the photoelectric conversion layer is 6nm or less, aggregation are sufficiently suppressed in the C 70 fullerene compounds, they never charge separation and charge transportation is inhibited.
  • the line roughness Rq (root mean square roughness) of the photoelectric conversion layer is a value (JISB0601) obtained by measuring an arbitrary place (5 ⁇ m ⁇ 5 ⁇ m) on the surface of the photoelectric conversion layer with an atomic force microscope.
  • FIG. 2 is a cross-sectional view showing one embodiment of the photovoltaic element of the present invention.
  • an anode 2 In the photovoltaic device 10 of the present invention, an anode 2, a photoelectric conversion layer 3, and a cathode 4 are formed in this order on a substrate 1.
  • the C 70 fullerene compound In the photoelectric conversion layer 3, the C 70 fullerene compound is added from the cathode 4 side to the anode 2. It exists with a high density difference on the side.
  • an electrode such as the anode 2 and the cathode 4, or a substrate on which the photoelectric conversion layer 3 can be selected can be selected and used.
  • films made by any method from inorganic materials such as alkali-free glass and quartz glass, organic materials such as polyester, polycarbonate, polyolefin, polyamide, polyimide, polyphenylene sulfide, polyparaxylene, epoxy resin and fluorine resin A board can be used.
  • the light transmittance of the substrate 1 is preferably 60-100%.
  • the light transmittance is a value given by the following equation.
  • Light transmittance (%) [transmitted light intensity (W / m 2 ) / incident light intensity (W / m 2 )] ⁇ 100
  • the anode 2 or the cathode 4 has light transmittance. It is sufficient that at least one of them has optical transparency, and both of them may have optical transparency.
  • having light transmittance means that incident light reaches the photoelectric conversion layer 3 and an electromotive force is generated. That is, when the light transmittance exceeds 0%, it is said to have light transmittance.
  • the light-transmitting electrode preferably has a light transmittance of 60 to 100% in all wavelength regions of 400 nm to 900 nm. Further, the thickness of the light-transmitting electrode is not limited as long as sufficient conductivity is obtained and varies depending on the material, but is preferably 20 nm to 300 nm. In addition, the electrode which does not have a light transmittance should just be electroconductive, and thickness is not specifically limited, either.
  • the electrode material it is preferable to use a conductive material having a high work function for the anode 2 and a conductive material having a low work function for the other cathode 4.
  • Conductive materials with large work functions include metals such as gold, platinum, chromium and nickel, transparent metal oxides such as indium and tin, and complex metal oxides (indium tin oxide (ITO), indium zinc oxide) Products (IZO) and the like, and conductive polymers are preferably used.
  • metals such as gold, platinum, chromium and nickel
  • transparent metal oxides such as indium and tin
  • complex metal oxides indium tin oxide (ITO), indium zinc oxide) Products (IZO) and the like
  • conductive polymers are preferably used.
  • the anode 2 more preferably has a hole extraction layer.
  • An interface state suitable for extracting carriers can be formed by the hole extraction layer. Furthermore, there is an effect of preventing a short circuit between the electrodes.
  • a conductive polymer such as a polythiophene polymer containing a dopant, a poly-p-phenylene vinylene polymer, a polyfluorene polymer, or a metal oxide such as molybdenum oxide may be used. Preferably used.
  • the polythiophene polymer, the poly-p-phenylene vinylene polymer, and the polyfluorene polymer refer to polymers having a thiophene skeleton, a p-phenylene vinylene skeleton, and a fluorene skeleton in the main chain, respectively.
  • molybdenum oxide or a polythiophene polymer such as polyethylenedioxythiophene (PEDOT) containing a dopant, particularly a mixture of PEDOT and polystyrene sulfonate (PSS) is more preferable.
  • the hole extraction layer may be formed by laminating a plurality of these materials, and the materials to be laminated may be different.
  • alkali metals such as lithium, alkaline earth metals such as magnesium and calcium, tin, silver, and aluminum are preferably used.
  • an electrode made of an alloy made of the above metal or a laminate of the above metal is also preferably used.
  • the cathode may have an electron extraction layer. Examples of the electron extraction layer include metal fluorides such as lithium fluoride and cesium fluoride, and phenanthroline compounds having electron transport properties such as bathocuproine.
  • the photoelectric conversion layer in the photovoltaic device of the present invention will be described.
  • the photoelectric conversion layer is sandwiched in said anode and cathode, having an electron-accepting organic semiconductor including at least an electron-donating organic semiconductor, a C 70 fullerene compounds.
  • C 70 fullerene compound is present with high density difference to the cathode side from the anode side. Since the C 70 fullerene compound is excellent in light absorption characteristics and electron transport properties, the photoelectric conversion layer preferably contains 1 to 100% by mass of the C 70 fullerene compound as an electron-accepting organic semiconductor. It is more preferable.
  • the photoelectric conversion layer may contain two or more kinds of electron donating organic semiconductors or electron accepting organic semiconductors.
  • the electron donating organic semiconductor and the electron accepting organic semiconductor form a mixed layer.
  • the content ratio of the electron-donating organic semiconductor and the electron-accepting organic semiconductor in the entire photoelectric conversion layer is not particularly limited, but the weight ratio of electron-donating organic semiconductor: electron-accepting organic semiconductor is 1 to 99:99 to 1.
  • the range is preferably 10 to 90:90 to 10 and more preferably 20 to 60:80 to 40.
  • the photoelectric conversion layer only needs to have a thickness sufficient for the electron-donating organic semiconductor and the electron-accepting organic semiconductor to generate a photovoltaic force by light absorption. Although it varies depending on the material, a thickness of 10 nm to 1000 nm is preferable, and 50 nm to 500 nm is more preferable.
  • the photoelectric conversion layer in the present invention may contain other components such as a surfactant, a binder resin, and a filler as long as the object of the present invention is not impaired.
  • An electron donating organic semiconductor will not be specifically limited if it is an organic substance which shows p-type semiconductor characteristics.
  • polythiophene polymer 2,1,3-benzothiadiazole-thiophene copolymer, quinoxaline-thiophene copolymer, thiophene-benzodithiophene copolymer, poly-p-phenylene vinylene polymer, Conjugated polymers such as poly-p-phenylene polymer, polyfluorene polymer, polypyrrole polymer, polyaniline polymer, polyacetylene polymer, polythienylene vinylene polymer, H 2 phthalocyanine (H 2 Pc), phthalocyanine compounds such as copper phthalocyanine (CuPc), zinc phthalocyanine (ZnPc), porphyrin compounds, N, N′-diphenyl-N, N′-di (3-methylphenyl) -4,4′-diphenyl-1 , 1′-diamine
  • the polythiophene polymer refers to a conjugated polymer having a thiophene skeleton in the main chain, and includes those having a side chain.
  • poly-3-alkylthiophene such as poly-3-methylthiophene, poly-3-butylthiophene, poly-3-hexylthiophene, poly-3-octylthiophene, poly-3-decylthiophene, poly- Poly-3-alkoxythiophene such as 3-methoxythiophene, poly-3-ethoxythiophene, poly-3-dodecyloxythiophene, poly-3-methoxy-4-methylthiophene, poly-3-dodecyloxy-4-methylthiophene And poly-3-alkoxy-4-alkylthiophene.
  • the 2,1,3-benzothiadiazole-thiophene copolymer refers to a conjugated copolymer having a thiophene skeleton and a 2,1,3-benzothiadiazole skeleton in the main chain.
  • Specific examples of the 2,1,3-benzothiadiazole-thiophene copolymer include the following structures. In the following formula, n represents a range of 1 to 1000.
  • the quinoxaline-thiophene copolymer refers to a conjugated copolymer having a thiophene skeleton and a quinoxaline skeleton in the main chain.
  • Specific examples of the quinoxaline-thiophene copolymer include the following structures. In the following formula, n represents a range of 1 to 1000.
  • the thiophene-benzodithiophene polymer refers to a conjugated copolymer having a thiophene skeleton and a benzodithiophene skeleton in the main chain.
  • Specific examples of the thiophene-benzodithiophene copolymer include the following structures. In the following formula, n represents a range of 1 to 1000.
  • the poly-p-phenylene vinylene polymer refers to a conjugated polymer having a p-phenylene vinylene skeleton in the main chain, and includes those having a side chain. Specifically, poly [2-methoxy-5- (2-ethylhexyloxy) -1,4-phenylenevinylene], poly [2-methoxy-5- (3 ′, 7′-dimethyloctyloxy) -1, 4-phenylene vinylene] and the like.
  • Examples of the C 70 fullerene compound used in the present invention include unsubstituted C 70 , [6,6] -phenyl-C71-butyric acid dodecyl ester, phenyl-C71-butyric acid methyl ester ([70] PCBM). And substituted C70 compounds such as
  • the electron-accepting organic semiconductor other than C 70 fullerene compound is not particularly limited as long as organic substances showing a n-type semiconductor characteristics.
  • C 70 fullerene compounds other than fullerene compounds and those of the unsubstituted, including C 60, C 76, C 78 , C 82, C 84, C 90, C 94, [6,6] - Phenyl-C61-butyric acid methyl ester ([6,6] -C61-PCBM, or [60] PCBM), [5,6] -phenyl-C61-butyric acid methyl ester, [6,6] -phenyl Examples thereof include substituted compounds such as —C61-butyric acid hexyl ester and [6,6] -phenyl-C61-butyric acid dodecyl ester.
  • two or more photoelectric conversion layers may be laminated (tandemized) via one or more charge recombination layers to form a series junction.
  • the charge recombination layer also serves as the cathode and anode of the adjacent photoelectric conversion layer.
  • a laminated structure of substrate / anode / first photoelectric conversion layer / first electron extraction layer / charge recombination layer / second photoelectric conversion layer / second electron extraction layer / cathode can be given.
  • the charge recombination layer is a cathode for the first photoelectric conversion layer and can be regarded as an anode of the second photoelectric conversion layer.
  • the organic semiconductor concentration difference in the first photoelectric conversion layer preferably exists from the anode to the charge recombination layer
  • the organic semiconductor concentration difference in the second photoelectric conversion layer is from the charge recombination layer. It preferably exists over the cathode.
  • the hole extraction layer described above may be provided between the anode and the first photoelectric conversion layer and between the charge recombination layer and the second photoelectric conversion layer.
  • the hole extraction layer described above may be provided between the bonding layers and between the second photoelectric conversion layer and the cathode.
  • the charge recombination layer used here needs to have light transmittance so that a plurality of photoelectric conversion layers can absorb light.
  • the charge recombination layer only needs to be designed so that holes and electrons are sufficiently recombined. Therefore, the charge recombination layer does not necessarily have to be a film, for example, a metal formed uniformly on the photoelectric conversion layer. It can be a cluster. Therefore, the charge recombination layer is a very thin metal having a light transmittance of about several angstroms to several tens of angstroms made of the above-mentioned gold, platinum, chromium, nickel, lithium, magnesium, calcium, tin, silver, aluminum, etc.
  • a uniform silver cluster can be formed by depositing silver so as to have a thickness of several angstroms to 1 nm on a quartz oscillator film thickness monitor using a vacuum deposition method.
  • the sol-gel method described in Advanced Materials, 2006, Vol. 18, pages 572-576 may be used. If it is a composite metal oxide such as ITO or IZO, the film may be formed by sputtering. These charge recombination layer formation methods and types may be appropriately selected in consideration of the non-destructive property to the photoelectric conversion layer at the time of charge recombination layer formation, the formation method of the next photoelectric conversion layer, and the like. .
  • a transparent electrode such as ITO (corresponding to an anode in this case) is formed on the substrate by sputtering or the like.
  • a desired p-type organic semiconductor material such as PEDOT
  • a spin coating method such as PEDOT
  • a bar coating method such as bar
  • a blade casting method such as blade casting
  • the solvent is removed using a vacuum thermostat or a hot plate to form a hole extraction layer.
  • a vacuum deposition method using a vacuum deposition machine can be applied.
  • an electron-donating organic semiconductor material is dissolved in a solvent to form a solution, which is applied on a transparent electrode (on the hole-extracting layer when a hole-extracting layer is provided) to form an electron-donating organic semiconductor layer To do.
  • the solvent used at this time is preferably an organic solvent, for example, methanol, ethanol, butanol, toluene, xylene, o-chlorophenol, acetone, ethyl acetate, ethylene glycol, tetrahydrofuran, dichloromethane, chloroform, dichloroethane, chlorobenzene, dichlorobenzene, Examples include chlorobenzene, chloronaphthalene, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, and ⁇ -butyrolactone.
  • an electron-accepting organic semiconductor material containing C 70 fullerene compound is dissolved in a solvent to make a solution, it is applied to the electron-donating organic semiconductor layer.
  • the coating solution penetrates the electron donating organic semiconductor layer to form the photoelectric conversion layer, thereby forming a photoelectric conversion layer having a concentration difference.
  • the solvent used at this time at least the solubility of the electron donating organic semiconductor is less than 5 g / L, the solubility of the C 70 fullerene compound is 5 g / L or more, and the solubility of the C 70 fullerene compound.
  • a second solvent having a boiling point of 30 ° C. or more higher than that of the first solvent is a value at room temperature and normal pressure.
  • the solubility of the electron donating organic semiconductor is less than 5 g / L, the solubility of the C 70 fullerene compound is not so high. Therefore, when only the first solvent is used, the solubility of the C 70 fullerene compound is insufficient. Aggregation of 70 fullerene compounds occurs. This is because the C 70 fullerene compound is dissolved in the first solvent at the time of coating, but the first solvent is vaporized and the C 70 fullerene compound is concentrated in the latter stage of drying. On the other hand, since the solubility of the C 70 fullerene compound is 20 g / L or more, the solubility of the electron-donating organic semiconductor that is a conjugated compound is high as in the case of the C 70 fullerene compound.
  • the electron-donating organic semiconductor layer is dissolved by the second solvent.
  • the aggregation of the C 70 fullerene compound can be prevented by using the first solvent and the second solvent in a range that does not impair insolubility in the electron-donating organic semiconductor layer. This is because during the coating and drying for the first solvent is a low boiling point vaporizes preferentially, drying becomes second solvent is the main component of the C 70 fullerene compound highly soluble in late throughout the drying process of the C 70 fullerene compound This is because high solubility in the solvent, that is, high dispersibility is maintained.
  • the mixing ratio of the first solvent and the second solvent is not particularly limited as long as the insolubility in the electron-donating organic semiconductor layer is not impaired, but the mass fraction of the first solvent: the second solvent is 50 to 99. It is preferably in the range of 9:50 to 0.1, more preferably in the range of 70 to 99:30 to 1, and still more preferably in the range of 90 to 99:10 to 1.
  • the solubility of the electron-donating organic semiconductor in the first solvent is not particularly limited as long as it is less than 5 g / L, but is preferably less than 1 g / L. Further, the solubility of the 1 C 70 fullerene compounds of the solvent is not particularly limited as long as 5 g / L or more, preferably 10 g / L or more.
  • the solubility of C 70 fullerene compounds of the second solvent is not particularly limited as long as 20 g / L or more, preferably 50 g / L or more, more preferably 100 g / L or more.
  • the boiling point of the second solvent is not particularly limited as long as it is 30 ° C. or higher than the first solvent, but is preferably 50 ° C. or higher and lower than 300 ° C., more preferably 90 ° C. or higher and lower than 200 ° C.
  • the first solvent is not particularly limited as long as it satisfies the above physical properties, but is preferably an organic solvent, such as dichloromethane, 1,2-dichloroethylene, 1,1,1,2-tetrachloroethane, 1,1,1, 3-tetrachloropropane, 1,2,2,3-tetrachloropropane, 1,1,2,3-tetrachloropropane, toluene, 1,3-dichloropropane, 1,3-dibromopropane, 1,2-dibromopropane, Examples thereof include 1-iodopropane.
  • organic solvent such as dichloromethane, 1,2-dichloroethylene, 1,1,1,2-tetrachloroethane, 1,1,1, 3-tetrachloropropane, 1,2,2,3-tetrachloropropane, 1,1,2,3-tetrachloropropane, toluene, 1,3-dichloropropane, 1,3-d
  • the second solvent is not particularly limited as long as it satisfies the above physical properties, but is preferably an organic solvent, such as 1,1,1,2-tetrachloroethane, chlorobenzene, 1,2-dichlorobenzene, 1,2,4. -Trichlorobenzene, 1-chloronaphthalene, 1-bromonaphthalene, 1-methylnaphthalene, 1,3-dibromopropane, 1,2-dibromopropane, dibromooctane, iodopropane, diiodooctane and the like.
  • organic solvent such as 1,1,1,2-tetrachloroethane, chlorobenzene, 1,2-dichlorobenzene, 1,2,4. -Trichlorobenzene, 1-chloronaphthalene, 1-bromonaphthalene, 1-methylnaphthalene, 1,3-dibromopropane, 1,2-dibromopropane, dibro
  • the combination of the first solvent and the second solvent includes dichloromethane and chlorobenzene, dichloromethane and 1,2-dichlorobenzene, dichloromethane and 1,2,4-trichlorobenzene, dichloromethane and 1-chloronaphthalene, dichloromethane and 1,3-dibromo.
  • the solvent of the electron-accepting organic semiconductor solution depends on the treatment step after coating the electron-accepting organic semiconductor solution, it may remain in the coating film in a small amount. It is possible to detect.
  • Residual solvent analysis methods include, for example, heated gas generation analysis methods, such as thermogravimetry-mass spectrometry (TG-MS) and temperature-programmed desorption-mass spectrometry (TPD-MS (Temperature Programmed). Desorption-Mass Spectrometry), Temperature-Degassing Analysis (TDS (Thermal Desorption Spectrometry)), Purge and Trap-Gas Chromatography-Mass Spectrometry (P & T-GC-MS (Purge & Trap-Gas Chromatography) -Using MS analysis (after re-dissolving the power generation layer, perform GC-MS analysis) It is possible to detect the solvent remaining in trace amounts in the coating film by.
  • heated gas generation analysis methods such as thermogravimetry-mass spectrometry (TG-MS) and temperature-programmed desorption-mass spectrometry (TPD-MS (Temperature Programmed). Desorption-Mass Spectrometry), Temperature-Degassing Analysis
  • a photoelectric conversion layer by applying an electron-accepting organic semiconductor solution onto an electron-donating organic semiconductor layer, spin coating, blade coating, slit die coating, screen printing coating, bar coater coating, mold coating, print transfer Any method may be used such as a method, a dip pulling up method, an ink jet method, a spray method, a vacuum deposition method, etc., as long as the formation method is selected according to the characteristics of the photoelectric conversion layer to be obtained, such as film thickness control and orientation control. Good.
  • the electron-donating organic material and the electron-accepting organic material of the present invention have a concentration of 1 to 50 g / L (the electron-donating organic material or the electron-accepting organic material of the present invention and a solvent
  • the mass concentration of the electron-donating organic material or electron-accepting organic material of the present invention is preferably with respect to the volume of the solution containing, and by this concentration, a homogeneous photoelectric conversion layer having a thickness of 5 to 200 nm can be obtained.
  • an annealing treatment may be performed under reduced pressure or under an inert atmosphere (nitrogen or argon atmosphere).
  • a preferable temperature for the annealing treatment is 40 ° C to 300 ° C, more preferably 50 ° C to 200 ° C. This annealing treatment may be performed after the formation of the cathode.
  • a photovoltaic element After formation of the photoelectric conversion layer, a photovoltaic element can be produced by forming a metal electrode such as Al or Ag (in this case, corresponding to a cathode) on the photoelectric conversion layer by vacuum deposition or sputtering.
  • a metal electrode such as Al or Ag (in this case, corresponding to a cathode)
  • the photovoltaic element of the present invention can be applied to various photoelectric conversion devices using a photoelectric conversion function, an optical rectification function, and the like.
  • photovoltaic cells such as solar cells
  • electronic devices such as optical sensors, optical switches, phototransistors
  • optical recording materials such as optical memories
  • the photoelectric conversion efficiency ⁇ (%) in each example / comparative example was determined by the following equation.
  • ⁇ (%) Isc (mA / cm 2 ) ⁇ Voc (V) ⁇ FF / irradiation light intensity (mW / cm 2 ) ⁇ 100
  • FF JVmax / (Isc (mA / cm 2 ) ⁇ Voc (V)) JVmax (mW / cm 2 ) is a value of the product of the current density and the applied voltage at the point where the product of the current density and the applied voltage is maximum between the applied voltage of 0 V and the open circuit voltage.
  • the solid obtained by filtration while hot was dissolved in 300 ml of chloroform, passed through a silica gel short column (eluent: chloroform), concentrated, and reprecipitated with methanol to obtain 354 mg of compound A-1 (yield 78 %).
  • the weight average molecular weight was 39500, the number average molecular weight was 16,600, and the degree of polymerization n was 47.4.
  • the obtained solid was dissolved in chloroform, passed through Celite (manufactured by Nacalai Tesque), and then a silica gel column (free solution, chloroform), and then the solvent was distilled off under reduced pressure.
  • the obtained solid was dissolved again in chloroform and then reprecipitated in methanol to obtain Compound A-2 (72 mg).
  • the weight average molecular weight was 45,300, the number average molecular weight was 22,000, and the degree of polymerization n was 44.
  • Example 1 By adding 1 mL of a chlorobenzene solution into a sample bottle containing 10 mg of (A-1), and ultrasonically irradiating for 30 minutes in an ultrasonic cleaner (US-2 manufactured by Iuchi Seieido Co., Ltd., output 120 W) An electron donating organic semiconductor solution A was obtained. Next, 1 mL of a dichloromethane (first solvent) solution mixed with 3% by mass of chlorobenzene (second solvent) was added to a sample bottle containing 8 mg of [70] PCBM (manufactured by Solene), and subjected to ultrasonic cleaning. The electron-accepting organic semiconductor solution B was obtained by ultrasonic irradiation for 30 minutes in the machine.
  • an ultrasonic cleaner US-2 manufactured by Iuchi Seieido Co., Ltd., output 120 W
  • An electron donating organic semiconductor solution A was obtained.
  • the solubility of (A-1) in dichloromethane (first solvent) was 1 g / L.
  • a glass substrate on which an ITO transparent conductive layer serving as an anode was deposited to 125 nm by sputtering was cut into 38 mm ⁇ 46 mm, and then ITO was patterned into a 38 mm ⁇ 13 mm rectangular shape by photolithography.
  • the light transmittance of the obtained substrate was measured with a Hitachi spectrophotometer U-3010. As a result, it was 85% or more in all wavelength regions from 400 nm to 900 nm.
  • the substrate was ultrasonically cleaned with an alkali cleaning solution (Semicoclean EL56, manufactured by Furuuchi Chemical Co., Ltd.) for 10 minutes, and then cleaned with ultrapure water. After this substrate was UV / ozone treated for 30 minutes, a PEDOT: PSS aqueous solution (PEDOT 0.8 mass%, PSS 0.5 mass%) was applied onto the substrate by spin coating, and heated and dried at 200 ° C. for 5 minutes on a hot plate. Then, a film was formed to a thickness of about 30 nm. The electron donating organic semiconductor solution A was dropped on the PEDOT: PSS layer, and an electron donating organic semiconductor layer was formed by spin coating.
  • an alkali cleaning solution Semicoclean EL56, manufactured by Furuuchi Chemical Co., Ltd.
  • the electron-accepting organic-semiconductor solution B was dripped on the electron-donating organic-semiconductor layer, and the photoelectric converting layer was formed with the spin coat method.
  • the substrate and the mask for the cathode are placed in a vacuum deposition apparatus, and the degree of vacuum in the apparatus is evacuated to 1 ⁇ 10 ⁇ 3 Pa or less, and the Al layer serving as the cathode is formed to a thickness of 80 nm by resistance heating. Vapor deposited.
  • the extraction electrodes were taken out from the upper and lower electrodes of the produced device, and a photovoltaic device having an area where the band-like ITO layer and the Al layer overlap each other was 5 mm ⁇ 5 mm was produced.
  • the upper and lower electrodes of the photovoltaic device thus fabricated were connected to a Keithley 2400 series source meter and irradiated with white light (AM1.5; 100 mW / cm 2 ) from the ITO layer side in the atmosphere.
  • the current value when the applied voltage was changed from ⁇ 1V to + 2V was measured.
  • the photoelectric conversion efficiency ( ⁇ ) was 4.85%.
  • the concentration difference A defined as the average slope is 1.2% / nm
  • the concentration difference B defined as the abundance difference.
  • the concentration difference C defined as the average abundance difference was 33%.
  • the concentration difference A which is an average inclination is 0.57% / nm
  • the concentration difference B which is an abundance difference is 38%
  • the density difference C which is an average abundance difference, was 10%.
  • Example 2 A photovoltaic device was prepared in exactly the same manner as in Example 1 except that the dichloromethane solution mixed with 3% by mass of chlorobenzene was used as the solvent for the electron-accepting organic semiconductor solution, and only the dichloromethane solvent was used. Measurements were made. As a result of calculating from the obtained current value, the photoelectric conversion efficiency ( ⁇ ) was 0.88%. Further, arbitrary photoelectric conversion layers 5 ⁇ m ⁇ 5 ⁇ m and 5 ⁇ m were measured with an atomic force microscope (Veeco, Dimension Edge). As a result, the surface roughness Ra was 45 nm and the line roughness Rq was 18 to 100 nm. Furthermore, when the film surface was observed with a laser microscope (manufactured by Keyence, VK-9700), [70] PCBM was agglomerated vigorously (FIG. 4).
  • Example 2 By adding 1 mL of a chlorobenzene solution into a sample bottle containing 10 mg of (A-2), and ultrasonically irradiating for 30 minutes in an ultrasonic cleaning machine (US-2 manufactured by Inoue Seieido Co., Ltd., output 120 W) An electron donating organic semiconductor solution D was obtained. Next, 1 mL of a dichloromethane (first solvent) solution in which 1,3-dibromopropane (second solvent) was mixed at a ratio of 20% by mass was placed in a sample bottle containing 10 mg of [70] PCBM (Solaine). In addition, an electron-accepting organic semiconductor solution E was obtained by ultrasonic irradiation for 30 minutes in an ultrasonic cleaner.
  • a dichloromethane (first solvent) solution in which 1,3-dibromopropane (second solvent) was mixed at a ratio of 20% by mass was placed in a sample bottle containing 10 mg of [70] PCBM (Solaine).
  • a photovoltaic device was produced and measured in the same manner as in Example 1 except that the solution D was used instead of the solution A, and the solution E was used instead of the solution B.
  • the photoelectric conversion efficiency ( ⁇ ) was 3.06%.
  • the concentration difference A as an average slope is 1.5% / nm
  • the concentration difference B as an abundance difference is 63%
  • the density difference C which is the average abundance difference, was 43%.
  • Example 1 and 2 and Comparative Examples 1 to 3 are summarized in Table 1. From the comparison between Example 1 and Comparative Examples 1 and 2, and from the comparison between Example 2 and Comparative Example 3, the photovoltaic device of the present invention in which [70] PCBM has a concentration difference in the photoelectric conversion layer It can be seen that the photoelectric conversion efficiency was improved. The importance of the physical properties of the solvent will be described below from the conversion efficiency of a photovoltaic device having [70] PCBM produced by the same method as in Example 1 having a concentration difference.
  • Example 3 Other than using a dichloromethane solution mixed with 3% by mass of chlorobenzene as a solvent for the electron-accepting organic semiconductor solution, a dichloromethane solution mixed with 3% by mass of 1,2-dichlorobenzene was used.
  • a photovoltaic device was prepared in the same manner as in Example 1 and measured. As a result of calculating from the obtained current value, the photoelectric conversion efficiency ( ⁇ ) was 4.66%. Further, as a result of measuring an arbitrary photoelectric conversion layer 5 ⁇ m ⁇ 5 ⁇ m and 5 ⁇ m with an atomic force microscope (Veeco, Dimension Edge), the surface roughness Ra was 0.2 nm and the line roughness Rq was 0.3 nm. It was.
  • Example 4 As a solvent for the electron-accepting organic semiconductor solution, a dichloromethane solution mixed with 3% by mass of 1,2,4-trichlorobenzene was used instead of the dichloromethane solution mixed with 3% by mass of chlorobenzene.
  • a photovoltaic device was produced in the same manner as in Example 1 and measured. As a result of calculating from the obtained current value, the photoelectric conversion efficiency ( ⁇ ) was 4.54%.
  • the surface roughness Ra was 0.3 nm
  • the line roughness Rq was 0.4 nm. It was.
  • Example 5 Example 1 except that a dichloromethane solution in which 1-chloronaphthalene was mixed in a proportion of 3% by mass was used instead of the dichloromethane solution in which chlorobenzene was mixed in a proportion of 3% by mass as a solvent for the electron-accepting organic semiconductor solution.
  • a photovoltaic device was produced in the same manner and measured. As a result of calculating from the obtained current value, the photoelectric conversion efficiency ( ⁇ ) was 3.54%.
  • Example 6 Example 1 except that a dichloromethane solution mixed with 3% by mass of 1,3-dibromopropane was used as a solvent for the electron-accepting organic semiconductor solution instead of a dichloromethane solution mixed with 3% by mass of chlorobenzene.
  • a photovoltaic device was prepared in the same manner as in Example 1 and measured. As a result of calculating from the obtained current value, the photoelectric conversion efficiency ( ⁇ ) was 1.83%.
  • the surface roughness Ra was 1.8 nm and the line roughness Rq was 4.7 nm. It was.
  • Example 7 As a solvent for the electron-accepting organic semiconductor solution, a dichloromethane solution in which 1,1,1,2-tetrachloroethane was mixed at a rate of 3% by mass was used instead of the dichloromethane solution in which chlorobenzene was mixed at a rate of 3% by mass. Other than that, a photovoltaic device was produced in the same manner as in Example 1 and measured. As a result of calculating from the obtained current value, the photoelectric conversion efficiency ( ⁇ ) was 3.08%.
  • Example 8 As a solvent of the electron-accepting organic semiconductor solution, instead of the dichloromethane solution were mixed at a ratio of chlorobenzene 3% by weight, 1,2-dichlorobenzene with a mixture toluene solution at a ratio of 3% by weight, C 70 fullerene compound As in Example 1, a photovoltaic device was prepared and measured in the same manner as in Example 1 except that [70] PCBM 8 mg was used instead of [70] PCBM 8 mg. As a result of calculating from the obtained current value, the photoelectric conversion efficiency ( ⁇ ) was 4.60%.
  • Example 9 As a solvent for the electron-accepting organic semiconductor solution, a 1,2-dibromopropane solution mixed with 3% by mass of 1,2-dichlorobenzene was used instead of the dichloromethane solution mixed with 3% by mass of chlorobenzene.
  • a photovoltaic device was prepared and measured in the same manner as in Example 1 except that 20 mg of [70] PCBM was used instead of 8 mg of [70] PCBM as the C 70 fullerene compound. As a result of calculating from the obtained current value, the photoelectric conversion efficiency ( ⁇ ) was 4.56%.
  • Example 10 As a solvent for the electron-accepting organic semiconductor solution, a 1-iodopropane solution in which 1,2-dichlorobenzene is mixed in a proportion of 3% by mass is used instead of a dichloromethane solution in which chlorobenzene is mixed in a proportion of 3% by mass.
  • a photovoltaic device was prepared and measured in the same manner as in Example 1 except that [70] PCBM 8 mg was used instead of [70] PCBM 8 mg as the 70 fullerene compound. As a result of calculating from the obtained current value, the photoelectric conversion efficiency ( ⁇ ) was 4.69%.
  • Example 11 As a solvent for the electron-accepting organic semiconductor solution, a 1,3-dichloropropane solution mixed with 3% by mass of 1,2-dichlorobenzene was used instead of the dichloromethane solution mixed with 3% by mass of chlorobenzene.
  • a photovoltaic device was prepared and measured in the same manner as in Example 1 except that 15 mg of [70] PCBM was used instead of 8 mg of [70] PCBM as the C 70 fullerene compound. As a result of calculating from the obtained current value, the photoelectric conversion efficiency ( ⁇ ) was 3.65%.
  • Example 1 and 3 to 11 and Comparative Examples 2 and 4 to 8 are summarized in Table 2. From the comparison between Examples 1 and 3 to 7 and Comparative Examples 2 and 4, Example 8 and Comparative Example 5, Example 9 and Comparative Example 6, Example 10 and Comparative Example 7, and Example 11 and Comparative Example 8 It can be seen that the difference in boiling point between the first solvent and the second solvent must be 30 ° C. or more. Next, the ratio of the first solvent to the second solvent will be described from the conversion efficiency of the photovoltaic device having [70] PCBM produced by the same method as in Example 1 having a concentration difference.
  • Example 12 As a solvent for the electron-accepting organic semiconductor solution, the same procedure as in Example 1 was performed except that a dichloromethane solution mixed with chlorobenzene at a ratio of 1% by mass was used instead of the dichloromethane solution mixed with chlorobenzene at a ratio of 3% by mass. A photovoltaic device was prepared and measured. As a result of calculating from the obtained current value, the photoelectric conversion efficiency ( ⁇ ) was 1.79%. Further, as a result of measuring arbitrary photoelectric conversion layers 5 ⁇ m ⁇ 5 ⁇ m and 5 ⁇ m with an atomic force microscope (Veeco, Dimension Edge), the surface roughness Ra was 0.5 nm, and the line roughness Rq was 0.3-5. .4 nm.
  • Example 13 As a solvent for the electron-accepting organic semiconductor solution, the same procedure as in Example 1 was performed except that a dichloromethane solution mixed with 3% by mass of chlorobenzene was used instead of a dichloromethane solution mixed with 3% by mass of chlorobenzene. A photovoltaic device was prepared and measured. As a result of calculating from the obtained current value, the photoelectric conversion efficiency ( ⁇ ) was 4.40%. Moreover, as a result of measuring arbitrary photoelectric conversion layers 5 ⁇ m ⁇ 5 ⁇ m and 5 ⁇ m with an atomic force microscope (Veeco, Dimension Edge), the surface roughness Ra was 1.2 nm, and the line roughness Rq was 1.5 nm. It was.
  • Example 14 As a solvent for the electron-accepting organic semiconductor solution, a dichloromethane solution mixed with 10% by mass of chlorobenzene was used instead of the dichloromethane solution mixed with 3% by mass of chlorobenzene. A photovoltaic device was prepared and measured. As a result of calculating from the obtained current value, the photoelectric conversion efficiency ( ⁇ ) was 3.33%. Moreover, as a result of measuring arbitrary photoelectric conversion layers 5 ⁇ m ⁇ 5 ⁇ m and 5 ⁇ m with an atomic force microscope (Veeco, Dimension Edge), the surface roughness Ra was 1.4 nm and the line roughness Rq was 1.8 nm. It was.
  • Example 15 As a solvent for the electron-accepting organic semiconductor solution, the same procedure as in Example 1 was conducted except that a dichloromethane solution mixed with chlorobenzene at a ratio of 3% by mass was used instead of a dichloromethane solution mixed with chlorobenzene at a ratio of 3% by mass. A photovoltaic device was prepared and measured. As a result of calculating from the obtained current value, the photoelectric conversion efficiency ( ⁇ ) was 2.87%. Moreover, as a result of measuring arbitrary photoelectric conversion layers 5 ⁇ m ⁇ 5 ⁇ m and 5 ⁇ m with an atomic force microscope (Veeco, Dimension Edge), the surface roughness Ra was 0.7 nm, and the line roughness Rq was 0.7 nm. It was.
  • a dichloromethane solution mixed with chlorobenzene at a ratio of 3% by mass was used instead of a dichloromethane solution mixed with chlorobenzene at a ratio of 3% by mass.
  • a photovoltaic device
  • Example 16 As a solvent for the electron-accepting organic semiconductor solution, a dichloromethane solution mixed with 50% by mass of chlorobenzene was used instead of the dichloromethane solution mixed with 3% by mass of chlorobenzene. A photovoltaic device was prepared and measured. As a result of calculating from the obtained current value, the photoelectric conversion efficiency ( ⁇ ) was 1.63%. Moreover, as a result of measuring arbitrary photoelectric conversion layers 5 ⁇ m ⁇ 5 ⁇ m and 5 ⁇ m with an atomic force microscope (Veeco, Dimension Edge), the surface roughness Ra was 0.5 nm, and the line roughness Rq was 0.4 nm. It was.
  • Veeco, Dimension Edge atomic force microscope

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Abstract

Le but de la présente invention est de fournir un élément de puissance photovoltaïque ayant une excellente efficacité de conversion photoélectrique et un procédé de fabrication de l'élément de puissance photovoltaïque. Cet élément de puissance photovoltaïque (10) comporte une couche de conversion photoélectrique (3) qui comprend un semi-conducteur organique donneur d'électrons et un semi-conducteur organique receveur d'électrons qui contient un composé fullerène C70 ; la couche de conversion photoélectrique (3) est prise en sandwich entre une anode (2) et une cathode (4). L'élément de puissance photovoltaïque (10) est caractérisé en ce que, dans la couche de conversion photoélectrique (3), il y a une grande différence de concentration du composé fullerène C70 entre le côté anode et le côté cathode.
PCT/JP2013/064220 2012-05-23 2013-05-22 Élément de puissance photovoltaïque et procédé de fabrication d'un élément de puissance photovoltaïque WO2013176180A1 (fr)

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